DE2027831A1 - Synthetic resins - Google Patents

Description

! Marriage to Goodyear Tire & Babber Co., Akron, Ohio / USA.

Synthetic resins

The invention relates to new synthetic resins and a process for their preparation. In particular, the Invention with hydrogenated synthetic resins.

Piperylene is known to exist in the presence of metal Halide catalysts are polymerized to produce polymers, which have hitherto been of little economic interest because of their physical properties, which make them unsuitable for technical applications made, It is also known that 2-methyl ~ 2 ~ butene, eic internal olefin, in the presence of ketallllaogenid-Katalyeatoren either not polymerized or products with low Forms molecular weights that are usually oily, so that

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these products are also of limited technical interest are.

It has now been found that olefin mixtures that consist of Piperylene and 2 ~ methyl-2-butene exist in the presence of Metal Halide Catalysts Forming a Series of New One and polymerize valuable products, made by the polymers of piperylene or 2-methyl-2 ~ butea such a polymerization, are different and stand for suitable for a variety of technical fields of application. These Products are resinous materials,

However, this valuable bass, aofera © ie does not stick in treated in a special way, the disadvantage of tesa they have a content of unpleasant smelling Snbetaäsen, .so that they can only be used to a limited extent. Also show they typically have a light yellow® color and are therefore not suitable for such uses® for which essentially colorless resins are required

The aim of the invention is the creation of new and valuable Go »polymers from piperylene and 2 ~ Sfetfayl» 2- »1rateB _< ,

The polymeric erfindungsgemäseen tiarsartigen Assen / consist of about 40 to about 80 weight ^ of units derived from piperylene derived ₉ and _t corresponding to about 60 to about 20 weight ^ of Kinheiten ,, of 2-M @ thyl-2- The unsaturation of the harsh haters has been reduced to a value of less than about 40 to about 85 ^: p of the original unsaturation.

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To carry out the invention, before the hydrogenation untreated resinous material by polymerization ice Mixture made up of about 20 to about 75 weight # Piperylene and about 80 to about 25% by weight 2-methyl-2-butene. The polymerization is in the presence carried out an anhydrous metal halide catalyst. Ss is usually useful when the too polymeric! - sizing mixture of about 35 to about 65% by weight Piperylene and about 65 means about 35 weight # 2-methyl-2-butene consists. In this way, the piperylene in the mixture enters the polymerization reaction at a higher rate Speed one than the 2-methyl-2-butene.

Various anhydrous Metal halide catalysts for the production of the non-treat 1st resinous material can be used. Representative examples of such catalysts are fluorides, Chlorides, bromides and iodides of certain metals / such as aluminum, tin and boron. Ser-like catalysts are for example aluminum chloride, tin (XV) chloride and boron trifluoride. Aluminum chloride and tin (I7) chloride are preferred.

When carrying out the polymerization reaction, the Hydrocarbon mixture brought into contact with the anhydrous metal halide catalyst. Usually the Catalyst is used in the form of individual particles, it being preferable to have the catalyst in the separated form use granular and preferably porous particles. Generally a particle size is from about 5 to about 200 mesh (0.075 - 3.000 mm) is sufficient, however larger or smaller particles can also be used can. The amount of catalyst used is not

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critical. However, such an amount of catalyst must be added as is sufficient for a polymerization Set gear SU. The catalyst can be the olefinic hydrocarbon mixture can be added. You can also do that procedure that the hydrocarbon mixture & © m catalyst admits. If necessary, the catalyst can uni the mixture of the hydrocarbons simultaneously or be added at intervals to a reactor, the reaction can be carried out continuously or batchwise according to known methods.

The polymerization reaction is ssweekmäeaiger Welse Ib In the presence of a diluent carried out * since ale ge » exothermic in a homely manner. However, by appropriate Mixing and cooling the ^ temperature controlled and the Reaction can be carried out without a diluent. Various diluents which εImI are inert to the extent that they cannot enter the Polymerieationereaktion be used. Representative examples of inert. Diluents are aliphatic © hydrocarbons, such as pentane, hexane and heptane aromatic hydrocarbons, such as toluene and * benzene, and not ~ converted hydrocarbons remaining in the reaction.

