AU747670B2 - Method for hydrogenating aromatic polymers in the presence of branched hydrocarbons - Google Patents

Method for hydrogenating aromatic polymers in the presence of branched hydrocarbons Download PDF

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AU747670B2
AU747670B2 AU33328/99A AU3332899A AU747670B2 AU 747670 B2 AU747670 B2 AU 747670B2 AU 33328/99 A AU33328/99 A AU 33328/99A AU 3332899 A AU3332899 A AU 3332899A AU 747670 B2 AU747670 B2 AU 747670B2
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aromatic
polymers
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Johann Rechner
Volker Wege
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Bayer AG
Teijin Ltd
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Teijin Ltd
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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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • 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
    • 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
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • 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
    • C08F216/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • 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
    • C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated

Description

WO 99/52953 PCT/EP99/02138 -1- A method of hydrogenating aromatic polymers in the presence of branched hydrocarbons The present invention relates to a method of hydrogenating aromatic polymers, which is characterised in that branched saturated hydrocarbons are used as solvents, which branched saturated hydrocarbons possess a maximum of one hydrogen atom at the branching point, a boiling temperature higher than 45 0 C and an ignition temperature (DIN 51794) higher than or equal to 280 0 C, or a mixture is used of solvents which contain these hydrocarbons with solvents which are customary for hydrogenation reactions. This invention also relates to the polymers produced in this manner.
The hydrogenation of aromatic polymers is already known. DE-AS 1 131 885 describes the hydrogenation of polystyrene in the presence of catalysts and solvents.
Aliphatic and cycloaliphatic hydrocarbons, ethers, alcohols and aromatic hydrocarbons are mentioned in general as solvents. A mixture of cyclohexane and tetrahydrofuran is cited as being preferred.
WO 96/34 896 US-A-5 612 422) describes a method of hydrogenating aromatic polymers, for example, in which hydrogenation is effected in the presence of a metal on a silica support as a hydrogenation catalyst, wherein the silica has a defined pore size distribution. Aliphatic or cycloaliphatic hydrocarbons are mentioned as solvents, and isopentane (2-methylbutane) is cited as a branched saturated hydrocarbon. Diethylene glycol dimethyl ether and tetrahydrofuran are cited as ethers.
EP-A-322 731 describes the production of what are predominantly syndiotactic polymers based on vinylcyclohexane, wherein a styrene-based polymer is hydrogenated in the presence of hydrogenation catalysts and solvents. Cycloaliphatic and aromatic hydrocarbons are mentioned as solvents.
The specialised solvents of the present invention are not mentioned.
WO 99/52953 PCT/EP99/02138 -2- Apart from isopentane, the hydrocarbons described in the aforementioned documents possess ignition temperatures lower than or equal to 260'C and are solvents which are not easy to handle in an industrial process. Solvents for an industrial process have to have sufficiently high ignition temperatures (DIN 51 794), since contact with hot metal surfaces, possibly in the presence of air, occurs during the work-up of polymers, and the processing temperatures employed for a polymer solution of hydrogenated polystyrene in the presence of solvent, for example, can reach or exceed 240'C. The possibility thus exists of ignition and explosion unless a sufficient temperature difference is maintained between the processing temperature and the ignition temperature.
Replacing the solvent before the work-up step for the production of granules is associated with considerable costs and engineering expenditure.
Measures which render the entire polymer work-up step inert, and which prevent the occurrence of solvent/air contact, are costly, and can scarcely be realised in practice for a large-scale industrial process, since the entire installation would have to be encapsulated under an inert gas, for example.
Apart from isopentane, the solvents which are known from the aforementioned documents (W096/34896; US 5 612 422) are capable of igniting without precautions of this type, or without other complex, expensive precautions, and constitute a considerable safety risk. However, isopentane is not a solvent for polystyrene, for example, and this solvent is thus unsuitable for the hydrogenation of this polymer. Moreover, as a solvent isopentane has the disadvantage of boiling at 28'C, which firstly makes the handling of solutions difficult and secondly results in costly cooling and condensation installations as a consequence of the requisite cooling during the work-up step.
