WO2001036503A1 - Copolymerization of ethylene and dienes - Google Patents
Copolymerization of ethylene and dienes Download PDFInfo
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- WO2001036503A1 WO2001036503A1 PCT/US2000/031604 US0031604W WO0136503A1 WO 2001036503 A1 WO2001036503 A1 WO 2001036503A1 US 0031604 W US0031604 W US 0031604W WO 0136503 A1 WO0136503 A1 WO 0136503A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
Definitions
- FIELD OF THE INVENTION Ethylene and dienes, and optionally other olefins can be copolymerized by using a polymerization catalyst which is a selected iron complex of a 2 , 6-pyridinecarboxaldehyde- bis(imine) or a 2 , 6-diacylpyridinebis (imine) .
- the resulting copolymers contain branches with olefin groups, and in some instances cyclic structures resulting from cyclization of certain of the dienes.
- Ethylene and its copolymers are important items of com- merce .
- nonconjugated external -internal diolefins such as 1 , 4-hexadiene (or other types of dienes having two olefinic groups of differing reactivities) must be used.
- 6-diacylpyridinebis may be used to copolymerize ethylene and various dienes, and that the resulting copolymers contain branches having terminal olefin groups.
- part of the diene which is incorporated into the copolymer is present as a saturated cyclic structure which is part of the polymer main chain.
- This invention concerns a process for preparing an olefin copolymer, comprising the step of contacting:
- an active copolymerization catalyst under conditions to copolymerize the monomers of the monomer component, wherein the active copolymerization catalyst comprises an iron complex of a tridentate ligand of the formula (I)
- R , ⁇ , R , R , R and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group, provided that any two of R 1 , R 2 and R 3 vicinal to one another, taken together may form a ring; and
- R 6 and R 7 are each independently aryl or substituted aryl .
- This invention also concerns an olefin copolymer comprising the repeat units:
- This copolymer may be derived when the monomer component comprises ethylene and one or more dienes of the above formula wherein n is 1, 2, 3 or 4.
- ml is 0 or an integer of from 5 to 28 (e.g., equal to n from the corresponding diene monomer)
- R 20 is as defined above (equal to R 20 from the corresponding ⁇ -olefin monomer) .
- the copolymers resulting from the process in general contain at least some residual olefinic unsaturation derived from the diene monomer (see repeat units (III) and (XII)) , but are preferably in and of themselves substantially non- crosslinked.
- this copolymer contains one or more of the repeat units
- the resulting copolymers are crosslinkable at least in part due to the presence of the residual olefinic unsaturation.
- This residual olefinic unsaturation may also be re- acted with a variety of functional compounds to impart various types of functionality to the copolymer.
- hydrocarbyl group is a univalent group containing only carbon and hydrogen.
- hydrocarbyls may be mentioned unsubstituted alkyls, cycloalkyls and aryls. If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms, and more preferably 1 to about 20 carbon atoms.
- substituted hydrocarbyl herein is meant a hydrocarbyl group that contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected (e.g., an inert functional group, see below) .
- the substituent groups also do not substantially detrimentally interfere with the polymerization process or operation of the polymerization catalyst system. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of "substituted” are chains or rings containing one or more heteroa- toms, such as nitrogen, oxygen and/or sulfur, and the free valence of the substituted hydrocarbyl may be to the het- eroatom. In a substituted hydrocarbyl, all of the hydrogens may be substituted, as in trifluoromethyl .
- inert functional group herein is meant a group, other than hydrocarbyl or substituted hydrocarbyl, that is inert under the process conditions to which the compound containing the group is subjected (although under other conditions such functionality may not be inert) .
- the inert functional groups also do not substantially interfere with any process described herein that the compound in which they are present may take part in.
- potential inert functional groups include halo, ester, keto (oxo) , amino, imino, carboxyl , phosphite, phosphonite, phosphine, phosphi- nite, thioether, amide, nitrile and ether.
- Preferred inert functional groups are halo, ester, amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether and amide.