A wide temperature range can be maintained to carry out the polymerization. The polymerization can be carried out at temperatures from about -20 to about 100 ° O, but usually the reaction is carried out at a temperature between about 0 and about 50 ° O. The pressure which prevails in the polymerization reaction is not critical. Ea can be atmospheric pressure or upper or subatmospheric pressure. In general

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A polymerization can be said to be satisfactory perform when the reaction is about under autogenous pressure is carried out, which is located in the reactor under the complies with the working conditions. This reaction time is generally not critical. She can be of some Stagger seconds to 12 stands or more.

You can untreated polymers by adding up to about 50% by weight of piperylene dimers or piperylene trimers or other unsaturated hydrocarbons, especially hydrocarbons containing 4-6 carbon atoms, and mixtures thereof to the mixture of piperylene and 2-methyl 2-butene can be modified. Representative examples of such hydrocarbons are butene and substituted butenes, for example 2-methy 1-1-butene, 2,3-2) imethyl-1-butene, 2,3-dimethyl 1-2-butene, 3 »3-dimethyl -1-butene, the pentenes and substituted pentenes, for example 1-pentene, 2-pentene, 2-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-1- pentene ₉ 4 ~ methyl-2-pentene _f the hexenes, such as 2-hexene, diolefins such as isoprene, and cyclic unsaturated hydrocarbons »for example cyclopentene, cyclohexene and 1,3-cyelopentadiene ,,

They are therefore characterized by the fact that they a molar ratio of units derived from piperylene to units derived from 2-methy 1-2-butene, | from about 2/3 to about 1/4 units. He follows the modification described above, then they can have up to about 25% by weight of units, the of piperylene dimers, piperylene trimers or other unsaturated ones Hydrocarbons containing 4-6 carbon atoms. '

0 08882/2 1-0 Ο '

The non-treated hard materials are also characterized by a “ && sb β ie © ine Gardaer-Parbe from magefilir: up to about 8, determined on the basis of a 50- - ^ igen mg ia toluene, one. Eweietangepianjfet iroa imgefälir: 80 to «Bgefita 110 ° 0 according to the ISfK method E28-98S« ad © in © Sinrezahl from about 0.6 to about 1.5, a saponification number vqb about 0.5 to about 25 and a specific tea eevloht From about 0.85 to about 1.0. The. In this way, the

the usually Erwüneclitereii Beroieli ¥ oa in ^ ef ate 90 to about 110 ° 0 tint mean in aliphatic
wise Pentane® hexane and
substances, such as Bensol wad Soluol, soluble «

According to the invention, the non-materials are reduced to mg

from less than about 40 # "to as little as $ 85 the lent unsaturation hydrogenated »Vorssisgswelse has aaa .hydrogenated Bar κ about 40 to about -85 # the unsaturation of the untreated 'Haraes on' The hydrogenation takes place in the presence of a solvent with a suitable hydrogenation catalyst

sator.

Various solvents can be used. Hydrogenation process can be used. Representative B © i ~ games are aliphatic, cycloaliphatic and aromatic Solvents, for example pentane, hexane, heptane, isoheptane, Ooten, Isooctane, Oyclohexan, Hethylcyclohe ^ can, Becalin » Tetralin, benzene, toluene, xylene and bioxane.

