WO1998030520A1 - Metal oxide solid acids as catalysts for the preparation of hydrocarbon resins - Google Patents

Metal oxide solid acids as catalysts for the preparation of hydrocarbon resins Download PDF

Info

Publication number
WO1998030520A1
WO1998030520A1 PCT/US1998/000010 US9800010W WO9830520A1 WO 1998030520 A1 WO1998030520 A1 WO 1998030520A1 US 9800010 W US9800010 W US 9800010W WO 9830520 A1 WO9830520 A1 WO 9830520A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal oxide
oxide solid
solid acid
monomers
catalyst
Prior art date
Application number
PCT/US1998/000010
Other languages
French (fr)
Inventor
Andrew Bell
John N. Kostas
Dennis G. Morrell
Laura M. Babcock
Original Assignee
Hercules Incorporated
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hercules Incorporated filed Critical Hercules Incorporated
Priority to EP98901668A priority Critical patent/EP0954516A1/en
Priority to CA002277295A priority patent/CA2277295A1/en
Priority to JP53096598A priority patent/JP2001508102A/en
Priority to AU58133/98A priority patent/AU5813398A/en
Publication of WO1998030520A1 publication Critical patent/WO1998030520A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/06Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/12Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
    • C08F4/14Boron halides or aluminium halides; Complexes thereof with organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F240/00Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02Monomers containing only one unsaturated aliphatic radical
    • C08F12/04Monomers containing only one unsaturated aliphatic radical containing one ring