- Particularly preferred examples of inert functional groups include halo (fluoro, chloro, bromo and iodo) and ether such as -OR 60 , wherein R 60 is hydrocarbyl or substi- tuted hydrocarbyl .
- catalyst activator a compound that reacts with a transition metal (iron) compound to form an activated catalyst species.
- a preferred catalyst activator is an alkylaluminum compound.
- alkylaluminum compound a compound in which at least one alkyl group is bound to an aluminum atom. Other groups such as alkoxide, hydride and halogen may also be bound to aluminum atoms in the compound.
- relatively noncoordinating or “weakly coordinat- ing” anions are meant those anions as are generally referred to in the art in this manner, and the coordinating ability of such anions is known and has been discussed in the literature. See, for instance, W. Beck et al . , Chem. Rev., vol. 88, pp. 1405-1421 (1988), and S.H. Strauss, Chem.
- BAF ⁇ ⁇ BAF tetrakis [3 , 5- bis (trifluoromethyDphenyl] borate ⁇ , SbF 6 " , PF 6 “ , and BF 4 " , trifluoromethanesulfonate, p-toluenesulfonate, (R f S0 2 ) 2 N ⁇ and (C 6 F 6 ) 4 B-.
- substantially non-crosslinked is meant that at least 80 weight percent, and preferably at least 90 weight percent, of the polymer is soluble in a solvent that usually dissolves such polymer.
- suitable solvents will often be a hydrocarbon or halogenated hydrocarbon solvent, such solution preferably being carried out above the melting point (if any) of the polyolefin.
- aryl is meant a monovalent aromatic group in which the free valence is to the carbon atom of an aromatic ring. An aryl may have one or more aromatic rings which may be fused, connected by single bonds or other groups.
- substituted aryl is meant a monovalent aromatic group substituted as set forth in the above definition of “substituted hydrocarbyl”. Similar to an aryl, a substituted aryl may have one or more aromatic rings which may be fused, connected by single bonds or other groups; however, when the substituted aryl has a heteroaromatic ring, the free valence in the substituted aryl group can be to a het- eroatom (such as nitrogen) of the heteroaromatic ring instead of a carbon.
- the polymerization process described herein uses as an active polymerization catalyst an iron complex of (I) .
- the same general conditions which are used to polymerize ethylene alone may be used for the copolymerizations described herein, except of course a diene will also be present.
- the amount of diene incorporated into the copolymer that is formed will depend on the relative amounts of ethylene and diene in the polymerization process. Since ethylene is in- corporated into the copolymer faster than the diene, as the amount of diene relative to the ethylene present in the polymerization process increases, the amount of diene incorporated into the copolymer will typically increase.
- each of R 1 , R 2 , R 3 , R 4 and R 5 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert func- tional group, provided that any two of R 1 , R 2 and R 3 vicinal to one another, taken together may form a ring; and R 6 and R 7 are aryl or substituted aryl.
- ligand (I) preferred formulas and compounds (and for their Fe complexes also) are found in previously incorporated US5955555, W099/12981, WO99/46302, WO99/46303, WO99/46304, WO99/46308, WO99/50318, W099/62963, W099/62967, WOOO/15646, WO00/24788, WO00/32641 and WO00/50470, and preferred groupings and compounds in these publications are also preferred herein.
- R 1 , R 2 and R 3 are hydrogen; and/or
- R 1 and R 3 are hydrogen, and R 2 is trifluoromethyl ;
- R y , R ,10 , R , R ⁇ l4 , R ⁇ l X 5 3 and R ,1 x 6 t> are each independently halogen, alkyl containing 1 to 6 carbon atoms, or hydrogen, and it is more preferred that each of these is hydrogen; and/or
- R 10 and R 15 are methyl ;
- R 8 and R 13 are each independently halogen, phenyl or alkyl containing 1 to 6 carbon atoms, and it is especially preferred that each R 8 and R 13 is alkyl containing 1-6 carbon atoms and is more preferred that R 8 and R 13 are methyl ; and/or R 12 and R 17 are each independently halogen, phenyl , hydrogen, or alkyl containing 1 to 6 carbon atoms, and it is especially preferred that each R 12 and R 17 is alkyl containing 1-6 carbon atoms, and it is more preferred that R 12 and R 17 are methyl ; and/or
- R 4 and R 5 are each independently halogen, thioalkyl, hydrogen or alkyl containing 1 to 6 carbon atoms, and it is especially preferred that R 4 and R 5 are each independently hydrogen or methyl ; and/or R 8 , R 10 , R 13 , R 15 and R 17 are hydrogen, and R 9 , R 11 , R 14 and R 16 are hydrocarbyl or substituted hydrocarbyl.
