GB1558491A - Hydrogenation of polymers - Google Patents

Hydrogenation of polymers Download PDF

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Publication number
GB1558491A
GB1558491A GB3596976A GB3596976A GB1558491A GB 1558491 A GB1558491 A GB 1558491A GB 3596976 A GB3596976 A GB 3596976A GB 3596976 A GB3596976 A GB 3596976A GB 1558491 A GB1558491 A GB 1558491A
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copolymer
hydrogenation
double bonds
trans
complex
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation

Description

(54) HYDROGENATION OF POLYMERS (71) We, BAYER AKTIENGESELLSCHAFT, of 509 Leverkusen, Germany, a body - corporate organised under the laws of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to a process for the production of partially hydrogenated copolymers of an a,ss-unsaturated carboxylic acid or derivatives thereof and a hydrocarbon containing conjugated double bonds.
Random copolymers of monomers such as these are known from German Patent Specifications Nos. 570,980 and 658,172. They are obtained by the emulsion copolymerisa tion of, for example, acrylonitrile with conjugated dienes, such as butadiene.
It is known from US-PS 3,700,637 that regularly alternating copolymers can be produced -from butadiene and acrylonitrile and can be hydrogenated by means of rhodium complexes as catalysts with the nitrile groups left intact.
In the context of the present invention, copolymers are both regularly alternating and also random copolymers of an a,ss-unsaturated carboxylic acid or derivative thereof and an unsaturated hydrocarbon containing conjugated double bonds. The back-bone of the copolymer consists entirely of carbon atoms.
Suitable carboxylic acids and their derivatives are, for example, (meth)acrylic acid, fumaric acid, their esters and amides, and also the corresponding carboxylic acid nitriles, such as (meth)acrylonitrile. Suitable conjugated dienes are, for example, butadiene, isoprene, dimethyl butadiene and piperylene. The process according to the invention is preferably used for the partial hydrogenation of copolymers of (meth)acrylic acid or derivatives thereof and butadiene. Copolymers of 90 to 45% by weight of butadiene and 10 to 55% by weight of acrylonitrile (based in each case on the copolymer total) are particularly preferred.
-In addition to the functional groups emanating from the carboxylic acid or its derivatives, for example the nitrile group, unsaturated structural units present in the above-mentioned copolymers are the vinyl groups formed during 1.2-bonding of the dienes used and the cis or trans-configuration olefinic double bonds formed during 1,4-bonding.
According to the invention, the copolymers are dissolved in suitable organic solvents and are-hydrogenated in the presence of a rhodium complex and, optionally, a ligand of the complex, e.g. triphenyl phosphine. at elevated temperature and pressure with any other functional groups, e.g. the nitrile group. left intact. In this connection, it has surprisingly been found that, in cases where chlorobenzene is used as solvent, the vinyl groups and the trans-configuration double bonds in the above-mentioned copolymers are completely hydrogenated in a selective manner. If on the other hand other solvents are used, the vinyl groups are completely hydrogenated, whereas the trans-configuration double bonds are only partially hydrogenated. The degree of hydrogenation of the trans-configuration double bonds amounts to between 10 and 90 %, based on the quantity of these double bonds, depending upon the solvent used. It was by no means foreseeable to the expert that the controlled use of certain solvents in a hydrogenation reaction carried out under identical conditions would enable the vinyl groups to be completely hydrogenated and the trans-configuration double bond to be completely or partially hydrogenated in a selective manner.
The present invention relates to a process for selective hydrogenation of the vinyl groups and trans-configuration double bonds in copolymers of an a p-unsaturated carboxylic acid or a derivative thereof and an unsaturated hydrocarbon containing conjugated double bonds, the back-bone of the copolymer consisting entirely of carbon atoms, distinguished by the fact that a 1 to 20 % solution of the copolymer in a suitable organic solvent is hydrogenated at 50 to 1500C and at 5 to 300 atms (absolute pressure) in the presence of 0.01 to 10 % by- weight of a catalyst of a complex compound of a monovalent or trivalent rhodium halide, and, optionally, 5 to 25 % by weight of the ligand bound in the complex (based in each case on dissolved copolymer). Selective hydrogenation of the vinyl groups and trans-configuration double bonds in the copolymers may be carried out in a chlorine-substituted aromatic solvent with from 6 to 12 carbon atoms, preferably chlorobenzene, as solvent. In this medium the polar groups (for example nitrile groups) do not undergo any demonstrable hydrogenation. If solutions of the copolymers in other solvents, such as for example toluene, benzene, xylene, dimethyl formamide, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, cyclohexanone or methylene chloride, are used in accordance with the invention, complete hydrogenation of the vinyl groups is accompanied by only partial hydrogenation of the trans-configuration double bonds.
The degree of hydrogenation of these double bonds is governed by the type of solvent used and decreases from around 90 to about 10 % in the order benzene > dimethylforma mide ~ xylene > ethyl acetate > toluene > methyl ethyl ketone > cyclohexanone > tetrahydrofuran > methylene chloride. Although not necessary, it is of course also possible to use solvent mixtures for the process according to the invention.