Definitions

  • This invention relates to metal oxide solid acids useful as catalysts for the polymerization of a feed stream containing at least one of pure monomer, C5 monomers, and
  • Hydrocarbon resins are low molecular weight, thermoplastic materials prepared via thermal or catalytic polymerization.
  • the resins may be derived from several different sources of monomers.
  • the monomer sources include cracked petroleum distillate from oil refining, turpentine fractions (e.g., terpenes from natural product distillation), paper mill byproduct streams, coal tar, and a variety of pure olefinic monomers.
  • the resulting hydrocarbon resins can range from viscous liquids to hard, brittle solids with colors ranging from water white to pale yellow, amber, or dark brown depending on the monomers used and the specific reaction conditions. Typically, pure monomer resins tend to be water white, C9 monomer resins tend to be brown, and C5 monomer resins tend to be yellow.
  • Hydrocarbon resins are used extensively as modifiers in adhesives, rubber, hot-melt coatings, printing inks, paint, flooring, and other applications.
  • the resins are usually used to modify other materials.
  • Pure monomer hydrocarbon resins can be prepared by cationic polymerization of styrene-based monomers such as styrene, alpha-methyl styrene, vinyl toluene, and other alkyl substituted styrenes using Friedel-Crafts polymerization catalysts such as Lewis acids (e.g., boron trifluoride (BF 3 ), complexes of boron trifluoride, aluminum trichloride (A1C1 3 ), alkyl aluminum chlorides).
  • Lewis acids e.g., boron trifluoride (BF 3 ), complexes of boron trifluoride, aluminum trichloride (A1C1 3 ), alkyl aluminum chlorides.
  • aliphatic C5 hydrocarbon resins can be prepared by cationic polymerization of a cracked petroleum feed containing C5 and C6 paraffins, olefins, and diolefins also referred to as "C5 monomers".
  • C5 monomers C5 monomers
  • These monomer streams are comprised of cationically polymerizable monomers such as 1,3-pentadiene which is the primary reactive component along with cyclopentene, pentene, 2-methyl-2-butene, 2-methyl-2-pentene, cyclopentadiene, and dicyclopentadiene.
  • the polymerizations are catalyzed using Friedel- Crafts polymerization catalysts such as Lewis acids (e.g., boron trifluoride (BF 3 ), complexes of boron trifluoride, aluminum trichloride (A1C1 3 ), or alkyl aluminum chlorides).
  • Lewis acids e.g., boron trifluoride (BF 3 ), complexes of boron trifluoride, aluminum trichloride (A1C1 3 ), or alkyl aluminum chlorides.
  • nonpolymerizable components in the feed include saturated hydrocarbons which can be codistilled with the unsaturated components such as pentane, cyclopentane, or 2-methylpentane.
  • This monomer feed can be copolymerized with C4 or C5 olefins or dimers as chain transfer agents.
  • aromatic C9 hydrocarbon resins can be prepared by cationic polymerization of aromatic C8, C9, and/or CIO unsaturated monomers derived from petroleum distillates resulting from naphtha cracking and are referred to as "C9 monomers".
  • C9 monomers These monomer streams are comprised of cationically polymerizable monomers such as styrene, alpha- methyl styrene, beta-methyl styrene, vinyl toluene, indene, dicyclopentadiene, divinylbenzene, and other alkyl substituted derivatives of these components.
  • the polymerizations are catalyzed using Friedel-Crafts polymerization catalysts such as Lewis acids (e.g., boron trifluoride (BF 3 ), complexes of boron trifluoride, aluminum trichloride (A1C1 3 ), alkyl aluminum chlorides).
  • Lewis acids e.g., boron trifluoride (BF 3 ), complexes of boron trifluoride, aluminum trichloride (A1C1 3 ), alkyl aluminum chlorides.
  • nonpolymerizable components include aromatic hydrocarbons such as xylene, ethyl benzene, cumene, ethyl toluene, indane, methylindane, naphthalene and other similar species. These nonpolymerizable components of the feed stream can be incorporated into the resins via alkylation reactions.
  • Lewis acids are effective catalysts for the cationic polymerization reactions to produce hydrocarbon resins, they have several disadvantages.
  • Conventional Lewis acids are single use catalysts which require processing steps to quench the reactions and neutralize the acids.
  • U.S. Patent No. 5,561,095 to CHEN et al. discloses a supported Lewis acid catalyst for polymerization of olefins, including C3-C23 alpha-olefins, to obtain polymers having number average molecular weights (Mn) ranging from about 300 to 300,000.
  • Exemplary Lewis acid supports include silica, silica-alumina, zeolites, and clays.
  • Example 1 of CHEN et al. discloses that a Lewis acid supported on silica is heated under vacuum.
  • U.S. Patent No. 3,652,707 to SAINES discloses Friedel-Crafts metal halide catalysts for polymerization of olefin hydrocarbons, including pentene, styrene and methylstyrene, to obtain polymers having a molecular weight of from about 700 to about 2500.
  • Zinc chloride is disclosed as one of the Friedel-Crafts metal halide catalysts.
  • European Patent Application 0 352 856 Al discloses use of aluminum triflate, cerium triflate, e.g., for oligomerization of C3 to C6 olefins to obtain oligomers having 6 to 24 carbon atoms.
  • GANDINI et al. "The Heterogeneous Cationic Polymerization of Aromatic
  • the present invention involves the preparation of hydrocarbon resins. More particularly, the present invention involves the use of metal oxide solid acid catalysts to polymerize a feed of hydrocarbon monomers.
  • Hydrocarbon resins are prepared from at least one of pure monomer, C5 monomers, and C9 monomers using relatively environmentally benign, recyclable, metal oxide solid acid catalysts in which freely-associated water may have been removed.
  • hydrocarbon resins are prepared by cationic polymerization (e.g., Friedel-Crafts) wherein a feed stream containing at least one of pure monomer, C5 monomers, and C9 monomers is treated with metal oxide solid acid catalyst.
  • the metal oxide solid acid catalysts are treated to remove freely- associated water associated with the solids to maximize catalyst acidity and activity toward the polymerization.
  • the catalyst may be calcined for a sufficient time to remove freely-associated water and/or the catalyst may be exposed to reduced atmospheric pressure.
  • the calcining may be at a temperature up to about 700°C, preferably at a temperature between about 50°C and 500°C.
  • the calcining may be under reduced atmospheric pressure for up to about 8 hours, preferably between about 1 hour to 4 hours.
  • the present invention is directed to a process for making a hydrocarbon resin, including polymerizing a feed stream comprising at least one member selected from the group consisting of pure monomer, C5 monomers, and C9 monomers in the presence of a metal oxide solid acid catalyst to produce a hydrocarbon resin, wherein substantially all freely-associated water has been removed from the metal oxide solid acid catalyst.
  • the metal oxide solid acid catalyst comprises heteropolyacid intercalated clay.
  • the metal oxide solid acid catalyst comprises at least one member selected from the group consisting of heteropolyacid and salts thereof comprising at least one member selected from the group consisting of tungstophosphoric acid, tungstosilicic acid, molybdophosphoric acid, molybdosilicic acid, mixed metal heteropolyacids, and salts thereof.
  • the metal oxide solid acid catalyst comprises at least one member selected from the group consisting of supported heteropolyacid and salts thereof comprising at least one member selected from the group consisting of silica supported heteropolyacid and salts thereof, sol-gel incorporated heteropolyacid and salts thereof, cation exchange resin supported heteropolyacid and salts thereof, clay supported heteropolyacid and salts thereof, clay intercalated heteropolyacid and salts thereof, mesoporous silica supported heteropolyacid and salts thereof, and mesoporous silica-alumina supported heteropolyacid and salts thereof.
  • the metal oxide solid acid catalyst may include sulfated zirconia, tungstated zirconia, sulfated titania, sulfated tungstate, acid functionalized organically bridged polysilsesquisiloxane, or niobic acid.
  • the metal oxide solid acid catalyst includes mixed oxide comprising at least one member selected from the group consisting of B 2 O 3 .Al 2 O 3 , Cr 2 O 3 .Al 2 O 3 , MoO 3 .Al 2 O 3 , ZrO 2 .Si0 2 , Ga 2 O 3 .SiO 2 , BeO,.SiO 2 , MgO.SiO 2 , CaO.SiO 2 , SrO.SiO 2 , Y 2 O 3 .SiO 2 , La 2 O 3 .SiO 2 , SnO.Si0 2 , PbO.SiO 2 , MoO 3 .Fe(MoO 4 ) 3 , MgO.B 2 O 3 , and TiO 2 .ZnO.
  • the metal oxide solid acid catalyst includes inorganic acid comprising at least one member selected from the group consisting of ZnO, Al 2 O 3 , TiO 2 , CeO 2 , As 2 O 3 , V 2 O 5 , Cr 2 O 3 , MoO 3 , ZnS, CaS, CaSO 4 , MnSO 4 , NiSO 4 , CuSO 4 , CoSO 4 , CdSO 4 , SrS0 4 , ZnS0 4 , MgSO 4 , FeS0 4 , BaS0 4 , KHSO 4 , K 2 S0 4 , (NH 4 ) 2 SO 4 , Al 2 (SO 4 ) 3 , Fe 2 (SO 4 ) 3 , Cr 2 (SO 4 ) 3 , Ca(NO 3 ) 2 , Bi(NO 3 ) 3 , Zn(NO 3 ) 2 , Fe(NO 3 ) 3 , CaCO 3 , BPO 4 , FePO 4 ,
  • the feed stream includes between about 20 wt% and 80 wt% monomers and about 80 wt% to 20 wt% of solvent.
  • the feed stream includes about 30 wt% to 70 wt% monomers and about 70 wt% to 30 wt% of solvent.
  • the feed stream includes about 50 wt% to 70 wt% monomers and about 50 wt% to 30 wt% of solvent.
  • the solvent may include an aromatic solvent.
  • the aromatic solvent may include at least one member selected from the group consisting of toluene, xylenes, and aromatic petroleum solvents.
  • the solvent may include an aliphatic solvent.
  • the invention may further include recycling the solvent.
  • the feed stream includes at least C5 monomers.
  • the feed stream may include at least C5 monomers, wherein cyclopentadiene and methylcyclopentadiene components are removed from the feed stream by heating at a temperature between about 100°C and 160°C and fractionating by distillation.
  • the C5 monomers may include at least one member selected from the group consisting of isobutylene, 2-methyl-2-butene, 1-pentene, 2-methyl-l-pentene, 2-methyl-2-pentene, 2- pentene, cyclopentene, cyclohexene, 1,3-pentadiene, 1 ,4-pentadiene, isoprene, 1 ,3- hexadiene, 1 ,4-hexadiene, cyclopentadiene, and dicyclopentadiene.
  • the feed stream may include at least C5 monomers, wherein the feed stream includes at least about 70 wt% of polymerizable monomers with at least about 50 wt% 1,3-pentadiene.
  • the C5 feed stream may contain low levels of isoprene, generally contains a portion of 2-methyl-2-butene, and may contain one or more cyclodiolefins.
  • the feed stream may include at least C5 monomers, wherein the feed stream further includes up to about 40 wt% of chain transfer agent, preferably up to about 20 wt% of chain transfer agent.
  • the chain transfer agent may include at least one member selected from the group consisting of C4 olefins, C5 olefins, dimers of C4 olefins, and dimers of C5 olefins.
  • the chain transfer agent may include at least one member selected from the group consisting of isobutylene, 2-methyl-l-butene, 2-methyl-2-butene, dimers thereof, and oligomers thereof.
  • the feed stream includes about 30 wt% to 95 wt% of C5 monomers and about 70 wt% to 5 wt% of a cofeed including at least one member selected from the group consisting of pure monomer, C9 monomers, and terpenes.
  • the feed stream includes about 50 wt% to 85 wt% of C5 monomers and about 50 wt% to 15 wt% of a cofeed including at least one member selected from the group consisting of pure monomer, C9 monomers, and terpenes.
  • the feed stream includes at least C9 monomers.
  • the C9 monomers may include at least one member selected from the group consisting of styrene, vinyl toluene, indene, dicyclopentadiene, and alkylated derivatives thereof.
  • the C9 monomers may include at least about 20 wt% polymerizable unsaturated hydrocarbons.
  • the C9 monomers may include about 30 wt% to 75 wt% polymerizable unsaturated hydrocarbons.
  • the C9 monomers may include about 35 wt% to 70 wt% polymerizable unsaturated hydrocarbons.
  • the feed stream includes about 30 wt% to 95 wt% of the C9 monomers and about 70 wt% to 5 wt% of a cofeed including at least one member selected from the group consisting of pure monomer, C5 monomers, and terpenes.
  • the feed stream includes about 50 wt% to 85 wt% of the C9 monomers and about 50 wt% to 15 wt% of a cofeed including at least one member selected from the group consisting of pure monomer, C5 monomers, and terpenes.
  • Many of the metal oxide solid acid catalysts function most effectively in the presence of a controlled amount of water in the monomer feed stream.
  • the feed stream should include less than about 500 ppm water, preferably less than about 200 ppm water, more preferably less than about 100 ppm water, and most preferably less than about 50 ppm water.
  • the feed stream is contacted with about 0.5 wt% to 30 wt%, preferably about 1 wt% to 20 wt%, more preferably about 3 wt% to 15 wt%, and most preferably 0.5 wt% to 5 wt% of the metal oxide solid acid catalyst based on monomer weight in a batch reactor.
  • the metal oxide solid acid catalyst is added to the feed stream.
  • the feed stream is added to a slurry of the metal oxide solid acid catalyst in solvent.
  • the feed stream may be passed over a fixed bed of the metal oxide solid acid catalyst.
  • the feed stream is cofed with a slurry of the metal oxide solid acid catalyst into a reactor.
  • the polymerization is carried out as a continuous process or as a batch process.
  • a reaction time in the batch process is about 30 minutes to 8 hours, preferably about 1 hour to 4 hours at reaction temperature.
  • the feed stream is polymerized at a reaction temperature between about -50°C and 150°C, preferably between about -20°C and 100°C, and more preferably between about 0°C and 70°C.
  • the polymerization is stopped by removing the metal oxide solid acid catalyst from the hydrocarbon resin.
  • the metal oxide solid acid catalyst may be removed from the hydrocarbon resin by filtration.
  • the hydrocarbon resin may be removed from a fixed bed reactor which includes the metal oxide solid acid catalyst.
  • the hydrocarbon resin is stripped to remove unreacted monomers, solvents, and low molecular weight oligomers.
  • the unreacted monomers, solvents, and low molecular weight oligomers may be recycled.
  • the hydrocarbon resin is separated from a hydrocarbon resin solution.
  • the feed stream includes at least pure monomer and the resulting hydrocarbon resin has a softening point as measured by ASTM-
  • the feed stream may include at least C5 monomers, wherein the softening point of the resulting hydrocarbon resin is between about 50°C and 150°C.
  • the feed stream may include at least C9 monomers, wherein the softening point of the resulting hydrocarbon resin is between about 70°C and 160°C.
  • the feed stream includes at least pure monomer, wherein the hydrocarbon resin has a number average molecular weight (Mn) ranging from about 400 to 2000, a weight average molecular weight (Mw) ranging from about 500 to 5000, a Z average molecular weight (Mz) ranging from about 500 to 10,000, and a polydispersity (PD) as measured by Mw/Mn between about 1.2 and 3.5, where Mn, Mw, and Mz are determined by size exclusion chromatography (SEC).
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mz Z average molecular weight
  • PD polydispersity
  • the feed stream includes at least C5 monomers, wherein the hydrocarbon resin has a number average molecular weight (Mn) of about 400 to 2000, a weight average molecular weight (Mw) of about 500 to 3500, a Z average molecular weight (Mz) of about 700 to 15,000, and a polydispersity (PD) as measured by Mw/Mn between about 1.2 and 5, where Mn, Mw, and Mz are determined by size exclusion chromatography (SEC).
  • the feed stream includes at least
  • the hydrocarbon resin has a number average molecular weight (Mn) of about 400 to 1200, a weight average molecular weight (Mw) of about 500 to 2000, a Z average molecular weight (Mz) of about 700 to 6000, and a polydispersity (PD) as measured by Mw/Mn between about 1.2 and 3.5, preferably 1.2 and 2.5, where Mn, Mw, and Mz are determined by size exclusion chromatography (SEC).
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mz Z average molecular weight
  • PD polydispersity
  • the hydrocarbon resin is hydrogenated.
  • a reference to a compound or component includes the compound or component by itself, as well as in combination with other compounds and components, such as mixtures of compounds.
  • a definition of the following terms will aid in the understanding of the present invention.
  • SOLID ACID a solid which changes the color of a basic Hammett indicator with a pK a ⁇ 0.
  • METAL OXIDE SOLID ACID a solid acid comprising a metal which is exclusively covalently bonded to oxygen, exclusive of alumino-silicates, e.g., including metal phosphates, metal nitrates, and metal sulfates.
  • HETEROPOLYACID a solid acid comprising a heteropolyacid counterion and a heteropolyacid anion having complementing charge.
  • HETEROPOLYACID COUNTERION a cationic species, e.g., H + , Na + , K + , Cs + , Al 3+ , or NH 3 + .
  • KEGGIN HETEROPOLYACID a heteropolyacid wherein the anion has the general formula XM 12 O 40 3" , wherein four oxygens form a central tetrahedron around the heteroatom X, and twelve terminal and twenty-four bridged oxygen atoms form twelve octahedra of metal atoms M.
  • HYDROCARBON RESIN a low molecular weight (i.e., a number average molecular weight of about 200 to less than about 3000 as determined by size exclusion chromatography (SEC)) thermoplastic polymer synthesized via thermal or catalytic polymerization of cracked petroleum distillates, terpenes, coal tar fractions, or pure olefinic monomers, wherein one of the monomers is at least a C5 or higher.
  • PURE MONOMER a composition comprising synthetically generated or highly purified monomer species, e.g., styrene from ethyl benzene or alpha-methyl styrene from cumene.
  • PURE MONOMER FEED STREAM a composition comprising any number of pure monomer species.
  • C5 MONOMERS a composition derived from petroleum processing, e.g., cracking, containing unsaturated hydrocarbons comprising C5 and/or C6 olefin species boiling in the range from about 20°C to 100°C at atmospheric pressure.
  • C9 MONOMERS a composition derived from petroleum processing, e.g., cracking, containing unsaturated aromatic C8, C9, and/or CIO olefin species with a boiling range of about 100°C to 300°C at atmospheric pressure.
  • FREELY-ASSOCIATED WATER water associated with a solid acid catalyst where the water is chemisorbed and/or physisorbed.
  • hydrocarbon resins are produced by using metal oxide solid acids as catalysts for the cationic polymerization of a feed stream containing at least one of pure monomer (e.g., styrene based monomers), C5 monomers, and C9 monomers.
  • Resins with softening points preferably in the range of about 5°C to 170°C, more preferably about 30°C to 150°C, can be prepared.
  • hydrocarbon resins are prepared through a polymerization reaction wherein a feed stream containing at least one of pure monomer, C5 monomers, and C9 monomers in a solvent are contacted with a metal oxide solid acid catalyst.
  • Metal oxide solid acid catalysts which are useful in the current invention include, but are not limited to, the following.
  • Heteropolyacid intercalated clays i.e., the heteropolyacid acts as a pillar between clay layers
  • Tungstophosphoric acid and salts including for example
  • heteropolyacids and salts thereof for example Silica supported, for example H 3 PWO 40 on silica Sol-gel incorporated, for example
  • H 3 PWO 40 on clay Clay intercalated heteropolyacids, for example clay intercalated with H 3 PWO 40 Mesoporous silica supported, for example H 3 P WO 40 supported on mesoporous silica
  • metal oxide solid acid catalysts As mentioned previously, the above list of metal oxide solid acid catalysts is not intended to be an exhaustive list. In selecting other metal oxide solid acid catalysts which may be useful in the present invention, it is generally true that the metal oxide solid acid catalyst should be more acidic than about -3 on the Hammett scale.
  • heteropolyacid salts include for example cesium, aluminum, potassium, sodium, and ammonium.
  • n should be less than 3 because a proton should be present to have catalytic action.
  • Concerning the supported heteropolyacids and salts thereof, during the development of supported catalyst systems, a first step in a catalytic process would be the identification of a catalyst which in its pure form catalyzes the desired transformation. Once a catalyst system is identified, one of the key development strategies is to support that catalyst on an support such that the active catalyst component is spread out over a large surface area.
  • Examples of this strategy include the supporting of noble metal catalysts on the surface of carbon or similar inert material for hydrogenation catalysts.
  • the crystallite size is 8 nm (nanometers)
  • only the surface atoms of this crystallite would normally catalyze the reaction.
  • heteropolyacids were supported on solids with high surface area.
  • the preferred unsupported catalyst is as a salt such as Cs 29 H 0 1 PW 12 O 40
  • the preferred supported heteropolyacid is the parent heteropolyacid H 3 PW ]2 O 40 .
  • Clays include naturally occurring clay minerals such as kaolinite, bentonite, attapulgite, montmorillonite, clarit, Fuller's earth, hectorite, and beidellite. Clays also include synthetic clays such as saponite and hydrotalcite. Clays further include montmorillonite clays treated with sulfuric or hydrochloric acid. Even further, clays include modified clays (i.e., clays modified by backbone element replacement), such as aluminum oxide pillared clays, cerium modified alumina pillared clays, and metal oxide pillared clays.
  • modified clays i.e., clays modified by backbone element replacement
  • supports include silica, silica-alumina, mesoporous silica, mesoporous silica-alumina, and ion exchange resins.
  • Other types of supports includes natural or synthetic zeolites such as zeolite Y, zeolite ⁇ (i.e., BEA), MFI (e.g., "Zeolite Sacony Mobil-5" (“ZSM-5”)), MEL (e.g., "Zeolite Sacony Mobil-11" (“ZSM-11”)), NaX, NaY, faujasite (i.e., FAU), and mordenite (i.e., MOR).
  • zeolite Y zeolite ⁇
  • MFI e.g., "Zeolite Sacony Mobil-5"
  • MEL e.g., "Zeolite Sacony Mobil-11"
  • NaX NaY
  • faujasite i.e., FAU
  • mordenite i.
  • the names BEA, MFI, MEL, FAU, and MOR are the framework structure type IUPAC definitions of the zeolites. Examples of acid functionalized organically bridged polysilsesquisiloxanes are found in U.S. Patent No. 5,475,162 to BRANDVOLD et al. and U.S. Patent No. 5,371,154 to BRANDVOLD et al., the disclosures of which are herein incorporated by reference in their entireties.
  • the metal oxide solid acid catalysts are treated to remove freely- associated water to maximize the catalyst acidity and activity toward the polymerization.
  • the freely-associated water may be removed by various techniques, including thermal treatment, reduced pressure treatment, dry atmosphere treatment such as nitrogen or air, or a combination thereof. While not wishing to be bound by theory, removing freely-associated water maximizes the acid strength of the metal oxide solid acid catalysts and makes the polymerizations more reproducible.
  • the freely-associated water is removed from the metal oxide solid acid catalyst by calcining which generally means heating the metal oxide solid acid catalyst to high temperature without fusing the catalyst.
  • the metal oxide solid acid catalyst may be calcined under an inert atmosphere, such as nitrogen or dry air, or under reduced pressure.
  • the calcining is preferably performed for up to about 8 hours or more, more preferably about 1 hour to 4 hours, preferably at temperatures up to about 700°C, more preferably about 100°C to 400°C.
  • the freely-associated water removed from the metal oxide solid acid catalyst may have been derived from water (physisorbed water) or hydroxyl groups (chemisorbed water) associated with the metal oxide solid acid catalyst.
  • removal of substantially all freely- associated water is meant removing all or essentially all physisorbed water and removing at least a majority of chemisorbed water. It is expected that by controlling the conditions under which the metal oxide solid acid catalyst is calcined, such as controlling the temperature or time under which the calcination step takes place, tailoring of the physical properties of the resultant resin, such as its softening point or its molecular weight, may be achieved.
  • the feed stream may include less than about 500 ppm water, preferably less than about 200 ppm water, more preferably less than about 100 ppm water, and most preferably less than about 50 ppm water.
  • Pure monomer feed streams may contain relatively pure styrene-based monomers such as styrene, alpha-methyl styrene, beta-methyl styrene, 4-methyl styrene, and vinyl toluene fractions.
  • the monomers can be used as pure components or as blends of two or more monomer feeds to give desired resin properties.
  • Preferred blends include about 20 wt% to 90 wt% alpha-methyl styrene with about 80 wt% to 10 wt% of one or more comonomers, preferably styrene, vinyl toluene, 4-methyl styrene or blends of these components.
  • Feed streams can be dried, if desired, and preferably contain less than about 200 ppm water, more preferably less than about 100 ppm water, and most preferably less than about 50 ppm water.
  • the petroleum feed streams contain unsaturated C5 and/or
  • cyclopentadiene and methylcyclopentadiene components are removed from the feed by heat soaking at temperatures preferably between about 100°C and 160°C, and fractionating by distillation.
  • Monomers found in these feedstocks may include but are not limited to olefins such as isobutylene, 2-methyl-2-butene, 1 -pentene, 2-methy 1- 1 - pentene, 2-methyl-2-pentene, as well as 2-pentene, cycloolefins such as cyclopentene, and cyclohexene, diolefins such as 1,3-pentadiene, 1 ,4-pentadiene, isoprene, 1,3-hexadiene, and 1 ,4-hexadiene, cyclodiolefins such as cyclopentadiene, dicyclopentadiene, and alkyl substituted derivatives and codimers of these cyclodiolefins.
  • Commercial samples of this type of feed include, but are not limited to "Naphtha Petroleum 3 Piperylenes" from
  • the C5 feed streams generally contain at least about 70 wt% polymerizable monomers with at least about 50 wt% 1,3-pentadiene.
  • the C5 feed stream may contain low levels of isoprene, generally contains 2-methyl-2-butene, and may contain one or more cyclodiolefins.
  • nonpolymerizable components in the feed may include saturated hydrocarbons which can be codistilled with the unsaturated components such as pentane, cyclopentane, or 2- methylpentane.
  • This monomer feed can be copolymerized with C4 or C5 olefins or dimers as chain transfer agents.
  • Chain transfer agents may be added to obtain resins with lower and narrower molecular weight distributions than can be prepared from using monomers alone. Chain transfer agents stop the propagation of a growing polymer chain by terminating the chain in a way which regenerates a polymer initiation site.
  • Components which behave as chain transfer agents in these reactions include but are not limited to isobutylene, 2-methyl-
  • feed streams can be dried if desired and preferably contain less than about 500 ppm water, more preferably less than about 200 ppm water, and most preferably less than about 50 ppm water.
  • the feed streams contain unsaturated aromatic C8, C9, and/or CIO monomers with a boiling range of about 100°C to 300°C at atmospheric pressure.
  • Aromatic C8-C10 feed streams (also referred to as C9 feed streams) can be derived from steam cracking of petroleum distillates. Monomers found in these feed stocks may include but are not limited to styrene, vinyl toluene, indene, dicyclopentadiene, and alkylated derivatives of these components.
  • the C9 feed stream generally contains at least about 20% by weight, preferably about 30% to 75% by weight, and most preferably about 35% to 70% by weight polymerizable unsaturated hydrocarbons. The remainder is generally alkyl substituted aromatics which can be incorporated into the resins by alkylation reactions. Feed streams can be dried if desired and preferably contain less than about 500 ppm water, more preferably less than about 200 ppm water, and most preferably less than about 50 ppm water.
  • the feed streams may be limited to pure monomer, C5 monomers, or C9 monomers.
  • cofeed streams can be used in combination with main feed streams of pure monomer, C5 monomers, or C9 monomers.
  • pure monomer, C5 monomers, C9 monomers, or even terpenes, and any combination thereof may serve as a cofeed stream.
  • Terpene feed stocks include but are not limited to d- limonene, alpha- and beta-pinene, as well as dipentene.
  • Resins from blends of main feed streams with cofeed streams may be prepared in the range of about 30 wt% to 95 wt% main feed with about 70 wt% to 5 wt% of a cofeed, preferably about 50-85 wt% main feed and about 50 wt% to 15 wt% cofeed.
  • the polymerization feed stream preferably contains between about 20 wt% and 80 wt% monomers, more preferably about 30 wt% to 70 wt%, and most preferably about 40 wt% to 70 wt%.
  • the feed may contain up to about 40 wt% of a chain transfer agent, more preferably up to about 20 wt%, chain transfer agents as discussed above.
  • the feed stream also contains about 80 wt% to 20 wt% of a solvent such as toluene, octane, higher boiling aromatic solvent, aliphatic solvent, or solvent blend.
  • the preferred solvents are aromatic solvents.
  • aromatic solvents typically toluene, xylenes, or light aromatic petroleum solvents such as "Aromatic 100” from Exxon Chemical Company, Houston, TX, "HiSol 10” from Ashland Chemical Incorporated, Columbus, OH, and "Cyclosol 53" from Shell Chemical Company, Houston, TX can be used. These solvents can be used fresh or recycled from the process.
  • the solvents generally contain less than about 200 ppm water, preferably less than about 100 ppm water, and most preferably less than about 50 ppm water.
  • the preferred solvents are aromatic solvents.
  • unreacted resin oil components are recycled through the process as solvent.
  • toluene, xylenes, or aromatic petroleum solvents such as "Solvesso 100” from Exxon Chemical Company, Houston, TX and "Shellsol A” from Shell Chemical
  • the solvents can be used fresh or recycled from the process.
  • the solvents generally contain less than about 500 ppm water, preferably less than about 200 ppm water, and most preferably less than about 50 ppm water.
  • the preferred solvents are aromatic solvents.
  • unreacted resin oil components are recycled through the process as solvent.
  • toluene, xylenes, or aromatic petroleum solvents such as "Solvesso 100" from Exxon Chemical Company, Houston, TX and "Shellsol A” from Shell Chemical Company, Houston, TX can be used.
  • These solvents can be used fresh or recycled from the process.