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The hydrogenation can be carried out batchwise or continuously. In general, it is carried out at a temperature of about 20 * 0 to the decomposition temperature of the resinous material. Bin preferred range is between about 100 and about 300 C. The ⁹ is suspended to carry out the hydrogenation pressures may be about Atmesphärendruok. Ss can also be superatmospheric pressure or subatosphere pressure. The hydrogenation is typically complied with

0%

pressures between atmospheric pressure and approximately 211 kg / cm » absolute (3000 palg) and preferably between about 7 and about 70 kg / cm, absolute (100-1000 psig). The reaction ·? seit is generally about 10 minutes to about 24 hours and preferably about 10 minutes to about 3 hours. "

Various hydrogenation catalysts can be used will. Metals from group TI and group Till of the Periodic Table of the Elements are typically used (see pages 448 and 449 of the 44th edition of "Handbook of Chemistry and Thyβice" published by the Chemical Rubber Publishing Co,). Representative examples for the various hydrogenation catalysts there are Palladium, platinum, cobalt, osmium,! Rhenium, ruthenium, Raney nickel, Niokelsulflde, nickel oxide, copper ohromite, Cobalt / molybdenum, chromium, holybdenum oxide, holybdenum sulfide, platinum oxide, cobalt oxide, rhenium oxide, ruthenium oxide, sponge iron, ^ Iron oxide, zinc sponge and zinc oxide.

Ea is usually two-fold, the catalyst on an in In the form of individual particles, the substrate with a particle size of about 1 to about 8 ^ is to be applied. That in the form of individual particles is a preventive

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It is porous and has a large surface area. For example, aluminum oxide, silica gel, various types of activated charcoal or the like come into question. For example, a hydrogenation catalyst Hlckel / kieselguhr exist, said catalyst typically "at a SDemperatiir of about 200 to about 45O ⁰ C for a period ▼ few hours on by JDartiberleiten of hydrogen is activated" Such treatment reduces at least a portion of the Nickel compound to elementary Hick ©! » generally from about 35 to about 40 percent by weight of the roll, with this amount varying from about 10 to about 50,56.

The amount of the elngesetsten Hydrogenation Catalyst® on non-reduced base, varies in typical catfish sswisohen about 0.1 and about 15 weight ^ and is vonsugswelse at 0.5 weights- ^ or above, based on the weight of the Polymers.

After the hydrogenation has progressed in the desired yield, the catalyst can be prepared by various methods be removed, for example by pl! tration, centrifugation, or the like.If the catalyst is magnetizable, then it can advantageously be removed by passing the solution or dispersion through a packed zone sent under the influence of a strong field, and "was by means of a permanent magnet or a Electromagnets. A typical packed zone consists of steel wool, small magnetic rings, or small magnetic sieves. Demagnetization of the packed zone enables the catalyst borrowings to be removed therefrom Zone.

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The resinous hats of the present invention are particularly useful as a modifier for natural rubber as well as for various synthetic rubbers, their relatively light color and their low content of odorous substances facilitate their use when such properties are particularly sought.

The following examples illustrate the invention without it to restrict. Unless otherwise stated, all rope and percentages relate to weight.

example 1

A hydrocarbon resin polymer is produced using the following method:

50 parts of heptane and 3.08 ropes of anhydrous aluminum chloride are placed in a suitable reactor. !The mixture is cooled to about 5 ° E. Under continuous Stir the mixture slowly over a period of 200 parts of a hydrocarbon mixture Minutes added. The hydrocarbon mixture possesses the following composition:

Component j £

2-pentene 4.8

2-methyl-2-butene 42.2

Isoprene 2.5

1,3-pentadiene (piperylene) 42.4

2,3-dimethyl-1-butene 2,6

unsaturated hydrocarbons containing 5-6 carbon atoms 5.5

100.0

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The temperature of the reaction is kept between approximately 5 and 10 ^° C. The catalyst is "deactivated lime and clay" using a stoichiometric amount of water. The clay is added as a filter aid. The mixture is then filtered to remove iron particles from the decomposed aluminum chloride, lime and ion. Bas Bach this example produced resin has a light yellow color (a Gardner color of about 6), a relatively strong unpleasant odor "particularly in a heating to about 40 ⁰ g, a softening point according to ASM E28-S8E of about 99 ° 0, and a Iodine of about 120 according to the Goodyear method AR-275A, the iodine number according to the Soodyear method AR-275A is determined in the manner * aase Ca) 0.20 g of a resin sample are dissolved in carbon tetrachloride and the solution measured with a Excess bromine is treated in the presence of water in the dark and in a bisted, the concentration of the bromine solution being O ₀ 20 η. The sample is "stored for a period of 15 minutes" in the ice bath and in the dark, then a 2% potassium iodide solution is added, whereupon the liberated iodine is enrUolctitrated using ifatriemia / mosialfate. A small amount of a starting indicator solution is added and the titration is continued until one drop results in a colorless solution.