The solutions contain from 1 to 20 % by weight and preferably from 2.5 to 10 % by weight of the copolymers, based on- the particular above-described solvent used for the process according to the invention.
From 0.01 to 10 % by weight and preferably from 0.1 to 5 % by weight (based on the dissolved copolymer) of a complex compound of monovalent or trivalent rhodium halides are added to the solutions of the copolymers as a catalyst for the hydrogenation reaction.
Suitable complex compounds correspond to the general formula (I): (RmB)3 Rh X, (I) in which R = C1-C8 alkyl, C6-C15 aryl or C7-C1.5 aralkyl, B = P, As, S or S=0, X = Cl or Br, m = 2 or 3, and n = 1 or 3.
Preferred complex compounds of this type are tris-(triphenyl phosphine)-rhodium(I) chloride, tris-(triphenyl phosphine)-rhodium(III)-chloride and tris-(dimethyl sulphoxide) rhodium(III)-chloride.
The pressure under which the hydrogenation reaction according to the invention is carried out may be varied within a wide range. Suitable pressures are in the range of from 5 to 300 atms and preferably in the range of from 50 to 100 atms. The hydrogenation reaction is carried out at temperatures in the range of from 50 to 1500C, and preferably at temperatures in the range of from 75 to 115"C. Under these conditions, the selective hydrogenation reaction is over after about 3 to 7 hours.
The catalyst may be separated off by the method described in DT-AS 1,558,395.
The hydrogenation product is separated off from the reaction solution by treatment with steam or by pouring into methanol and is subsequently dried under reduced pressure at a temperature of approximately 70"C.
Qualitative and quantitative determination of the hydrogenated double bonds and double bonds still present in the copolymers hydrogenated in accordance with the invention is carried out by IR-spectroscopic analysis. For further characterisation the iodine number and the glass transition temperature of the hydrogenation products are determined (in case of the glass transition temperature by thermomechanical analysis (TMA) and shear modulus measurement); The copolymers hydrogenated by the process according to the invention show increased tensile strength for increased elongation at break and. in addition. improved elasticity.
They are vulcanisable rubbers which may be used as temperature-resistant materials, for example in the sealing field.
Three different acrylonitrile-butadiene copolymers are used in the following Examples.
The percentages quoted are always per cent by weight.
The quantities of catalysts and triphenyl phosphine quoted in the Examples are based in each case on the dissolved copolymer.
Copolymer I: of 82% of butadiene and 18% of acrylonitrile Copolymer II: of 72% of butadiene and 28% of acrylonitrile Copolymer III: of 62% of butadiene and 38% of acrylonitrile (based in each case on the copolymer total).
Example 1 1% of [(C6H5)3P]3 RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer I in chlorobenzene, followed by hydrogenation for 5.5 hours at 100 C/60 atms.
On completion of hydrogenation, the catalyst is separated off in accordance with DT-AS 1,558,395. The reaction products are precipitated by pouring the reaction solution into methanol, and are subsequently dried under reduced pressure at approximately 70 C.
The hydrogenation product obtained has the following properties: Degree of hydrogenation: 100% of the vinyl and 100% of the trans-double bonds Glass transition temperature: Tg = -31 C Iodine Number: INo. = 14 The hydrogenation products of the following Examples are worked up and characterised in the same way as described in Example 1.
Example 2 1% of [(C6H5)3P]RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer II in chlorobenzene, followed by hydrogenation for 4.5 hours at 100 C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of the vinyl and 100% of the trans-double bonds Glass transition temperature: Tg = -30 C Iodine Number: INo. = 26 Example 3 1% of [(C6H5)3P]3 RhlllCl3 and 10% of (C6Hs)3P are added to a 2.5% solution of copolymer II in chlorobenzene, followed by hydrogenation for 5.5 hours at 1000C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of the vinyl- and 100% of the trans-double bonds Glass transition temperature: Ta -30 C Iodine number: o. = 22 Example 4 1% of [(C6H5)3P]3Rh'Cl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer III in chlorobenzene, followed by hydrogenation for 6 hours at 1000C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of the vinyl- and 100% of the trans-double bonds Glass transition temperature: Tg = -27 C Iodine Number: INo. = 22 Example 5 1% of [(C6H5)3P]3 RhICl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer I in the toluene, followed by hydrogenation for 4.5 hours at 100 C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of the vinyl- and 48% of the trans-double bond Glass transition temperature: Tg = -43 C Iodine Number: INo. = 50 Example 6 1% of [(C6H5)3P]3 RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer II in the toluene, followed by hydrogenation for 5.2 hours at 100 C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of the vinyl- and 42% of the trans-double