  • the solvents generally contain less than about 200 ppm water, preferably less than about 100 ppm water, and most preferably less than about 50 ppm water.
  • the metal oxide solid acids are preferably used at a level of about 0.1 wt% to 30 wt% based on the weight of the monomer.
  • the metal oxide solid acid concentration is preferably about 0.1 to 15 wt%, more preferably about 0.5 wt% to 10 wt%, and most preferably about 0.5 wt% to 8 wt%.
  • the metal oxide solid acid concentration is preferably about 0.5 wt% to 30 wt%, more preferably about 1 wt% to 20 wt%, and most preferably about 3 wt% to 15 wt%.
  • the metal oxide solid acid concentration is preferably about 0.5 wt% to 30 wt%, more preferably about 1 wt% to 20 wt%, and most preferably about 3 wt% to 15 wt%.
  • a second important variable in the reaction is the reaction sequence, i.e., the order and manner in which reactants are combined.
  • the catalyst can be added to a solution of the monomers incrementally while controlling the reaction temperature.
  • the monomer can be added incrementally to a slurry of the metal oxide solid acid catalyst in a solvent. For a set catalyst level and reaction temperature, substantially lower softening point resins are obtained when the monomer is added to a catalyst slurry.
  • the molecular weight averages of the resins were measured using size exclusion chromatography, SEC.
  • the column set for the analysis consisted of four Waters "Ultrastyrogel” columns of 500, 500, 1000, and 100 A pore size, in series, (Part Nos. WAT
  • the molecular weight calibration was calculated from the peak elution times of a standard set of narrow molecular weight distribution polystyrene polymers.
  • the calibration set encompassed 18 standards ranging in peak molecular weight from 162 to 43,900.
  • the peak molecular weight of a narrow molecular weight standard is defined as equal to
  • the calibration curve is defined by a third degree polynomial curve fit of a plot of log MW vs. V e /V r , where V c is the elution volume of the standard and V r is the elution volume of the reference peak, oxygen, present as dissolved air in the injected solution.
  • the columns and detector cell Hewlett-Packard Differential Refractometer are maintained at 40°C.
  • the solvent (mobile phase) was tetrahydrofuran containing 250 ppm butylated hydroxytoluene (BHT, 2,6-di-tert-butyl-4- methylphenol) as a stabilizer (the tetrahydrofuran with BHT being available from Burdick and Jackson, Muskegon, MI).
  • BHT butylated hydroxytoluene
  • the mobile phase reservoir is purged with helium and is maintained at a flow rate of 1 milliliter per minute. Under these conditions, BHT eluted at 35.86 minutes.
  • the resins produced using the current invention have number average molecular weights (Mn) ranging from about 400 to 2000, weight average molecular weights (Mw) ranging from about 500 to 5000, Z average molecular weights (Mz) ranging from about 500 to 10,000, and polydispersities (PD) as measured by Mw/Mn between about 1.2 and 3.5, typically between about 1.2 and 2.5.
  • Mn number average molecular weights
  • Mw weight average molecular weights
  • Mz Z average molecular weights
  • PD polydispersities
  • the resins produced using the current invention have number average molecular weights (Mn) ranging from about 400 to 2000, weight average molecular weights (Mw) ranging from about 500 to 3500, Z average molecular weights (Mz) ranging from about 700 to 15,000, and polydispersities (PD) as measured by Mw/Mn between about 1.2 and 5, typically between about 1.2 and 3.5.
  • Mn number average molecular weights
  • Mw weight average molecular weights
  • Mz Z average molecular weights
  • PD polydispersities
  • the resins produced using the current invention have number average molecular weights (Mn) ranging from about 400 to 1200, weight average molecular weights (Mw) ranging from about 500 to 2000, Z average molecular weights (Mz) ranging from about 700 to 6000, and polydispersities (PD) as measured by Mw/Mn between about 1.2 and 3.5, typically between about 1.2 and 2.5.
  • Mn number average molecular weights
  • Mw weight average molecular weights
  • Mz Z average molecular weights
  • PD polydispersities
  • narrower polydispersities (PD) and lower molecular weights are obtained when the monomer is added to the catalyst solution than when the catalyst is added to the monomer.
  • polydispersities (PD) more narrow than those obtained using traditional Lewis acid Friedel-Crafts catalysts can be obtained using metal oxide solid acids if desired.
  • the above data is from Examples 4 and 13 which, as noted above, have similar but different reaction conditions.
  • polydispersities (PD) more narrow than those obtained using traditional Lewis acid Friedel-Crafts catalysts can be obtained using metal oxide solid acids if desired.
  • Narrow polydispersity is important to ensure compatibility of resin with polymers in end use applications.
  • a third important reaction variable is the reaction temperature.
  • Polymerization temperatures between about -50°C and 150°C can be used in these reactions, however, more preferred reaction temperatures are between about -20°C and 100°C, most preferred temperatures are between about 0 ° C and 70 ° C .
  • the reaction temperature is preferably between about -50°C and 100°C, more preferably between about -20°C and 75°C, and most preferably between about -10°C and 60°C.
  • the reaction temperature is preferably between about -50°C and 100°C, more preferably between about -20°C and 75°C, and most preferably between about -10°C and 70°C.
  • the reaction temperature is preferably between about 0°C and 150°C, more preferably between about 10°C and 120°C, and most preferably between about 20°C and 110°C. Temperature is found to have a significant effect on the properties of the resulting resins. Higher molecular weight and high softening point resins are prepared at lower reaction temperatures.
  • the reaction time at reaction temperature is preferably between about 30 minutes and 8 hours, and more preferably between about 1 hour and 4 hours.
  • the polymerization process can be carried out as a continuous, semi-batch, or batch process in such diverse reactors as continuous, batch, semi-batch, fixed bed, fluidized bed, and plug flow.
  • a solution of the monomers can be passed over the catalyst in a fixed bed, or the monomers can be cofed with a catalyst slurry into a continuous reactor.
  • the reaction may be stopped by physically separating the solid catalysts from the products. Physical separation may render the reaction solution neutral. Furthermore, physical separation can be performed by simple filtration or by separation of the resin solutions from a fixed catalyst bed. As a result, physical separation is easy and complete such that, for some metal oxide solid acid catalysts, acid functionality and catalyst residue are not left in the resin product.
  • metal oxide solid acid catalysts minimizes or eliminates the need for extra processing steps to quench the reactions, neutralize the catalyst, and filter the catalyst salt residues from the resulting products.
  • the resin solution can be stripped to remove unreacted hydrocarbons, solvents, and low molecular weight oligomers which can be recycled through the process.
  • water white resins can be obtained from this invention in yields of up to about 99% based on starting monomer.
  • Resins obtained from this invention typically have softening points as measured by ASTM-E28 "Standard Test Method for Softening Point by Ring and Ball Apparatus" (revised 1996), varying from preferably about 5°C to 170°C, more preferably from about 30°C to 150°C.
  • the softening points preferably range from about 5°C to 170°C, more preferably from about 50°C to 150°C.
  • the softening point preferably ranges from about 5°C to 170°C, more preferably from about 50°C to 150°C, and most preferably about 70°C to 130°C.
  • the softening point is preferably up to about 170°C, and the softening point range is most preferably from about 70°C to 160°C.
  • Flowable resin or those that are liquids at room temperature can also be prepared if desired using proper reaction conditions.
  • the resins of the current invention can be used as modifiers in adhesives, sealants, printing inks, protective coatings, plastics, road markings, flooring, and as dry cleaning retexturizing agents.
  • the metal oxide solid acid catalysts of the present invention offer several advantages over Lewis acids (e.g., A1C1 3 , AlBr 3 , BF 3 , complexes of BF 3 , TiCl 4 , and others which are traditionally used for Friedel-Crafts polymerizations). Many of these advantages are a result of the acid sites being an integral part of the solid catalysts. Because the acid sites are an integral part of the solid catalyst, contamination of the resin products or solvents with catalyst residues is minimal. As a result, the metal oxide solid acid catalysts do not impart color to the hydrocarbon resins due to catalyst residues. If pure styrene-based monomers are used, the resulting resins can be water white.
  • Lewis acids e.g., A1C1 3 , AlBr 3 , BF 3 , complexes of BF 3 , TiCl 4 , and others which are traditionally used for Friedel-Crafts polymerizations.
  • Many of these advantages are a result of the acid sites
  • the metal oxide solid acid catalysts of the present invention can generally be regenerated and recycled to thereby minimize waste disposal of spent catalyst.
  • the Lewis acids are generally single use catalysts.
  • the metal oxide solid acid catalysts of the present invention are nonhazardous when compared with traditional Lewis acid catalysts such as BF 3 and A1C1 3 .
  • the catalysts of the present invention generally do not generate corrosive or hazardous liquid or gaseous acids on exposure to moisture.
  • Examples. Examples 1-26 involve pure monomer resins, Examples 41-55 involve C5 resins, and Example 56 involves C9 resins. These examples are non-limiting and do not restrict the scope of the invention.
  • the potassium and ammonium salts were prepared according to the following procedures.
  • the molecular weight of the heteropolytungstic acid, H 3 PW 12 O 40 .xH 2 O was calculated by determining the number of associated waters by measuring the weight loss at 300°C by thermogravimetric analysis and calculating the equivalent weight as water.
  • the potassium or ammonium salts, K 3 PW 12 O 40 .xH 2 O or (NH 4 ) 3 PW 12 O 40 .xH 2 O were prepared by charging the acid, H 3 PW 12 O 40 .xH 2 O, 20 g, 6.1 mmol, (Aldrich, Milwaukee, WI) to a 500 ml single neck round bottom flask containing a magnetic stirring bar.
  • n) PW ]2 O 40 where (CATION) is any cationic counter ion, can be prepared similarly by changing the phosphotungstic acid to metal carbonate ratio. Prior to use, the phosphotungstic acid salts were pretreated at 250°C (unless otherwise noted in Table 1) for 30 minutes under flowing nitrogen to remove bound water.
  • the cesium salt of the phosphotungstic acid was prepared according to the following procedures.
  • the molecular weight of the heteropolytungstic acid, H 3 PW 12 O 40 .xH 2 O was calculated by determining the number of associated waters by measuring the weight loss at 300°C by thermogravimetric analysis and calculating the equivalent weight as water.
  • the cesium heteropolytungstic acid salt, Cs 29 H 0 ,PW I2 O 40 was prepared by charging the acid,
  • the acid was dissolved in 185 ml of distilled water.
  • Cesium carbonate, 4.32 g, 13.3 mmol, (Aldrich, Milwaukee, WI) was dissolved in 35 ml of distilled water and added dropwise to the vigorously stirred heteropolyacid solution over 25 minutes. The resulting solution was stirred at room temperature for 2 hours and reduced to dryness at 100°C, 0.25 mm Hg. The product was recovered as a fine white powder.
  • a range of Cs salts were prepared by changing the phosphotungstic acid to cesium carbonate ratio, e.g., as shown in Table 3.
  • the aluminum salt was prepared according to the following procedures.
  • the molecular weight of the heteropolytungstic acid, H 3 PW I2 O 40 .xH 2 O was calculated by determining the number of associated waters by measuring the weight loss at 300°C by thermogravimetric analysis and calculating the equivalent weight as water.
  • the aluminum heteropolytungstic acid salt, AlPW 12 O 40 .xH 2 O was prepared by charging the acid,
  • the acid was combined with 60 ml of diethyl ether (Aldrich, Milwaukee, WI).
  • Aluminum trisisopropoxide, Al(OCH 3 ) 2 ) 3 1.25 grams, 6.1 mmol (Aldrich, Milwaukee, WI) was combined with 40 ml of diethyl ether and added dropwise to the stirred heteropolyacid solution. The resulting solution was stirred at
  • Keggin heteropolyacids as catalysts for the polymerization of styrene based pure monomer.
  • Salts of Keggin phosphotungstic acid are found to be active catalysts for the preparation of hydrocarbon resins with styrene based pure monomer.
  • a 250 milliliter three neck flask was equipped with an overhead stirrer, reflux condenser, gas inlet and outlet ports, a thermometer, and a dropping addition funnel.
  • the flask was charged with 86.6 grams of alpha-methyl styrene (reagent grade, Aldrich, Milwaukee, WI), 36.6 grams styrene (reagent grade, Aldrich, Milwaukee, WI), and 36.6 grams toluene (reagent grade, Aldrich, Milwaukee, WI).
  • the solvent and monomers were dried over alumina prior to use.
  • the reaction mixture was cooled to 0°C with an ice bath.
  • the catalyst noted in Table 1 1.0 grams (unless otherwise noted), was added to the stirred reaction flask over approximately one minute. An exotherm of up to 5°C was typically observed.
  • the reaction solution was stirred at 0°C for 6 hours.
  • the resulting resin solutions were then vacuum filtered from the catalyst while still cold.
  • the reaction flask and catalyst filter cake were rinsed with approximately 100 milliliters of toluene.
  • the resin was stripped of solvent and volatile products at 0.25 mm Hg while gradually increasing the temperature to 170°C and maintaining the strip temperature for 15 minutes upon complete removal of volatile components.
  • the resins produced using various phosphotungstic acid salts have the properties listed in Table 1.
  • the resins produced have the properties listed in Table 2.
  • Example 13 a jacketed 250 milliliter three neck flask was equipped with an overhead stirrer, reflux condenser, gas inlet and outlet ports, a thermometer, and a dropping addition funnel.
  • the nitrogen flushed flask was charged with toluene solvent, 36.3 g, (Aldrich, Milwaukee, WI) which had been dried over activated 4 angstrom molecular sieves and cesium heteropolytungstic acid, Cs 29 H 0 ] PW 12 O 40 , 1.0 gram, prepared as described in Examples 1 - 10 above and calcined at 400°C for 30 minutes.
  • the catalyst slurry was cooled to approximately -2°C using a cooling bath recirculated through the reactor jacket.
  • the monomers 61.6 grams of alpha-methyl styrene and 61.6 grams styrene (both reagent grade, Aldrich, Milwaukee, WI), were dried over alumina and added to a dropping addition funnel attached to the reaction flask. The monomers were added to the catalyst slurry dropwise over approximately 20 minutes while maintaining the reaction temperature between -6.0 and -2.0°C. The reaction solution was then held at -2.0°C to give a total reaction time of 2 hours.
  • the resulting resin solutions were vacuum filtered from the catalyst at room temperature.
  • the reaction flask and catalyst filter cake were rinsed with approximately 50 milliliters of toluene.
  • the resin was stripped of solvent and volatile products at 0.06 mm Hg by gradually heating the solution to 175°C and maintaining this strip temperature for 15 minutes upon complete removal of volatile components.
  • the resin produced in Example 13 has the following properties.
  • Example 13 Since the reactions of Example 13 and Example 4 are similar, the properties of the resin of Example 13 which involves monomer addition to catalyst may be compared with the properties of the resin of Example 4 which involves catalyst addition to monomer. As previously noted, narrower polydispersities (PD) and lower molecular weights are obtained when the monomer is added to the catalyst solution than when the catalyst is added to the monomer.
  • PD polydispersity
  • PD Mw/Mn
  • the solvent and monomers were dried over alumina prior to use.
  • the cesium phosphotungstic acid salt catalyst was pretreated at 250°C for 30 minutes under flowing nitrogen to remove bound water.
  • the reaction mixture was cooled to 0°C by recirculating water from an ice bath in the reactor jacket.
  • the catalyst 0.5 to 1.0 wt% based on monomers, was added to the stirred reaction flask. An exotherm of 5°C was typical.
  • the reaction solution was stirred at 0°C for 2.5 hours.
  • the resulting resin solutions were vacuum filtered from the catalyst at room temperature.
  • the reaction flask and catalyst filter cake were rinsed with approximately 100 milliliters of toluene.
  • the resin was stripped of solvent and volatile products at 0.5 mm Hg by gradually heating the solution to 185°C and maintaining this strip temperature for 15 minutes upon complete removal of volatiles.
  • the reaction apparatus and procedures were similar to those outlined in Examples 14-20 with the following exceptions.
  • the catalyst was charged to the reaction solution in three equal portions over the first 30 minutes of the reaction.
  • the catalyst was collected after each polymerization by filtration, washed in refluxing toluene, heated to 150°C for 30 minutes under flowing nitrogen, and reused.
  • the resins produced have the properties listed in Table 4.
  • Example 24 a 50:50 alpha-methyl styrene/styrene mixture was polymerized in toluene at 0-10°C by using Cs 3 PW 12 O 40 .
  • the resin produced in Example 24 had the following properties.
  • Example 25 a neat monomer 50:50 alpha-methyl styrene/styrene mixture was polymerized by using Cs 3 PW 12 O 40 .
  • the resin produced in Example 25 was an essentially colorless, brittle solid at room temperature and had the following properties.
  • Example 26 a 50:50 alpha-methyl styrene/styrene mixture was polymerized in toluene at 0-10°C by using Cs 2 5 H 05 PW 12 O 40 to essentially quantitative yield.
  • the resin produced in Example 26 was a semi-solid at room temperature and had the following properties. Molecular Weight
  • EXAMPLE 27 This example demonstrates the use of cesium modified heteropolyacids to polymerize pure monomer.
  • a 500 milliliter three neck flask was equipped with a cooling jacket, overhead stirrer, reflux condenser, gas inlet and outlet ports, thermometer, and dropping addition funnel. The flask was charged with 86.6 grams of vinyl toluene (Deltech Corporation, Baton Rouge LA), 36.6 grams of alpha-methyl styrene (reagent grade, Aldrich, Milwaukee, WI), and 100 grams of toluene (reagent grade, Aldrich, Milwaukee, WI). Prior to the reaction, the vinyl toluene was dried over molecular sieve and anhydrous calcium chloride (reagent grade, Aldrich, Milwaukee, WI). Also prior to the reaction, the toluene was dried over 3 angstrom molecular sieves.
  • the catalyst was filtered from the resin solution.
  • the resin solution was rotary evaporated with a final condition of 45 minutes at a bath temperature of 190°C at ⁇ 5 mm Hg.
  • the resultant yield was 68.3 grams or 55 %.
  • the softening point of the resin was 92°C.
  • the number average, weight average, and Z average molecular weights as determined by SEC were 809, 2009, 4888.
  • the catalysts were prepared by using an incipient wetness technique. Three different loadings of heteropolyacid on a silica were prepared according to the following technique.
  • heteropolyacid, phosphotungstic acid (Aldrich, Milwaukee, WI) was dissolved in 150 ml water and then slowly added to 100 grams of silica gel, "Davisil Grade 710". The resultant wet silica gel was dried in a 75°C oven for at least 24 hours. The amount of heteropolyacid added to the 100 grams of silica gel is shown in Table 5 below. TABLE 5
  • a 500 milliliter three neck flask was equipped with a cooling jacket, overhead stirrer, reflux condenser, gas inlet and outlet ports, thermometer, and dropping addition funnel.
  • the flask was charged with 36.6 grams of styrene (reagent grade, Aldrich, Milwaukee, WI ), 86.6 grams of alpha-methyl styrene (reagent grade, Aldrich, Milwaukee, WI), and 100 grams of toluene (reagent grade, Aldrich, Milwaukee, WI).
  • the styrene and alpha-methyl styrene were dried over molecular sieve and alumina (reagent grade, Aldrich, Milwaukee, WI).
  • the toluene was dried over 3 angstrom molecular sieves.
  • the catalyst was added to the reaction mixture.
  • the reaction temperature was maintained at 0°C ⁇ 6°C for 180 minutes.
  • the catalyst was filtered from the resin solution.
  • the resin solution was rotary evaporated with a final condition of 45 minutes with a bath temperature of 190°C at ⁇ 5 mm Hg.
  • the catalysts were prepared by using an incipient wetness technique. "Silica Grade 57" (W. R. Grace, Boca Raton, Florida) was ground up in mortar pestle. The material that passed through a 30 mesh screen, but not a 60 mesh screen was used for the preparations. The heteropolyacid, phosphotungstic acid (Aldrich, Milwaukee, WI), 12.5 grams, was dissolved in 73 ml of water and then slowly added to 50 grams of the silica. The resultant wet silica gel was dried in a 75°C oven for at least 24 hours.
  • Resins were prepared with this catalyst according to the following procedure. The difference in each of the examples is the calcination temperature of the catalyst, as indicated in Table 7 below.
  • a 500 milliliter three neck flask was equipped with a cooling jacket, overhead stirrer, reflux condenser, gas inlet and outlet ports, thermometer, and dropping addition funnel.
  • the flask was charged with 36.6 grams of styrene (reagent grade, Aldrich, Milwaukee, WI ), 86.6 grams of alpha-methyl styrene (reagent grade, Aldrich, Milwaukee, WI ), and 100 grams of toluene (reagent grade, Aldrich, Milwaukee, WI).
  • the styrene and alpha-methyl styrene were dried over molecular sieve and alumina (reagent grade, Aldrich, Milwaukee, WI).
  • the toluene was dried over 3 angstrom molecular sieves.
  • the catalyst was added to the reaction mixture.
  • the reaction temperature was maintained at 0°C ⁇ 6°C for 180 minutes.
  • the catalyst was filtered from the resin solution.
  • the resin solution was rotary evaporated with a final condition of 45 minutes with a bath temperature of 190°C at ⁇ 5 mm Hg.
  • the resulting resins have the properties listed in Table 7.
  • the catalysts were prepared by using an incipient wetness technique.
  • the heteropolyacid 2.81 grams of phosphotungstic acid (Aldrich, Milwaukee, WI) was dissolved in 20 ml of water and added to the silica/"RHS" mixture. Then, the solid mixture was tumbled in a rotary evaporatory for 2 hours followed by rotary evaporation for 1 hour at 110°C at 3 mm Hg. These samples were furthered dried overnight in a vacuum oven at 116°C. The catalyst was then calcined at 200°C for 2 hours.
  • phosphotungstic acid Aldrich, Milwaukee, WI
  • silica Grade 57 (W. R. Grace, Boca Raton, Florida) was ground up in mortar pestle. The material that passed through a 30 mesh screen, but not a 60 mesh screen was used for the preparations.
  • the silica 25 grams, was wetted with 37 ml of "RHS" (Hercules Incorporated, Wilmington, Delaware) (The 28 ml was selected based on tests that showed that the silica sample would absorb 37 ml of water with no liquid water present.).
  • the heteropolyacid 2.81 grams of phosphotungstic acid (Aldrich, Milwaukee, WI) was dissolved in 20 ml of water and added to the silica RHS mixture.
  • the catalyst synthesis strategy of these Examples was suggested by a paper which was presented at the International Chemical Congress of Pacific Basin Societies, Dec 17-22, 1995 by Y. Izumi, the disclosure of which is herein incorporated by reference in its entirety.
  • the strategy involves using a sol gel technique to incorporate the heteropolyacid or cesium modified heteropolyacid into the silica gel structure.
  • the resulting gel was transferred to another round bottom flask and the gel dehydrated by rotary evaporating at 50°C and 50 mm Hg until no more water/ethanol was evaporated from the gel.
  • the material was calcined in a tube furnace under a flow of dry nitrogen at 250°C for 16 hours.
  • Keggin heteropolyacids as catalysts for the polymerization of piperylene, a C5 monomer feed.
  • Catalyst 2 wt% based on monomer, prepared according to Catalyst Preparation Methods was added to an 8 ounce reaction vessel fitted with a rubber septum cap and sparged with nitrogen.
  • Resins produced have the properties listed in Table 10.
  • This example illustrates the effect of monomer addition to a slurry of the catalyst in a solvent, involving a C5 monomer feed.
  • a 500 milliliter three neck flask was equipped with an overhead stirrer, reflux condenser, gas inlet and outlet ports, thermometer, and a dropping addition funnel.
  • the flask was charged with 60 grams of toluene (reagent grade, Aldrich Milwaukee, WI) and 2.8 g of Cs 29 H 0 ,PW,,O 40 catalyst, prepared in accordance with the procedure of Examples 41-45 and calcined at 375-400°C under a dry nitrogen purge for 30 minutes.
  • the monomer, 140 grams piperylene concentrate Naphtha Petroleum 3 "Piperylenes" Lyondell Petrochemical Company, Houston, TX
  • the monomers and solvent were dried over 4 angstrom molecular sieves.
  • the reaction solution was heated to 50°C and the monomer was added to the reaction flask from the dropping addition funnel over 25 minutes The reaction solution was stirred at 50°C for 4-5 hours.
  • the resulting resin solution was then vacuum filtered from the heteropolyacid catalyst at room temperature.
  • the reaction flask and catalyst filter cake were rinsed with approximately 100 milliliters of toluene.
  • the solvent and volatile components were removed from the resin solution by heating the reaction solution slowly to 100°C at 2-5 mm Hg.
  • the reaction products were stripped for an additional 30 minutes when the temperature reached 100°C.
  • the resin produced has the following properties.
  • the catalyst, Cs 29 H 0 ,PW, ,O 40 prepared in accordance with the procedure of Examples 41-45 and calcined under dry nitrogen as described in Table 1 1 below, was added to the reaction flask against a nitrogen purge in 4 equal increments one hour apart. The total reaction time was seven hours.
  • the resulting resin solution was then vacuum filtered from the heteropolyacid catalyst at room temperature.
  • the reaction flask and catalyst filter cake were rinsed with approximately 100 milliliters of toluene.
  • the resin oil was placed in a round-bottom flask which was fitted with a distillation head with an adaptor for an inlet tube, thermometer, and attached to a condenser and receiving flask.
  • the resin oil was heated to 235°C with a nitrogen purge followed by a steam purge at 235-245°C to remove light oil products.
  • the steam purge was continued until less than 1 ml of oil was collected per 100 ml of steam condensate or until 1000 ml of steam condensate was collected.
  • the steam purge was followed by a nitrogen purge at 235°C to remove water from the remaining resin.
  • the resin produced has the properties listed in Table 11.
  • a 500 milliliter three neck flask was equipped with an overhead stirrer, reflux condenser, gas inlet and outlet ports, thermometer, liquid addition funnel, and solid addition funnel.
  • the flask was charged with 60 grams toluene (reagent grade, Aldrich Milwaukee, WI) and approximately 1/3 of the total catalyst charge.
  • the catalysts were prepared as described in Examples 41-45 and calcined at 250-265°C under a nitrogen purge for 1 hour. The catalyst slurry was heated to 30°C.
  • Piperylene concentrate Naphtha Petroleum 3 "Piperylenes” Lyondell Petrochemical Company, Houston, TX
  • 140 grams was added to the nitrogen purged reaction flask via the dropping addition funnel over 15 minutes maintaining the reaction temperature at 30°C and stirred at 30°C for an additional 30 minutes.
  • the monomers and solvent were dried over 4 angstrom molecular sieves.
  • the remaining heteropolyacid catalyst, total catalyst charge is 10 wt% total based on monomer, was added to the reaction solution in seven increments 15 minutes apart from the solid addition funnel maintaining the reaction at 30°C.
  • the reaction solution was held at 30°C for an additional 5 hours after the last catalyst addition.
  • the resulting resin solution was then vacuum filtered from the heteropolyacid catalyst at room temperature.
  • the reaction flask and catalyst filter cake were rinsed with approximately 100 milliliters of toluene.
  • the resin oil was placed in a round-bottom flask which was fitted with a distillation head with an adaptor for an inlet tube, thermometer, and attached to a condenser and receiving flask.
  • the resin oil was heated to 235°C with a nitrogen purge followed by a steam purge at 235-245°C to remove the light oil products.
  • the steam purge was continued until less than 1 ml of oil was collected per 100 ml of steam condensate or until 1000 ml of steam condensate was collected.
  • the steam purge was followed by a nitrogen purge at 235°C to remove water from the remaining resin.
  • the resins produced have the properties listed in Table 12.
  • the catalyst from the reactions was collected by centrifugation of the reaction solution.
  • the solid catalyst was washed four times with hot toluene and dried under vacuum at 100°C for 1-1.5 hours prior to reuse.
  • the resins produced have the properties listed in Table 13.
  • a 500 milliliter three neck flask was equipped with a cooling jacket, overhead stirrer, reflux condenser, gas inlet and outlet ports, thermometer, and dropping addition funnel.
  • the flask was charged with 66.2 grams of "LRO-90” (Lyondell Petrochemical Company, Houston, TX), 66.2 grams of "RHS", (Recycled Hydrogenation Solvent, Hercules Incorporated, Wilmington, Delaware) (RHS being similar to "OMS", Organic Mineral Spirits, Exxon Chemical Company, Houston, TX), and 100 grams of toluene (reagent grade, Aldrich, Milwaukee, WI).
  • LRO and RHS had been mixed prior to the reaction and dried over anhydrous calcium chloride (reagent grade, Aldrich, Milwaukee, WI).
  • the toluene was dried over 3 angstrom molecular sieves prior to use.
  • the catalyst 6.12 grams of Cs 29 H 0 ,PW 12 O 40 , was dried at 200°C for 30 minutes. A portion of the catalyst, 3.0 grams, was added to initiate the reaction. The reaction temperature was maintained at 10°C and 0.75 grams of additional catalyst added after 45 and 100 minutes. After 140 minutes, the reaction flask was heated to maintain 40°C. The total reaction time was 345 minutes.
  • the catalyst was filtered from the resin solution.
  • the resin solution was rotary evaporated with a final condition of 45 minutes with a bath temperature of 190°C at ⁇ 5 mm Hg.
  • the resultant yield was 14.3 grams.
  • the softening point of the resin was 65°C.
  • the number average, weight average, and Z average molecular weights as determined by SEC were 421, 729, 1348.