- Ligand (I) and the preferred embodiments thereof may be made by any of the procedures described in the previously incorporated references, as well as in WO99/50273 and WOOO/08034 (both of which are also incorporated by reference herein for all purposes as if fully set forth) .
- ligand (I) may be made by the reaction of a compound of the formula (VI)
- R 1 , R 2 R 3 , R 4 and R 5 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group, provided that any two of R 1 , R 2 and R 3 vicinal to one another, taken together may form a ring; and R 6 and R 7 are aryl or substituted aryl.
- the iron complex may be added directly as a complex that will polymerize the monomer component, may be added as another complex that may be activated by another compound (catalyst activator) such as an alkylaluminum compound, or may be formed in situ.
- alyst activator such as an alkylaluminum compound
- “Pure” Fe complexes may be exemplified by the formula (I)FeX n , wherein each X is an anion, n is 1, 2 or 3 so that the total number of negative charges on the X groups is equal to the oxidation state of the Fe in the pure Fe complex.
- each X is a monovalent anion, more pref- erably selected from the group consisting of a halide and a carboxylate, and especially a halide such as chloride or bromide .
- These pure Fe complexes may in and of themselves be active catalysts, or they may be activated (or made more ac- tive) preferably by preparation in situ by contact with a catalyst activator in a variety of methods as disclosed in the previously incorporated references. Generally, it has been found that the most active catalysts are those that have been contacted with a catalyst activator.
- the monomer component may be polymerized by contacting a first compound W, which is a neutral Lewis acid capable of abstracting X " to form WX " , with an iron halide complex of ligand (I) (or other X " complex of (I)), provided that the anion formed is a weakly coordinating anion; or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion.
- W a neutral Lewis acid capable of abstracting X " to form WX "
- an iron halide complex of ligand (I) or other X " complex of (I)
- a neutral Lewis acid or a cationic Lewis or Bronsted acid may also alkylate or add a hydride to the metal, i.e., cause an alkyl group or hydride to become bonded to the metal atom, or a separate compound is added to add the alkyl or hydride group .
- a preferred neutral Lewis acid which can alkylate the metal, is a selected alkyl aluminum compound, such as R 20 3 A1, R 20 3 A1C1, R 20 A1C1 2 , and "R 20 AlO" (alkylaluminoxanes) , wherein R 20 is alkyl containing 1 to 25 carbon atoms, preferably 1 to 4 carbon atoms .
- Suitable alkyl aluminum compounds include methylaluminoxane (which is an oligomer with the general formula [MeAlO] , (C 2 H 5 ) 2 A1C1, (C 2 H 5 )AlCl 2 and [ (CH 3 ) 2 CHCH 2 ] 3 A1.
- Metal hydrides such as NaBH 4 may be used to bond hydride groups to the transition metal.
- the temperature at which the copolymerization is carried out is preferably about -100°C to about +200°C, more preferably about -60°C to about 150°C, and especially preferably about -50°C to about 100°C.
- the copolymerization process may be run in the presence of various liquids, particularly aprotic organic liquids.
- the catalyst system, and/or monomers and/or polyole- fin may be soluble or insoluble in these liquids, but obviously these liquids should not prevent the polymerization from occurring.