bonds Glass transition temperature: Tg = -26 C Iodine Number: INo. = 95 Example 7 1% of [(C6H5)3P]3 RhICl and 10% (C6H5)3P are added to a 2.5% solution of copolymer III in toluene, followed by hydrogenation for 5 hours at 100 C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of the vinyl- and 30% of the trans-double bonds Glass transition temperature: Tg = -26 C Iodine number: INo. = 60 Example 8 1% of [(CH3)2S=0]3 RhIIICl3 and 10% of (CH3)2S=0 are added to a 2.5% solution of copolymer II in chlorobenzene, followed by hydrogenation for 7.5 hours at 1000C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of the vinyl- and 100% of the trans-double bonds Glass transition temperature: T = -290C Iodine number: INo. = 29 Example 9 1% of [(C6H5)3P]3 RhIIICl3 and 10% of (C6H5)3P are added to a 2.5% solution of copolymer II in benzene, followed by hydrogenation for 6.2 hours at 100 C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of the vinyl- and 90% of the trans-double bonds Glass transition temperature: Ta = -30 C Iodine number: INo. = 19 Example 10 1% of [(C6H5)3P]3 RhlCl and 10% of (C6H5)P are added to a 2.5% solution of copolymer II in ethyl acetate, followed by hydrogenation for 5.5 hours at 1000C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of the vinyl- and 50% of the trans-double bonds Glass transition temperature: T = -38 C Iodine number: INo. = 77 Example 11 1% of [(C6H5)3P]3 RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer II in methyl ethyl ketone, followed by hydrogenation for 6 hours at 100 C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of the vinyl- and 40% of the trans-double bonds Glass transition temperature: Tg = -39 C Iodine number: INo. = 119 Example 12 1% of [C6G5)3P]3 RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer II in xylene, followed by hydrogenation for 6.5 hours at 100 C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of the vinyl- and 59% of the trans-double bonds Glass transition temperature: T = -39 C Iodine number: INo. = 73 Example 13 1% of [(C6H5)3P]3 RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer II in dimethyl formamide, followed by hydrogenation for 4 hours at 100 C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of vinyl- and 59% of the trans-double bonds Glass transition temperature: Tg = -42 C Iodine number: INo. = 144 Example 14 1% of [(C6H5)3P]3 RhCl and 1 % of (C6H5)3P are added to a 2.5% solution of copolymer II in cyclohexanone, followed by hydrogenation for 4 hours at 100 C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of vinyl- and 38% of the trans-double bonds Glass transition temperature: Tg = -41 C Iodine number: INo. = 114 Example 15 1% of[C6H5)3P]3 RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer II in tetrahydrofuran, followed by hydrogenation for 3.2 hours at 100 C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of the vinyl- and 31% of the trans-double bonds Glass transition temperature: Tg = -39 C Iodine number: INo. = 113 Example 16 1% of [(C6H5)3P]3 RhCl and 10% of (C6H5)3P are added to a 2.5% solution of copolymer II in methylene chloride, followed by hydrogenation for 6.5 hours at 100 C/60 atms.
The hydrogenation product has the following properties: Degree of hydrogenation: 100% of the vinyl- and 12% of the trans-double bonds Glass transition temperature: Tg = -40 C Iodine number: INo. = 160 The results of Examples 1 to 16 are summarized in Table 1 below: TABLE 1 Co- Degree of hydrogenation(%) Example polymer Solvent Catalyst vinyl- trans-double bonds Tg INo.
1 I chlorobenzene [(C6H5)3P]3RhICl 100 100 -31 14 2 II " " 100 100 -30 26 3 II " [(C6H5)3P]RhIIICl3 100 100 -30 22 4 III " [(C6H5)3P]3RhICl 100 100 -27 22 5 I toluene " " 100 48 - 43 50 6 II " " 100 42 -26 95 7 III " " 100 38 -26 60 8 II chlorobenezene [(CH3)2S=0]3RhIIICl3 100 100 -29 29 9 II benzene [(C6H5)3P]3RhIIICl3 100 90 -30 19 10 II ethyl acetate [(C6H5)3P[3RhICl 100 50 -38 77 11 II methyl ethyl " 100 40 -39 119 ketone 12 II xylene " 100 59 -39 73 13 II dimethyl " 100 59 -42 144 formamide 14 II cyclohexanone " 100 38 -41 114 15 II tetrahydrofuran " 100 31 -39 113 16 II methylene " 100 12 -40 160 chloride

Claims (12)

WHAT WE CLAIM IS:
1. A process for the selective hydrogenation of the vinyl groups and trans-configuration double bonds in a copolymer of an a,ss-unsaturated carboxylic acid or a derivative thereof and an unsaturated hydrocarbon containing conjugated double bonds, the back-bone of the copolymer consisting entirely of carbon atoms, which comprises hydrogenating a 1 to 20% solution of the copolymer in an organic solvent at a temperature of from 50 to 1500C and at pressure of from 5 to 300 atmospheres in the presence of from 0.01 to 10% by weight of a complex of a monovalent or trivalent rhodium halide as a catalyst and, optionally, from 5 to 25% by weight of the ligand bound in the complex (based in each case on the dissolved copolymer).
2. A process as claimed in Claim 1, wherein the solvent is a chlorine-substituted aromatic solvent with from 6 to 12 carbon atoms, and the vinyl groups and the trans-configuration double bonds are completely hydrogenated in a selective manner.