Abstract

Metal oxide solid acids are used as catalysts for the polymerization of a feed stream containing at least one of pure monomer (e.g., styrene based monomers), C5 monomers, and C9 monomers to produce hydrocarbon resins. Freely-associated water may be removed from the solid acid catalyst prior to use. Resins with softening points (Ring and Ball) in the range of about 5 °C to 170 °C can be prepared. These catalysts offer advantages over the traditional Friedel-Crafts polymerization catalysts since the acid sites are an integral part of the solid. The solid acid catalysts are relatively nonhazardous, reusable catalysts which eliminate or at least reduce contamination of the resulting resin products with acid residues or by-products.

Description

METAL OXIDE SOLID ACIDS AS CATALYSTS FOR THE PREPARATION OF HYDROCARBON RESINS
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application claims the priority under 35 U.S.C. § 119(e) of U.S.
Provisional Application No. 60/035,217, filed January 8, 1997; U.S. Provisional Application
No. 60/034,579, filed January 9, 1997; and U.S. Provisional Application No. 60/035,797, filed January 10, 1997; the disclosures of which are herein expressly incorporated by reference in their entirety.
BACKGROUND OF THE INVENTION 1.Field of the Invention
This invention relates to metal oxide solid acids useful as catalysts for the polymerization of a feed stream containing at least one of pure monomer, C5 monomers, and
C9 monomers to produce a hydrocarbon resin, to processes of preparing hydrocarbon resins using solid acid catalysts, and to hydrocarbon resins produced by such processes. 2. Discussion of Background
Hydrocarbon resins are low molecular weight, thermoplastic materials prepared via thermal or catalytic polymerization. The resins may be derived from several different sources of monomers. The monomer sources include cracked petroleum distillate from oil refining, turpentine fractions (e.g., terpenes from natural product distillation), paper mill byproduct streams, coal tar, and a variety of pure olefinic monomers.
The resulting hydrocarbon resins can range from viscous liquids to hard, brittle solids with colors ranging from water white to pale yellow, amber, or dark brown depending on the monomers used and the specific reaction conditions. Typically, pure monomer resins tend to be water white, C9 monomer resins tend to be brown, and C5 monomer resins tend to be yellow.
Hydrocarbon resins are used extensively as modifiers in adhesives, rubber, hot-melt coatings, printing inks, paint, flooring, and other applications. The resins are usually used to modify other materials.
Pure monomer hydrocarbon resins can be prepared by cationic polymerization of styrene-based monomers such as styrene, alpha-methyl styrene, vinyl toluene, and other alkyl substituted styrenes using Friedel-Crafts polymerization catalysts such as Lewis acids (e.g., boron trifluoride (BF3), complexes of boron trifluoride, aluminum trichloride (A1C13), alkyl aluminum chlorides).
Similarly, aliphatic C5 hydrocarbon resins can be prepared by cationic polymerization of a cracked petroleum feed containing C5 and C6 paraffins, olefins, and diolefins also referred to as "C5 monomers". These monomer streams are comprised of cationically polymerizable monomers such as 1,3-pentadiene which is the primary reactive component along with cyclopentene, pentene, 2-methyl-2-butene, 2-methyl-2-pentene, cyclopentadiene, and dicyclopentadiene. The polymerizations are catalyzed using Friedel- Crafts polymerization catalysts such as Lewis acids (e.g., boron trifluoride (BF3), complexes of boron trifluoride, aluminum trichloride (A1C13), or alkyl aluminum chlorides). In addition to the reactive components, nonpolymerizable components in the feed include saturated hydrocarbons which can be codistilled with the unsaturated components such as pentane, cyclopentane, or 2-methylpentane. This monomer feed can be copolymerized with C4 or C5 olefins or dimers as chain transfer agents.
Also, aromatic C9 hydrocarbon resins can be prepared by cationic polymerization of aromatic C8, C9, and/or CIO unsaturated monomers derived from petroleum distillates resulting from naphtha cracking and are referred to as "C9 monomers". These monomer streams are comprised of cationically polymerizable monomers such as styrene, alpha- methyl styrene, beta-methyl styrene, vinyl toluene, indene, dicyclopentadiene, divinylbenzene, and other alkyl substituted derivatives of these components. The polymerizations are catalyzed using Friedel-Crafts polymerization catalysts such as Lewis acids (e.g., boron trifluoride (BF3), complexes of boron trifluoride, aluminum trichloride (A1C13), alkyl aluminum chlorides). In addition to the reactive components, nonpolymerizable components include aromatic hydrocarbons such as xylene, ethyl benzene, cumene, ethyl toluene, indane, methylindane, naphthalene and other similar species. These nonpolymerizable components of the feed stream can be incorporated into the resins via alkylation reactions.
Although Lewis acids are effective catalysts for the cationic polymerization reactions to produce hydrocarbon resins, they have several disadvantages. Conventional Lewis acids are single use catalysts which require processing steps to quench the reactions and neutralize the acids.
Further, conventional Lewis acids also require removal of catalyst salt residues from the resulting resin products. Once the salt residues generated from the catalyst neutralization are removed, the disposal of these residues presents an additional cost. Therefore, it is of particular interest to reduce the amount of catalyst residues, particularly halogen-containing species generated in these reactions. Another problem involved in using conventional Lewis acid catalysts, such as A1C13 and BF3, is that they are hazardous materials. These conventional Lewis acid catalysts generate highly corrosive acid gases on exposure to moisture, (e.g., HF, HC1).
In addition to the traditional Lewis acids, work has been done with certain solid acid catalysts. BITTLES et al., "Clay-Catalyzed Reactions of Olefins. I. Polymerization of Styrene", Journal of Polymer Science: Part A. Vol. 2, pp. 1221-31 (1964) and BITTLES et al., "Clay-Catalyzed Reactions of Olefins. II. Catalyst Acidity and Measurement", Journal of Polymer Science: Part A. Vol. 2, pp. 1847-62 (1964), the disclosures of which are herein expressly incorporated by reference in their entirety, together disclose polymerization of styrene with acid clay catalysts to obtain polymers having molecular weights between 440 and 2000 as determined by freezing point depression of benzene solutions. These documents disclose that the catalyst was prepared for polymerization by heating under vacuum, and that if the catalyst adsorbed moisture, the activity of the catalyst could be restored by reheating under vacuum.
SALT, "The Use of Activated Clays as Catalysts in Polymerisation Processes, with Particular Reference to Polymers of Alpha Methyl Styrene", Clay Minerals Bulletin. Vol.
2, pp. 55-58 (1948), the disclosure of which is herein incorporated by reference in its entirety, discloses polymerization of styrene and/or alpha-methyl styrene by using a clay catalyst to obtain polymers that range from dimers to molecular weights of about 3000.
U.S. Patent No. 5,561,095 to CHEN et al., the disclosure of which is herein incorporated by reference in its entirety, discloses a supported Lewis acid catalyst for polymerization of olefins, including C3-C23 alpha-olefins, to obtain polymers having number average molecular weights (Mn) ranging from about 300 to 300,000. Exemplary Lewis acid supports include silica, silica-alumina, zeolites, and clays. Example 1 of CHEN et al. discloses that a Lewis acid supported on silica is heated under vacuum. U.S. Patent No. 3,799,913 to WHEELER et al., the disclosure of which is herein incorporated by reference in its entirety, discloses Friedel-Crafts catalysts for polymerization of polymerizable constituents, including alpha-methyl styrene, indene, vinyl toluene and styrene, to obtain polymers having a number average molecular weight (Mn) ranging from about 350 to 1200. Zinc chloride is disclosed as one of the Friedel-Crafts catalysts.
U.S. Patent No. 3,652,707 to SAINES, the disclosure of which is herein incorporated by reference in its entirety, discloses Friedel-Crafts metal halide catalysts for polymerization of olefin hydrocarbons, including pentene, styrene and methylstyrene, to obtain polymers having a molecular weight of from about 700 to about 2500. Zinc chloride is disclosed as one of the Friedel-Crafts metal halide catalysts.
PENG et al., "Electrophilic Polymerization of 1 ,3-Pentadiene Initiated by Aluminum Triflate", Eur. Polvm. J. Vol. 30, No. 1, pp. 69-77 (1994), the disclosure of which is herein incorporated by reference in its entirety, discloses aluminum triflate for polymerization of piperylene to obtain polymers having varying number average molecular weights.
European Patent Application 0 352 856 Al, the disclosure of which is herein incorporated by reference in its entirety, discloses use of aluminum triflate, cerium triflate, e.g., for oligomerization of C3 to C6 olefins to obtain oligomers having 6 to 24 carbon atoms. GANDINI et al., "The Heterogeneous Cationic Polymerization of Aromatic
Monomers by Aluminum Triflate", Polymer Preprints. American Chemical Society, pp. 359- 360 (1996), the disclosure of which is herein incorporated by reference in its entirety, discloses use of aluminum triflate for polymerization of C9 related monomers to obtain a polymer having a number average molecular weight (Mn) around 3000. This document also discloses that aluminum triflate could be useful for the direct "resinification" of mixtures of aromatic monomers and solvents arising from specific petroleum cuts.
Other documents, the disclosures of which are herein incorporated by reference in their entireties, which generally disclose the use of solid acid catalysts to polymerize monomers for the preparation of resins include U.S. Patent No. 4,068,062 to LEPERT, U.S. Patent No. 4,130,701 to LEPERT, U.S. Patent No. 4,245,075 to LEPERT, and U.S. Patent
No. 4,824,921 to LUVINH.
SUMMARY OF THE INVENTION The present invention involves the preparation of hydrocarbon resins. More particularly, the present invention involves the use of metal oxide solid acid catalysts to polymerize a feed of hydrocarbon monomers.
Hydrocarbon resins are prepared from at least one of pure monomer, C5 monomers, and C9 monomers using relatively environmentally benign, recyclable, metal oxide solid acid catalysts in which freely-associated water may have been removed. In the present invention, hydrocarbon resins are prepared by cationic polymerization (e.g., Friedel-Crafts) wherein a feed stream containing at least one of pure monomer, C5 monomers, and C9 monomers is treated with metal oxide solid acid catalyst. Before use, the metal oxide solid acid catalysts are treated to remove freely- associated water associated with the solids to maximize catalyst acidity and activity toward the polymerization. For example, prior to use, the catalyst may be calcined for a sufficient time to remove freely-associated water and/or the catalyst may be exposed to reduced atmospheric pressure. For instance, the calcining may be at a temperature up to about 700°C, preferably at a temperature between about 50°C and 500°C. The calcining may be under reduced atmospheric pressure for up to about 8 hours, preferably between about 1 hour to 4 hours.
In accordance with one aspect, the present invention is directed to a process for making a hydrocarbon resin, including polymerizing a feed stream comprising at least one member selected from the group consisting of pure monomer, C5 monomers, and C9 monomers in the presence of a metal oxide solid acid catalyst to produce a hydrocarbon resin, wherein substantially all freely-associated water has been removed from the metal oxide solid acid catalyst.
In one aspect of the present invention, the metal oxide solid acid catalyst comprises heteropolyacid intercalated clay.
In accordance with another feature of the present invention, the metal oxide solid acid catalyst comprises at least one member selected from the group consisting of heteropolyacid and salts thereof comprising at least one member selected from the group consisting of tungstophosphoric acid, tungstosilicic acid, molybdophosphoric acid, molybdosilicic acid, mixed metal heteropolyacids, and salts thereof. The heteropolyacid and salts thereof may be CsπH(3.n)PW12O40 where n = 2 to less than 3, preferably 2.50 - 2.98.
In accordance with a feature of the present invention, the metal oxide solid acid catalyst comprises at least one member selected from the group consisting of supported heteropolyacid and salts thereof comprising at least one member selected from the group consisting of silica supported heteropolyacid and salts thereof, sol-gel incorporated heteropolyacid and salts thereof, cation exchange resin supported heteropolyacid and salts thereof, clay supported heteropolyacid and salts thereof, clay intercalated heteropolyacid and salts thereof, mesoporous silica supported heteropolyacid and salts thereof, and mesoporous silica-alumina supported heteropolyacid and salts thereof.
In accordance with yet another feature of the present invention, the metal oxide solid acid catalyst may include sulfated zirconia, tungstated zirconia, sulfated titania, sulfated tungstate, acid functionalized organically bridged polysilsesquisiloxane, or niobic acid. In accordance with a feature of the present invention, the metal oxide solid acid catalyst includes mixed oxide comprising at least one member selected from the group consisting of B2O3.Al2O3, Cr2O3.Al2O3, MoO3.Al2O3, ZrO2.Si02, Ga2O3.SiO2, BeO,.SiO2, MgO.SiO2, CaO.SiO2, SrO.SiO2, Y2O3.SiO2, La2O3.SiO2, SnO.Si02, PbO.SiO2, MoO3.Fe(MoO4)3, MgO.B2O3, and TiO2.ZnO. In accordance with yet another feature of the present invention, the metal oxide solid acid catalyst includes inorganic acid comprising at least one member selected from the group consisting of ZnO, Al2O3, TiO2, CeO2, As2O3, V2O5, Cr2O3, MoO3, ZnS, CaS, CaSO4, MnSO4, NiSO4, CuSO4, CoSO4, CdSO4, SrS04, ZnS04, MgSO4, FeS04, BaS04, KHSO4, K2S04, (NH4)2SO4, Al2(SO4)3, Fe2(SO4)3, Cr2(SO4)3, Ca(NO3)2, Bi(NO3)3, Zn(NO3)2, Fe(NO3)3, CaCO3, BPO4, FePO4, CrPO4, Ti3(PO4)4, Zr3(PO4)4, Cu3(PO4)2, Ni3(PO4)2, AlPO4,
Zn3(PO4)2, and Mg3(PO4)2.
In accordance with another feature of the invention, the feed stream includes between about 20 wt% and 80 wt% monomers and about 80 wt% to 20 wt% of solvent. Preferably, the feed stream includes about 30 wt% to 70 wt% monomers and about 70 wt% to 30 wt% of solvent. More preferably, the feed stream includes about 50 wt% to 70 wt% monomers and about 50 wt% to 30 wt% of solvent. The solvent may include an aromatic solvent. The aromatic solvent may include at least one member selected from the group consisting of toluene, xylenes, and aromatic petroleum solvents. The solvent may include an aliphatic solvent. The invention may further include recycling the solvent. In accordance with a feature of the invention, the feed stream includes at least C5 monomers. The feed stream may include at least C5 monomers, wherein cyclopentadiene and methylcyclopentadiene components are removed from the feed stream by heating at a temperature between about 100°C and 160°C and fractionating by distillation. The C5 monomers may include at least one member selected from the group consisting of isobutylene, 2-methyl-2-butene, 1-pentene, 2-methyl-l-pentene, 2-methyl-2-pentene, 2- pentene, cyclopentene, cyclohexene, 1,3-pentadiene, 1 ,4-pentadiene, isoprene, 1 ,3- hexadiene, 1 ,4-hexadiene, cyclopentadiene, and dicyclopentadiene. The feed stream may include at least C5 monomers, wherein the feed stream includes at least about 70 wt% of polymerizable monomers with at least about 50 wt% 1,3-pentadiene. The C5 feed stream may contain low levels of isoprene, generally contains a portion of 2-methyl-2-butene, and may contain one or more cyclodiolefins.
The feed stream may include at least C5 monomers, wherein the feed stream further includes up to about 40 wt% of chain transfer agent, preferably up to about 20 wt% of chain transfer agent. The chain transfer agent may include at least one member selected from the group consisting of C4 olefins, C5 olefins, dimers of C4 olefins, and dimers of C5 olefins. The chain transfer agent may include at least one member selected from the group consisting of isobutylene, 2-methyl-l-butene, 2-methyl-2-butene, dimers thereof, and oligomers thereof.
In accordance with a feature of the invention, the feed stream includes about 30 wt% to 95 wt% of C5 monomers and about 70 wt% to 5 wt% of a cofeed including at least one member selected from the group consisting of pure monomer, C9 monomers, and terpenes. Preferably, the feed stream includes about 50 wt% to 85 wt% of C5 monomers and about 50 wt% to 15 wt% of a cofeed including at least one member selected from the group consisting of pure monomer, C9 monomers, and terpenes.
In accordance with another feature of the invention, the feed stream includes at least C9 monomers. The C9 monomers may include at least one member selected from the group consisting of styrene, vinyl toluene, indene, dicyclopentadiene, and alkylated derivatives thereof. The C9 monomers may include at least about 20 wt% polymerizable unsaturated hydrocarbons. The C9 monomers may include about 30 wt% to 75 wt% polymerizable unsaturated hydrocarbons. The C9 monomers may include about 35 wt% to 70 wt% polymerizable unsaturated hydrocarbons.
In accordance with a feature of the invention, the feed stream includes about 30 wt% to 95 wt% of the C9 monomers and about 70 wt% to 5 wt% of a cofeed including at least one member selected from the group consisting of pure monomer, C5 monomers, and terpenes. Preferably, the feed stream includes about 50 wt% to 85 wt% of the C9 monomers and about 50 wt% to 15 wt% of a cofeed including at least one member selected from the group consisting of pure monomer, C5 monomers, and terpenes. Many of the metal oxide solid acid catalysts function most effectively in the presence of a controlled amount of water in the monomer feed stream. In accordance with this feature of the invention, the feed stream should include less than about 500 ppm water, preferably less than about 200 ppm water, more preferably less than about 100 ppm water, and most preferably less than about 50 ppm water.
In accordance with yet another feature of the invention, the feed stream is contacted with about 0.5 wt% to 30 wt%, preferably about 1 wt% to 20 wt%, more preferably about 3 wt% to 15 wt%, and most preferably 0.5 wt% to 5 wt% of the metal oxide solid acid catalyst based on monomer weight in a batch reactor.
In accordance with a feature of the invention, the metal oxide solid acid catalyst is added to the feed stream.
In accordance with another feature of the invention, the feed stream is added to a slurry of the metal oxide solid acid catalyst in solvent. The feed stream may be passed over a fixed bed of the metal oxide solid acid catalyst.
In accordance with yet another feature of the invention, the feed stream is cofed with a slurry of the metal oxide solid acid catalyst into a reactor.
In accordance with a feature of the invention, the polymerization is carried out as a continuous process or as a batch process. A reaction time in the batch process is about 30 minutes to 8 hours, preferably about 1 hour to 4 hours at reaction temperature.
In accordance with a feature of the invention, the feed stream is polymerized at a reaction temperature between about -50°C and 150°C, preferably between about -20°C and 100°C, and more preferably between about 0°C and 70°C.
In accordance with another feature of the invention, the polymerization is stopped by removing the metal oxide solid acid catalyst from the hydrocarbon resin. The metal oxide solid acid catalyst may be removed from the hydrocarbon resin by filtration. The hydrocarbon resin may be removed from a fixed bed reactor which includes the metal oxide solid acid catalyst.
In accordance with a feature of the invention, the hydrocarbon resin is stripped to remove unreacted monomers, solvents, and low molecular weight oligomers. The unreacted monomers, solvents, and low molecular weight oligomers may be recycled.
In accordance with a feature of the invention, the hydrocarbon resin is separated from a hydrocarbon resin solution.
In accordance with a feature of the invention, the feed stream includes at least pure monomer and the resulting hydrocarbon resin has a softening point as measured by ASTM-
E28 "Standard Test Method for Softening Point by Ring and Ball Apparatus", between about
5°C and 170°C. The feed stream may include at least C5 monomers, wherein the softening point of the resulting hydrocarbon resin is between about 50°C and 150°C. The feed stream may include at least C9 monomers, wherein the softening point of the resulting hydrocarbon resin is between about 70°C and 160°C.
In accordance with a feature of the invention, the feed stream includes at least pure monomer, wherein the hydrocarbon resin has a number average molecular weight (Mn) ranging from about 400 to 2000, a weight average molecular weight (Mw) ranging from about 500 to 5000, a Z average molecular weight (Mz) ranging from about 500 to 10,000, and a polydispersity (PD) as measured by Mw/Mn between about 1.2 and 3.5, where Mn, Mw, and Mz are determined by size exclusion chromatography (SEC).
In accordance with a feature of the invention, the feed stream includes at least C5 monomers, wherein the hydrocarbon resin has a number average molecular weight (Mn) of about 400 to 2000, a weight average molecular weight (Mw) of about 500 to 3500, a Z average molecular weight (Mz) of about 700 to 15,000, and a polydispersity (PD) as measured by Mw/Mn between about 1.2 and 5, where Mn, Mw, and Mz are determined by size exclusion chromatography (SEC). In accordance with another feature of the invention, the feed stream includes at least
C9 monomers, wherein the hydrocarbon resin has a number average molecular weight (Mn) of about 400 to 1200, a weight average molecular weight (Mw) of about 500 to 2000, a Z average molecular weight (Mz) of about 700 to 6000, and a polydispersity (PD) as measured by Mw/Mn between about 1.2 and 3.5, preferably 1.2 and 2.5, where Mn, Mw, and Mz are determined by size exclusion chromatography (SEC).
In accordance with another feature of the invention, the hydrocarbon resin is hydrogenated.
DETAILED DESCRIPTION OF THE INVENTION The particulars shown herein are by way of example and for purposes of illustrative discussion of the various embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of the invention. In this regard, no attempt is made to show details of the invention in more detail than is necessary for a fundamental understanding of the invention, the description making apparent to those skilled in the art how the several forms of the invention may be embodied in practice.
All percent measurements in this application, unless otherwise stated, are measured by weight based upon 100% of a given sample weight. Thus, for example, 30% represents 30 weight parts out of every 100 weight parts of the sample.
Unless otherwise stated, a reference to a compound or component includes the compound or component by itself, as well as in combination with other compounds and components, such as mixtures of compounds. Before further discussion, a definition of the following terms will aid in the understanding of the present invention.
SOLID ACID: a solid which changes the color of a basic Hammett indicator with a pKa < 0.
METAL OXIDE SOLID ACID: a solid acid comprising a metal which is exclusively covalently bonded to oxygen, exclusive of alumino-silicates, e.g., including metal phosphates, metal nitrates, and metal sulfates.
HETEROPOLYACID: a solid acid comprising a heteropolyacid counterion and a heteropolyacid anion having complementing charge.
HETEROPOLYACID COUNTERION: a cationic species, e.g., H+, Na+, K+, Cs+, Al3+, or NH3 +.
HETEROPOLYACID ANION: an anion having the general formula XxMmOy z-, where X = a heteroatom or central atom which is different from M; M = an early transition metal in highest oxidation state; O = oxygen; z- = the charge of the anion; and x, m, and y represent the molar ratio of the atomic components X, M, and O respectively; and where M is, e.g., Mo, W, V, Nb, or Ta; and where X is, e.g., P, Si, or As.
KEGGIN HETEROPOLYACID: a heteropolyacid wherein the anion has the general formula XM12O40 3", wherein four oxygens form a central tetrahedron around the heteroatom X, and twelve terminal and twenty-four bridged oxygen atoms form twelve octahedra of metal atoms M. HYDROCARBON RESIN: a low molecular weight (i.e., a number average molecular weight of about 200 to less than about 3000 as determined by size exclusion chromatography (SEC)) thermoplastic polymer synthesized via thermal or catalytic polymerization of cracked petroleum distillates, terpenes, coal tar fractions, or pure olefinic monomers, wherein one of the monomers is at least a C5 or higher. PURE MONOMER: a composition comprising synthetically generated or highly purified monomer species, e.g., styrene from ethyl benzene or alpha-methyl styrene from cumene. PURE MONOMER FEED STREAM: a composition comprising any number of pure monomer species.
C5 MONOMERS: a composition derived from petroleum processing, e.g., cracking, containing unsaturated hydrocarbons comprising C5 and/or C6 olefin species boiling in the range from about 20°C to 100°C at atmospheric pressure.
C9 MONOMERS: a composition derived from petroleum processing, e.g., cracking, containing unsaturated aromatic C8, C9, and/or CIO olefin species with a boiling range of about 100°C to 300°C at atmospheric pressure.
FREELY-ASSOCIATED WATER: water associated with a solid acid catalyst where the water is chemisorbed and/or physisorbed.
As a general overview of the present invention, hydrocarbon resins are produced by using metal oxide solid acids as catalysts for the cationic polymerization of a feed stream containing at least one of pure monomer (e.g., styrene based monomers), C5 monomers, and C9 monomers. Resins with softening points (Ring and Ball) preferably in the range of about 5°C to 170°C, more preferably about 30°C to 150°C, can be prepared. These catalysts offer advantages over the traditional Lewis acid polymerization catalysts since the acid sites are an integral part of the solid.
Looking at the present invention in more detail, hydrocarbon resins are prepared through a polymerization reaction wherein a feed stream containing at least one of pure monomer, C5 monomers, and C9 monomers in a solvent are contacted with a metal oxide solid acid catalyst. Metal oxide solid acid catalysts which are useful in the current invention include, but are not limited to, the following.
Heteropolyacid intercalated clays (i.e., the heteropolyacid acts as a pillar between clay layers)
Heteropolyacids and salts thereof, for example
Tungstophosphoric acid and salts, including for example
CsnH(3_n)PWI2O40, e.g., where n = 2 to less than 3, and more preferably 2.50 to 2.98
Tungstosilicic acid and salts Molybdophosphoric acid and salts Molybdosilicic acid and salts Mixed metal heteropolyacids and salts
Supported heteropolyacids and salts thereof, for example Silica supported, for example H3PWO40 on silica Sol-gel incorporated, for example
CsnH(3_n)PWO40 incorporated in sol-gel Cation exchange resin supported, for example
H3PWO40 on cation exchange resin Clay supported, for example
H3PWO40 on clay Clay intercalated heteropolyacids, for example clay intercalated with H3PWO40 Mesoporous silica supported, for example H3P WO40 supported on mesoporous silica
Mesoporous silica-alumina supported, for example
H3PWO40 on mesoporous silica-alumina
Sulfated zirconia
Tungstated zirconia
Sulfated titania
Sulfated tungstates
Acid functionalized organically bridged polysilsesquisiloxanes
Niobic acid
Mixed Oxides
B2O3.Al2O3 Cr2O3.Al2O3 MoO3.Al2O3 ZrO2.SiO2
Ga2O3.SiO2 BeO2.SiO2
MgO.SiO2 CaO.SiO2 SrO.SiO2
Y2O3.SiO2 La2O3.SiO2 SnO.SiO2 PbO.SiO2 MoO3.Fe(MoO4)3
MgO.B2O3 TiO2.ZnO
Inorganic Acids ZnO
Al2O3 TiO2 CeO2 As2O3 V2O5
Cr2O3
MoO3
CaSO4
MnSO 4,
NiSO4
CuSO4
CoSO4
CdSO4
SrSO
ZnSO4
MgSO4 FeSO4 BaSO4 KHSO,
K2SO4
(NH4),SO4
Al2(SO4)3
Fe,(SO4)3
Cr2(SO4)3
Ca(NO3)2
Bi(NO3)3
Zn(NO3)2
Fe(NO3)3
CaCO3
BPO4
FePO4
CrPO4
Ti3(PO4)4
Zr3(PO4)4
Cu3(PO4)2
Ni3(PO4)2
AlPO4
Zn3(PO4)2 g3(PO4)2
As mentioned previously, the above list of metal oxide solid acid catalysts is not intended to be an exhaustive list. In selecting other metal oxide solid acid catalysts which may be useful in the present invention, it is generally true that the metal oxide solid acid catalyst should be more acidic than about -3 on the Hammett scale.
Concerning the heteropolyacid salts, desirable counterions include for example cesium, aluminum, potassium, sodium, and ammonium.
Concerning the tungstophosphoric salts, it is noted that n should be less than 3 because a proton should be present to have catalytic action. Concerning the supported heteropolyacids and salts thereof, during the development of supported catalyst systems, a first step in a catalytic process would be the identification of a catalyst which in its pure form catalyzes the desired transformation. Once a catalyst system is identified, one of the key development strategies is to support that catalyst on an support such that the active catalyst component is spread out over a large surface area.
Examples of this strategy include the supporting of noble metal catalysts on the surface of carbon or similar inert material for hydrogenation catalysts. In the case of heteropolyacids where the crystallite size is 8 nm (nanometers), only the surface atoms of this crystallite would normally catalyze the reaction. Thus, to increase the efficiency of using the heteropolyacids, heteropolyacids were supported on solids with high surface area. Although the preferred unsupported catalyst is as a salt such as Cs29H0 1PW12O40, the preferred supported heteropolyacid is the parent heteropolyacid H3PW]2O40. Reference is made to OKUHARA et al., "Catalytic Chemistry of Heteropoly Compounds", Advances in Catalysis. Vol. 41, pp. 113-252 (1996), and MISONO et al., "Solid Superacid Catalysts", Chemtech. pp 23-29 (November 1993); the disclosures of which are herein incorporated by reference in their entireties.
Supports for the supported metal oxides include clays. Clays include naturally occurring clay minerals such as kaolinite, bentonite, attapulgite, montmorillonite, clarit, Fuller's earth, hectorite, and beidellite. Clays also include synthetic clays such as saponite and hydrotalcite. Clays further include montmorillonite clays treated with sulfuric or hydrochloric acid. Even further, clays include modified clays (i.e., clays modified by backbone element replacement), such as aluminum oxide pillared clays, cerium modified alumina pillared clays, and metal oxide pillared clays. In addition to clays, other supports include silica, silica-alumina, mesoporous silica, mesoporous silica-alumina, and ion exchange resins. Other types of supports includes natural or synthetic zeolites such as zeolite Y, zeolite β (i.e., BEA), MFI (e.g., "Zeolite Sacony Mobil-5" ("ZSM-5")), MEL (e.g., "Zeolite Sacony Mobil-11" ("ZSM-11")), NaX, NaY, faujasite (i.e., FAU), and mordenite (i.e., MOR). The names BEA, MFI, MEL, FAU, and MOR are the framework structure type IUPAC definitions of the zeolites. Examples of acid functionalized organically bridged polysilsesquisiloxanes are found in U.S. Patent No. 5,475,162 to BRANDVOLD et al. and U.S. Patent No. 5,371,154 to BRANDVOLD et al., the disclosures of which are herein incorporated by reference in their entireties. Before use, the metal oxide solid acid catalysts are treated to remove freely- associated water to maximize the catalyst acidity and activity toward the polymerization. The freely-associated water may be removed by various techniques, including thermal treatment, reduced pressure treatment, dry atmosphere treatment such as nitrogen or air, or a combination thereof. While not wishing to be bound by theory, removing freely-associated water maximizes the acid strength of the metal oxide solid acid catalysts and makes the polymerizations more reproducible.
The freely-associated water is removed from the metal oxide solid acid catalyst by calcining which generally means heating the metal oxide solid acid catalyst to high temperature without fusing the catalyst. The metal oxide solid acid catalyst may be calcined under an inert atmosphere, such as nitrogen or dry air, or under reduced pressure. The calcining is preferably performed for up to about 8 hours or more, more preferably about 1 hour to 4 hours, preferably at temperatures up to about 700°C, more preferably about 100°C to 400°C. The freely-associated water removed from the metal oxide solid acid catalyst may have been derived from water (physisorbed water) or hydroxyl groups (chemisorbed water) associated with the metal oxide solid acid catalyst. By removal of substantially all freely- associated water is meant removing all or essentially all physisorbed water and removing at least a majority of chemisorbed water. It is expected that by controlling the conditions under which the metal oxide solid acid catalyst is calcined, such as controlling the temperature or time under which the calcination step takes place, tailoring of the physical properties of the resultant resin, such as its softening point or its molecular weight, may be achieved.
Many of the metal oxide solid acid catalysts function most effectively in the presence of a controlled amount of water in the monomer feed stream. For instance, the feed stream may include less than about 500 ppm water, preferably less than about 200 ppm water, more preferably less than about 100 ppm water, and most preferably less than about 50 ppm water.
Pure monomer feed streams may contain relatively pure styrene-based monomers such as styrene, alpha-methyl styrene, beta-methyl styrene, 4-methyl styrene, and vinyl toluene fractions. The monomers can be used as pure components or as blends of two or more monomer feeds to give desired resin properties. Preferred blends include about 20 wt% to 90 wt% alpha-methyl styrene with about 80 wt% to 10 wt% of one or more comonomers, preferably styrene, vinyl toluene, 4-methyl styrene or blends of these components. In addition, other alkylated styrenes can be used as monomers in this invention such as t-butyl styrene or phenyl styrene. Feed streams can be dried, if desired, and preferably contain less than about 200 ppm water, more preferably less than about 100 ppm water, and most preferably less than about 50 ppm water. In the case of C5 resins, the petroleum feed streams contain unsaturated C5 and/or
C6 olefins and diolefins boiling in the range from about 20°C to 100°C, preferably about 30°C to 70°C. In some cases, cyclopentadiene and methylcyclopentadiene components are removed from the feed by heat soaking at temperatures preferably between about 100°C and 160°C, and fractionating by distillation. Monomers found in these feedstocks may include but are not limited to olefins such as isobutylene, 2-methyl-2-butene, 1 -pentene, 2-methy 1- 1 - pentene, 2-methyl-2-pentene, as well as 2-pentene, cycloolefins such as cyclopentene, and cyclohexene, diolefins such as 1,3-pentadiene, 1 ,4-pentadiene, isoprene, 1,3-hexadiene, and 1 ,4-hexadiene, cyclodiolefins such as cyclopentadiene, dicyclopentadiene, and alkyl substituted derivatives and codimers of these cyclodiolefins. Commercial samples of this type of feed include, but are not limited to "Naphtha Petroleum 3 Piperylenes" from
Lyondell Petrochemical Company, Houston, TX, regular "Piperylene Concentrate" or "Super Piperylene Concentrate" both from Shell Nederland Chemie B.V., Hoogvilet, the Netherlands. The C5 feed streams generally contain at least about 70 wt% polymerizable monomers with at least about 50 wt% 1,3-pentadiene. The C5 feed stream may contain low levels of isoprene, generally contains 2-methyl-2-butene, and may contain one or more cyclodiolefins.
Also concerning C5 monomer feed streams, in addition to the reactive components, nonpolymerizable components in the feed may include saturated hydrocarbons which can be codistilled with the unsaturated components such as pentane, cyclopentane, or 2- methylpentane. This monomer feed can be copolymerized with C4 or C5 olefins or dimers as chain transfer agents. Chain transfer agents may be added to obtain resins with lower and narrower molecular weight distributions than can be prepared from using monomers alone. Chain transfer agents stop the propagation of a growing polymer chain by terminating the chain in a way which regenerates a polymer initiation site. Components which behave as chain transfer agents in these reactions include but are not limited to isobutylene, 2-methyl-
1-butene, 2-methyl-2-butene or dimers or oligomers of these species. The chain transfer agent can be added to the reaction in pure form or diluted in a solvent. Feed streams can be dried if desired and preferably contain less than about 500 ppm water, more preferably less than about 200 ppm water, and most preferably less than about 50 ppm water.
In the case of C9 monomer resins, the feed streams contain unsaturated aromatic C8, C9, and/or CIO monomers with a boiling range of about 100°C to 300°C at atmospheric pressure. Aromatic C8-C10 feed streams (also referred to as C9 feed streams) can be derived from steam cracking of petroleum distillates. Monomers found in these feed stocks may include but are not limited to styrene, vinyl toluene, indene, dicyclopentadiene, and alkylated derivatives of these components. Commercial samples of this type of feed include but are not limited to "LRO-90" from Lyondell Petrochemical Company, Houston, TX, "DSM C9 Resinfeed Classic" from DSM, Geleen, the Netherlands, "RO-60" and "RO-80" from Dow Chemical Company of Midland, Michigan, and "Dow Resin Oil 60-L" from the
Dow Chemical Company of Terneuzen, the Netherlands. The C9 feed stream generally contains at least about 20% by weight, preferably about 30% to 75% by weight, and most preferably about 35% to 70% by weight polymerizable unsaturated hydrocarbons. The remainder is generally alkyl substituted aromatics which can be incorporated into the resins by alkylation reactions. Feed streams can be dried if desired and preferably contain less than about 500 ppm water, more preferably less than about 200 ppm water, and most preferably less than about 50 ppm water.
The feed streams may be limited to pure monomer, C5 monomers, or C9 monomers. Alternatively, cofeed streams can be used in combination with main feed streams of pure monomer, C5 monomers, or C9 monomers. Depending upon the main feed stream, pure monomer, C5 monomers, C9 monomers, or even terpenes, and any combination thereof, may serve as a cofeed stream. Terpene feed stocks include but are not limited to d- limonene, alpha- and beta-pinene, as well as dipentene. Resins from blends of main feed streams with cofeed streams may be prepared in the range of about 30 wt% to 95 wt% main feed with about 70 wt% to 5 wt% of a cofeed, preferably about 50-85 wt% main feed and about 50 wt% to 15 wt% cofeed.
The polymerization feed stream preferably contains between about 20 wt% and 80 wt% monomers, more preferably about 30 wt% to 70 wt%, and most preferably about 40 wt% to 70 wt%. In the case of C5 resins, the feed may contain up to about 40 wt% of a chain transfer agent, more preferably up to about 20 wt%, chain transfer agents as discussed above. The feed stream also contains about 80 wt% to 20 wt% of a solvent such as toluene, octane, higher boiling aromatic solvent, aliphatic solvent, or solvent blend.
Regarding the solvents, for pure monomer polymerization, the preferred solvents are aromatic solvents. Typically toluene, xylenes, or light aromatic petroleum solvents such as "Aromatic 100" from Exxon Chemical Company, Houston, TX, "HiSol 10" from Ashland Chemical Incorporated, Columbus, OH, and "Cyclosol 53" from Shell Chemical Company, Houston, TX can be used. These solvents can be used fresh or recycled from the process. The solvents generally contain less than about 200 ppm water, preferably less than about 100 ppm water, and most preferably less than about 50 ppm water.
For C5 polymerization, the preferred solvents are aromatic solvents. Generally, unreacted resin oil components are recycled through the process as solvent. In addition to the recycled solvents, toluene, xylenes, or aromatic petroleum solvents such as "Solvesso 100" from Exxon Chemical Company, Houston, TX and "Shellsol A" from Shell Chemical
Company, Houston, TX can be used. These solvents can be used fresh or recycled from the process. The solvents generally contain less than about 500 ppm water, preferably less than about 200 ppm water, and most preferably less than about 50 ppm water.
For C9 polymerization, the preferred solvents are aromatic solvents. Generally, unreacted resin oil components are recycled through the process as solvent. In addition to the recycled solvents, toluene, xylenes, or aromatic petroleum solvents such as "Solvesso 100" from Exxon Chemical Company, Houston, TX and "Shellsol A" from Shell Chemical Company, Houston, TX can be used. These solvents can be used fresh or recycled from the process. The solvents generally contain less than about 200 ppm water, preferably less than about 100 ppm water, and most preferably less than about 50 ppm water.
Concerning the polymerization reaction conditions, a first important variable is the amount of metal oxide solid acid catalyst which is used. The metal oxide solid acids are preferably used at a level of about 0.1 wt% to 30 wt% based on the weight of the monomer. For pure monomer resins, the metal oxide solid acid concentration is preferably about 0.1 to 15 wt%, more preferably about 0.5 wt% to 10 wt%, and most preferably about 0.5 wt% to 8 wt%. For C5 monomers, the metal oxide solid acid concentration is preferably about 0.5 wt% to 30 wt%, more preferably about 1 wt% to 20 wt%, and most preferably about 3 wt% to 15 wt%. For C9 monomers, the metal oxide solid acid concentration is preferably about 0.5 wt% to 30 wt%, more preferably about 1 wt% to 20 wt%, and most preferably about 3 wt% to 15 wt%.