- Suitable liquids include alkanes, cycloal- kanes, selected halogenated hydrocarbons, and aromatic hydrocarbons. Specific useful solvents include hexane, toluene and benzene .
- the copolymerizations herein may also initially be car- ried out in the solid state (assuming the complex of (I) is a solid) or by, for instance, supporting the complex on a substrate such as silica or alumina or an organic substrate such as a polymer, activating it with a needed Lewis or Bronsted acid and exposing it to the monomer mixture.
- the support may also be able to take the place of the Lewis or Bronsted acid, for instance an acidic clay such as mont- morillonite.
- Another method of making a supported catalyst is to start a polymerization or at least make an iron complex of another olefin or oligomer of an olefin such as 1- hexene on a support such as silica or alumina.
- heterogeneous catalysts may be used to catalyze polymerization in the gas phase or the liquid phase.
- gas phase is meant that the monomers are transported to contact with the catalyst particle while they are in the gas phase.
- Hydrogen may be used as a chain transfer agent in all of the polymerization processes described herein. Other methods and/or preferred methods of carrying out the polymerization are found in previously incorporated US5955555, W099/12981,
- WO99/46302 WO99/46303, WO99/46304, WO99/46308, WO99/50318, W099/62963, W099/62967, WO00/15646, WO00/24788, WOOO/32641 and WOOO/50470, and reference may be had thereto for further details .
- Other olefin polymerization catalysts such as metallo- cene type, Ziegler-Natta type and/or other late transition metal catalysts, may also be present to (co) polymerize some or all of the olefins present. See, for example, previously incorporated W099/12981, WO99/46302 and WO99/50318, as well as W098/38228 (which is also incorporated by reference herein for all purposes as if fully set forth) .
- oligomers and copolymers of ethylene and diene are made. They may range in molecular weight from oligomers, to lower molecular weight oils and waxes, to higher molecular weight polyolefins.
- One preferred product is a polymer with a degree of polymerization (DP) of about 10 or more, preferably about 40 or more.
- DP is meant the average number of repeat (monomer) units in a polymer molecule.
- n is >0 (an integer) , more preferably n is 1, 2, 3, 4, 6, 8, 10, or 12, and especially preferably n is 2, 3, 4 or 6, and more preferably n is 2 or 4 and/or
- R 19 is hydrogen or methyl, more preferably hydrogen.
- Specific useful dienes include 1 , 3 -butadiene, 1,4- pentadiene, 1 , 5-hexadiene, 1 , 6-heptadiene, 1 , 7-octadiene, 1 , 9-decadiene, and 1 , 4-hexadiene . More than one diene may be used in the polymerization, and the resulting polymerization will of course contain repeat units derived from each (see below) .
- n is 0 or greater than 4, and/or often when R 19 is not hydrogen, the diene is polymerized to give repeat unit (III) , wherein n is equal to m.
- n is 4 or less (but not 0, and usually when R 19 is hydrogen) , some of the diene is incorporated into the polymer as cyclic units, and sometimes it is believed that these cyclic units also include a group derived from ethylene.
- n (diene is 1,7- octadiene) , one finds (see below) 1 , 2 -enchained cyclohexane rings in the polymers, that is repeat unit (IV) wherein p is 4.
- the 1 , 4 -enchained cyclohexane rings in the 1, 5-hexadiene copolymer are believed to arise from addition polymerization of one end of the 1 , 5-hexadiene, addition of an ethylene molecule, and then cyclization of the other end of the original 1 , 5-hexadiene molecule.
- 1,4- pentadiene and 1 , 6-heptadiene cyclic structures are also obtained in the resulting polymers (see the Examples) by what is believed to be similar mechanisms.
- m is 4 or more, it is believed that (V) is not present is the polymer (meaning it is not detected by 13 C NMR as described herein) .
- An ⁇ -olefin may optionally be present in the monomer component.
- R 20 is methyl or ethyl, more preferably methyl. It is preferred that less than 10 mole percent of the repeat units in the polymer are derived from the ⁇ -olefin. In another preferred polymer, it is preferred that the ⁇ -olefin is not present in the polymerization.