3. A process as claimed in Claim 1, wherein the solvent is toluene, benzene, ethyl acetate, methyl ethyl ketone, xylene, dimethyl formamide, cyclohexanone, tetrahydrofuran or methylene chloride, and from 10 and 90% of the trans-configuration double bonds, in addition to the vinyl groups, are hydrogenated, depending upon the solvent used.
4. A process as claimed in any of Claims 1 to 3, wherein the copolymer to be hydrogenated is a copolymer of (meth)acrylic acid, an ester or amide thereof or (meth)acrylonitrile, with butadiene, isoprene, dimethyl butadiene or piperylene.
5. A process as claimed in any of Claims 1 to 4, wherein the copolymer is a butadiene-acrylonitrile copolymer of from 90 to 45% by weight of butadiene and from 10 to 55% by weight of acrylonitrile (based in each case on the copolymer total).
6. A process as claimed in any of claims 1 to 5, wherein the complex corresponds to the general formula (I): (RmB)3 Rh Xn (I) in which R = C-C8 alkyl, C6-C15 aryl or C7C15 aralkyl, B = P, As, S or S=0, X = Cl or Br, m = 2 or 3, and n = 1 or 3.
7. A process as claimed in any of Claims 1 to 6, wherein the hydrogenation is carried out in the presence of from 0.1 to 5% of the complex.
8. A process as claimed in any of Claims 1 to 7, wherein the hydrogenation temperature is from 75 to 1150C.
9. A process as claimed in any of Claims 1 to 8, wherein the hydrogenation pressure is from 50 to 100 atmospheres.
10. A process as claimed in any of claims 1 to 9, wherein the rhodium complex has sulphur-containing ligands.
11. A process as claimed in Claim 1, substantially as herein described with reference to any of the specific Examples.
12. A copolymer when hydrogenated by a process as claimed in any of Claims 1 to 11.
GB3596976A 1975-09-03 1976-08-31 Hydrogenation of polymers Expired GB1558491A (en)

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Cited By (76)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3229871A1 (en) * 1981-08-11 1983-02-24 Nippon Zeon Co., Ltd., Tokyo OIL-RESISTANT RUBBER COMPOSITION
DE3232692A1 (en) * 1981-09-02 1983-03-17 Nippon Zeon Co., Ltd., Tokyo CO-VULCANIZABLE RUBBER COMPOSITION
DE3248378A1 (en) * 1981-12-28 1983-07-14 Nippon Zeon Co., Ltd., Tokyo Oil- and degradation-resistant rubber article
GB2123837A (en) * 1982-07-13 1984-02-08 Bayer Ag Shaped articles for use in the exploration for and/or production of petroleum and natural gas
US4581417A (en) * 1983-08-19 1986-04-08 Bayer Aktiengesellschaft Production of hydrogenated nitrile rubbers
US4675248A (en) * 1983-10-29 1987-06-23 Bayer Aktiengesellschaft Polymer mixtures and co-vulcanizates produced therefrom
AU567132B2 (en) * 1982-12-08 1987-11-12 Polysar Ltd. Sulphur vulcanizable nitrile rubber composition
EP0270020A2 (en) * 1986-12-01 1988-06-08 Polysar Limited Resin cure
US4812528A (en) * 1987-07-06 1989-03-14 University Of Waterloo Polymer hydrogenation process
US4857632A (en) * 1988-06-13 1989-08-15 Polysar Limited Residue removal process
EP0111412B1 (en) * 1982-12-08 1989-08-30 Polysar Limited Polymer hydrogenation process
US4876314A (en) * 1988-11-09 1989-10-24 Shell Oil Company Hydrogenation process
US4879349A (en) * 1987-11-05 1989-11-07 Shell Oil Company Selective hydrogenation process
US4879352A (en) * 1988-12-30 1989-11-07 Polysar Limited Adducts of an aminoalcohol and nitrile rubber
US4892928A (en) * 1988-10-12 1990-01-09 Shell Oil Company Hydrogenation process
US4914160A (en) * 1988-06-23 1990-04-03 Hormoz Azizian Deuteration of unsaturated polymers and copolymers
US4944926A (en) * 1988-08-01 1990-07-31 Polysar Limited Method to treat rhodium-containing solutions
US4970254A (en) * 1988-09-22 1990-11-13 Shell Oil Company Method for hydrogenating functionalized polymer and products thereof
US4978771A (en) * 1985-11-19 1990-12-18 Bayer Aktiengesellschaft Process for the selective hydrogenation of unsatuated compounds
US4985540A (en) * 1989-11-20 1991-01-15 Polysar Limited Process for removing rhodium-containing catalyst residue from hydrogenated nitrile rubber
US5001199A (en) * 1987-11-05 1991-03-19 Shell Oil Company Selective hydrogenation process
US5030779A (en) * 1989-06-08 1991-07-09 Shell Oil Company Hydrogenation catalyst and hydrogenation process wherein said catalyst is used
US5057581A (en) * 1990-05-02 1991-10-15 University Of Waterloo Polymer hydrogenation process