From this analysis, the iodine number can be calculated in the following way:

S. I s NxB

O 0.0356 20

Moles / kg - 1/2 (BA) χ IT iodine number »25.4 moles / kg

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3? μ Normality of the bromine solution Say potassium iodide

C »ml of the hattrium thiosulphate required for standardization

B «ml of the sodium thioeulphate required for the blank sample ■■■ - ■ '

A'β ml of the sodium thiosulphate required for the sample The normality of sodium thlosulfate Weight of the sample.

The relatively strong unpleasant odor of the Harcsee prepared läset easily in such a manner to determine "that about 10 g are added * sealed preceded the bottle and is at least about 12 hours (stored at about 25 ⁰ C In a 225 g-Flasohe. Sann is the cap β of the bottle is removed, whereupon you can smell the odor on the bottle

Example 2

A hydrogenation reactor is purged and flushed with old nitrogen 1354 parts of a solution charged containing 900 parts of hexane and 454 contains ropes of a resinous mass prepared according to Example 1. Bas Bars has a softening point of about 99 ° 0, a Gardner color of about 7, and a Bronsahl of about 120. The reactor becomes then with 33 ropes one in the form of individual particles present Nicke1-B ^ drierungskatalysatore charged, the available under the designation G49A from the Girdler Chemicals Department of Chemetron Chemicals.

The polymer consists of about 40 weight ^ des Barges and correspondingly about 60% by weight of an unsaturated monomer, light hydrocarbons and heptane. Sine

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Material balance of the reaction shows the following Hans has approximate composition:

Components

2-methyl-2-butene 37

Isoprene 1 ».5"

Piperylene (1 _# 3-Pentadiene) 55 Other ingredients. 6.5

100.0

The reactor is placed under a pressure of 70 kg / om, absolute (1000 pe ig) using hydrogen and gradually heated while introducing τοη hydrogen into the system to maintain the pressure. The temperature is raised from about 20 to about 185 ° ö and held at this value for a period of 60 minutes. The pressure is then reduced to about atmospheric pressure and the treated solution is filtered through a pressure filter to remove the catalyst. The hydrogenated polymer is then removed and analyzed. It is found that it has an iodine number of 93 ai2f & iei @ t. The off separated harsartige Haterial has a softening point of 94 ⁰ C contemporary of ASÜM method E28-58HÜ. an eardner color of 1 as well as a considerably reduced and practically negligible content of odorous substances, as can be determined with the help of the flash test described above.

Example 3

Following the method described in Example 1, a resinous Hasse and mixed with hexane to form a solution, followed by that described in Example 2 Method is hydrogenated. In performing this example

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however, a palladium catalyst is used as the hydrogenation catalyst and the pressure is 35 kg / cm, absolute (500 psig). The temperature is 160 ^° C. and the hydrogenation time is 15 minutes. The palladium catalyst is available under the designation G-81-B. It consists of 3 f> palladium on activated carbon and is also marketed by Chemetron Chemicals. The hydrogenated polymers obtained has a softening point of 93 ⁰ C ₉ a Gardner color of 1 and a substantially reduced and practically vernaohlässigbaren content of odor components, as can be determined by means of the mentioned bottle tests.