- the copolymer of ethylene and diene (and optionally the ⁇ -olefin) contains about 0.1 to 20 mole percent of incorporated diene, more preferably about 1 to about 10 mole percent, based on the total number of repeat units present derived from ethylene, and the diene and ⁇ -olefins (if any) .
- copolymers described above are useful as molding resins especially as resins which may be crosslinked using methods known in the art, for example, with free radicals or sulfur-type cures, or irradiation.
- the copolymers prior to crosslinking by one of the above methods are in and of themselves preferably substantially non-crosslinked.
- the copolymers may also be functionalized by reaction of the residual unsaturation with a variety of functional reactants in a manner and of a type consistent with that disclosed in the literature. Such functional groups may, for example, be capable of undergoing further reaction, and/or may be capable of imparting desirable properties not otherwise possessed by the base copolymer.
- Such functional groups include, for example, halogen, hydroxyl , amino, amido, carboxyl, acyl and epoxy, and derviatives thereof such as salts, esters, ethers and anhydrides.
- Potential end uses for such functionalized materials are numerous depending on the type of functionalization and polymer properties. See, for example, US5811379 and US5880241, both of which are incorporated by reference herein for all purposes as if fully set forth.
- Mn - number average molecular weight P - indicates the rest of the polymer chain PDI - weight average molecular weight/number average molecular weight
- PMAO-IP An improved performance PMAO from Akzo-Nobel, Inc .
- TCB - 1 , 2 4-triclhorobenzene
- Spectra are referenced to the solvent TCB high field resonance at 127.914 ppm.
- a DEPT 135 spectrum was done on most samples to distinguish methyls and methines from methylenes . Methyls were distinguished from methines by chemical shift. Integrals of unique carbons in each structure were measured. These integrals are accurate to +/- 5% relative for larger signal and +/- 10 or 20% relative for smaller signals.
- a polymer hydrocarbyl branch is meant a methyl group to a methine or quaternary carbon atom or a group of consecutive methylenes terminated at one end by a methyl group and connected at the other end to a methine or quaternary carbon atom.
- EOC is end-of-chain. Assignments reference to following naming scheme:
- xBy:By is a branch of length y carbons; x is the carbon being discussed, the methyl at the end of the branch is numbered 1. Thus the second carbon from the end of a butyl branch is 2B4. Branches of length y or greater are designated as y + .
- ⁇ B (beta beta) B denotes the central methylene in the following PCHRCH 2 CH 2 CH 2 CHRP .
- Methylenes that are three or more carbons from a methine are designated as ⁇ + ( amma "1" ) .
- Example 1 In a drybox under nitrogen, (VIII) (1.9 mg) was placed in ⁇ 8 ml anhydrous toluene in a vial. 1 , 9-Decadiene (19 ml, filtered through activated Al 2 0 3 and stored over activated molecular sieves), anhydrous toluene (30 ml) and PMAO (0.7 ml, Akzo, 10.3 wt% Al in toluene) were placed in a Hoke® cylinder and the cylinder closed. The containers were re- moved from the drybox. The decadiene slurry was placed in a 100 ml Parr ® stirred autoclave under N 2 . Stirring was started and the reactor heated to 41°C.
- Example 2 In a drybox under nitrogen, (VIII) (6.0 mg) was placed in a Schlenk flask and anhydrous toluene (10 ml) and 1,9- decadiene (5 ml, filtered through activated A1 2 0 3 and stored over activated molecular sieves) were added. The flask was sealed and removed from the drybox. It was flushed with ethylene and PMAO-IP (0.9 ml, Akzo, 12.8 wt% Al in toluene) added with vigorous stirring.
- Example 3 In a drybox under nitrogen, (VIII) (0.9 mg) was placed in -5 ml anhydrous toluene in a vial. 1 , 7-Octadiene (20 ml, filtered through activated Al 2 0 3 and stored over activated molecular sieves), anhydrous toluene (30 ml) and PMAO (0.5 ml, Akzo, 10.3 wt% Al in toluene) were placed in a Hoke® cylinder and sealed. The containers were removed from the drybox. The octadiene slurry was placed in a 100 ml Parr ® stirred autoclave under N 2 . Stirring was started and the reactor heated to 47°C.