US5057582A (en) * 1988-12-23 1991-10-15 Shell Oil Company Hydrogenation catalyst and hydrogenation process wherein said catalyst is used
US5075388A (en) * 1990-12-13 1991-12-24 Rempel Garry L Amine modified hydrogenation of nitrile rubber
US5208296A (en) * 1992-09-02 1993-05-04 Polysar Rubber Corporation Nitrile rubber hydrogenation
US5210151A (en) * 1992-09-02 1993-05-11 Polysar Rubber Corporation Hydrogenation of nitrile rubber
US5241013A (en) * 1992-09-02 1993-08-31 Polysar Rubber Corporation Catalytic hydrogenation of nitrile rubber
US5244965A (en) * 1988-01-19 1993-09-14 Polysar Limited Polymer solution treatment process
US5258467A (en) * 1992-09-02 1993-11-02 Polysar Rubber Corporation Catalytic solution hydrogenation of nitrile rubber
USRE34548E (en) * 1985-11-19 1994-02-15 Bayer Aktiengesellschaft Process for the selective hydrogenation of unsaturated compounds
US5314741A (en) * 1992-10-07 1994-05-24 The Goodyear Tire & Rubber Company Rubber article having protective coating
US6214922B1 (en) 1998-03-06 2001-04-10 Bayer Inc. Nitrile polymer vulcanizate and process for the production thereof
US6307624B1 (en) 1997-08-21 2001-10-23 Bayer Ag Process for the preparation of partially hydrogenated acrylonitrile-butadiene rubbers (HNBR) with on-line application of Raman spectroscopy
EP1219640A2 (en) * 2000-12-28 2002-07-03 Bayer Inc. Hydrogenation of nitrile rubber
WO2002100905A1 (en) 2001-06-12 2002-12-19 Bayer Inc. Process for the preparation of low molecular weight hydrogenated nitrile rubber
US6538071B1 (en) 1999-09-07 2003-03-25 Bayer Aktiengesellschaft Rubber mixtures for roller coatings
US6573333B2 (en) 2000-08-22 2003-06-03 Bayer Aktiengesellschaft Mixtures of olefin polymers and nitrile rubbers
US6646059B2 (en) 2000-11-06 2003-11-11 Bayer Inc. Process for removing iron-and rhodium-containing catalyst residues from hydrogenated nitrile rubber
WO2004113389A2 (en) * 2003-06-26 2004-12-29 Versamatrix A/S High capacity poly(alkylene)glycol based amino polymers
US6844412B2 (en) 2002-07-25 2005-01-18 Lord Corporation Ambient cured coatings and coated rubber products therefrom
US6929769B2 (en) 2002-01-23 2005-08-16 Bayer Aktiengesellschaft Nitrile rubber mixtures with a low tendency towards mold contamination
US6946526B2 (en) 2002-01-31 2005-09-20 Bayer Inc. Nitrile polymer vulcanizate and process for the production thereof
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US7091284B2 (en) 2000-08-25 2006-08-15 Bayer Ag Hydrogenated nitrile rubbers with improved low-temperature properties
US7265185B2 (en) * 2000-04-10 2007-09-04 Lanxess Inc. Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses
US7345115B2 (en) * 2005-03-18 2008-03-18 Lanxess Inc. Organic solvent-free hydrogenation of diene-based polymers
US7385010B2 (en) * 2005-03-18 2008-06-10 Lanxess Inc. Hydrogenation of diene-based polymer latex
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US7579410B2 (en) 2004-02-23 2009-08-25 Lanxess Inc. Process for the preparation of low molecular weight nitrile rubber
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US11286325B2 (en) 2017-12-21 2022-03-29 Arlanxeo Deutschland Gmbh Nitrile-diene-carboxylic acid ester copolymers
US11311868B2 (en) 2018-07-23 2022-04-26 Arlanxeo Deutschland Gmbh Use of catalysts for the metathesis of nitrile rubber
US11407843B2 (en) 2017-12-08 2022-08-09 Arlanxeo Deutschland Gmbh Process for producing nitrile rubbers using ruthenium complex catalysts
CN115505053A (en) * 2022-10-19 2022-12-23 中国科学院青岛生物能源与过程研究所 Hydrogenated butadiene-valeronitrile rubber and preparation method and application thereof
US11673130B2 (en) 2018-12-12 2023-06-13 Arlanxeo Deutschland Gmbh Catalyst system containing a metathesis catalyst and at least one phenolic compound and a process for metathesis of nitrile-butadiene rubber (NBR) using the catalyst system
US11827726B2 (en) 2018-12-17 2023-11-28 Arlanxeo Deutschland Gmbh Process for producing PEG acrylate-HNBR copolymer
US11958924B2 (en) 2018-12-17 2024-04-16 Arlanxeo Deutschland Gmbh Process for preparing HNBR solutions with alternative solvents

Families Citing this family (79)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54132647A (en) * 1978-04-06 1979-10-15 Nippon Zeon Co Ltd Vulcanizable rubber composition having improved ozon crack and oil resistance