A second important variable in the reaction is the reaction sequence, i.e., the order and manner in which reactants are combined. In one reaction sequence, the catalyst can be added to a solution of the monomers incrementally while controlling the reaction temperature. Alternatively, in another reaction sequence, the monomer can be added incrementally to a slurry of the metal oxide solid acid catalyst in a solvent. For a set catalyst level and reaction temperature, substantially lower softening point resins are obtained when the monomer is added to a catalyst slurry. As discussed in more detail in the following paragraphs, lower molecular weights and narrow polydispersity, i.e., Mw/Mn, as measured by size exclusion chromatography, are obtained when the monomer is added to the catalyst solution compared with resins where the catalyst is added to the monomer.
The molecular weight averages of the resins were measured using size exclusion chromatography, SEC. The column set for the analysis consisted of four Waters "Ultrastyrogel" columns of 500, 500, 1000, and 100 A pore size, in series, (Part Nos. WAT
010571, 010571, 010572, 010570 respectively) available from Waters Corporation, Milford, MA. The molecular weight calibration was calculated from the peak elution times of a standard set of narrow molecular weight distribution polystyrene polymers. The calibration set encompassed 18 standards ranging in peak molecular weight from 162 to 43,900. The peak molecular weight of a narrow molecular weight standard is defined as equal to
(MwMn)'Λ (ASTM test method D3536-76). The calibration curve is defined by a third degree polynomial curve fit of a plot of log MW vs. Ve/Vr, where Vc is the elution volume of the standard and Vr is the elution volume of the reference peak, oxygen, present as dissolved air in the injected solution. The columns and detector cell (Hewlett-Packard Differential Refractometer) are maintained at 40°C. The solvent (mobile phase) was tetrahydrofuran containing 250 ppm butylated hydroxytoluene (BHT, 2,6-di-tert-butyl-4- methylphenol) as a stabilizer (the tetrahydrofuran with BHT being available from Burdick and Jackson, Muskegon, MI). The mobile phase reservoir is purged with helium and is maintained at a flow rate of 1 milliliter per minute. Under these conditions, BHT eluted at 35.86 minutes. Samples are dissolved in THF, 0.25% wt/vol, and filtered through a 0.45 micron pore size "TEFLON" (polytetrafluoroethylene) membrane filter prior to injection (200 microliters) into the chromatograph. The reported molecular weights are the "polystyrene equivalent" molecular weights as calculated from the calibration curve.
For the pure monomer resins, the resins produced using the current invention have number average molecular weights (Mn) ranging from about 400 to 2000, weight average molecular weights (Mw) ranging from about 500 to 5000, Z average molecular weights (Mz) ranging from about 500 to 10,000, and polydispersities (PD) as measured by Mw/Mn between about 1.2 and 3.5, typically between about 1.2 and 2.5. For the C5 hydrocarbon resins, the resins produced using the current invention have number average molecular weights (Mn) ranging from about 400 to 2000, weight average molecular weights (Mw) ranging from about 500 to 3500, Z average molecular weights (Mz) ranging from about 700 to 15,000, and polydispersities (PD) as measured by Mw/Mn between about 1.2 and 5, typically between about 1.2 and 3.5. For the C9 hydrocarbon resins, the resins produced using the current invention have number average molecular weights (Mn) ranging from about 400 to 1200, weight average molecular weights (Mw) ranging from about 500 to 2000, Z average molecular weights (Mz) ranging from about 700 to 6000, and polydispersities (PD) as measured by Mw/Mn between about 1.2 and 3.5, typically between about 1.2 and 2.5.
As mentioned previously, narrower polydispersities (PD) and lower molecular weights are obtained when the monomer is added to the catalyst solution than when the catalyst is added to the monomer. Taking into consideration the effect of the reaction sequence, polydispersities (PD) more narrow than those obtained using traditional Lewis acid Friedel-Crafts catalysts can be obtained using metal oxide solid acids if desired. For instance, when pure monomer is added to 0.8 wt% Cs29H0 ,PW12O40 catalyst at a temperature of -6 to -2°C over 20 minutes, the hydrocarbon resin product has an Mw of 1540, an Mn of 720, an Mz of 3920, and a polydispersity (PD=Mw/Mn) of 2.2. In comparison, when 0.8 wt% of the Cs29H0 ,PW12O40 catalyst is added to pure monomer at a temperature of 0°C over 1 minute, the hydrocarbon resin product has an Mw of 3100, an Mn of 1170, an Mz of 7080, and a polydispersity (PD=Mw/Mn) of 2.7. The above data is from Examples 4 and 13 which, as noted above, have similar but different reaction conditions.
In view of the above, polydispersities (PD) more narrow than those obtained using traditional Lewis acid Friedel-Crafts catalysts can be obtained using metal oxide solid acids if desired. Narrow polydispersity is important to ensure compatibility of resin with polymers in end use applications.
A third important reaction variable is the reaction temperature. Polymerization temperatures between about -50°C and 150°C can be used in these reactions, however, more preferred reaction temperatures are between about -20°C and 100°C, most preferred temperatures are between about 0 ° C and 70 ° C . For pure monomer, the reaction temperature is preferably between about -50°C and 100°C, more preferably between about -20°C and 75°C, and most preferably between about -10°C and 60°C. For C5 monomers, the reaction temperature is preferably between about -50°C and 100°C, more preferably between about -20°C and 75°C, and most preferably between about -10°C and 70°C. For C9 monomers, the reaction temperature is preferably between about 0°C and 150°C, more preferably between about 10°C and 120°C, and most preferably between about 20°C and 110°C. Temperature is found to have a significant effect on the properties of the resulting resins. Higher molecular weight and high softening point resins are prepared at lower reaction temperatures. The reaction time at reaction temperature is preferably between about 30 minutes and 8 hours, and more preferably between about 1 hour and 4 hours.
The polymerization process can be carried out as a continuous, semi-batch, or batch process in such diverse reactors as continuous, batch, semi-batch, fixed bed, fluidized bed, and plug flow. For instance, in continuous processes, a solution of the monomers can be passed over the catalyst in a fixed bed, or the monomers can be cofed with a catalyst slurry into a continuous reactor.
The reaction may be stopped by physically separating the solid catalysts from the products. Physical separation may render the reaction solution neutral. Furthermore, physical separation can be performed by simple filtration or by separation of the resin solutions from a fixed catalyst bed. As a result, physical separation is easy and complete such that, for some metal oxide solid acid catalysts, acid functionality and catalyst residue are not left in the resin product.
Thus, use of metal oxide solid acid catalysts minimizes or eliminates the need for extra processing steps to quench the reactions, neutralize the catalyst, and filter the catalyst salt residues from the resulting products.
Once the metal oxide solid acid catalyst and resin solution are separated, the resin solution can be stripped to remove unreacted hydrocarbons, solvents, and low molecular weight oligomers which can be recycled through the process. When pure monomer is reacted, water white resins can be obtained from this invention in yields of up to about 99% based on starting monomer.
Resins obtained from this invention typically have softening points as measured by ASTM-E28 "Standard Test Method for Softening Point by Ring and Ball Apparatus" (revised 1996), varying from preferably about 5°C to 170°C, more preferably from about 30°C to 150°C. For pure monomer, the softening points preferably range from about 5°C to 170°C, more preferably from about 50°C to 150°C. For C5 hydrocarbon resins, the softening point preferably ranges from about 5°C to 170°C, more preferably from about 50°C to 150°C, and most preferably about 70°C to 130°C. For C9 hydrocarbon resins, the softening point is preferably up to about 170°C, and the softening point range is most preferably from about 70°C to 160°C. Flowable resin or those that are liquids at room temperature can also be prepared if desired using proper reaction conditions.
After the resin is produced, it may be subsequently subjected to hydrogenation to reduce coloration and improve color stability. Hydrogenation of resins is well known in the art. For a discussion of hydrogenation, reference is made to U.S. Patent No. 5,491,214 to DAUGHENBAUGH et al., which is incorporated herein by reference in its entirety.
The resins of the current invention can be used as modifiers in adhesives, sealants, printing inks, protective coatings, plastics, road markings, flooring, and as dry cleaning retexturizing agents.
The metal oxide solid acid catalysts of the present invention offer several advantages over Lewis acids (e.g., A1C13, AlBr3, BF3, complexes of BF3, TiCl4, and others which are traditionally used for Friedel-Crafts polymerizations). Many of these advantages are a result of the acid sites being an integral part of the solid catalysts. Because the acid sites are an integral part of the solid catalyst, contamination of the resin products or solvents with catalyst residues is minimal. As a result, the metal oxide solid acid catalysts do not impart color to the hydrocarbon resins due to catalyst residues. If pure styrene-based monomers are used, the resulting resins can be water white.
The metal oxide solid acid catalysts of the present invention can generally be regenerated and recycled to thereby minimize waste disposal of spent catalyst. In contrast, the Lewis acids are generally single use catalysts.
Further, the metal oxide solid acid catalysts of the present invention are nonhazardous when compared with traditional Lewis acid catalysts such as BF3 and A1C13. The catalysts of the present invention generally do not generate corrosive or hazardous liquid or gaseous acids on exposure to moisture.
The present invention will be further illustrated by way of the following Examples which are preceded by Catalyst Preparation Methods which are incorporated by the
Examples. Examples 1-26 involve pure monomer resins, Examples 41-55 involve C5 resins, and Example 56 involves C9 resins. These examples are non-limiting and do not restrict the scope of the invention.
Unless stated otherwise, all percentages, parts, etc. presented in the examples are by weight. CATALYST PREPARATION H3PW12O40 was prepared by calcining hydrated salts at 250°C under a flow of dry nitrogen.
The potassium and ammonium salts were prepared according to the following procedures. The molecular weight of the heteropolytungstic acid, H3PW12O40.xH2O, was calculated by determining the number of associated waters by measuring the weight loss at 300°C by thermogravimetric analysis and calculating the equivalent weight as water. The potassium or ammonium salts, K3PW12O40.xH2O or (NH4)3PW12O40.xH2O, were prepared by charging the acid, H3PW12O40.xH2O, 20 g, 6.1 mmol, (Aldrich, Milwaukee, WI) to a 500 ml single neck round bottom flask containing a magnetic stirring bar. The acid was dissolved in 125 ml distilled water. Potassium carbonate, 1.26 g, 9.15 mmol, (Aldrich, Milwaukee, WI) or ammonium carbonate, 0.88 g, 9.15 mmol, (Aldrich, Milwaukee, WI) was dissolved in 25 ml distilled water and added dropwise to the vigorously stirred heteropolyacid solution over approximately 12 minutes. The resulting solution was stirred at room temperature for 2 hours and reduced to dryness at 100°C, 0.25 mm Hg. The products were recovered as fine white powders. A range of salts with the formula (CATION)nH(3.n)PW]2O40, where (CATION) is any cationic counter ion, can be prepared similarly by changing the phosphotungstic acid to metal carbonate ratio. Prior to use, the phosphotungstic acid salts were pretreated at 250°C (unless otherwise noted in Table 1) for 30 minutes under flowing nitrogen to remove bound water.
The cesium salt of the phosphotungstic acid was prepared according to the following procedures. The molecular weight of the heteropolytungstic acid, H3PW12O40.xH2O, was calculated by determining the number of associated waters by measuring the weight loss at 300°C by thermogravimetric analysis and calculating the equivalent weight as water. The cesium heteropolytungstic acid salt, Cs29H0 ,PWI2O40, was prepared by charging the acid,
H3PW12O40.xH2O 30 g, 9.2 mmol, (Aldrich, Milwaukee, WI) to a 500 ml single neck round bottom flask containing a magnetic stirring bar. The acid was dissolved in 185 ml of distilled water. Cesium carbonate, 4.32 g, 13.3 mmol, (Aldrich, Milwaukee, WI) was dissolved in 35 ml of distilled water and added dropwise to the vigorously stirred heteropolyacid solution over 25 minutes. The resulting solution was stirred at room temperature for 2 hours and reduced to dryness at 100°C, 0.25 mm Hg. The product was recovered as a fine white powder. A range of Cs salts were prepared by changing the phosphotungstic acid to cesium carbonate ratio, e.g., as shown in Table 3. The aluminum salt was prepared according to the following procedures. The molecular weight of the heteropolytungstic acid, H3PWI2O40.xH2O, was calculated by determining the number of associated waters by measuring the weight loss at 300°C by thermogravimetric analysis and calculating the equivalent weight as water. The aluminum heteropolytungstic acid salt, AlPW12O40.xH2O, was prepared by charging the acid,
H3PWI2O40.xH2O 20 g, 6.1 mmol, (Aldrich, Milwaukee, WI) to a 500 ml single neck round bottom flask containing a magnetic stirring bar. The acid was combined with 60 ml of diethyl ether (Aldrich, Milwaukee, WI). Aluminum trisisopropoxide, Al(OCH3)2)3, 1.25 grams, 6.1 mmol (Aldrich, Milwaukee, WI) was combined with 40 ml of diethyl ether and added dropwise to the stirred heteropolyacid solution. The resulting solution was stirred at
25°C for 12 hours. The precipitated solids were filtered from the reaction solution, washed with 25 ml portions of diethyl ether, and dried under vacuum (0.15 mm Hg) at 80°C to constant weight. The product was recovered as a fine white powder.
EXAMPLES 1 -10
These examples illustrate the use of Keggin heteropolyacids as catalysts for the polymerization of styrene based pure monomer. Salts of Keggin phosphotungstic acid are found to be active catalysts for the preparation of hydrocarbon resins with styrene based pure monomer. A 250 milliliter three neck flask was equipped with an overhead stirrer, reflux condenser, gas inlet and outlet ports, a thermometer, and a dropping addition funnel. The flask was charged with 86.6 grams of alpha-methyl styrene (reagent grade, Aldrich, Milwaukee, WI), 36.6 grams styrene (reagent grade, Aldrich, Milwaukee, WI), and 36.6 grams toluene (reagent grade, Aldrich, Milwaukee, WI). The solvent and monomers were dried over alumina prior to use.
The reaction mixture was cooled to 0°C with an ice bath. The catalyst noted in Table 1, 1.0 grams (unless otherwise noted), was added to the stirred reaction flask over approximately one minute. An exotherm of up to 5°C was typically observed. The reaction solution was stirred at 0°C for 6 hours. The resulting resin solutions were then vacuum filtered from the catalyst while still cold. The reaction flask and catalyst filter cake were rinsed with approximately 100 milliliters of toluene. The resin was stripped of solvent and volatile products at 0.25 mm Hg while gradually increasing the temperature to 170°C and maintaining the strip temperature for 15 minutes upon complete removal of volatile components.
The resins produced using various phosphotungstic acid salts have the properties listed in Table 1.
TABLE 1
Figure imgf000027_0001
a. Catalyst was calcined at 400°C b. 0.5 grams catalyst used
The fully substituted heteropolyacid in Examples 2, 5, 8, 9, and 10 show resin formation higher than expected for a catalyst where all the acid sites have been replaced. This indicates that the preparation of these catalysts did not fully replace all protons from the H3PW12O40 base material leaving residual acid functionality on the catalyst, and this residual acid functionality should be responsible for the observed catalytic behavior. As noted above, a proton should be present to have catalytic activity. In the case where the reaction was forced to completion by use of excess counter ion (e.g., see Example 20), the catalyst activity is decreased as expected. EXAMPLES 11-13
The following examples illustrate the effect of adding monomer to a catalyst slurry in solvent for the preparation of hydrocarbon resins with styrene based pure monomer using heteropolyacid catalysts. These examples also serve to illustrate the use of molybdenum based heteropolyacids.
Xylene, 50 milliliters (Aldrich, Milwaukee, WI) and either H3PMo12O40 or Na3PW12O40, 0.5 grams (Osram Sylvania Inc., Towanda, PA) which had been calcined at 250°C for one hour under vacuum were added to a nitrogen flushed reaction vessel fitted with a magnetic stirring bar and a thermocouple thermometer. The catalyst slurry was cooled to -5°C and the monomers, alpha-methyl styrene (25.0 grams, 0.19 mol) and styrene (25.0 grams, 0.22 mol) (both from Aldrich, Milwaukee, WI), were added over two minutes to the stirred solution. An exotherm of approximately 10°C was observed for both reactions. The solutions were stirred at 0°C for 10 to 15 minutes and then allowed to warm to room temperature. The reaction solution was stirred at room temperature for approximately 15 hours. The reaction solutions were filtered from the solid catalysts and the solvent and volatile products were removed on a rotary evaporator at 100°C at 0.5 mm Hg.
The resins produced have the properties listed in Table 2.
TABLE 2
Figure imgf000028_0001
For Example 13, a jacketed 250 milliliter three neck flask was equipped with an overhead stirrer, reflux condenser, gas inlet and outlet ports, a thermometer, and a dropping addition funnel. The nitrogen flushed flask was charged with toluene solvent, 36.3 g, (Aldrich, Milwaukee, WI) which had been dried over activated 4 angstrom molecular sieves and cesium heteropolytungstic acid, Cs29H0 ]PW12O40, 1.0 gram, prepared as described in Examples 1 - 10 above and calcined at 400°C for 30 minutes. The catalyst slurry was cooled to approximately -2°C using a cooling bath recirculated through the reactor jacket. The monomers, 61.6 grams of alpha-methyl styrene and 61.6 grams styrene (both reagent grade, Aldrich, Milwaukee, WI), were dried over alumina and added to a dropping addition funnel attached to the reaction flask. The monomers were added to the catalyst slurry dropwise over approximately 20 minutes while maintaining the reaction temperature between -6.0 and -2.0°C. The reaction solution was then held at -2.0°C to give a total reaction time of 2 hours.
The resulting resin solutions were vacuum filtered from the catalyst at room temperature. The reaction flask and catalyst filter cake were rinsed with approximately 50 milliliters of toluene. The resin was stripped of solvent and volatile products at 0.06 mm Hg by gradually heating the solution to 175°C and maintaining this strip temperature for 15 minutes upon complete removal of volatile components.
The resin produced in Example 13 has the following properties.
Resin yield 21% Softening Point 97°C
Molecular Weight
Mn 720
Mw 1540
Mz 3920 PD 2.2
Since the reactions of Example 13 and Example 4 are similar, the properties of the resin of Example 13 which involves monomer addition to catalyst may be compared with the properties of the resin of Example 4 which involves catalyst addition to monomer. As previously noted, narrower polydispersities (PD) and lower molecular weights are obtained when the monomer is added to the catalyst solution than when the catalyst is added to the monomer. In Example 13, when pure monomer is added to 0.8 wt% Cs2 9H0 1PW12O40 catalyst at a temperature of -6 to -2°C over 20 minutes, the hydrocarbon resin product has an Mw of 1540, an Mn of 720, an Mz of 3920, and a polydispersity (PD=Mw/Mn) of 2.2. In comparison, in Example 4, when 0.8 wt% of the Cs29H0 ιPW12O40 catalyst is added to pure monomer at a temperature of 0°C over 1 minute, the hydrocarbon resin product has an Mw of 3100, an Mn of 1170, an Mz of 7080, and a polydispersity (PD=Mw/Mn) of 2.7. EXAMPLES 14-20
These examples illustrate the use of cesium salts of a Keggin heteropolyacid as catalysts for the polymerization of styrene based pure monomer to prepare hydrocarbon resins. A jacketed 500 milliliter three neck flask was equipped with an overhead stirrer, reflux condenser, gas inlet and outlet ports, a thermometer, and a dropping addition funnel.
The flask was charged with 86.6 grams of alpha-methyl styrene (reagent grade, Aldrich,
Milwaukee, WI), 36.6 grams styrene (reagent grade, Aldrich, Milwaukee, WI), and 36.6 grams toluene (reagent grade, Aldrich, Milwaukee, WI). The solvent and monomers were dried over alumina prior to use. The cesium phosphotungstic acid salt catalyst was pretreated at 250°C for 30 minutes under flowing nitrogen to remove bound water. The reaction mixture was cooled to 0°C by recirculating water from an ice bath in the reactor jacket. The catalyst, 0.5 to 1.0 wt% based on monomers, was added to the stirred reaction flask. An exotherm of 5°C was typical. The reaction solution was stirred at 0°C for 2.5 hours.
The resulting resin solutions were vacuum filtered from the catalyst at room temperature. The reaction flask and catalyst filter cake were rinsed with approximately 100 milliliters of toluene. The resin was stripped of solvent and volatile products at 0.5 mm Hg by gradually heating the solution to 185°C and maintaining this strip temperature for 15 minutes upon complete removal of volatiles.
The resins produced using various cesium phosphotungstic acid salts have the properties listed in Table 3. Examples 14-18 are in accordance with the present invention, whereas Comparison Examples 19 and 20 are for comparison purposes.
TABLE 3
Figure imgf000031_0001
EXAMPLES 21 -23
These examples serve to illustrate the reuse of the cesium phosphotungstic acid catalysts for the preparation of hydrocarbon resins with styrene based pure monomer.
The reaction apparatus and procedures were similar to those outlined in Examples 14-20 with the following exceptions. The catalyst was charged to the reaction solution in three equal portions over the first 30 minutes of the reaction. The catalyst was collected after each polymerization by filtration, washed in refluxing toluene, heated to 150°C for 30 minutes under flowing nitrogen, and reused.
The resins produced have the properties listed in Table 4.
TABLE 4
Figure imgf000031_0002
EXAMPLES 24-26 These examples illustrate the use of heteropolyacids for the polymerization of pure monomer.
For Comparison Example 24, a 50:50 alpha-methyl styrene/styrene mixture was polymerized in toluene at 0-10°C by using Cs3PW12O40. The resin produced in Example 24 had the following properties.
Softening Point (R&B) 68°C
Molecular Weight
Mn 650
Mw 1349
Mz 3280
PD 2.08
For Comparison Example 25, a neat monomer 50:50 alpha-methyl styrene/styrene mixture was polymerized by using Cs3PW12O40. The resin produced in Example 25 was an essentially colorless, brittle solid at room temperature and had the following properties.
Softening Point (R&B) 105°<
Molecular Weight
Mn 953
Mw 2315
Mz 5288
PD 2.42
For Example 26, a 50:50 alpha-methyl styrene/styrene mixture was polymerized in toluene at 0-10°C by using Cs2 5H05PW12O40 to essentially quantitative yield. The resin produced in Example 26 was a semi-solid at room temperature and had the following properties. Molecular Weight
Mn 380
Mw 612
Mz 1582
PD 1.75
EXAMPLE 27 This example demonstrates the use of cesium modified heteropolyacids to polymerize pure monomer. A 500 milliliter three neck flask was equipped with a cooling jacket, overhead stirrer, reflux condenser, gas inlet and outlet ports, thermometer, and dropping addition funnel. The flask was charged with 86.6 grams of vinyl toluene (Deltech Corporation, Baton Rouge LA), 36.6 grams of alpha-methyl styrene (reagent grade, Aldrich, Milwaukee, WI), and 100 grams of toluene (reagent grade, Aldrich, Milwaukee, WI). Prior to the reaction, the vinyl toluene was dried over molecular sieve and anhydrous calcium chloride (reagent grade, Aldrich, Milwaukee, WI). Also prior to the reaction, the toluene was dried over 3 angstrom molecular sieves.
After drying 1.48 grams of Cs29H0 ,PW12O40 at 200°C for 30 minutes, the catalyst was added to the reaction mixture. The reaction temperature was maintained at -5°C ± 2°C for 10 minutes and then raised to 0°C ± 2°C and held at that temperature for an additional 170 minutes for a total reaction time of 180 minutes.
At the end of the reaction time, the catalyst was filtered from the resin solution. The resin solution was rotary evaporated with a final condition of 45 minutes at a bath temperature of 190°C at < 5 mm Hg. The resultant yield was 68.3 grams or 55 %. The softening point of the resin was 92°C. The number average, weight average, and Z average molecular weights as determined by SEC were 809, 2009, 4888.
EXAMPLES 28-31 These examples illustrate using supported cesium modified and unmodified heteropolyacids to polymerize pure monomer.
SUPPORTED CATALYST PREPARATION
The catalysts were prepared by using an incipient wetness technique. Three different loadings of heteropolyacid on a silica were prepared according to the following technique.
The heteropolyacid, phosphotungstic acid (Aldrich, Milwaukee, WI) was dissolved in 150 ml water and then slowly added to 100 grams of silica gel, "Davisil Grade 710". The resultant wet silica gel was dried in a 75°C oven for at least 24 hours. The amount of heteropolyacid added to the 100 grams of silica gel is shown in Table 5 below. TABLE 5
Figure imgf000034_0001
POLYMERIZATION
A 500 milliliter three neck flask was equipped with a cooling jacket, overhead stirrer, reflux condenser, gas inlet and outlet ports, thermometer, and dropping addition funnel. The flask was charged with 36.6 grams of styrene (reagent grade, Aldrich, Milwaukee, WI ), 86.6 grams of alpha-methyl styrene (reagent grade, Aldrich, Milwaukee, WI), and 100 grams of toluene (reagent grade, Aldrich, Milwaukee, WI). Prior to the reaction, the styrene and alpha-methyl styrene were dried over molecular sieve and alumina (reagent grade, Aldrich, Milwaukee, WI). Also prior to use, the toluene was dried over 3 angstrom molecular sieves.
After drying 5.0 grams of the supported heteropolyacid at 400°C for 60 minutes, the catalyst was added to the reaction mixture. The reaction temperature was maintained at 0°C ± 6°C for 180 minutes.
At the end of the reaction time, the catalyst was filtered from the resin solution. The resin solution was rotary evaporated with a final condition of 45 minutes with a bath temperature of 190°C at < 5 mm Hg.
The resulting resins had the properties listed in Table 6. Examples 28-30 are in accordance with the present invention, whereas Comparison Example 31 is for comparison purposes.
TABLE 6
Figure imgf000035_0001
EXAMPLES 32-34 These examples illustrate the use of supported metal oxide solid acids to polymerize pure monomer.
SUPPORTED CATALYST PREPARATION
The catalysts were prepared by using an incipient wetness technique. "Silica Grade 57" (W. R. Grace, Boca Raton, Florida) was ground up in mortar pestle. The material that passed through a 30 mesh screen, but not a 60 mesh screen was used for the preparations. The heteropolyacid, phosphotungstic acid (Aldrich, Milwaukee, WI), 12.5 grams, was dissolved in 73 ml of water and then slowly added to 50 grams of the silica. The resultant wet silica gel was dried in a 75°C oven for at least 24 hours.
POLYMERIZATION
Resins were prepared with this catalyst according to the following procedure. The difference in each of the examples is the calcination temperature of the catalyst, as indicated in Table 7 below.
A 500 milliliter three neck flask was equipped with a cooling jacket, overhead stirrer, reflux condenser, gas inlet and outlet ports, thermometer, and dropping addition funnel. The flask was charged with 36.6 grams of styrene (reagent grade, Aldrich, Milwaukee, WI ), 86.6 grams of alpha-methyl styrene (reagent grade, Aldrich, Milwaukee, WI ), and 100 grams of toluene (reagent grade, Aldrich, Milwaukee, WI). Prior to the reaction, the styrene and alpha-methyl styrene were dried over molecular sieve and alumina (reagent grade, Aldrich, Milwaukee, WI). Also prior to use, the toluene was dried over 3 angstrom molecular sieves.
The catalyst was added to the reaction mixture. The reaction temperature was maintained at 0°C ± 6°C for 180 minutes.
At the end of the reaction time, the catalyst was filtered from the resin solution. The resin solution was rotary evaporated with a final condition of 45 minutes with a bath temperature of 190°C at < 5 mm Hg. The resulting resins have the properties listed in Table 7.
TABLE 7
Figure imgf000036_0001
EXAMPLES 35 and 36 These examples describe an attempt to position heteropolyacid at openings of pores of a silica support, and use of the supported catalyst to polymerize pure monomer.
CATALYST PREPARATION
The catalysts were prepared by using an incipient wetness technique.
CATALYST PREPARATION FOR EXAMPLE 35
"Silica Grade 57" (W. R. Grace, Boca Raton, Florida) was ground up in mortar pestle. The material that passed through a 30 mesh screen, but not a 60 mesh screen was used for the preparations. The silica, 25 grams, was wetted with 28 ml of "RHS" (The amount of "RHS" of 28 ml was selected based on tests that showed that the silica sample would absorb 36.5 ml of water with no liquid water present.).
The heteropolyacid, 2.81 grams of phosphotungstic acid (Aldrich, Milwaukee, WI) was dissolved in 20 ml of water and added to the silica/"RHS" mixture. Then, the solid mixture was tumbled in a rotary evaporatory for 2 hours followed by rotary evaporation for 1 hour at 110°C at 3 mm Hg. These samples were furthered dried overnight in a vacuum oven at 116°C. The catalyst was then calcined at 200°C for 2 hours.
CATALYST PREPARATION FOR EXAMPLE 36
"Silica Grade 57" (W. R. Grace, Boca Raton, Florida) was ground up in mortar pestle. The material that passed through a 30 mesh screen, but not a 60 mesh screen was used for the preparations. The silica, 25 grams, was wetted with 37 ml of "RHS" (Hercules Incorporated, Wilmington, Delaware) (The 28 ml was selected based on tests that showed that the silica sample would absorb 37 ml of water with no liquid water present.). The heteropolyacid, 2.81 grams of phosphotungstic acid (Aldrich, Milwaukee, WI) was dissolved in 20 ml of water and added to the silica RHS mixture. Then, the solid mixture was tumbled in a rotary evaporatory for 2 hours followed by rotary evaporation for 1 hour at 110°C at 3 mm Hg. These samples were furthered dried overnight in a vacuum oven at 116°C. The catalyst was calcined at 200°C for 2 hours.
POLYMERIZATION
Resins were prepared in accordance with the procedure of Examples 32-34. The resulting hydrocarbon resin had the properties listed in Table 8.
TABLE 8
Figure imgf000037_0001
EXAMPLES 37-40 These examples describe an attempt to position heteropolyacid in cell walls of a silica support, and use of the supported catalyst to polymerize pure monomer.
CATALYST PREPARATION
The catalyst synthesis strategy of these Examples was suggested by a paper which was presented at the International Chemical Congress of Pacific Basin Societies, Dec 17-22, 1995 by Y. Izumi, the disclosure of which is herein incorporated by reference in its entirety. The strategy involves using a sol gel technique to incorporate the heteropolyacid or cesium modified heteropolyacid into the silica gel structure.
To a 1 liter round bottom flask was added 10 grams of Cs29H0 1PW12O. The cesium heteropolyacid had been prepared by the method noted in Catalyst Preparation Methods. Ethyl alcohol, 250 ml of 200 proof, was added and the solution was mixed for 1 hour. Then, 100 ml of water and 0.07 grams of 36 % hydrochloric acid were added. Then, 277 grams of tetraethyl orthosilicate, 98 % (Aldrich, Milwaukee, WI ) was added to the stirred solution over 60 minutes. The solution was held at 40°C for 60 minutes. A reflux condenser was then added to the flask and the solution refluxed for 4 hours.
The resulting gel was transferred to another round bottom flask and the gel dehydrated by rotary evaporating at 50°C and 50 mm Hg until no more water/ethanol was evaporated from the gel. The material was calcined in a tube furnace under a flow of dry nitrogen at 250°C for 16 hours.
Similar preparations were done for H3PWI2O40, Cs2 5H0 5PWl2O40, and Cs27H03PW12O40.
POLYMERIZATIONS
Resins were prepared in accordance with the procedure of Examples 32-34, but if the reaction exothermed, the catalyst was added incrementally to control the exotherm at 0°C ± 5°C. The resulting hydrocarbon resin had the properties listed in Table 9.
TABLE 9
Figure imgf000038_0001
EXAMPLES 41-45 These examples illustrate the use of Keggin heteropolyacids as catalysts for the polymerization of piperylene, a C5 monomer feed. Catalyst, 2 wt% based on monomer, prepared according to Catalyst Preparation Methods was added to an 8 ounce reaction vessel fitted with a rubber septum cap and sparged with nitrogen. Toluene, 25 milliliters, (reagent grade, Aldrich, Milwaukee, WI) was dried over 4 angstrom molecular sieves and added to the reaction vessel via syringe. Piperylene 25 milliliters, (90% technical grade, Aldrich, Milwaukee, WI) was added to the stirred catalyst solution at 0°C to maintain an exotherm of under 10°C (unless otherwise stated). After the monomer was added, the reaction solution was stirred at room temperature (unless otherwise stated) for 16 hours and then filtered. The volatile components were removed from the reaction solution under vacuum (0.2-0.5 mm Hg) with heating to 90°C.
Resins produced have the properties listed in Table 10.
TABLE 10
Figure imgf000039_0001
1. Reaction performed at 55°C
2. Reaction exotherm kept below 5°C
EXAMPLE 46
This example illustrates the effect of monomer addition to a slurry of the catalyst in a solvent, involving a C5 monomer feed.
A 500 milliliter three neck flask was equipped with an overhead stirrer, reflux condenser, gas inlet and outlet ports, thermometer, and a dropping addition funnel. The flask was charged with 60 grams of toluene (reagent grade, Aldrich Milwaukee, WI) and 2.8 g of Cs29H0 ,PW,,O40 catalyst, prepared in accordance with the procedure of Examples 41-45 and calcined at 375-400°C under a dry nitrogen purge for 30 minutes. The monomer, 140 grams piperylene concentrate (Naphtha Petroleum 3 "Piperylenes" Lyondell Petrochemical Company, Houston, TX) was added to the dropping addition funnel. Prior to use, the monomers and solvent were dried over 4 angstrom molecular sieves. The reaction solution was heated to 50°C and the monomer was added to the reaction flask from the dropping addition funnel over 25 minutes The reaction solution was stirred at 50°C for 4-5 hours. The resulting resin solution was then vacuum filtered from the heteropolyacid catalyst at room temperature. The reaction flask and catalyst filter cake were rinsed with approximately 100 milliliters of toluene. The solvent and volatile components were removed from the resin solution by heating the reaction solution slowly to 100°C at 2-5 mm Hg. The reaction products were stripped for an additional 30 minutes when the temperature reached 100°C. The resin produced has the following properties.
Yield 14%
MW - SEC Mn 630
Mw 1360
Mz 5240
EXAMPLES 47 and 48
These examples illustrate the addition of the powdered catalyst incrementally to a stirred solution of the monomer in solvent, involving a C5 monomer feed. A 500 milliliter three neck flask was equipped with an overhead stirrer, reflux condenser, gas inlet and outlet ports, and thermometer. The flask was charged with 60 grams toluene (reagent grade, Aldrich Milwaukee, WI) and 140 grams piperylene concentrate (Naphtha Petroleum 3 "Piperylenes" Lyondell Petrochemical Company, Houston, TX) via syringe. Prior to use, the monomers and solvent were dried over 4 angstrom molecular sieves. The catalyst, Cs29H0 ,PW, ,O40, prepared in accordance with the procedure of Examples 41-45 and calcined under dry nitrogen as described in Table 1 1 below, was added to the reaction flask against a nitrogen purge in 4 equal increments one hour apart. The total reaction time was seven hours.
The resulting resin solution was then vacuum filtered from the heteropolyacid catalyst at room temperature. The reaction flask and catalyst filter cake were rinsed with approximately 100 milliliters of toluene.
After catalyst filtration, the resin oil was placed in a round-bottom flask which was fitted with a distillation head with an adaptor for an inlet tube, thermometer, and attached to a condenser and receiving flask. The resin oil was heated to 235°C with a nitrogen purge followed by a steam purge at 235-245°C to remove light oil products. The steam purge was continued until less than 1 ml of oil was collected per 100 ml of steam condensate or until 1000 ml of steam condensate was collected. The steam purge was followed by a nitrogen purge at 235°C to remove water from the remaining resin.
The resin produced has the properties listed in Table 11.
TABLE 11
Figure imgf000041_0001
EXAMPLES 49-51
These examples illustrate the effect of the cesium to proton ratio in the Keggin heteropolyacid catalysts on the polymerization of piperylene concentrate, involving a C5 monomer feed.
A 500 milliliter three neck flask was equipped with an overhead stirrer, reflux condenser, gas inlet and outlet ports, thermometer, liquid addition funnel, and solid addition funnel. The flask was charged with 60 grams toluene (reagent grade, Aldrich Milwaukee, WI) and approximately 1/3 of the total catalyst charge. The catalysts were prepared as described in Examples 41-45 and calcined at 250-265°C under a nitrogen purge for 1 hour. The catalyst slurry was heated to 30°C. Piperylene concentrate (Naphtha Petroleum 3 "Piperylenes" Lyondell Petrochemical Company, Houston, TX), 140 grams, was added to the nitrogen purged reaction flask via the dropping addition funnel over 15 minutes maintaining the reaction temperature at 30°C and stirred at 30°C for an additional 30 minutes. The monomers and solvent were dried over 4 angstrom molecular sieves. The remaining heteropolyacid catalyst, total catalyst charge is 10 wt% total based on monomer, was added to the reaction solution in seven increments 15 minutes apart from the solid addition funnel maintaining the reaction at 30°C. The reaction solution was held at 30°C for an additional 5 hours after the last catalyst addition.
The resulting resin solution was then vacuum filtered from the heteropolyacid catalyst at room temperature. The reaction flask and catalyst filter cake were rinsed with approximately 100 milliliters of toluene.
After catalyst filtration, the resin oil was placed in a round-bottom flask which was fitted with a distillation head with an adaptor for an inlet tube, thermometer, and attached to a condenser and receiving flask. The resin oil was heated to 235°C with a nitrogen purge followed by a steam purge at 235-245°C to remove the light oil products. The steam purge was continued until less than 1 ml of oil was collected per 100 ml of steam condensate or until 1000 ml of steam condensate was collected. The steam purge was followed by a nitrogen purge at 235°C to remove water from the remaining resin.
The resins produced have the properties listed in Table 12.
TABLE 12
Figure imgf000042_0001
EXAMPLES 52-55
These examples illustrate the reuse of cesium salts of Keggin heteropolyacids for the polymerization of piperylene concentrate, involving a C5 monomer feed.
The procedures are similar to those described for Examples 49-51 except the catalyst loading is 11 wt% based on monomer, the reaction temperature is 50°C, five additions of catalyst are carried out after the piperylene is added to the reaction solution, and the solution is maintained at reflux for 3 hours after the last catalyst addition.
The catalyst from the reactions was collected by centrifugation of the reaction solution. The solid catalyst was washed four times with hot toluene and dried under vacuum at 100°C for 1-1.5 hours prior to reuse. The resins produced have the properties listed in Table 13.
TABLE 13
Figure imgf000043_0001
EXAMPLE 56
This example demonstrates that C9 resins can be prepared with cesium modified heteropolyacids.
A 500 milliliter three neck flask was equipped with a cooling jacket, overhead stirrer, reflux condenser, gas inlet and outlet ports, thermometer, and dropping addition funnel. The flask was charged with 66.2 grams of "LRO-90" (Lyondell Petrochemical Company, Houston, TX), 66.2 grams of "RHS", (Recycled Hydrogenation Solvent, Hercules Incorporated, Wilmington, Delaware) (RHS being similar to "OMS", Organic Mineral Spirits, Exxon Chemical Company, Houston, TX), and 100 grams of toluene (reagent grade, Aldrich, Milwaukee, WI). The LRO and RHS had been mixed prior to the reaction and dried over anhydrous calcium chloride (reagent grade, Aldrich, Milwaukee, WI). The toluene was dried over 3 angstrom molecular sieves prior to use.
The catalyst, 6.12 grams of Cs29H0 ,PW12O40, was dried at 200°C for 30 minutes. A portion of the catalyst, 3.0 grams, was added to initiate the reaction. The reaction temperature was maintained at 10°C and 0.75 grams of additional catalyst added after 45 and 100 minutes. After 140 minutes, the reaction flask was heated to maintain 40°C. The total reaction time was 345 minutes.
At the end of the reaction, the catalyst was filtered from the resin solution. The resin solution was rotary evaporated with a final condition of 45 minutes with a bath temperature of 190°C at < 5 mm Hg. The resultant yield was 14.3 grams. The softening point of the resin was 65°C. The number average, weight average, and Z average molecular weights as determined by SEC were 421, 729, 1348.
While the invention has been described in connection with certain preferred embodiments so that aspects thereof may be more fully understood and appreciated, it is not intended to limit the invention to these particular embodiments. On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included within the scope of the invention as defined by the appended claims.