The object of the present invention was that the solvent used should dissolve the polymer starting material, and should result in the practically complete WO 99/52953 PCTIEP99/02138 -3hydrogenation of aromatic units, with the reaction product being dissolved, to provide a system which can be fed directly to the work-up step, with a temperature difference (of at least 15 with respect to the Celsius temperature scale) being maintained between the processing temperature and the ignition temperature of the solvent.
It has now been found that certain branched hydrocarbons possess the requisite properties, and a large-scale process for the hydrogenation of aromatic polymers and the polymer work-up step thereof are thereby considerably simplified. The present method is distinguished in that the hydrogenated polymer solution can be fed directly to the work-up step and no complex technical measures are necessary in order to exclude solvent/air contact at a surface at temperatures higher than or equal to the ignition temperature. Another advantage of using these specialised branched .hydrocarbons is that the solvent can be separated from the polymer at higher 15 temperatures, which results in lower residual contents of solvent and higher throughputs of polymer.
The present invention relates to a method of hydrogenating aromatic polymers, "wherein the degree of hydrogenation is 90% optionally in the presence of catalysts, 20 wherein branched saturated hydrocarbons are used, as solvents, which branched hydrocarbons possess at most one hydrogen atom at the branching point, a boiling Stemperature higher than 45 0 C and an ignition temperature (DIN 51794) above 280'C, or a mixture is used of hydrocarbons such as these with solvents which are suitable for hydrogenation reactions.
The reaction is generally conducted at concentrations by volume of the branched saturated hydrocarbons of 0.1 100 preferably 1 80 most preferably 70 with respect to the total solvent.
In general, the method according to the invention results in the practically complete hydrogenation of aromatic units. As a rule, the degree of hydrogenation is 80 RL, preferably 90 more preferably 99 most preferably 99.5 to 100 The WO 99/52953 PCTIEP99/02138 -4degree of hydrogenation can be determined by NMR or UV spectroscopy, for example.
The aromatic polymers which are used as starting materials are selected, for example, from polystyrene, which is optionally substituted within the phenyl ring and/or at the vinyl group, or from copolymers thereof with monomers selected from the group consisting of olefins, (meth)acrylates or mixtures thereof. Other suitable polymers include aromatic polyethers, particularly polyphenylene oxide, aromatic polycarbonates, aromatic polyesters, aromatic polyamides, polyphenylenes, polyxylylenes, polyphenylene vinylenes, polyphenylene ethylenes, polyphenylene sulphides, polyaryl ether ketones, aromatic polysulphones, aromatic polyether sulphones and aromatic polyimides, as well as mixtures and copolymers thereof, optionally copolymers with aliphatic compounds.
Suitable substituents in the phenyl ring include Ci-C4 alkyl groups, such as methyl and ethyl, Ci-C4 alkoxy groups, such as methoxy or ethoxy, and aromatic compounds which are incorporated by condensation and which are bonded to the phenyl ring via a hydrocarbon atom or via two carbon atoms, comprising phenyl, biphenyl or naphthyl.
Suitable substituents on the vinyl group include Ci-C4 alkyl groups, such as methyl, ethyl and n- or iso-propyl, particularly methyl in the a-position.
Suitable olefinic comonomers include ethylene, propylene, isoprene, isobutylene, butadiene, cyclohexadiene, cyclohexene, cyclopentadiene, norbornene, which is optionally substituted, dicyclopentadiene, which is optionally substituted, tetracyclododecenes, which are optionally substituted, or dihydrocyclopentadienes, which are optionally substituted, CI-Cs, preferably Ci-C4 alkyl esters of (meth)acrylic acid, particularly preferably the methyl or ethyl esters, WO 99/52953 PCT/EP99/02138 CI-Cs, preferably Ci-C4 alkyl ethers of vinyl alcohol, particularly preferably the methyl or ethyl ethers, CI-Cs, preferably Ci-C4 alkyl esters of vinyl alcohol, particularly preferably esters of ethanoic acid, derivatives of maleic acid, preferably maleic anhydride, and derivatives of acrylonitrile, preferably acrylonitrile and methacrylonitrile.
The aromatic polymers generally have molecular weights Mw of 1000 to 10,000,000, preferably 60,000 to 1,000,000, most preferably 70,000 to 600,000, as determined by light scattering.