GB2070023B (en) * 1980-02-25 1984-10-24 Johnson Matthey Co Ltd Hydrogenation process
JPS5876436A (en) * 1981-11-02 1983-05-09 Nippon Zeon Co Ltd Deterioration-resistant rubber member
DE3618907A1 (en) * 1986-06-05 1987-12-10 Bayer Ag COMPOSITIONS FROM PRE-TREATED FIBER MATERIAL AND VOLCANISES FROM HNBR
JPS6451405A (en) * 1987-08-24 1989-02-27 Mitsubishi Chem Ind Hydrogenation of unsaturated nitrile polymer
US5093426A (en) * 1988-10-22 1992-03-03 Japan Synthetic Rubber Co., Ltd. Hydrogenated copolymer rubber, rubber composition comprising said rubber and rubber product obtained from the rubber
DE3921263A1 (en) * 1989-06-29 1991-01-24 Bayer Ag METHOD FOR SELECTIVELY HYDROGENATING OILefINS CONTAINING NITRILE GROUPS
DE4032597A1 (en) * 1990-10-13 1992-04-16 Bayer Ag RECOVERY OF HYDRATION CATALYSTS FROM SOLUTIONS OF HYDRATED NITRILE RUBBER
US6777026B2 (en) 2002-10-07 2004-08-17 Lord Corporation Flexible emissive coatings for elastomer substrates
DE10212702A1 (en) * 2002-03-21 2003-10-09 Stockhausen Chem Fab Gmbh Basic polymer obtained by hydrogenation
CA2487744A1 (en) 2004-11-18 2006-05-18 Lanxess Inc. Peroxide curable rubber composition comprising hnbr
EP1760093B1 (en) 2005-08-30 2011-12-21 LANXESS Deutschland GmbH Use of catalysts for the metathesis degradation of nitrile rubber
DE102005042265A1 (en) 2005-09-06 2007-03-08 Lanxess Deutschland Gmbh Crosslinkable compositions, thermoplastic elastomers obtainable therefrom and their use
DE102005047115A1 (en) 2005-09-30 2007-04-05 Lanxess Deutschland Gmbh Crosslinkable compositions, processes for their preparation and their use
DE102005061627A1 (en) * 2005-12-21 2007-06-28 Lanxess Deutschland Gmbh Synthetic rubber with narrow molecular weight distribution, a process for its preparation and its use
DE102005061628A1 (en) 2005-12-21 2007-06-28 Lanxess Deutschland Gmbh Hydrogenated nitrile rubber with narrow molecular weight distribution, a process for its preparation and its use
DE102006008521A1 (en) 2006-02-22 2007-08-23 Lanxess Deutschland Gmbh Use of a specified ruthenium or osmium catalyst in the metathesis of nitrile rubbers results in improvements in activity and in gel prevention
DE102006008520A1 (en) 2006-02-22 2007-08-23 Lanxess Deutschland Gmbh New catalyst system comprising a metathesis catalyst and a salt of a mono-, di- or tri-valent cation other than copper, used for metathesis reactions, e.g. for the degradation of nitrile rubber
WO2007102827A1 (en) 2006-03-09 2007-09-13 Ticona Llc Flexible, hydrocarbon-resistant polyarylenesulfide compounds and articles
US8877306B2 (en) 2006-03-09 2014-11-04 Manoj Ajbani Compatibalized blends of polyphenylene sulfide and thermoplastic vulcanizate
US7666950B2 (en) 2006-06-01 2010-02-23 Lanxess Deutschland Gmbh Process for preparing hydrogenated nitrile rubbers
DE102006040569A1 (en) 2006-08-30 2008-03-06 Lanxess Deutschland Gmbh Process for the metathesis degradation of nitrile rubbers
DE102007024010A1 (en) 2007-05-22 2008-11-27 Lanxess Deutschland Gmbh nitrile rubbers
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DE102007039695A1 (en) 2007-08-22 2009-02-26 Lanxess Deutschland Gmbh New ruthenium- and osmium-carbene-complex catalysts, which are bonded with chiral carbon atoms or over double bonds at a catalyst base skeleton, useful e.g. in metathesis-reactions, preferably in ring closing metathesis reactions
DE102007039525A1 (en) 2007-08-21 2009-02-26 Lanxess Deutschland Gmbh Process for metathesis degradation of nitrile rubber
EP2027920B1 (en) 2007-08-21 2014-10-08 LANXESS Deutschland GmbH Catalysts for metathesis reactions
EP2028194B1 (en) 2007-08-21 2010-05-12 Lanxess Deutschland GmbH Metathesis of nitrile rubbers in the presence of transition metal complex catalysts
DE102007039526A1 (en) 2007-08-21 2009-02-26 Lanxess Deutschland Gmbh Catalyst systems and their use for metathesis reactions
EP2712809A1 (en) 2007-10-19 2014-04-02 Lord Corporation Suspension system for aircraft auxilliary power unit with elastomeric member
US8623981B2 (en) 2008-01-29 2014-01-07 Lanxess Deutschland Gmbh Nitrile rubbers which optionally contain alkylthio terminal groups and which are optionally hydrogenated
EP2147721A1 (en) 2008-07-08 2010-01-27 Lanxess Deutschland GmbH Catalyst systems and their use in metathesis reactions