Claims

What is claimed is:
1. A process for making a hydrocarbon resin, comprising polymerizing a feed stream comprising at least one member selected from the group consisting of pure monomer, C5 monomers, and C9 monomers in the presence of a metal oxide solid acid catalyst to produce a hydrocarbon resin, wherein substantially all freely-associated water has been removed from the metal oxide solid acid catalyst.
2. The process of claim 1 , wherein water removal from the metal oxide solid acid catalyst comprises calcining at a temperature up to about 700┬░C.
3. The process of claim 1 , wherein the metal oxide solid acid catalyst comprises heteropolyacid intercalated clay.
4. The process of claim 1 , wherein the metal oxide solid acid catalyst comprises at least one member selected from the group consisting of heteropolyacid and salts thereof comprising at least one member selected from the group consisting of tungstophosphoric acid, tungstosilicic acid, molybdophosphoric acid, molybdosilicic acid, mixed metal heteropolyacids, and salts thereof.
5. The process of claim 4, wherein the heteropolyacid and salts thereof comprises CsnH(3.n)PW12O40 where n = 2 to less than 3.
6. The process of claim 1 , wherein the metal oxide solid acid catalyst comprises at least one member selected from the group consisting of supported heteropolyacid and salts thereof comprising at least one member selected from the group consisting of silica supported heteropolyacid and salts thereof, sol-gel incorporated heteropolyacid and salts thereof, cation exchange resin supported heteropolyacid and salts thereof, clay supported heteropolyacid and salts thereof, clay intercalated heteropolyacid and salts thereof, mesoporous silica supported heteropolyacid and salts thereof, and mesoporous silica- alumina supported heteropolyacid and salts thereof.
7. The process of claim 1 , wherein the metal oxide solid acid catalyst comprises sulfated zirconia.
8. The process of claim 1 , wherein the metal oxide solid acid catalyst comprises tungstated zirconia.
9. The process of claim 1 , wherein the metal oxide solid acid catalyst comprises sulfated titania.
10. The process of claim 1 , wherein the metal oxide solid acid catalyst comprises sulfated tungstate.
11. The process of claim 1 , wherein the metal oxide solid acid catalyst comprises acid functionalized organically bridged polysilsesquisiloxane.
12. The process of claim 1 , wherein the metal oxide solid acid catalyst comprises niobic acid.
13. The process of claim 1 , wherein the metal oxide solid acid catalyst comprises mixed oxide comprising at least one member selected from the group consisting of B2O3.Al2O3, Cr2O3.Al2O3, MoO3.Al2O3, ZrO2.SiO2, Ga2O3.SiO2, BeO2.SiO2, MgO.SiO2, CaO.SiO2, SrO.SiO2, Y 3SiO , La Q .jSiO ,2 SnO.SiO , PbO.SiO , -MoO .Fe(MoO ) , 4 3 MgO.B2O3, and TiO2.ZnO.
14. The process of claim 1 , wherein the metal oxide solid acid catalyst comprises inorganic acid comprising at least one member selected from the group consisting of ZnO, Al2O3, TiO2, CeO2, As2O3, V2O5, Cr2O3, MoO3, ZnS, CaS, CaSO4, MnSO4, NiSO4, CuSO4, CoSO4, CdSO 4 SrSO 4 ZnSO 4 MgSO 4 FeSO 4 BaSO 4 KHSO 4 K SO 4 (NH ) SQ , 4 Al2(SO4)3, Fe2(SO4)3, Cr2(SO4)3, Ca(NO3)2, Bi(NO3)3, Zn(NO3)2, Fe(NO3)3, CaCO3, BPO4,
FePO4, CrPO4, Ti3(PO4)4, Zr3(PO4)4, Cu3(PO4)2, Ni,(PO4^ AlPO4, Zn,(PO4^, and Mg,(PO4), .
15. The process of claim 1, wherein the feed stream comprises at least pure monomer, and wherein the pure monomer comprises at least one member selected from the group consisting of styrene, alpha-methyl styrene, beta-methyl styrene, 4-methyl styrene, and vinyl toluene fractions.
16. The process of claim 1, wherein the feed stream comprises at least C5 monomers comprising at least one member selected from the group consisting of isobutylene, 2-methyl-2-butene, 1 -pentene, 2-methyl-l -pentene, 2-methyl-2-pentene, 2- pentene, cyclopentene, cyclohexene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,3- hexadiene, 1 ,4-hexadiene, cyclopentadiene, and dicyclopentadiene.
17. The process of claim 1, wherein the feed stream comprises at least C9 monomers comprising at least one member selected from the group consisting of styrene, vinyl toluene, indene, dicyclopentadiene, and alkylated derivatives thereof.
18. The process of claim 1 , wherein the feed stream is contacted with about 0.1 wt% to 30 wt% of the metal oxide solid acid catalyst based on monomer weight in a batch reactor.
19. The process of claim 1, wherein the metal oxide solid acid catalyst is added to the feed stream.
20. The process of claim 1, wherein the feed stream is added to a slurry of the metal oxide solid acid catalyst in solvent.
21. The process of claim 1 , wherein the feed stream is polymerized at a reaction temperature between about -50┬░C and 150┬░C.
22. The process of claim 1, wherein the feed stream comprises at least pure monomer, and wherein the hydrocarbon resin has a number average molecular weight (Mn) ranging from about 400 to 2000, a weight average molecular weight (Mw) ranging from about 500 to 5000, a Z average molecular weight (Mz) ranging from about 500 to 10,000, and a polydispersity (PD) as measured by Mw/Mn between about 1.2 and 3.5, where Mn, Mw, and Mz are determined by size exclusion chromatography (SEC).
23. The process of claim 1, wherein the feed stream comprises at least C5 monomers, and wherein the hydrocarbon resin has a number average molecular weight (Mn) of about 400 to 2000, a weight average molecular weight (Mw) of about 500 to 3500, a Z average molecular weight (Mz) of about 700 to 15,000, and a polydispersity (PD) as measured by Mw/Mn between about 1.2 and 5, where Mn, Mw, and Mz are determined by size exclusion chromatography (SEC).
24. The process of claim 1, wherein the feed stream comprises at least C9 monomers, and wherein the hydrocarbon resin has a number average molecular weight (Mn) of about 400 to 1200, a weight average molecular weight (Mw) of about 500 to 2000, a Z average molecular weight (Mz) of about 700 to 6000, and a polydispersity (PD) as measured by Mw/Mn between about 1.2 and 3.5, where Mn, Mw, and Mz are determined by size exclusion chromatography (SEC).
25. The process of claim 5, wherein n = 2.50 to 2.98.
PCT/US1998/000010 1997-01-08 1998-01-07 Metal oxide solid acids as catalysts for the preparation of hydrocarbon resins WO1998030520A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP98901668A EP0954516A1 (en) 1997-01-08 1998-01-07 Metal oxide solid acids as catalysts for the preparation of hydrocarbon resins
CA002277295A CA2277295A1 (en) 1997-01-08 1998-01-07 Metal oxide solid acids as catalysts for the preparation of hydrocarbon resins
JP53096598A JP2001508102A (en) 1997-01-08 1998-01-07 Metal oxide solid acids as catalysts for the production of hydrocarbon resins
AU58133/98A AU5813398A (en) 1997-01-08 1998-01-07 Metal oxide solid acids as catalysts for the preparation of hydrocarbon resins

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US3521797P 1997-01-08 1997-01-08
US3457997P 1997-01-09 1997-01-09
US3579797P 1997-01-10 1997-01-10
US60/035,797 1997-01-10
US60/034,579 1997-01-10
US60/035,217 1997-01-10

Publications (1)

Publication Number Publication Date
WO1998030520A1 true WO1998030520A1 (en) 1998-07-16

Family

ID=27364695

Family Applications (4)

Application Number Title Priority Date Filing Date
PCT/US1998/000012 WO1998030587A2 (en) 1997-01-08 1998-01-07 Metal halide solid acids and supported metal halides as catalysts for the preparation of hydrocarbon resins
PCT/US1998/000010 WO1998030520A1 (en) 1997-01-08 1998-01-07 Metal oxide solid acids as catalysts for the preparation of hydrocarbon resins
PCT/US1998/000011 WO1998030521A1 (en) 1997-01-08 1998-01-07 Fluorinated solid acids as catalysts for the preparation of hydrocarbon resins
PCT/US1998/000009 WO1998030519A1 (en) 1997-01-08 1998-01-07 Solid acids as catalysts for the preparation of hydrocarbon resins

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/US1998/000012 WO1998030587A2 (en) 1997-01-08 1998-01-07 Metal halide solid acids and supported metal halides as catalysts for the preparation of hydrocarbon resins

Family Applications After (2)

Application Number Title Priority Date Filing Date
PCT/US1998/000011 WO1998030521A1 (en) 1997-01-08 1998-01-07 Fluorinated solid acids as catalysts for the preparation of hydrocarbon resins
PCT/US1998/000009 WO1998030519A1 (en) 1997-01-08 1998-01-07 Solid acids as catalysts for the preparation of hydrocarbon resins

Country Status (9)

Country Link
US (4) US6281309B1 (en)
EP (4) EP0963365B1 (en)
JP (4) JP2001508103A (en)
KR (4) KR20000070006A (en)
CN (4) CN1249733A (en)
AU (4) AU5730998A (en)
CA (4) CA2277292A1 (en)
DE (2) DE69818018T2 (en)
WO (4) WO1998030587A2 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001040438A2 (en) * 1999-11-30 2001-06-07 Curis, Inc. Methods and compositions for regulating lymphocyte activity
JP2003503563A (en) * 1999-06-24 2003-01-28 ザ ルブリゾル コーポレイション Ammonium heteropolyacid-catalyzed polymerization of olefins
US6872692B2 (en) 2001-09-21 2005-03-29 Exxonmobil Research And Engineering Company Synthetic hydrocarbon fluid
US8168178B2 (en) 1999-11-30 2012-05-01 Curis, Inc. Methods and compositions for regulating lymphocyte activity

Families Citing this family (88)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19704482A1 (en) * 1997-02-06 1998-08-13 Basf Ag Process for the production of halogen-free, reactive polyisobutene
US6025534A (en) * 1998-04-07 2000-02-15 Bp Amoco Corporation Olefin polymerization process
DE19915108A1 (en) 1999-04-01 2000-10-05 Bayer Ag Supported catalysts with a donor-acceptor interaction
US6479598B1 (en) 1999-07-20 2002-11-12 Exxonmobil Chemical Patents Inc. Petroleum resins and their production with BF3 catalyst
CN1361798A (en) * 1999-07-20 2002-07-31 埃克森化学专利公司 Petroleum resins and their production with supported catalyst
US6265478B1 (en) 1999-08-18 2001-07-24 The Goodyear Tire & Rubber Company Polymeric resinous material derived from limonene dicyclopentadiene indene and alpha-methyl styrene
US6403743B1 (en) 1999-09-14 2002-06-11 Exxonmobil Chemical Patents Inc. Petroleum resins and their production with supported catalyst
JP3389176B2 (en) * 1999-11-17 2003-03-24 科学技術振興事業団 Polymer-supported Lewis acid catalyst
SG97842A1 (en) * 2000-02-02 2003-08-20 Bp Amoco Corp Olefin polymerization process
US6274527B1 (en) * 2000-03-27 2001-08-14 Mohammed Belbachir Composition and method for catalysis using bentonites
JP2002079088A (en) * 2000-09-07 2002-03-19 Showa Denko Kk Catalyst for manufacturing lower aliphatic carboxylic acid ester, method for manufacturing the same and method for manufacturing lower aliphatic carboxylic acid ester by the catalyst
JP2002079089A (en) * 2000-09-07 2002-03-19 Showa Denko Kk Catalyst for manufacturing lower aliphatic carboxylic acid ester, method for manufacturing the same and method for manufacturing lower aliphatic carboxylic acid ester by catalyst
US6677269B2 (en) * 2001-05-17 2004-01-13 George A Olah Environmentally safe alkylation of aliphatic and aromatic hydrocarbons with olefins using solid HF-equivalent catalysts
US7145051B2 (en) * 2002-03-22 2006-12-05 Exxonmobil Chemical Patents Inc. Combined oxydehydrogenation and cracking catalyst for production of olefins
US7087803B2 (en) * 2002-10-25 2006-08-08 Haldor Topsoe A/S Method for the recovery of perfluorinated sulphonic acid
US7125817B2 (en) * 2003-02-20 2006-10-24 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
WO2004071656A1 (en) * 2003-02-05 2004-08-26 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
US7122494B2 (en) * 2003-02-05 2006-10-17 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
US7122493B2 (en) * 2003-02-05 2006-10-17 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
US7122492B2 (en) * 2003-02-05 2006-10-17 Exxonmobil Chemical Patents Inc. Combined cracking and selective hydrogen combustion for catalytic cracking
JP4041409B2 (en) * 2003-02-05 2008-01-30 独立行政法人科学技術振興機構 Polycyclic aromatic carbon-based solid strong acid
US7119153B2 (en) * 2004-01-21 2006-10-10 Jensen Michael D Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength
US7717893B2 (en) 2004-06-04 2010-05-18 The Procter & Gamble Company Absorbent articles comprising a slow recovery elastomer
US7905872B2 (en) 2004-06-04 2011-03-15 The Procter & Gamble Company Absorbent articles comprising a slow recovery stretch laminate
US8419701B2 (en) 2005-01-10 2013-04-16 The Procter & Gamble Company Absorbent articles with stretch zones comprising slow recovery elastic materials
CA2620260A1 (en) * 2005-01-26 2006-08-03 The Procter & Gamble Company Disposable pull-on diaper having a low force, slow recovery elastic waist
JP5102943B2 (en) * 2005-05-25 2012-12-19 Jx日鉱日石エネルギー株式会社 Solid phosphoric acid catalyst and olefin dimerization reaction method using the same
JP4987860B2 (en) * 2005-06-08 2012-07-25 ザ プロクター アンド ギャンブル カンパニー Absorbent article containing slowly recovering elastomer
DE102005055818A1 (en) * 2005-11-21 2007-05-24 Basf Ag Process for the preparation of highly reactive isobutene homo- or copolymers by means of metal-containing catalyst complexes
EP1882704A1 (en) * 2006-07-26 2008-01-30 Total Petrochemicals France Process for reducing residuals content in vinyl aromatic polymers
DE102006061204A1 (en) * 2006-12-22 2008-06-26 BSH Bosch und Siemens Hausgeräte GmbH Hard floor nozzle for vacuum-cleaning and wiping, has housing shell formed with rectangular contour, and holding unit provided for holding wiping cloth on lower side of wiper unit support, which is connected to moisture transfer device
EP1900763A1 (en) * 2006-09-15 2008-03-19 Rütgers Chemicals GmbH process to prepare a hydrocarbon resin
EP1900762A1 (en) * 2006-09-15 2008-03-19 Rütgers Chemicals GmbH Process for the preparation of hydrocarbon resins
US8828916B2 (en) 2006-12-28 2014-09-09 Chevron Oronite Company Llc Method to prepare nonylated diphenylamine using recycle sequential temperatures
HUE042388T2 (en) 2007-06-07 2019-06-28 Albemarle Corp Adducts, adducts and oligomers, or adducts, oligomers and low molecular weight polymers, and their preparation
JP2010533211A (en) * 2007-07-13 2010-10-21 ピラマル ヘルスケア リミテッド Process for producing 1,2,2,2-tetrafluoroethyl difluoromethyl ether (desflurane)
US8323257B2 (en) 2007-11-21 2012-12-04 The Procter & Gamble Company Absorbent articles comprising a slow recovery stretch laminate and method for making the same
CA2708864A1 (en) * 2007-12-13 2009-06-18 The Procter & Gamble Company Absorbent article with composite sheet comprising elastic material
JP2011505947A (en) * 2007-12-13 2011-03-03 ザ プロクター アンド ギャンブル カンパニー Absorbent article provided with composite sheet containing elastic material
US8309780B2 (en) * 2007-12-21 2012-11-13 Exxonmobil Research And Engineering Company Process for making olefin oligomers and alkyl benzenes in the presence of mixed metal oxide catalysts
US8993684B2 (en) 2008-06-06 2015-03-31 Albemarle Corporation Low molecular weight brominated polymers, processes for their manufacture and their use in thermoplastic formulations
US20090318884A1 (en) * 2008-06-20 2009-12-24 Axel Meyer Absorbent structures with immobilized absorbent material
CN102232089B (en) * 2008-12-02 2013-11-13 雅宝公司 Bromination of telomer mixtures derived from toluene and styrene
EP2479210A1 (en) * 2008-12-02 2012-07-25 Albemarle Corporation Branched and star-branched styrene polymers, telomers, and adducts, their synthesis, their bromination, and their uses
JO3423B1 (en) * 2008-12-02 2019-10-20 Albemarle Corp Brominated Flame Retardants And Precursors Therefor
SG171741A1 (en) * 2008-12-02 2011-07-28 Albemarle Corp Toluene and styrene derived telomer distributions and brominated flame retardants produced therefrom
JO3059B1 (en) 2009-05-01 2017-03-15 Albemarle Corp Bromination of low molecular weight aromatic polymer compositions
SG175134A1 (en) 2009-05-01 2011-12-29 Albemarle Corp Pelletized low molecular weight brominated aromatic polymer compositions
US8502012B2 (en) * 2009-06-16 2013-08-06 The Procter & Gamble Company Absorbent structures including coated absorbent material
US8455415B2 (en) * 2009-10-23 2013-06-04 Exxonmobil Research And Engineering Company Poly(alpha-olefin/alkylene glycol) copolymer, process for making, and a lubricant formulation therefor
WO2011114707A1 (en) * 2010-03-17 2011-09-22 出光興産株式会社 Catalyst for olefin oligomerization reaction
US9017305B2 (en) 2010-11-12 2015-04-28 The Procter Gamble Company Elastomeric compositions that resist force loss and disintegration
JP5788522B2 (en) 2010-11-12 2015-09-30 ザ プロクター アンド ギャンブルカンパニー Elastomer composition that resists degradation
US20120123373A1 (en) 2010-11-12 2012-05-17 David Harry Melik Elastomeric compositions that resist force loss and disintegration
JP2012107158A (en) * 2010-11-19 2012-06-07 Tosoh Corp Method for producing petroleum resin
JP5838546B2 (en) * 2010-11-19 2016-01-06 東ソー株式会社 Method for producing Lewis acidic solid acid catalyst for petroleum resin production
EP2699542B1 (en) * 2011-04-18 2016-10-12 Solvay Specialty Polymers USA, LLC. Process for the manufacture of dihalodiphenylsulfones
CN103649045B (en) 2011-04-18 2016-03-16 索维特殊聚合物有限责任公司 For the manufacture of the method originating in organic acid dihalo diphenyl sulfone
CN102399346A (en) * 2011-07-29 2012-04-04 长春工业大学 Catalysis system and method for preparing m-pentadiene petroleum resin
US8946365B2 (en) * 2012-01-18 2015-02-03 Eastman Chemical Company Low molecular weight polystyrene resin and methods of making and using the same
CN105142588B (en) 2013-05-03 2019-05-28 宝洁公司 Absorbent article including stretching lamilate
ES2769027T3 (en) 2013-05-03 2020-06-24 Mondi Gronau Gmbh Extensible laminate
WO2014179370A1 (en) 2013-05-03 2014-11-06 The Procter & Gamble Company Absorbent articles comprising stretch laminates
GB2527713B (en) 2013-05-03 2020-01-08 Procter & Gamble Absorbent articles comprising stretch laminates
WO2014179371A1 (en) 2013-05-03 2014-11-06 The Procter And Gamble Company Absorbent articles comprising stretch laminates
CN106311284A (en) * 2015-06-17 2017-01-11 江苏国立化工科技有限公司 Solid acid catalyst, and application thereof in synthesis of rubber antioxidant DTPD
CN105482039B (en) * 2015-12-29 2017-10-24 广东工业大学 A kind of method that Petropols are prepared by raw material of C9 cuts
CN107022051B (en) * 2016-02-01 2019-07-09 江西福安路润滑材料有限公司 A kind of polyalkylene succinic acid imide ashless dispersant and the preparation method and application thereof
CN106008817B (en) * 2016-06-26 2018-06-05 广西众昌树脂有限公司 The method of modifying of Petropols
EP3747414A1 (en) 2016-08-12 2020-12-09 The Procter & Gamble Company Method and apparatus for assembling absorbent articles
KR101959112B1 (en) * 2016-10-27 2019-03-15 한화토탈 주식회사 Preparation method of isobutene oligomer from C4 hydrocarbon stream containing isobutene
US11008444B2 (en) 2016-12-19 2021-05-18 Eastman Chemical Company Tires comprising polyindane resins and uses thereof
US10851270B2 (en) 2016-12-19 2020-12-01 Eastman Chemical Company Adhesives comprising polyindane resins
US10328422B2 (en) 2017-04-21 2019-06-25 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Acidic catalyst
CA3092183C (en) * 2018-02-14 2023-09-05 Rain Carbon Germany Gmbh Method for manufacturing hydrocarbon resins and their hydrogenation products
CA3094986A1 (en) * 2018-03-26 2019-10-03 Phospholutions Llc Selecting and applying metal oxides and clays for plant growth
CN108503743A (en) * 2018-04-11 2018-09-07 青岛海佳助剂有限公司 Compounded rubber and preparation method thereof and purposes
CN109180851B (en) * 2018-11-13 2020-08-14 南京工程学院 High-temperature-resistant guanidyl strong base resin and preparation method thereof
CN109553714B (en) * 2018-12-05 2022-01-11 江苏麒祥高新材料有限公司 Preparation method of oligomer for improving wet skid resistance of rubber
CN109824811A (en) * 2018-12-08 2019-05-31 濮阳班德路化学有限公司 A kind of preparation method of Alpha-Methyl benzene second dilute liquid resin
CN109851715B (en) * 2019-01-26 2019-12-27 乐清市智格电子科技有限公司 Hydrogenated petroleum resin and preparation method thereof
CN111234106A (en) * 2020-03-11 2020-06-05 恒河材料科技股份有限公司 Preparation method of liquid modified aromatic hydrocarbon petroleum resin
CN111548806B (en) * 2020-05-12 2021-06-01 天津大学 Method for treating carbon deposit on surface of hydrocarbon fuel cracking furnace in two-stage mode
US20230279194A1 (en) * 2020-07-15 2023-09-07 The Regents Of The University Of California Process for catalytic upcycling of hydrocarbon polymers to alkylaromatic compounds
CN114433229B (en) * 2020-10-20 2024-01-30 中国石油化工股份有限公司 Catalyst for preparing alkylene carbonate, and preparation method and application thereof
CN112279964A (en) * 2020-10-29 2021-01-29 遂川海州树脂有限公司 Method for preparing modified m-pentadiene petroleum resin by using composite catalyst
WO2022235860A1 (en) * 2021-05-06 2022-11-10 Eastman Chemical Company Recycle content c5 hydrocarbon resins and methods of making and using the same
CN114289042B (en) * 2022-01-10 2023-05-30 万华化学集团股份有限公司 Mesoporous solid acid catalyst, preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3374285A (en) * 1964-12-29 1968-03-19 Gulf Research Development Co Process for the polymerization of propylene
JPS57102825A (en) * 1980-12-19 1982-06-26 Nippon Oil & Fats Co Ltd Preparation of isobutylene oligomer
JPH0812601A (en) * 1994-07-01 1996-01-16 Cosmo Sogo Kenkyusho:Kk Production of alpha-alkylstyrene oligomer