- Example 4 In a drybox under nitrogen, (VIII) (6.0 mg) was placed in a Schlenk flask and anhydrous toluene (10 ml) and 1,7- octadiene (5 ml, filtered through activated Al 2 0 3 and stored over activated molecular sieves) were added. The flask was sealed and removed from the drybox. It was flushed with ethylene and PMAO-IP (0.9 ml, Akzo, 12.8 wt% Al in toluene) added with vigorous stirring. The reaction was maintained at -14-35 kPa ethylene for 30 min after which it was quenched by addition of MeOH/10% HCl.
- Example 6 In a drybox under nitrogen, (VIII) (6.0 mg) was placed in a Schlenk flask and anhydrous toluene (10 ml) and 1,5- hexadiene (5 ml, filtered through activated Al 2 0 3 and stored over activated molecular sieves) added. The flask was sealed and removed from the drybox. The flask was flushed with ethylene and PMAO-IP (0.9ml, Akzo, 12.8 wt% Al in tolu- ene) added with vigorous stirring. The reaction was maintained at -14-35 kPa ethylene for 30 min after which it was quenched by addition of MeOH/10% HCl.
- PMAO-IP 0.9ml, Akzo, 12.8 wt% Al in tolu- ene
- Example 7 In a drybox under nitrogen, (VIII) (6.0 mg) was placed in a Schlenk flask and anhydrous toluene (10 ml) and 1,6- heptadiene (5 ml, filtered through activated Al 2 0 3 and stored over activated molecular sieves) were added. The flask was sealed and removed from the drybox. It was flushed with ethylene and PMAO-IP (0.9 ml, Akzo, 12.8 wt% Al in toluene) added with vigorous stirring. The reaction was maintained at -14-35 kPa ethylene for 30 min after which it was quenched by addition of MeOH/10% HCl.
- Example 9 In a drybox under nitrogen, (VIII) (6.0 mg) was placed in a Schlenk flask and solution of 1 , 3 -butadiene in anhydrous toluene (20 ml, 5.96 wt% butadiene) was added. The flask was sealed and removed from the drybox. It was flushed with ethylene and PMAO-IP (0.9 ml, Akzo, 12.8 wt% Al in toluene) added with vigorous stirring. The reaction was maintained at -14-35 kPa ethylene for 30 min after which it was quenched by addition of MeOH/10% HCl.
- PMAO-IP 0.9 ml, Akzo, 12.8 wt% Al in toluene
- Example 10 In a drybox under nitrogen, (VIII) (6.0 mg) was placed in a Schlenk flask and anhydrous toluene (10 ml) and 1,4- hexadiene (5 ml, filtered through activated Al 2 0 3 and stored over activated molecular sieves) were added. The flask was sealed and removed from the drybox. It was flushed with ethylene and PMAO-IP (0.9 ml, Akzo, 12.8 wt% Al in toluene) added with vigorous stirring. The reaction was maintained at -14-35 kPa ethylene for 30 min after which it was quenched by addition of MeOH/10% HCl.