EP2147932A1 (en) 2008-07-24 2010-01-27 LANXESS Inc. Process for the continuous hydrogenation of carbon-carbon double bonds in an unsaturated polymer to produce a hydrogenated polymer
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EP2554558A1 (en) 2011-08-02 2013-02-06 Lanxess Deutschland GmbH Method for producing nitrile rubbers in organic solvents
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EP3784390A1 (en) 2018-04-27 2021-03-03 ARLANXEO Deutschland GmbH Use of ruthenium and osmium catalysts for the metathesis of nitrile rubber
EP3827029A1 (en) 2018-07-23 2021-06-02 ARLANXEO Deutschland GmbH Method for producing hydrogenated nitrile rubber and hnbr compositions thereof
JP7434277B2 (en) 2018-07-23 2024-02-20 アランセオ・ドイチュランド・ゲーエムベーハー Hydrogenation of nitrile rubber
WO2020126343A1 (en) 2018-12-19 2020-06-25 Arlanxeo Deutschland Gmbh Electrode composition for a cathode of a cell of a lithium-ion battery, a cathode slurry composition, a cathode and the battery incorporating it

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3700637A (en) * 1970-05-08 1972-10-24 Shell Oil Co Diene-nitrile rubbers
US3898208A (en) * 1971-06-21 1975-08-05 Dow Chemical Co Hydrogenation of oil-insoluble diene polymers
DE2303753A1 (en) * 1972-01-31 1973-08-09 Schwermasch Liebknecht Veb K Sealing cpds - with good oil resistance based on butadiene -acrylonitrile rubber

Cited By (96)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3229871A1 (en) * 1981-08-11 1983-02-24 Nippon Zeon Co., Ltd., Tokyo OIL-RESISTANT RUBBER COMPOSITION
DE3232692A1 (en) * 1981-09-02 1983-03-17 Nippon Zeon Co., Ltd., Tokyo CO-VULCANIZABLE RUBBER COMPOSITION
DE3248378A1 (en) * 1981-12-28 1983-07-14 Nippon Zeon Co., Ltd., Tokyo Oil- and degradation-resistant rubber article
GB2123837A (en) * 1982-07-13 1984-02-08 Bayer Ag Shaped articles for use in the exploration for and/or production of petroleum and natural gas
AU567132B2 (en) * 1982-12-08 1987-11-12 Polysar Ltd. Sulphur vulcanizable nitrile rubber composition
EP0111412B1 (en) * 1982-12-08 1989-08-30 Polysar Limited Polymer hydrogenation process
US4581417A (en) * 1983-08-19 1986-04-08 Bayer Aktiengesellschaft Production of hydrogenated nitrile rubbers
US4675248A (en) * 1983-10-29 1987-06-23 Bayer Aktiengesellschaft Polymer mixtures and co-vulcanizates produced therefrom
US4978771A (en) * 1985-11-19 1990-12-18 Bayer Aktiengesellschaft Process for the selective hydrogenation of unsatuated compounds
USRE34548E (en) * 1985-11-19 1994-02-15 Bayer Aktiengesellschaft Process for the selective hydrogenation of unsaturated compounds
EP0270020A2 (en) * 1986-12-01 1988-06-08 Polysar Limited Resin cure
US4774288A (en) * 1986-12-01 1988-09-27 Polysar Limited Resin cure system for hydrogenated nitrile polymer
EP0270020A3 (en) * 1986-12-01 1988-10-05 Polysar Limited Resin cure
US4812528A (en) * 1987-07-06 1989-03-14 University Of Waterloo Polymer hydrogenation process
US4879349A (en) * 1987-11-05 1989-11-07 Shell Oil Company Selective hydrogenation process
US5001199A (en) * 1987-11-05 1991-03-19 Shell Oil Company Selective hydrogenation process
US5244965A (en) * 1988-01-19 1993-09-14 Polysar Limited Polymer solution treatment process
US4857632A (en) * 1988-06-13 1989-08-15 Polysar Limited Residue removal process
US4914160A (en) * 1988-06-23 1990-04-03 Hormoz Azizian Deuteration of unsaturated polymers and copolymers
US4944926A (en) * 1988-08-01 1990-07-31 Polysar Limited Method to treat rhodium-containing solutions
US4970254A (en) * 1988-09-22 1990-11-13 Shell Oil Company Method for hydrogenating functionalized polymer and products thereof
US4892928A (en) * 1988-10-12 1990-01-09 Shell Oil Company Hydrogenation process
US4980331A (en) * 1988-11-09 1990-12-25 Shell Oil Company Hydrogenation catalyst and hydrogenation process wherein said catalyst is used
US4876314A (en) * 1988-11-09 1989-10-24 Shell Oil Company Hydrogenation process
US5057582A (en) * 1988-12-23 1991-10-15 Shell Oil Company Hydrogenation catalyst and hydrogenation process wherein said catalyst is used
US4879352A (en) * 1988-12-30 1989-11-07 Polysar Limited Adducts of an aminoalcohol and nitrile rubber
US5030779A (en) * 1989-06-08 1991-07-09 Shell Oil Company Hydrogenation catalyst and hydrogenation process wherein said catalyst is used
US4985540A (en) * 1989-11-20 1991-01-15 Polysar Limited Process for removing rhodium-containing catalyst residue from hydrogenated nitrile rubber