The polymers may possess a linear chain structure, or may also comprise branching points due to co-units graft copolymers). The branching centres may comprise star-shaped polymers, for example, or may comprise other geometric forms of the primary, secondary, tertiary or optionally quaternary polymer structure.
The copolymers may exist as random polymers, or alternatively they may exist as block copolymers.
Block copolymers comprise di-blocks, tri-blocks, multi-blocks and star-shaped block copolymers.
The polymer starting materials are generally known WO 94/21 694).
The solvents which are preferably used are branched hydrocarbons of formula which have boiling temperatures above 45 0 C and ignition temperatures (DIN 51 794) higher than or equal to 280 0
C.
S
R
4 R2 (I)
R
R
3 WO 99/52953 PCT/EP99/02138 -6wherein the R 2
R
3 and R 4 radicals represent straight chain or branched Ci-Cio alkyl radicals and a maximum of one of the R 2
R
3 and R 4 radicals may also represent hydrogen, The following are particularly preferred: 2,2,3-trimethylbutane; 2,2-dimethylbutane; 2,3-dimethylbutane; methylcyclopentane; 2-methylpentane; 3-methylpentane; 3,3-diethylpentane; 2,4-dimethylpentane; 2,2-dimethylpentane, 2,3-dimethylpentane; 2,4-dimethyl-3-ethylpentane; 2,2,3-tri-methylpentane; 2,3,3-trimethylpentane; 2,2,4-trimethylpentane (isooctane); 2,2,3,3-tetramethylpentane; 2,2,3,4-tetramethylpentane; 2,3,3,4-tetramethylpentane; 2-methylhexane; 3-methylhexane; 2-methyl-4-ethylhexane; tert.butylcyclohexane; 2-methylheptane; 2,5,5-trimethylheptane; 3,3-dimethylheptane; 2,2,5-trimethylheptane.
The solvent which is particularly preferred for the hydrogenation of polystyrene and derivatives thereof is methylcyclopentane, which is a good solvent by comparison with the hydrocarbons which are known for hydrogenation from the aforementioned documents, and which has a boiling temperature of 72 0 C and an ignition temperature of 315 0
C.
The amount of catalyst used is described in WO 96/34896 for example.
The amount of catalyst used depends on the process which is carried out. This process may be effected continuously, semi-continuously or batch-wise.
In a continuous system, the time of reaction is significantly shorter, and is influenced by the dimensions of the reaction vessel. In a continuous procedure, the WO 99/52953 PCT/EP99/02138 -7trickling system and the reactor bottom system, which both comprise fixed catalysts, are operated as far as possible as a system comprising suspended catalyst which is recycled, for example. The fixed catalysts may exist in the form of tablets or as extruded shapes.
The polymer concentrations with respect to the total weight of solvent and polymer generally range from 80 to 1, preferably 50 to 10, particularly 40 to 15 by weight.
Hydrogenation of the polymer starting material is generally conducted by methods which are generally known WO 94/21 694, WO 96/34 895, EP-A-322 731).
There is a multiplicity of known hydrogenation catalysts which can be used as catalysts. The preferred metal catalysts are cited, for example, in WO 94/21 694 or WO 96/34 896. Any catalyst which is known for hydrogenation reactions can be used. Suitable catalysts comprise both those of large surface area 100 600 m 2 and small average pore sizes 20 500 A) and those which have a small surface area 10 m 2 and which have a large average pore size which is characterised in that 98 of the pore volume is defined as being larger than 600 A about 1000 4000 A) (see US-A 5,654,253, US-A 5,612,422, JP-A 03076706, for example). Raney nickel, nickel on silica, alumina or silica/alumina, nickel on carbon as a support, and/or noble metal catalysts, e.g. Pt, Ru, Rh, Pd, are used in particular.
The reaction is generally conducted at temperatures between 0 and 500'C, preferably between 20 and 250'C, particularly preferably between 60 and 200'C.
The solvents which can customarily be used for hydrogenation reactions are described in DE-AS 1 131 885, for example (see above).
The reaction is generally conducted at pressures of 1 bar to 1000 bar, preferably to 300 bar, particularly preferably 40 to 200 bar.