Example 4

A resinous mass is prepared according to the method described in Example 1 and mixed with hexane to form a solution, followed by hydrogenation according to the method described in Example 2. However, a platinum catalyst is used. The hydrogenation conditions are as follows: The pressure is 35 kg / em, absolute (500 psig), the emperatur 160 ⁰ O and the hydrogenation time 15 minutes!. The catalyst is sold under the name Gf-1225. It is a $ 5 platinum on charcoal catalyst that is also available from Chemetron Chemicals. The hydrogenated resin obtained has a softening point of 99 ^° C., a Gardner color of 1 and a noticeably reduced and practically negligible content of odor sub- i

-punch, as can be determined from the bottle test mentioned leaves.

Example 5

A resinous mass is made according to that described in Example 1 Method prepared and treated with hexane to form a

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Mixed solution. Then the method described in Example 2 is hydrogenated. However, the GS-1225 KLatijakatalyaator used in Example 4 is used. The hydrogenation is carried out at a pressure of 35 kg / cm, abaolut (500 psig) "at a temperature of about 185 ⁰ OWM for a period of about 50 minutes. The resulting hydrogenated resin has a softening point of 97 ⁰ O, a Gardner- larte vo »" J, eis © iodine number ven 54 and a significantly reduced and practically veaaaaehlasaigbaren content of odor constituents , as can be determined with the help of the .Klasohentests »

Example 6

A resinous mass is produced according to the method described in Beiopiel 1 and mixed with Heaaa to form a solution. Then the method described in Example 2 is hydrogenated. However, it is the G-SI-B-Palladiuntotalysator used "The% driertuagsreal £ tioi3 is (500 psig) under a pressure of 35 kg / cm ₉ absolutely carried out at a temperature of about 185 ⁰ G during a hand, breakdown of about 30 minutes" , The Ijdrierte Harz achieved a softening point of 97 ^a C _s for a Gardner color of 1, an iodine number of 60 and a morKLicfe reduced and practically negligible content of odor components, as can be determined by the hash test described «,

The resinous masses produced according to the invention have a basic structure made up of units which differ from piperylene derive, as well as from units that. derived from 2 ~ methyl-2-butene, they have a noticeably reduced level of saturation have and, surprisingly, only smell very weakly. Typically the original is resinous

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Hate a Jodisahl of around 100 to around HO. this is achieved without destroying the good heat stable! tat. the unusually good quality and the excellent color of the originally resin-like cash register. About that In addition, the Hans according to the invention has an opposite untreated hair improved color, such as from Gardner color, of less than about 2 and preferably about 1 or below. The heat stability is also improved.

Furthermore, the inventive lake bars are more economically attractive for use as a tackifying gown than the various adhesives based on rubber and | synthetic rubber including the pressure-sensitive Adhesives and Heiseohmels-ElebBtoffe. That Hans leaves eich but use the production of transparent overspray, and was due to its lower content of scented sub-petaneen, its better color, as well as its retained Thermal stability and tackifying properties.

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Claims (1)