US5057581A (en) * 1990-05-02 1991-10-15 University Of Waterloo Polymer hydrogenation process
US5075388A (en) * 1990-12-13 1991-12-24 Rempel Garry L Amine modified hydrogenation of nitrile rubber
US5241013A (en) * 1992-09-02 1993-08-31 Polysar Rubber Corporation Catalytic hydrogenation of nitrile rubber
US5208296A (en) * 1992-09-02 1993-05-04 Polysar Rubber Corporation Nitrile rubber hydrogenation
US5258467A (en) * 1992-09-02 1993-11-02 Polysar Rubber Corporation Catalytic solution hydrogenation of nitrile rubber
US5210151A (en) * 1992-09-02 1993-05-11 Polysar Rubber Corporation Hydrogenation of nitrile rubber
US5314741A (en) * 1992-10-07 1994-05-24 The Goodyear Tire & Rubber Company Rubber article having protective coating
US6307624B1 (en) 1997-08-21 2001-10-23 Bayer Ag Process for the preparation of partially hydrogenated acrylonitrile-butadiene rubbers (HNBR) with on-line application of Raman spectroscopy
US6451902B2 (en) 1998-03-06 2002-09-17 Bayer Inc. Nitrile polymer vulcanizate and process for the production thereof
US6214922B1 (en) 1998-03-06 2001-04-10 Bayer Inc. Nitrile polymer vulcanizate and process for the production thereof
US6538071B1 (en) 1999-09-07 2003-03-25 Bayer Aktiengesellschaft Rubber mixtures for roller coatings
US7265185B2 (en) * 2000-04-10 2007-09-04 Lanxess Inc. Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses
US6765064B2 (en) 2000-08-22 2004-07-20 Bayer Aktiengesellschaft Mixtures of olefin polymers and nitrile rubbers
US6573333B2 (en) 2000-08-22 2003-06-03 Bayer Aktiengesellschaft Mixtures of olefin polymers and nitrile rubbers
US7091284B2 (en) 2000-08-25 2006-08-15 Bayer Ag Hydrogenated nitrile rubbers with improved low-temperature properties
US6646059B2 (en) 2000-11-06 2003-11-11 Bayer Inc. Process for removing iron-and rhodium-containing catalyst residues from hydrogenated nitrile rubber
US6683136B2 (en) 2000-12-28 2004-01-27 Bayer Inc. Epoxidized soybean oil enhanced hydrogenation of nitrile copolymer
EP1219640A3 (en) * 2000-12-28 2002-11-13 Bayer Inc. Hydrogenation of nitrile rubber
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US7037982B2 (en) 2001-01-17 2006-05-02 Bayer Aktiengesellschaft Rubber mixtures for roll coverings
US6673881B2 (en) 2001-06-12 2004-01-06 Bayer Inc. Process for the preparation of low molecular weight hydrogenated nitrile rubber
WO2002100905A1 (en) 2001-06-12 2002-12-19 Bayer Inc. Process for the preparation of low molecular weight hydrogenated nitrile rubber
US6929769B2 (en) 2002-01-23 2005-08-16 Bayer Aktiengesellschaft Nitrile rubber mixtures with a low tendency towards mold contamination
US6946526B2 (en) 2002-01-31 2005-09-20 Bayer Inc. Nitrile polymer vulcanizate and process for the production thereof
US6844412B2 (en) 2002-07-25 2005-01-18 Lord Corporation Ambient cured coatings and coated rubber products therefrom
WO2004113389A2 (en) * 2003-06-26 2004-12-29 Versamatrix A/S High capacity poly(alkylene)glycol based amino polymers
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US7579410B2 (en) 2004-02-23 2009-08-25 Lanxess Inc. Process for the preparation of low molecular weight nitrile rubber
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US9321910B2 (en) 2005-12-14 2016-04-26 Lanxess Deutschland Gmbh Microgel-containing vulcanizable composition based on hydrogenated nitrile rubber
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US8664315B2 (en) 2008-01-29 2014-03-04 Lanxess Deutschland Gmbh Nitrile rubbers which optionally contain alkylthio terminal groups and which are optionally hydrogenated
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US9598506B2 (en) 2011-10-21 2017-03-21 Arlanxeo Deutschland Gmbh Catalyst compositions and their use for hydrogenation of nitrile rubber
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US9494262B2 (en) 2012-04-13 2016-11-15 Ticona Llc Automotive fuel lines including a polyarylene sulfide
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US11091577B2 (en) 2015-05-26 2021-08-17 Zeon Corporation Nitrile group-containing highly saturated copolymer rubber
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IT1121670B (en) 1986-04-10
JPS5232095A (en) 1977-03-10
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FR2322878A1 (en) 1977-04-01

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