WO 99/52953 PCT/EP99/02138 -8- Examples: Examples 1 and 2 A 1 litre autoclave was flushed with inert gas. The polymer solution and the catalyst were added (Table). After closing the autoclave, it was repeatedly subjected to the action of protective gas and then hydrogen. After releasing the pressure, the respective hydrogen pressure was set and the batch was heated to the corresponding reaction temperature with stirring. After hydrogen absorption had set in, the reaction pressure was held constant.
The time of reaction was the time from heating up the batch to the time of complete hydrogenation of the polystyrene, or for incomplete hydrogenation was the time until the hydrogen absorption approached its saturation value.
After the reaction was terminated, the polymer solution was filtered. The product was precipitated in methanol and dried. The isolated product had the physical properties listed in the Table.
A 99/5293 ACE ble Hydrogenation of polystyrene as a fuinction of the solvent system PCTIEP99/02 138 Example No. Weight of Solvent Weight of Reaction H2 pressure Time of Degree of Ignition temperature of the polystyrene catalyst temperature (bar) reaction hydrogenation) solvent (OC) (mi)n (DIN51794)
(OC)
1 00 2300 13.5 4 150 875(psig) 110 98.4 260 Comparison CYH 612 422) 2100.2 2) 200 12.5 3 160 100 360 100 315 According to the MCP 460 ivention 100
MTBE
1) 2) 3) 4)
CYH
Determined by 'H NMR spectroscopy polystyrene Type 158 k, Mw 280,000 g/mole, BASF AG, Ludwigshafen, Germany Engelhard, Ni-S 136 P, nickel on silica/alumina US-A-S 612 422, 5 platinum/silica cyclohexane, MCP methylcyclopentane, MTBE methyl tert. -butyl ether W099/5293 PCT/EP99/02138 The platinum catalyst (Table) resulted in the hydrogenation of polystyrene in cyclohexane at 140 0 C (comparative example Cyclohexane has an ignition temperature of 260 0 C and leads to problems when working up the product, since solvent/air contact on hot metal surfaces at temperatures approaching the ignition temperature has to be avoided. The method according to the invention (example 2) resulted in complete hydrogenation compared with comparative example 1, but all the solvents used had ignition temperatures above 310 0
C.
The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement or any form of suggestion that the prior art forms part of the common general knowledge in Australia.
0* 0 S000.
0 0 *e• 000 0 0 0 **00 *ee 00** 0*

Claims (15)

1. A method of hydrogenating aromatic polymers wherein the degree of hydrogenation is 90%, optionally in the presence of catalysts, wherein branched saturated hydrocarbons are used as solvents, which branched hydrocarbons possess at most one hydrogen atom at the branching point, a boiling temperature higher than 45 0 C and an ignition temperature (DIN 51794) above 280 0 C, or a mixture is used of solvents which contain these hydrocarbons with solvents which are suitable for hydrogenation reactions.
2. The method according to claim 1, wherein the degree of hydrogenation is 2 99%,
3. The method according to claim 1, wherein the degree of homogenation is 99.5 to 100%.
4. A method according to anyone of claims 1 to 3, wherein branched hydrocarbons of formula are used as solvents, R 2 (I) R C R2 the R 2 and R radicals represent straight chain or branched G-Clo alkyl radicals and a maximum of one of the R 3 and R 4 radicals may also represent hydrogen. A method according to anyone of claims 1 to 4, wherein the solvent is selected from at least one of the following solvents: P:\WPDOCS\CRN\SPEC7525080.sp.doc-28/2/2 2- 2,2,3-trimethylbutane; 2,2-dimethylbutane; 2,3-dimethylbutane; methyl- cyclopentane; 2-methylpentane; 3-methylpentane; 3,3-diethylpentane; 2,4- dimethyl-pentane; 2,2-dimethylpentane, 2,3-dimethylpentane; 2,4-dimethyl- 3-ethyl-pentane; 2,2,3-tri-methylpentane; 2,3,3-trimethylpentane; 2,2,4- trimethylpentane (iso-octane); 2,2,3,3-tetramethylpentane; 2,2,3,4-tetra- methylpentane; 2,3,3,4-tetramethylpentane; 2-methylhexane; 3-methyl- hexane; 2-methyl-4-ethylhexane; tert.-butylcyclohexane; 2-methylheptane; 2,5,5-trimethylheptane; 3,3-dimethylheptane; 2,2,5-trimethylheptane.