Family Cites Families (343)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2734046A (en) 1956-02-07 Steam or
US31443A (en) * 1861-02-19 Felly-machine
US2301966A (en) 1936-04-02 1942-11-17 Michel Richard Process for the manufacture of valuable products from olefins
US2460692A (en) * 1943-06-24 1949-02-01 Allied Chem & Dye Corp Polymerization of resin oils with mixed clay and organic acid catalyst
US2455225A (en) * 1944-08-15 1948-11-30 Pennsyivania Ind Chemical Corp Method of making styrene resin
US2507864A (en) * 1947-03-25 1950-05-16 Texas Co Polymerization of olefins
US2559576A (en) * 1947-06-25 1951-07-03 Universal Oil Prod Co Process for polymerization with tetraborohypophosphoric acid catalyst
US2632777A (en) * 1949-01-06 1953-03-24 Universal Oil Prod Co Production of hydrocarbon conjunct polymers
US2626290A (en) * 1950-03-30 1953-01-20 Standard Oil Dev Co Process for polymerizing olefins with a phosphoric acid slurry catalyst
US2642402A (en) * 1950-04-27 1953-06-16 Standard Oil Dev Co Olefin polymerization catalyst and its preparation
US2721889A (en) * 1950-07-28 1955-10-25 Exxon Research Engineering Co Olefin polymerization process
US2626291A (en) * 1950-10-19 1953-01-20 Standard Oil Dev Co Solid phosphoric acid slurry polymerization process
US2694686A (en) 1950-12-01 1954-11-16 Standard Oil Dev Co Phosphoric acid catalysts comprising a calcined silicon phosphoric base
NL85283C (en) * 1951-07-31 1900-01-01
US2758143A (en) * 1951-10-01 1956-08-07 Exxon Research Engineering Co Olefin polymerization process
US2751331A (en) * 1951-11-13 1956-06-19 Texas Co Process for selectively polymerizing diolefins
US2772317A (en) * 1952-03-28 1956-11-27 Exxon Research Engineering Co Polymerization catalyst and processes
US2745890A (en) * 1952-03-29 1956-05-15 Exxon Research Engineering Co Process for production of polymer hydrocarbons
US2766312A (en) 1952-08-19 1956-10-09 Exxon Research Engineering Co Process for polymerizing olefins
US2766311A (en) * 1952-08-28 1956-10-09 Exxon Research Engineering Co Combination catalytic polymerization process
US2744084A (en) * 1952-09-26 1956-05-01 Exxon Research Engineering Co Olefin polymerization process using hydrogenated naphtha solvent
US2753382A (en) 1952-12-01 1956-07-03 Exxon Research Engineering Co Polymers from piperylene concentrates
US2767234A (en) * 1952-11-01 1956-10-16 Exxon Research Engineering Co Multi-stage polymerization of olefins with suspended catalyst
US2728804A (en) * 1952-11-01 1955-12-27 Exxon Research Engineering Co Multi-stage polymerization process
US2753325A (en) * 1952-12-22 1956-07-03 Exxon Research Engineering Co Resins from selected distillates
US2775577A (en) * 1952-12-23 1956-12-25 Exxon Research Engineering Co Controlled isobutylene polymerization
US2739143A (en) * 1952-12-29 1956-03-20 Exxon Research Engineering Co Process for the preparation of polyisobutylene with a slurry catalyst
US2779753A (en) * 1952-12-29 1957-01-29 Exxon Research Engineering Co Process for preparing high molecular polymers from isobutylene
US2732398A (en) * 1953-01-29 1956-01-24 cafiicfzsojk
US2849428A (en) * 1953-06-24 1958-08-26 Exxon Research Engineering Co Process for the preparation of a dissolved aluminum chloride catalyst
US2773051A (en) * 1953-07-03 1956-12-04 Exxon Research Engineering Co Preparation of resins from c5 fractions and cyclopentadiene dimers
US2833746A (en) 1953-12-23 1958-05-06 Ethyl Corp Acrylonitrile-isobutylene-styrene interpolymer
US2816944A (en) * 1954-05-14 1957-12-17 Exxon Research Engineering Co Polymerization of liquid olefins in the presence of a boron fluoride-phosphoric acidcatalyst
US2831037A (en) 1954-06-01 1958-04-15 Universal Oil Prod Co Conversion of bicyclo-olefins
US2786878A (en) * 1954-06-08 1957-03-26 Exxon Research Engineering Co Olefin polymerization process
US2887472A (en) * 1954-09-30 1959-05-19 Standard Oil Co Production of solid polyethylene by a catalyst consisting essentially of an alkali metal and an adsorbent alumina-containing material
USRE24568E (en) 1955-02-28 1958-11-18 Manufacture of solid catalysts
US2852580A (en) * 1955-09-26 1958-09-16 Universal Oil Prod Co Preparation of polyisoolefins
IT572923A (en) 1956-02-02
DE1071340B (en) 1956-03-08 1959-12-17 Esso Research and Engineering Company Elizabeth N J (V St A) Process for the production of polyisoolefmcn
US3017400A (en) * 1956-11-02 1962-01-16 Universal Oil Prod Co Polymerization of olefins
US2914517A (en) * 1956-12-24 1959-11-24 Universal Oil Prod Co Polymerization of olefins to solid polymers
US2878240A (en) 1956-12-24 1959-03-17 Universal Oil Prod Co Polymerization of olefins to solid polymers
US2938018A (en) * 1957-11-22 1960-05-24 Universal Oil Prod Co Production of hard olefin polymers
US3054787A (en) 1958-03-17 1962-09-18 Dal Mon Research Co Catalytic process
US2945845A (en) * 1958-04-28 1960-07-19 Universal Oil Prod Co Polymerization of olefins with complex catalyst comprising platinum or palladium
US2987511A (en) * 1958-07-10 1961-06-06 Universal Oil Prod Co Process for polymerizing olefinic hydrocarbons
US3006906A (en) * 1958-07-21 1961-10-31 Universal Oil Prod Co Preparation of polymers of isobutylene and an alkylene diamine
US2976338A (en) 1958-12-08 1961-03-21 Exxon Research Engineering Co Process and catalyst for polymerization
US3006905A (en) * 1959-02-16 1961-10-31 Universal Oil Prod Co Preparation of copolymers
US3037970A (en) * 1959-02-16 1962-06-05 Universal Oil Prod Co Copolymer of an unsaturated side chain aromatic compound and an alkylene diamine
US3024226A (en) 1959-11-23 1962-03-06 Texaco Inc Polymerization process
US3000868A (en) 1959-12-30 1961-09-19 Pennsylvania Ind Chemical Corp Vinyl toluene-alpha methyl styrene polymers
US3136729A (en) * 1960-06-16 1964-06-09 Phillips Petroleum Co Catalyst compositions and process of preparation
US3113165A (en) * 1960-09-01 1963-12-03 Universal Oil Prod Co Polymerization of unsaturated organic compounds
US3154595A (en) * 1960-09-29 1964-10-27 Universal Oil Prod Co Olefin polymerization catalyzed by aminated alkali metal
US3190936A (en) * 1961-02-16 1965-06-22 Texaco Inc Process for regenerating an adsorbent and a catalyst support in a polymerization operation
US3109041A (en) * 1961-02-16 1963-10-29 Texaco Inc Polymerization of isobutylene
US3166545A (en) * 1961-04-06 1965-01-19 Texaco Inc Polymerization of isobutylene with an aluminum-titanium dioxide-titanium tetrachloride catalyst
US3112350A (en) 1961-06-12 1963-11-26 Universal Oil Prod Co Polymerization of olefins using a solid phosphoric acid catalyst
US3133127A (en) * 1961-11-10 1964-05-12 Texaco Inc Polymerization process
US3179649A (en) * 1961-12-11 1965-04-20 Dow Chemical Co Polymerization catalyst mixture of a bismuthine, a cuprous salt, and a lewis acid
US3347678A (en) * 1961-12-27 1967-10-17 Grindstedvaerket As Processing citrus fruits
NL288801A (en) 1962-02-12
US3128318A (en) * 1962-06-18 1964-04-07 Universal Oil Prod Co Alkali metal amide catalysts and their use in polymerizing olefins
US3190938A (en) * 1962-11-01 1965-06-22 Exxon Research Engineering Co Polymerization of olefins
US3248341A (en) * 1963-02-13 1966-04-26 Universal Oil Prod Co Method of admixing a phosphoric acid and an absorbent and precipitating with ammonia
US3418304A (en) * 1963-09-13 1968-12-24 Exxon Research Engineering Co Polymerization catalyst
US3244767A (en) * 1964-01-24 1966-04-05 Universal Oil Prod Co Polymerization process using oxygenated sulfur-phosphoric acid catalyst
US3383378A (en) * 1964-04-22 1968-05-14 Universal Oil Prod Co Polymerization of ethylene
US3347676A (en) 1964-04-30 1967-10-17 Du Pont Photopolymerizable compositions and process
US3244768A (en) 1964-10-19 1966-04-05 Texaco Inc Catalytic polymerization of propylene
US3364191A (en) * 1964-11-03 1968-01-16 Universal Oil Prod Co Olefin-aromatic hydrocarbon copolymers
FR1464009A (en) * 1965-01-27 1966-07-22 Texaco Development Corp Improvements to processes and catalysts for isomerizing isomerizable hydrocarbons
US3801559A (en) 1965-04-16 1974-04-02 Goodyear Tire & Rubber Poly-1-chloro cyclooctadiene
US3426007A (en) 1965-10-21 1969-02-04 Exxon Research Engineering Co Polymerization catalyst system
US3867361A (en) 1966-03-28 1975-02-18 Goodyear Tire & Rubber A process for the polymerization of cyclic olefins
US3420809A (en) * 1966-08-12 1969-01-07 Exxon Research Engineering Co Catalyst for ethylene polymerization
US3426089A (en) * 1966-08-30 1969-02-04 Universal Oil Prod Co Polymerization process
US3457189A (en) * 1966-08-30 1969-07-22 Universal Oil Prod Co Fluorided refractory oxide catalyst and preparation thereof
US3472791A (en) 1966-09-12 1969-10-14 Universal Oil Prod Co Method of spherical catalyst preparation
US3499877A (en) * 1966-09-19 1970-03-10 Standard Oil Co Dimethyl alpha-methyl styrene polymers
DE1963684U (en) 1967-02-25 1967-07-06 Agfa Gevaert Ag BASE PLATE FOR A PHOTOGRAPHIC ENLARGEMENT DEVICE.
US3607959A (en) * 1967-06-16 1971-09-21 Texaco Inc Catalyst for hydrocarbon conversion
US3734866A (en) 1967-06-26 1973-05-22 Goodyear Tire & Rubber Preparation of polymeric aromatic compositions
US3515769A (en) * 1967-06-30 1970-06-02 Universal Oil Prod Co Polymerization process
US3427275A (en) 1967-08-16 1969-02-11 Reichhold Chemicals Inc Vinyl aromatic-acrylic copolymers and process of producing the same
US3497568A (en) * 1967-09-29 1970-02-24 Texaco Inc Continuous process for polymerizing olefins
US3464929A (en) 1968-05-09 1969-09-02 Universal Oil Prod Co Hydrocarbon conversion catalyst comprising a halogen component combined with a support containing alumina and finely divided crystalline aluminosilicate particles
US3463744A (en) 1968-06-03 1969-08-26 Universal Oil Prod Co Control of acid activity of a hydrocarbon conversion catalyst comprising a halogen component combined with a support containing alumina and crystalline aluminosilicate particles
US3689434A (en) * 1968-07-29 1972-09-05 Texaco Inc Catalyst for hydrocarbon conversion
US3577400A (en) * 1968-08-26 1971-05-04 Goodyear Tire & Rubber Novel catalysts for the polymerization of alicyclic olefins
US3689471A (en) * 1968-08-26 1972-09-05 Goodyear Tire & Rubber Ternary catalyst systems for the polymerization of cycle olefins
US3624060A (en) * 1969-01-31 1971-11-30 Goodyear Tire & Rubber Binary catalyst systems for the polymerization of unsaturated alicyclic monomers
US3586616A (en) 1969-03-14 1971-06-22 Minnesota Mining & Mfg Bis(perfluoroalkylsulfonyl)methane metal salts in cationic polymerization
US3842019A (en) 1969-04-04 1974-10-15 Minnesota Mining & Mfg Use of sulfonic acid salts in cationic polymerization
US3640981A (en) 1969-04-23 1972-02-08 Reichhold Chemicals Inc Vinyl toluene-alpha methyl styrene co-polymers and method of preparing the same
US3597406A (en) 1969-04-30 1971-08-03 Goodyear Tire & Rubber Polymers of hydrocarbon substituted 1,5-cyclooctadienes and methods for their polymerization
US3630981A (en) * 1969-06-09 1971-12-28 Pennsylvania Ind Chemical Corp Copolymers of alpha methyl styrene and vinyl toluene and process of preparation
US4063011A (en) 1969-06-09 1977-12-13 Hercules Incorporated Alpha methyl styrene and vinyl toluene and processes of preparation
US3956250A (en) 1969-06-09 1976-05-11 Hercules Incorporated Alpha methyl styrene and vinyl toluene and processes of preparation
US3609098A (en) * 1969-08-21 1971-09-28 Phillips Petroleum Co Haloester and cuprous salt polymerization catalyst systems
US3652707A (en) * 1969-09-16 1972-03-28 Texaco Inc Process for the polymerization of olefin hydrocarbons
US3652706A (en) * 1969-09-16 1972-03-28 Texaco Inc Polymerization of olefins
BE757752A (en) 1969-10-27 1971-04-01 Goodyear Tire & Rubber NEW CATALYSTS FOR OPEN-CYCLE POLYMERIZATION OF UNSATURE ALICYCLIC COMPOUNDS
US3644220A (en) 1969-11-13 1972-02-22 Exxon Research Engineering Co Metal halide containing zeolites and method for their preparation
US3661870A (en) 1969-11-24 1972-05-09 Goodyear Tire & Rubber Isobutylene,1,3-butadiene,methyl butene copolymers
US3692872A (en) * 1969-12-04 1972-09-19 Goodyear Tire & Rubber Preparation of graft, block and crosslinked unsaturated polymers and copolymers by olefin metathesis
US3669947A (en) * 1970-02-02 1972-06-13 Velsicol Chemical Corp Process for the production of alpha-methylstyrene polymer
US3652487A (en) * 1970-02-05 1972-03-28 Goodyear Tire & Rubber Process for the polymerization of alicyclic monomer masterbatches
US3753962A (en) 1970-03-16 1973-08-21 Atlas Chem Ind Recovery of a water soluble polymer powder from an aqueous gel of said polymer
US3631212A (en) * 1970-04-20 1971-12-28 Universal Oil Prod Co Preparation of polyarylpolyalkanes
US3711425A (en) * 1970-06-25 1973-01-16 Texaco Inc Fluorided metal alumina catalysts
US3717586A (en) 1970-06-25 1973-02-20 Texaco Inc Fluorided composite alumina catalysts
US3692695A (en) 1970-06-25 1972-09-19 Texaco Inc Fluorided composite alumina catalysts
US3657205A (en) * 1970-09-03 1972-04-18 Goodyear Tire & Rubber Preparation of high 1 4-polypentadienes
US3657208A (en) * 1970-11-02 1972-04-18 Goodyear Tire & Rubber Ternary catalyst systems for the polymerization of cyclic olefins
US3956180A (en) 1970-12-28 1976-05-11 Texaco Development Corporation Hydrocarbon soluble molybdenum catalysts
US3721632A (en) * 1970-12-30 1973-03-20 Cities Service Co Method of catalyst preparation
US3746696A (en) 1971-03-25 1973-07-17 Goodyear Tire & Rubber Catalyst systems for polymerizing alicyclic olefins
JPS5017231B2 (en) * 1971-10-26 1975-06-19
US3772401A (en) 1971-10-27 1973-11-13 Texaco Inc Continuous 2-methyl-1-alkene polymerization process
US3753961A (en) 1971-12-03 1973-08-21 Goodyear Tire & Rubber Resinous composition
US3799913A (en) 1971-12-30 1974-03-26 Neville Chemical Co Production of hydrocarbon resin compositions from alpha-methyl styrene,indene and vinyl toluene
US3772255A (en) 1972-06-07 1973-11-13 Goodyear Tire & Rubber Ring-opening polymerization of cycloolefins
JPS5033862B2 (en) 1972-10-21 1975-11-04
JPS5312187B2 (en) 1973-03-29 1978-04-27
US3888789A (en) 1972-12-15 1975-06-10 Universal Oil Prod Co Preparation of polymerization catalyst systems
US3987109A (en) 1972-12-27 1976-10-19 Universal Oil Products Company Polymerization of polyfunctional phenols
US3932332A (en) 1973-02-16 1976-01-13 Hercules Incorporated Copolymers of alpha-methylstyrene and styrene and uses thereof
US3975336A (en) 1973-05-14 1976-08-17 The Goodyear Tire & Rubber Company Polymers of nonconjugated 1,4-dienes
US3926882A (en) 1973-11-23 1975-12-16 Standard Oil Co Alpha-methyl styrene/tertiary butyl styrene/olefin terepolymer resins and hot melt adhesives containing the same
US3997471A (en) 1974-04-01 1976-12-14 The Goodyear Tire & Rubber Company Cycloolefin metathesis catalyst
US3945986A (en) 1974-04-01 1976-03-23 The Goodyear Tire & Rubber Company Metathesis of cycloolefins
US3935179A (en) 1974-04-01 1976-01-27 The Goodyear Tire & Rubber Company Cycloolefin metathesis
US4010113A (en) 1974-04-01 1977-03-01 The Goodyear Tire & Rubber Company Catalyst for metathesis of cycloolefins
US3943116A (en) 1974-06-21 1976-03-09 The Goodyear Tire & Rubber Company Method for preparing high cis polyalkenamers
US3932553A (en) 1974-07-26 1976-01-13 Exxon Research And Engineering Company Oligomerization of propylene
US4020254A (en) 1974-09-30 1977-04-26 The Goodyear Tire & Rubber Company Metathesis polymerization of cycloolefins
US3929737A (en) 1974-09-30 1975-12-30 Goodyear Tire & Rubber Maleic anhydride-modified resin backbone
US4127710A (en) 1974-10-02 1978-11-28 Phillips Petroleum Company Copolymerization of a 1,3-cyclodiene and a linear conjugated diene
US4064335A (en) 1974-11-11 1977-12-20 The Goodyear Tire & Rubber Company Polymers of nonconjugated 1,4-dienes
US4028272A (en) 1974-11-22 1977-06-07 The Goodyear Tire & Rubber Company Process of polymerization of conjugated diolefins using iron catalysts and sulfur ligands
DE2500025C3 (en) 1975-01-02 1978-04-20 Chemische Werke Huels Ag, 4370 Marl Use of polydodecenamers as reinforcing resins for elastomers
US4153771A (en) 1975-01-15 1979-05-08 The Goodyear Tire & Rubber Company Hydrocarbon resin prepared from antimony pentafluoride or ferric chloride
US3992322A (en) 1975-04-11 1976-11-16 Universal Oil Products Company Preparation of polymerization catalyst systems
US4009228A (en) 1975-05-12 1977-02-22 The Goodyear Tire & Rubber Company Primary amine-modified anhydride resin
US4013736A (en) 1975-07-16 1977-03-22 Exxon Research And Engineering Company Synthesis of low viscosity low pour point hydrocarbon lubricating oils
GB1537852A (en) 1975-07-30 1979-01-04 Exxon Research Engineering Co Petroleum resins
US4062801A (en) 1975-08-11 1977-12-13 Vop Inc. Catalyst regeneration method
SU859391A1 (en) 1976-02-24 1981-08-30 Институт Химии Башкирского Филиала Ан Ссср Method of producing coloured polymeric material,polymethylmetacrylate,polystyrene or polyvinylacetate
US4205160A (en) 1976-03-11 1980-05-27 The Goodyear Tire & Rubber Company Indane containing polymers
US4105843A (en) 1976-04-15 1978-08-08 Mitsui Petrochemical Industries Ltd. Process for producing hydrocarbon resins having improved color and thermal stability by heat treatment with an α,βunsaturated anhydride
US4071669A (en) 1976-06-24 1978-01-31 The Goodyear Tire & Rubber Company Metal salts of modified anhydride resin
GB1587120A (en) * 1976-10-19 1981-04-01 Exxon Research Engineering Co Petroleum resins
US4038471A (en) 1976-10-29 1977-07-26 The Goodyear Tire & Rubber Company Method for preparing high-cis polyalkenamers
JPS608695B2 (en) 1977-01-26 1985-03-05 帝人株式会社 Polyester manufacturing method
US4217409A (en) 1977-05-12 1980-08-12 Dai Nippon Insatsu Kabushiki Kaisha Image forming material comprising polyacids of Mo or W or their salts or complexes
US4359406A (en) 1977-06-17 1982-11-16 Exxon Research And Engineering Co. Highly dispersed supported group VIII metal-phosphorus compounds, and highly dispersed, supported group VIII metal-arsenic and a process for making said compounds
US4146692A (en) 1977-08-25 1979-03-27 Exxon Research & Engineering Co. Process and product for manufacture of elastomeric co- or terpolymers
US4171414A (en) 1977-08-25 1979-10-16 Exxon Research & Engineering Co. Catalyst composition for an improved polymerization process of isoolefins and multiolefins
US4137390A (en) 1977-09-07 1979-01-30 The Goodyear Tire & Rubber Company Process for the polymerization of cycloolefins
US4172932A (en) 1977-09-07 1979-10-30 The Goodyear Tire & Rubber Company Process for the preparation of polymers of cyclopentene or copolymers of cyclopentene with unsaturated alicyclic compounds
USRE31443E (en) 1977-12-05 1983-11-15 Phillips Petroleum Company Treatment of silica
US4248735A (en) 1979-06-01 1981-02-03 Phillips Petroleum Company Treatment of silica
US4230840A (en) 1977-12-26 1980-10-28 Mitsui Petrochemical Industries Ltd. Process for producing hydrocarbon resins having improved color and thermal stability
US4168357A (en) 1978-04-05 1979-09-18 The Goodyear Tire & Rubber Company Preparation of high cis-1,4-polypentadiene
GB2027721A (en) 1978-06-27 1980-02-27 Exxon Research Engineering Co Petroleum resins
US4233139A (en) 1978-07-25 1980-11-11 Exxon Research & Engineering Co. Acid catalyzed hydrocarbon conversion processes utilizing a catalyst comprising a Group IVB, VB or VIB metal oxide on an inorganic refractory oxide support
US4239874A (en) 1979-02-21 1980-12-16 The Goodyear Tire & Rubber Company Cyclopentene copolymerization process
IT1129809B (en) 1979-03-26 1986-06-11 Ugine Kuhlmann CATALYTIC COMPOSITION FOR THE CONVERSION OF HYDROCARBONS AND PROCEDURE FOR THE DEHYDRATION OF PERFLUOROALCANSOLPHONIC ACIDS INTENDED TO BE PART OF THE BEAUTIFUL COMPOSITION
US4363746A (en) 1979-05-29 1982-12-14 Phillips Petroleum Company Composition of matter and method of preparing same, catalyst, method of producing the catalyst and polymerization process employing the catalyst
US4565795A (en) 1979-12-07 1986-01-21 Phillips Petroleum Company Polymerization and catalysts
US4843133A (en) 1979-12-07 1989-06-27 Phillips Petroleum Company Polymerization and catalysts
US4299731A (en) 1980-02-06 1981-11-10 Phillips Petroleum Company Large pore volume olefin polymerization catalysts
US4384086A (en) 1980-02-06 1983-05-17 Phillips Petroleum Company Large pore volume olefin polymerization catalysts
US4294724A (en) 1980-02-06 1981-10-13 Phillips Petroleum Company Titanium impregnated silica-chromium catalysts
US4368303A (en) 1980-02-06 1983-01-11 Phillips Petroleum Company Titanium impregnated silica-chromium catalysts
US4296001A (en) 1980-02-06 1981-10-20 Phillips Petroleum Company Titanium impregnated silica-chromium catalysts
US4345055A (en) 1980-02-06 1982-08-17 Phillips Petroleum Company Polymerization with titanium impregnated silica-chromium catalysts
US4422957A (en) 1980-05-02 1983-12-27 Phillips Petroleum Company Methods of producing polyolefins using supported high efficiency polyolefin catalyst components
US4618661A (en) 1980-05-02 1986-10-21 Phillips Petroleum Company Supported high efficiency polyolefin catalyst component and methods of making and using the same
US4425257A (en) 1980-05-02 1984-01-10 Phillips Petroleum Company Supported high efficiency polyolefin catalyst component and methods of making and using the same
US4347158A (en) 1980-05-02 1982-08-31 Dart Industries, Inc. Supported high efficiency polyolefin catalyst component and methods of making and using the same
US4301034A (en) 1980-05-21 1981-11-17 Phillips Petroleum Company Silica from single phase controlled hydrolysis of silicate ester
US4339559A (en) 1980-05-21 1982-07-13 Phillips Petroleum Company Polymerization using silica from single phase controlled hydrolysis of silicate ester
US4328090A (en) 1980-07-31 1982-05-04 Exxon Research & Engineering Co. Process for production of hydrogenated hydrocarbon polymers and catalyst useful therefore
US4367352A (en) * 1980-12-22 1983-01-04 Texaco Inc. Oligomerized olefins for lubricant stock
US4444968A (en) 1980-12-31 1984-04-24 Phillips Petroleum Company Olefin polymerization with phosphate supported zerovalent chromium
US4364854A (en) 1980-12-31 1982-12-21 Phillips Petroleum Company Acid gelling aluminum phosphate from concentrated mass and catalyst containing same
US4442274A (en) 1980-12-31 1984-04-10 Phillips Petroleum Company Polymerization process using a phosphate containing support for vanadium catalyst
US4397765A (en) 1980-12-31 1983-08-09 Phillips Petroleum Company Phosphated alumina or aluminum phosphate chromium catalyst
US4444962A (en) 1980-12-31 1984-04-24 Phillips Petroleum Company Polymerization process using catalysts with acid gelled aluminum phosphate base
US4364840A (en) 1980-12-31 1982-12-21 Phillips Petroleum Company Phosphated silica-chromium catalyst with boron-containing cocatalyst
US4364841A (en) 1980-12-31 1982-12-21 Phillips Petroleum Company Phosphate containing support with zerovalent chromium
JPS57149233A (en) * 1981-03-11 1982-09-14 Showa Denko Kk Preparation of isobutene oligomer
US4391737A (en) 1981-06-11 1983-07-05 The Goodyear Tire & Rubber Company Catalysts for ring-opening copolymerization of cycloolefins
US4415715A (en) 1981-06-11 1983-11-15 The Goodyear Tire & Rubber Company Catalysts for ring-opening copolymerization of cycloolefins
US4434280A (en) 1981-09-17 1984-02-28 Phillips Petroleum Company Polymerization process using surface heat treated silica-containing catalyst base
US4378306A (en) 1981-09-17 1983-03-29 Phillips Petroleum Company Surface heat treatment of silica-containing catalyst base
US4677174A (en) 1986-04-21 1987-06-30 American Colloid Company Water absorbent styrene-acrylic acid copolymers
US4419268A (en) 1981-11-20 1983-12-06 Phillips Petroleum Company Partially hydrolyzed silicate treatment of catalyst support
US4424320A (en) 1981-11-25 1984-01-03 Phillips Petroleum Company Polymerization with a silica base catalyst having titanium incorporated through use of peroxide
US4382022A (en) 1981-11-25 1983-05-03 Phillips Petroleum Company Silica having titanium incorporated through use of peroxide
US4434313A (en) * 1981-12-14 1984-02-28 Exxon Research And Engineering Co. Preparation of linear olefin products
US4442275A (en) 1982-03-09 1984-04-10 Phillips Petroleum Company Polymerization process using catalyst having aqueous titanation of support with solubilized Ti(OR)4
US4434243A (en) 1982-03-09 1984-02-28 Phillips Petroleum Company Aqueous titanation of catalyst support containing chromium with solubilized Ti(OR)4
US4454367A (en) 1982-03-23 1984-06-12 Toa Nenryo Kogyo Kabushiki Kaisha Process for the low polymerization of isobutene
US4424139A (en) 1982-03-30 1984-01-03 Phillips Petroleum Company Catalyst comprising a phosphate and with a bis-(cyclopentadienyl)chromium(II) compound
US4444966A (en) 1982-05-05 1984-04-24 Phillips Petroleum Company Polymerization using phosphated alumina or aluminum phosphate chromium catalyst
US4719271A (en) 1982-05-21 1988-01-12 Phillips Petroleum Company Polymerization of olefins
US4536358A (en) 1982-06-17 1985-08-20 Uop Inc. Process for the production of high surface area catalyst supports
US4395578A (en) 1982-06-18 1983-07-26 Texaco, Inc. Oligomerization of olefins over boron trifluoride in the presence of a transition metal cation-containing promoter
US4439543A (en) 1982-08-05 1984-03-27 Phillips Petroleum Company Co Reduced chromyl halide on silica catalyst
US4403088A (en) 1982-08-05 1983-09-06 The Goodyear Tire & Rubber Company Plastic resin prepared from meta or para-diisopropenylbenzene and method of preparation
EP0101205B1 (en) 1982-08-13 1987-01-07 Exxon Research And Engineering Company Process for preparing polyisobutylene
US4555496A (en) 1982-08-20 1985-11-26 Phillips Petroleum Company Supported polyolefin catalyst components and methods of making and using the same
US4436948A (en) 1982-09-07 1984-03-13 Phillips Petroleum Company Catalyst compositions
US4780513A (en) 1982-09-30 1988-10-25 Exxon Research & Engineering Co. Modified Lewis acid catalyzed polymerization
US4520222A (en) 1982-12-10 1985-05-28 Phillips Petroleum Company Polymerization catalyst and deodorizing agent and process of use
US4463212A (en) * 1982-12-10 1984-07-31 Uop Inc. Selective oligomerization of olefins
US4425226A (en) 1982-12-10 1984-01-10 Phillips Petroleum Company Polymerization catalyst and deodorizing agent
US4444904A (en) 1983-05-26 1984-04-24 Exxon Research & Engineering Co. Process for synthesizing a multicomponent acidic catalyst composition containing zirconium by an organic solution method
GB8317510D0 (en) 1983-06-28 1983-08-03 Exxon Research Engineering Co Petroleum resins
US4558170A (en) 1983-06-29 1985-12-10 Exxon Research & Engineering Co. Polyisobutylene process
US4801364A (en) 1983-07-15 1989-01-31 Uop Separation and conversion processes using metal aluminophosphates
US4520121A (en) 1983-10-28 1985-05-28 Inkrott Kenneth E Magnesium halide hydrates and polymerization catalysts prepared therefrom
US4699962A (en) 1984-01-30 1987-10-13 Phillips Petroleum Company Olefin polymerization
US4791086A (en) 1984-01-30 1988-12-13 Phillips Petroleum Company Olefin polymerization
US4744970A (en) 1984-04-13 1988-05-17 Union Carbide Corporation Cobalt-aluminum-phosphorus-silicon-oxide molecular sieves
US4686092A (en) 1984-04-13 1987-08-11 Union Carbide Corporation Manganese-aluminum-phosphorus-silicon-oxide molecular sieves
US4793833A (en) 1984-04-13 1988-12-27 Uop Manganese-aluminum-phosphorus-silicon-oxide molecular sieves
US4824554A (en) 1984-04-13 1989-04-25 Uop Processes for the use of cobalt-aluminum-phosphorus-silicon-oxide molecular sieve compositions
US4846956A (en) 1984-04-13 1989-07-11 Uop Manganese-aluminum-phosphorus-silicon-oxide Molecular sieves
US4894213A (en) 1984-04-13 1990-01-16 Uop Arsenic-aluminum-phosphorus-silicon-oxide molecular sieve compositions
US5073351A (en) 1984-06-01 1991-12-17 Mobil Oil Corporation Production of middle distillate range hydrocarbons by light olefin upgrading
US4547479A (en) 1984-07-02 1985-10-15 Phillips Petroleum Company Polyphosphate in chromium catalyst support
US4588703A (en) 1984-07-18 1986-05-13 Phillips Petroleum Company Polyolefin polymerization process and catalyst
JPS6136758A (en) 1984-07-30 1986-02-21 Ricoh Co Ltd Positive-chargeable toner for dry process electrophotography
US4567153A (en) 1984-08-13 1986-01-28 Exxon Research & Engineering Co. Polymerization catalyst comprising copulverized solid magnesium compound and solid halide of scandium
US4732936A (en) 1984-11-20 1988-03-22 Hercules Incorporated Alpha methylstyrene and para methylstyrene copolymers
US4618595A (en) 1984-12-12 1986-10-21 Phillips Petrolem Company Polymerization of olefins
US4575538A (en) 1984-12-20 1986-03-11 Phillips Petroleum Company Olefin polymerization
US4596862A (en) 1984-12-24 1986-06-24 Phillips Petroleum Company Olefin polymerization using chromium on fluorided aluminophosphate
US4681866A (en) 1985-04-01 1987-07-21 Phillips Petroleum Company Polymerization catalyst, method of making and use therefor
US4619980A (en) 1985-04-01 1986-10-28 Phillips Petroleum Company Polymerization catalyst, method of making and use therefor
EP0202965B1 (en) 1985-04-09 1989-09-27 Kawasaki Steel Corporation Oligomer resins and processes for their preparation
US4757044A (en) 1985-04-17 1988-07-12 The Standard Oil Company Lanthanide metal salts of heteropolyanions as catalysts for alcohol conversion
JPS61280439A (en) 1985-05-13 1986-12-11 Idemitsu Kosan Co Ltd Production of alkenyl aromatic hydrocarbon derivative
US5330949A (en) 1985-06-17 1994-07-19 Idemitsu Petrochemical Company, Ltd. Method for producing polyolefin
US4604438A (en) 1985-08-12 1986-08-05 Uop Inc. High temperature thermoset terpolymers
US4626519A (en) 1985-09-06 1986-12-02 Phillips Petroleum Company Supported polyolefin catalyst components and methods of making and using same
US4680351A (en) 1985-09-06 1987-07-14 Phillips Petroleum Company Supported polyolefin catalyst components and methods of making and using same
US4711866A (en) 1986-02-05 1987-12-08 Exxon Chemical Patents Inc. Adamantane polymerization catalyst
US4684707A (en) 1986-02-10 1987-08-04 Exxon Chemical Patents Inc. Low color, high softening point aromatic resin and method for its production
US4868343A (en) 1986-04-16 1989-09-19 Catalytica Inc. Acid catalyzed process
US5008468A (en) 1986-04-16 1991-04-16 Catalytica, Inc. Acid catalyzed process
US4820773A (en) 1986-04-21 1989-04-11 American Colloid Company Water absorbent resins prepared by polymerization in the presence of styrene-maleic anhydride copolymers
ZW15187A1 (en) 1986-08-29 1989-03-22 Ici Australia Operations Detonator system
US5110778A (en) 1986-10-17 1992-05-05 Olah George A Boron aluminum and gallium perfluoro alkanesulfonate and resinsulfonate catalysts
US4721559A (en) 1986-10-17 1988-01-26 Olah George A Boron, aluminum and gallium perfluoro alkanesulfonate and resinsulfonate catalysts
DE3635710A1 (en) 1986-10-21 1988-04-28 Basf Ag METHOD FOR PRODUCING HOMOS AND COPOLYMERISATES OF ETHENS BY PHILLIPS CATALYSIS
US4719190A (en) 1986-10-22 1988-01-12 University Of Florida Hydrocarbon conversion and polymerization catalyst and method of making and using same
US4929800A (en) 1986-10-22 1990-05-29 University Of Florida Hydrocarbon conversion and polymerization catalyst and method of making and using same
CA1283997C (en) 1986-12-12 1991-05-07 Frank Joung-Yei Chen Fixed bed process for polymerizing liquid butenes
US4982045A (en) 1986-12-12 1991-01-01 Exxon Chemical Patents Inc. Fixed bed process for polymerizing liquid butenes
US5384299A (en) 1987-01-30 1995-01-24 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US4788171A (en) 1987-02-02 1988-11-29 Philips Petroleum Company Phosphated calcined alumina
US4952544A (en) 1987-03-05 1990-08-28 Uop Stable intercalated clays and preparation method
US4957889A (en) 1987-03-05 1990-09-18 Uop Stable intercalated clays and preparation method
US4987200A (en) 1987-06-08 1991-01-22 Exxon Chemical Patents Inc. Preparation of polymer incorporating masked functional group-containing monomers
US4849572A (en) 1987-12-22 1989-07-18 Exxon Chemical Patents Inc. Process for preparing polybutenes having enhanced reactivity using boron trifluoride catalysts (PT-647)
US4879425A (en) 1988-05-26 1989-11-07 Phillips Petroleum Company Oligomerization of olefins
US4948768A (en) 1988-05-26 1990-08-14 Phillips Petroleum Company Catalyst composition for oligomerization of olefins
IT1226550B (en) * 1988-07-29 1991-01-24 Enichem Anic Spa SELECTIVE OLEFINE OLIGOMERIZATION PROCESS AND NEW CATALYST FOR THIS PROCESS.
US4845066A (en) 1988-08-25 1989-07-04 Phillips Petroleum Company Preparation of pillared clay
US5017662A (en) 1988-09-15 1991-05-21 Exxon Chemical Patents, Inc. Selective catalytic process for preparing N-halothiosulfonamide modified EPDM terpolymers
US4956420A (en) 1988-09-15 1990-09-11 Exxon Chemical Patents Inc. Selective catalytic process for controlled modification of ethylene-(alpha-olefin)-diene monomer terpolymer with halothisulfonamide
US4900704A (en) 1988-09-29 1990-02-13 Phillips Petroleum Company Peptized and phosphated inorganic oxides and catalysts supported on said oxides
ATE124707T1 (en) 1988-10-26 1995-07-15 Exxon Chemical Patents Inc METHOD FOR PRODUCING POLY-N-BUTYLENE FROM A BUTYLENE CUT USING ALUMINUM CHLORIDE CATALYSTS.
US5326921A (en) 1988-10-26 1994-07-05 Exxon Chemical Patents Inc. AlCl3 -catalyzed process for preparing poly-N-butenes from mixed butenes
US4952739A (en) 1988-10-26 1990-08-28 Exxon Chemical Patents Inc. Organo-Al-chloride catalyzed poly-n-butenes process
US4935576A (en) 1988-11-25 1990-06-19 Exxon Chemical Patents Inc. Polybutene process
US5177288A (en) 1988-11-25 1993-01-05 Exxon Chemical Patents Inc. Polybutene process
US5081086A (en) 1988-12-29 1992-01-14 Uop Solid phosphoric acid catalyst
US4912279A (en) 1988-12-29 1990-03-27 Uop Solid phosphoric acid catalyst
JP3063908B2 (en) 1989-03-13 2000-07-12 ザ ダウ ケミカル カンパニー Method for producing polymer by anionic polymerization
US5225493A (en) 1989-03-13 1993-07-06 The Dow Chemical Company Anionic polymerization process
CA2012370C (en) 1989-04-04 1998-10-20 Hsien-Chang Wang Ozone-resistant butyl elastomers
US5198563A (en) 1989-08-10 1993-03-30 Phillips Petroleum Company Chromium compounds and uses thereof
US5331104A (en) 1989-08-10 1994-07-19 Phillips Petroleum Company Chromium compounds and uses thereof
US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
US5073531A (en) 1990-05-07 1991-12-17 Phillips Petroleum Company Olefin polymerization catalysts and preparation method
US5284811A (en) 1990-05-14 1994-02-08 Phillips Petroleum Company Polymerization catalysts and processes
US5200379A (en) 1990-06-07 1993-04-06 Phillips Petroleum Company Olefin polymerization using supported pentadienyl derivative-transition metal complexes
US5075394A (en) 1990-06-07 1991-12-24 Phillips Petroleum Company Olefin polymerization using supported pentadienyl derivative-transition metal complexes
JP2545006B2 (en) 1990-07-03 1996-10-16 ザ ダウ ケミカル カンパニー Addition polymerization catalyst
JPH0764757B2 (en) 1990-09-20 1995-07-12 出光石油化学株式会社 Method for producing olefin oligomer
US5365010A (en) 1990-09-26 1994-11-15 Catalytica, Inc. Method for regenerating Lewis acid-promoted transition alumina catalysts used for isoparaffin alkylation by calcination
US5326923A (en) 1990-09-26 1994-07-05 Catalytica, Inc. Method for regenerating certain acidic hydrocarbon conversion catalysts by solvent extraction
US5328956A (en) 1990-11-13 1994-07-12 Kao Corporation Propylene (co)polymer and process for the preparation of the same
CA2057126A1 (en) 1990-12-07 1992-06-08 Naoya Yabuuchi Production of surface-modified organic particles
US5139761A (en) 1990-12-17 1992-08-18 Uop Modified zeolite omega and processes for preparing and using same
JP2851715B2 (en) 1991-04-09 1999-01-27 出光興産株式会社 Thermoplastic resin composition
US5401817A (en) 1991-05-09 1995-03-28 Phillips Petroleum Company Olefin polymerization using silyl-bridged metallocenes
US5347026A (en) 1993-06-11 1994-09-13 Phillips Petroleum Company Fluorene compounds and methods for making
US5436305A (en) 1991-05-09 1995-07-25 Phillips Petroleum Company Organometallic fluorenyl compounds, preparation, and use
US5191132A (en) 1991-05-09 1993-03-02 Phillips Petroleum Company Cyclopentadiene type compounds and method for making
US5466766A (en) 1991-05-09 1995-11-14 Phillips Petroleum Company Metallocenes and processes therefor and therewith
US5393911A (en) 1991-05-09 1995-02-28 Phillips Petroleum Company Cyclopentadiene type compounds and method for making
US5399636A (en) 1993-06-11 1995-03-21 Phillips Petroleum Company Metallocenes and processes therefor and therewith
BE1006694A5 (en) 1991-06-22 1994-11-22 Basf Ag PREPARATION PROCESS EXTREMELY REACTIVE polyisobutenes.
US5288677A (en) 1991-06-28 1994-02-22 Exxon Chemical Patents Inc. Immobilized Lewis acid catalysts
US5113034A (en) 1991-08-05 1992-05-12 Exxon Research And Engineering Company Dimerization catalyst and process therefor
US5246900A (en) 1991-08-23 1993-09-21 Phillips Petroleum Company Olefin polymerization catalysts and processes of making the same
US5198512A (en) 1991-12-16 1993-03-30 Phillips Petroleum Company Polymerization catalyst and process
US5338812A (en) 1991-12-24 1994-08-16 Phillips Petroleum Company Olefin polymerization
US5453410A (en) 1992-01-06 1995-09-26 The Dow Chemical Company Catalyst composition
US5350723A (en) 1992-05-15 1994-09-27 The Dow Chemical Company Process for preparation of monocyclopentadienyl metal complex compounds and method of use
CA2093462C (en) 1992-06-16 1999-01-26 Joel Leonard Martin Olefin polymerization, catalyst, and precursor therefor
US5362825A (en) 1992-07-13 1994-11-08 Phillips Petroleum Company Catalysts for polymerizing olefins and methods
US5206314A (en) 1992-08-31 1993-04-27 Phillips Petroleum Company Polyolefin polymerization process, process of producing catalyst, and catalyst
US5461127A (en) 1992-09-22 1995-10-24 Idemitsu Kosan Co., Ltd. Polymerization catalysts and process for producing polymers
US5382420A (en) 1992-09-25 1995-01-17 Exxon Research & Engineering Company ECR-33: a stabilized rare-earth exchanged Q type zeolite
US5414187A (en) 1992-10-30 1995-05-09 Catalytica, Inc. Acid catalyst and use thereof in alkylation of olefins with tertiary alkanes
US5272124A (en) 1992-11-20 1993-12-21 Phillips Petroleum Company Ethylene polymerization catalyst comprising a nickel compound and an aromatic carboxylic acid compound
US5332708A (en) 1992-11-23 1994-07-26 Phillips Petroleum Company Catalyst compositions and catalytic processes
US5324881A (en) 1992-12-22 1994-06-28 Mobil Oil Corp. Supported heteropoly acid catalysts for isoparaffin-olefin alkylation reactions
US5366945A (en) 1992-12-22 1994-11-22 Mobil Oil Corp. Supported heteropoly acid catalysts
US5350819A (en) 1993-02-19 1994-09-27 Exxon Chemical Patents Inc. Carbocationic catalysts and process for using said catalysts
TW272214B (en) 1993-03-26 1996-03-11 Hercules Inc
WO1994028036A1 (en) * 1993-05-20 1994-12-08 Exxon Chemical Patents Inc. Heterogeneous lewis acid-type catalysts
US5354721A (en) 1993-06-22 1994-10-11 Phillips Petroleum Company Organo-aluminoxy product and use
US5414180A (en) 1993-07-14 1995-05-09 Phillips Petroleum Company Organo-aluminoxy product and use
US5350726A (en) 1993-09-03 1994-09-27 Exxon Chemical Patents Inc. Carbocationic catalysts and process for using said catalysts
US5403803A (en) 1993-09-28 1995-04-04 Exxon Chemical Patents Inc. Carbocationic catalyst and process for its use
US5475162A (en) 1993-11-09 1995-12-12 Uop Acid functionalized organically-bridged polysilsesquioxanes as catalysts for acid catalyzed reactions
US5371154A (en) 1993-11-09 1994-12-06 Uop Process for forming acid functionalized organically-bridged polysilsesquioxanes
DE69513810T2 (en) * 1994-03-31 2000-05-25 Infineum Usa Lp POLYMERIZATION REACTIONS OF HYDROCARBONS WITH CARRIER CATALYST CONTAINING LEWISS ACID
US5561095A (en) 1994-03-31 1996-10-01 Exxon Chemical Patents Inc. Supported lewis acid catalysts for hydrocarbon conversion reactions
US5446102A (en) 1994-08-10 1995-08-29 Bridgeston, Corporation Olefin metathesis catalysts for degelling polymerization reactors
US5661097A (en) * 1994-08-12 1997-08-26 The Dow Chemical Company Supported olefin polymerization catalyst
US5710225A (en) 1996-08-23 1998-01-20 The Lubrizol Corporation Heteropolyacid catalyzed polymerization of olefins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3374285A (en) * 1964-12-29 1968-03-19 Gulf Research Development Co Process for the polymerization of propylene
JPS57102825A (en) * 1980-12-19 1982-06-26 Nippon Oil & Fats Co Ltd Preparation of isobutylene oligomer
JPH0812601A (en) * 1994-07-01 1996-01-16 Cosmo Sogo Kenkyusho:Kk Production of alpha-alkylstyrene oligomer