Abstract
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EP00980472A EP1237964A1 (en) | 1999-11-19 | 2000-11-16 | Copolymerization of ethylene and dienes |
JP2001538990A JP2003514931A (en) | 1999-11-19 | 2000-11-16 | Copolymerization of ethylene and diene |
AU17727/01A AU1772701A (en) | 1999-11-19 | 2000-11-16 | Copolymerization of ethylene and dienes |
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US16641699P | 1999-11-19 | 1999-11-19 | |
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US9586872B2 (en) | 2011-12-30 | 2017-03-07 | Chevron Phillips Chemical Company Lp | Olefin oligomerization methods |
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EP0985673A2 (en) * | 1998-09-09 | 2000-03-15 | Sumitomo Chemical Company, Limited | Modified aluminium oxy compound, polymerization catalyst and process for producing olefin polymer and alkenyl aromatic hydrocarbon polymer |
WO2001000686A1 (en) * | 1999-06-25 | 2001-01-04 | Bayer Aktiengesellschaft | Method for copolymerizing polar and non-polar monomers |
-
2000
- 2000-11-16 EP EP00980472A patent/EP1237964A1/en not_active Withdrawn
- 2000-11-16 WO PCT/US2000/031604 patent/WO2001036503A1/en not_active Application Discontinuation
- 2000-11-16 JP JP2001538990A patent/JP2003514931A/en active Pending
- 2000-11-16 AU AU17727/01A patent/AU1772701A/en not_active Abandoned
Patent Citations (4)
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US5916989A (en) * | 1995-01-24 | 1999-06-29 | E. I. Du Pont De Nemours And Company | Polymers of C4 and higher α-olefins |
WO1999002472A1 (en) * | 1997-07-11 | 1999-01-21 | E.I. Du Pont De Nemours And Company | Manufacture of alpha-olefins |
EP0985673A2 (en) * | 1998-09-09 | 2000-03-15 | Sumitomo Chemical Company, Limited | Modified aluminium oxy compound, polymerization catalyst and process for producing olefin polymer and alkenyl aromatic hydrocarbon polymer |
WO2001000686A1 (en) * | 1999-06-25 | 2001-01-04 | Bayer Aktiengesellschaft | Method for copolymerizing polar and non-polar monomers |
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WO2002102861A2 (en) * | 2001-06-15 | 2002-12-27 | Eni S.P.A. | Process for the (co)polymerization of conjugated dienes |
WO2002102861A3 (en) * | 2001-06-15 | 2003-11-20 | Eni Spa | Process for the (co)polymerization of conjugated dienes |
US7994376B2 (en) | 2004-02-19 | 2011-08-09 | Chevron Phillips Chemical Company Lp | Olefin oligomerization |
US7820581B2 (en) | 2004-02-20 | 2010-10-26 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US9550841B2 (en) | 2004-02-20 | 2017-01-24 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US8993822B2 (en) | 2004-02-20 | 2015-03-31 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US8329608B2 (en) | 2004-02-20 | 2012-12-11 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US7728161B2 (en) | 2005-07-21 | 2010-06-01 | Chevron Phillips Chemical Company Lp | Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization |
US7727926B2 (en) | 2005-07-21 | 2010-06-01 | Chevron Phillips Chemical Company Lp | Diimine metal complexes, methods of synthesis, and method of using in oligomerization and polymerization |
US7728160B2 (en) | 2005-07-21 | 2010-06-01 | Chevron Phillips Chemical Company Lp | Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization |
US7977269B2 (en) | 2005-07-21 | 2011-07-12 | Chevron Phillips Chemical Company Lp | Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization |
US7910670B2 (en) | 2005-08-19 | 2011-03-22 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
CN102863577A (en) * | 2005-11-09 | 2013-01-09 | 米其林集团总公司 | Copolymer of ethylene and butadiene |
CN101274290B (en) * | 2007-03-30 | 2011-04-20 | 中国石油天然气股份有限公司 | Late transition metal catalyst and preparation method and application thereof |
US7902415B2 (en) | 2007-12-21 | 2011-03-08 | Chevron Phillips Chemical Company Lp | Processes for dimerizing or isomerizing olefins |
US9586872B2 (en) | 2011-12-30 | 2017-03-07 | Chevron Phillips Chemical Company Lp | Olefin oligomerization methods |
US9944661B2 (en) | 2016-08-09 | 2018-04-17 | Chevron Phillips Chemical Company Lp | Olefin hydroboration |
Also Published As
Publication number | Publication date |
---|---|
EP1237964A1 (en) | 2002-09-11 |
AU1772701A (en) | 2001-05-30 |
JP2003514931A (en) | 2003-04-22 |
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