6. A method according to anyone of the preceding claims, wherein a mixture of solvents is used which contains at least one branched, saturated hydrocarbon and at least one solvent which can be used for hydrogenation reactions.
7. A method according to anyone of the preceding claims, wherein the concentration by volume of saturated, branched hydrocarbons in relation to the *o total solvent ranges from 0.1 to 100%. 15 8. A method according to anyone of the preceding claims, wherein the concentration by volume of saturated, branched hydrocarbons ranges from 1 to
9. A method according to anyone of the preceding claims, wherein the 20 concentration by volume of saturated, branched hydrocarbons ranges from 5 to A method according to anyone of the preceding claims, wherein the polymer concentration ranges from 80 to 1 by weight with respect to the total weight of solvent and polymer.
11. A method according to anyone of the preceding claims, wherein the polymer concentration ranges from 50 to 10 by weight with respect to the total weight of solvent and polymer. W099/5293 PCTIEP99/02138 -13-
12. A method according to anyone of the preceding claims, wherein the polymer concentration ranges from 40 to 15 by weight with respect to the total; weight of solvent and polymer.
13. A method according to anyone of the preceding claims, wherein the aromatic polymers are selected from the group consisting of the following polymers: polystyrene, which is optionally substituted within the phenyl ring and/or at the vinyl group, or copolymers thereof, aromatic polyethers, aromatic polyesters, aromatic polyamides, polyphenylenes, polyxylylenes, polyphenylene vinylenes, polyphenylene ethylenes, polyphenylene sulphides, polyaryl ether ketones, aromatic polysulphones, aromatic polyether ,sulphones and aromatic polyimides, as well as mixtures and copolymers thereof, optionally copolymers with aliphatic compounds. 15 14. A method according to claim 13, wherein the aromatic polymers are selected 15 from the group consisting of the following polymers: polystyrene, which is optionally substituted within the phenyl ring and/or at the vinyl group, or copolymers thereof with monomers selected from the group comprising olefins, (meth)acrylates or mixtures thereof.
15. A method according to claim 14, wherein the comonomers are selected from D ethylene, propylene, isoprene, isobutylene, butadiene, cyclohexadiene, cyclohexene, cyclopentadiene, norbornene, which is optionally substituted, dicyclopentadiene, which is optionally substituted, tetracyclododecenes, which are optionally substituted, or dihydrocyclopentadienes, which are optionally substituted, CI-Cs alkyl esters of (meth)acrylic acid, CI-Cs alkyl ethers of vinyl alcohol, W099/5293 PCT/EP99/02138 -14- Ci-Cs alkyl esters of vinyl alcohol, derivatives of maleic acid; derivatives of acrylonitrile.
16. A method according to anyone of the preceding claims, wherein the aromatic polymers have (weight average) molecular weights of 1000 to 10,000,000.
17. A method according to anyone of the preceding claims, wherein the aromatic polymers have (weight average) molecular weights of 60,000 to 1,000,000.
18. Hydrogenated polymers obtained by a method according to anyone of the preceding claims.
19. Methods of hydrogenating aromatic polymers, or hydrogenated polymers produced thereby, substantially as hereinbefore described with reference to the °Examples. DATED this 28th day of February, 2002 BAYER AKTIENGESELLSCHAFT AND TEIJIN LIMITED By their Patent Attorneys DAVIES COLLISON CAVE S*
AU33328/99A 1998-04-08 1999-03-29 Method for hydrogenating aromatic polymers in the presence of branched hydrocarbons Ceased AU747670B2 (en)

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DE19815737 1998-04-08
DE19815737A DE19815737A1 (en) 1998-04-08 1998-04-08 Process for the hydrogenation of aromatic polymers in the presence of branched hydrocarbons
PCT/EP1999/002138 WO1999052953A1 (en) 1998-04-08 1999-03-29 Method for hydrogenating aromatic polymers in the presence of branched hydrocarbons

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CA (1) CA2327485A1 (en)
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3023201A (en) * 1955-10-26 1962-02-27 Phillips Petroleum Co Process for removal of catalyst from hydrogenated polymer solutions
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GB1020720A (en) * 1963-12-26 1966-02-23 Shell Int Research Process for the catalytic hydrogenation of block copolymers
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