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 6, no. 191 (C - 127) 30 September 1982 (1982-09-30) *
PATENT ABSTRACTS OF JAPAN vol. 96, no. 5 31 May 1996 (1996-05-31) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003503563A (en) * 1999-06-24 2003-01-28 ザ ルブリゾル コーポレイション Ammonium heteropolyacid-catalyzed polymerization of olefins
WO2001040438A2 (en) * 1999-11-30 2001-06-07 Curis, Inc. Methods and compositions for regulating lymphocyte activity
WO2001040438A3 (en) * 1999-11-30 2004-02-19 Curis Inc Methods and compositions for regulating lymphocyte activity
US8168178B2 (en) 1999-11-30 2012-05-01 Curis, Inc. Methods and compositions for regulating lymphocyte activity
US6872692B2 (en) 2001-09-21 2005-03-29 Exxonmobil Research And Engineering Company Synthetic hydrocarbon fluid

Also Published As

Publication number Publication date
CN1249735A (en) 2000-04-05
EP0964844B1 (en) 2003-09-10
EP0954516A1 (en) 1999-11-10
DE69815301T2 (en) 2003-12-11
US6608155B2 (en) 2003-08-19
DE69815301D1 (en) 2003-07-10
JP2001509185A (en) 2001-07-10
US6310154B1 (en) 2001-10-30
DE69818018D1 (en) 2003-10-16
CN1249733A (en) 2000-04-05
AU5813498A (en) 1998-08-03
US6281309B1 (en) 2001-08-28
JP2001511194A (en) 2001-08-07
US6133386A (en) 2000-10-17
WO1998030521A1 (en) 1998-07-16
CA2277292A1 (en) 1998-07-16
DE69818018T2 (en) 2004-04-01
WO1998030519A1 (en) 1998-07-16
CA2277295A1 (en) 1998-07-16
CA2277294A1 (en) 1998-07-16
KR20000070004A (en) 2000-11-25
EP0964844A1 (en) 1999-12-22
WO1998030587A2 (en) 1998-07-16
AU5730998A (en) 1998-08-03
AU5813298A (en) 1998-08-03
KR20000070006A (en) 2000-11-25
JP2001508102A (en) 2001-06-19
CN1249732A (en) 2000-04-05
AU5813398A (en) 1998-08-03
EP0970117A2 (en) 2000-01-12
KR20000070007A (en) 2000-11-25
CN1249734A (en) 2000-04-05
WO1998030587A3 (en) 1998-08-13
US20020183465A1 (en) 2002-12-05
KR20000070009A (en) 2000-11-25
EP0963365A1 (en) 1999-12-15
CA2277297A1 (en) 1998-07-16
JP2001508103A (en) 2001-06-19
EP0963365B1 (en) 2003-06-04

Similar Documents

Publication Publication Date Title
US6133386A (en) Metal oxide solid acids as catalysts for the preparation of hydrocarbon resins
US5561095A (en) Supported lewis acid catalysts for hydrocarbon conversion reactions
WO1995026814A1 (en) Supported lewis acid catalysts derived from superacids useful for hydrocarbon conversion reactions
US6479598B1 (en) Petroleum resins and their production with BF3 catalyst
US6346585B1 (en) Ammonium heteropolyacid catalized polymerization of olefins
KR20240016976A (en) Polyisobutene with high content of specific double bond isomers
US5932778A (en) Shutdown process for olefin polymerization reactor
EP1208125A1 (en) Petroleum resins and their production with bf 3?catalyst
US5294697A (en) Procedure for the preparation of colorless hydrocarbon resins
MXPA96004507A (en) Lewis acid catalysts supported for hydrocarbon conversion reactions

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 98803007.1

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM GW HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZW AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AT BE CH DE DK ES FI FR GB GR IE IT

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2277295

Country of ref document: CA

Ref document number: 2277295

Country of ref document: CA

Kind code of ref document: A

Ref document number: 1998 530965

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1019997006219

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 1998901668

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1998901668

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1019997006219

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1998901668

Country of ref document: EP

WWR Wipo information: refused in national office

Ref document number: 1019997006219

Country of ref document: KR