- 16 -patent claims 1. Polymeric resinous compounds, characterized by about 40 to about 80% by weight of units derived from piperylene and about 60 to about 20% by weight of units derived from 2-methyl-2-butene, wherein the resinous hasse has a softening point of at least about 85 ⁰ O and its unsaturation has been reduced to a value of about 40 to about 85 % of the original unsaturation of the resinous hasse by hydrogenation. 2. Hasse according to claim 1, characterized in that it has a soaping number of from about 0.5 to about 25 and has been modified to contain up to about 25 weight units of at least another unsaturated hydrocarbon derived from a Fiperylendlmeren or Piperjlentrimeren or from another unsaturated hydrocarbon which Contains 4 - 6 carbon atoms 3. Hasse according to spoke 2, characterized in that the other unsaturated hydrocarbon containing 4-6 carbon atoms from baten or a substituted butene, a Pentene or a substituted pentene, a hexene or a cyclic unsaturated hydrocarbon 4. Cash register according to claim 2, characterized in that the unsaturated hydrocarbon containing 4-6 carbon atoms from messengers, 2-methy1-1-butene, 2,3-dimethyl-1-butene, £, 3-dinethyl-2-butene, 3,3-3) i » ethyl-1-butene, 1-pentene, 2-pentene, 009882/2100 ORIGINAL INSPECTED 2-Μβthy1-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-1-pentene, 4-methyl-2-pentene, 2-hexene »isoprene» Cyclopentene, oyolohexene or 1,3-cyolopentadiene stable, 5. Composition according to claim 2, characterized in that it in, the catfish is modified that they are up to 25 weight-j6 of units which are derived from an unsaturated hydrocarbon derived from a piperylene dimer or Piperylenetriineren consists of - 6. Composition according to claim 1, characterized geksnnseiohnet that it has a softening point τοη at least about 85 ⁰ C hesitat and a terrelation of units that are derived from τοη piperylene »βα units that are derived from τοπ 2-methyl-2-butene, τοη about 2 / 3 to about 4/1 and has the structure of the mass obtained by dividing a haraea after a cathode "which consists in polymerizing a mixture consisting of about 20 to about 75% by weight of piperylenes and about 80 up to about 25% by weight of 2-methyl-2-butene, the polymerization being carried out at a temperature between about O ⁹ O and about 50% in the presence of an anhydrous metal halide catalyst, which is made from aluminum chloride or Zi2mfl?} - ehlorld consists »and the flattening of the Haraes to a value τοη approximately 40 to un | «About 85 % of the original unsaturation has been reduced by hydrogenation. 7, Hasse: also claim 6, thereby rewarding »that she in the * Ve Lee aodif has been lit, that they are up to * ~ It contains 25 units of weaknesses which can be derived from at least "one" other unsaturated wax. that of a Plperylendiatren »a.Piperrlentrieeren or 009882/2100 ORIGINAL / NSPECTED • in · »other unsaturated hydrocarbons old 4-6 Carbon atoms. 8. mass according to Anspruoh. 6, characterized in that the hydrogenation is carried out at an ice temperature of about 20 to about 300 + Qt Jedooh. below the decomposition temperature of the bar-like material, under a pressure of about Atmosphlrendruok bla about 211 kg / om ² , absolute (3000 psig) and in the presence of an agent of an allphatic, eyoloaliphatic or aromatic hydrocarbon, with SIoJtSl ₉ palladium as the hydrogenation catalyst, Platinum «cobalt» osmium » Tftathaninm, Haney-Iickel, a Hiokelsulild, Hickelcoyd, gaperorolt, Kobelt / MolybdSn, chromium, molybdenum oxide, MoIyb- ? latlnoocjd «XobaltooQfd« HhenliUBOS ^ d, SlBenachvaaa »Elaenocxyd, Zlnksohvaam or Zinkoiyd been used 1st. 9 »Hasse according to inapruoh 8 _f daduroh characterized that the hydrogenation has been carried out with the use of a hydrogenation catalyst, which is deposited on a substrate lying in the form of binellellohon, the substrate being best on aluminum oxide, silicon dioxide or diatomaceous earth. . ^: '· ■' - '' .- ^: '.-' ■ ■. ■■ '. ;; - ^: '-; .r _n ;; · -: ■■■>: £ Process for the preparation of the polymeric resinous Mass according to claim 1, characterized by that. Polymerize a mixture of about 20 to about 75% piperylene and about 80 to about 25% by weight of 2-methyl-2-butene in the presence of an anhydrous Halides to the aluminum, tin or boron halides a temperature »flat about -20 and about 100 * C a bar is made and its saturation on a 009882/2100 INSPECTED Value of about 40 to about 85 pounds of the original unsaturation of the resin is reduced by hydrogenation, the hydrogenation at a temperature of about 20 to about 30O ⁰ Q, but below the decomposition temperature of the resin, and at a pressure of about Ataoephfirendrack to approximately 211 kg / cm ² , absolute (300 ° peig) is carried through. 11. The method according to claim 1O _1, characterized in that the anhydrous halide used consists of aluminum chloride. 009882/2100 OBlGWAL IHSPECTED ■ '· "' COPV