CN100526353C - 制备低分子量氢化丁腈橡胶的方法 - Google Patents
制备低分子量氢化丁腈橡胶的方法 Download PDFInfo
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- CN100526353C CN100526353C CNB2005800057615A CN200580005761A CN100526353C CN 100526353 C CN100526353 C CN 100526353C CN B2005800057615 A CNB2005800057615 A CN B2005800057615A CN 200580005761 A CN200580005761 A CN 200580005761A CN 100526353 C CN100526353 C CN 100526353C
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 229920013649 Paracril Polymers 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical group ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- -1 sulphinyl Chemical group 0.000 claims description 4
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
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- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 241000370738 Chlorion Species 0.000 claims 1
- 239000012442 inert solvent Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 10
- 238000005649 metathesis reaction Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011089 mechanical engineering Methods 0.000 abstract description 2
- 229910052762 osmium Inorganic materials 0.000 abstract description 2
- 150000002825 nitriles Chemical class 0.000 description 13
- 239000000126 substance Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
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- 229920001971 elastomer Polymers 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- 206010011416 Croup infectious Diseases 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 201000010549 croup Diseases 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- FCHGUOSEXNGSMK-UHFFFAOYSA-N 1-tert-butylperoxy-2,3-di(propan-2-yl)benzene Chemical class CC(C)C1=CC=CC(OOC(C)(C)C)=C1C(C)C FCHGUOSEXNGSMK-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- UDQCDDZBBZNIFA-UHFFFAOYSA-N 4-methyl-1,3-dihydrobenzimidazole-2-thione Chemical compound CC1=CC=CC2=C1NC(=S)N2 UDQCDDZBBZNIFA-UHFFFAOYSA-N 0.000 description 1
- CWIYBOJLSWJGKV-UHFFFAOYSA-N 5-methyl-1,3-dihydrobenzimidazole-2-thione Chemical compound CC1=CC=C2NC(S)=NC2=C1 CWIYBOJLSWJGKV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HIJXATGBSXFXCG-UHFFFAOYSA-N C1(=CC=CC=C1)C(Cl)Cl.[Ru] Chemical compound C1(=CC=CC=C1)C(Cl)Cl.[Ru] HIJXATGBSXFXCG-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010077 mastication Methods 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001639 phenylmethylene group Chemical group [H]C(=*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000013031 physical testing Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 125000005590 trimellitic acid group Chemical group 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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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
- 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
- C08F236/12—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 with nitriles
-
- 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
- C08C19/08—Depolymerisation
-
- 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
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/42—Nitriles
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
通过在氢气和任选的至少一种共烯烃的存在下进行一种方法来制备比现有技术中已知的那些具有更低分子量和更窄分子量分布的氢化丁腈橡胶聚合物。根据该方法，让底物同时进行复分解反应和氢化反应。反应在亚烷基钌或亚烷基锇基催化剂的存在下进行。生产的氢化丁腈橡胶的分子量(Mw)为20，000至250，000，门尼粘度(ML1+4，100℃)为1至50，以及MWD小于2.6。得到的氢化丁腈橡胶被用于机动车、电气、机械工程和造船工业。
Description
技术领域
本发明涉及一种用于生产比本领域中已知的那些具有更低分子量和更窄分子量分布的氢化丁腈橡胶聚合物的方法，其特征在于该方法在氢气和任选的至少一种共烯烃的存在下进行。
背景技术
氢化丁腈橡胶(HNBR)，其是通过丙烯腈-丁二烯橡胶(丁腈橡胶；NBR，包括至少一种共轭二烯、至少一种不饱和腈和任选另外的共聚单体的共聚物)的选择性加氢而制备的，是一种特殊的橡胶，其具有很好的耐热性、优异的耐臭氧性和耐化学性以及优异的耐油性。加上该橡胶的高水平机械性能(特别是高耐磨性)，HNBR已经在机动车(密封件、软管、轴承衬垫)、油(定子、井口密封件、阀片)、电气(电缆护套)、机械工程(轮子、辊)和造船(管道密封件、套管)工业等中得到广泛应用不令人惊讶。
可商购的HNBR的门尼粘度为55到105，分子量为200,000到500,000g/mol，多分散性大于3.0以及残余双键(RDB)含量为1到18％(根据IR光谱)。
加工HNBR中的一种限制为较高的门尼粘度。原则上，具有更低分子量和更低门尼粘度的HNBR将具有更好的可加工性。已经进行了多种尝试，通过素炼(机械分解)和通过化学方法(例如使用强酸)来降低聚合物分子量，但是此类方法具有一些缺点，它们导致在聚合物中引入官能团(例如羧酸和酯基)以及改变聚合物的微观构造。这一点在聚合物性能中产生不利的变化。另外，由于它们的特有性质，这些类型的方法从本质上产生具有宽分子量分布的聚合物。
使用现有技术难以制造具有低门尼粘度(<55)和改善的可加工性但具有与那些现有橡胶相同微观构造的氢化丁腈橡胶。将NBR氢化以生产HNBR导致原料聚合物的门尼粘度升高。这种门尼粘度升高比率(MIR)通常为大约2，取决于聚合物的品级、氢化程度和原料性质。此外，与NBR本身生产有关的限制决定了HNBR原料的低粘度范围。目前，可用的最低门尼粘度产品之一为
VP KA 8837(购自Bayer)，其门尼粘度为55(ML 1+4，在100℃下)以及RDB为18％。
同时未决申请PCT/CA 02/00967、PCT/CA 02/00966和PCT/CA02/00965公开了一种制备任选氢化的丁腈橡胶的方法，包括在至少一种共烯烃的存在下使丁腈橡胶反应。所述同时未决申请公开了可以在氢化和复分解反应中使用相同的催化剂。但是，本发明公开了复分解反应可以在氢气存在下进行。
发明概述
我们现已发现，可以通过在氢气和任选的至少一种共烯烃存在下使丁腈橡胶复分解来制备比本领域中已知的那些具有更低分子量和更窄分子量分布的氢化丁腈橡胶。由此，本发明的方法可以在一步中生产分子量(Mw)为20,000到250,000，门尼粘度(ML 1+4，在100℃下)为1到50以及MWD(或多分散指数)小于2.6的氢化丁腈橡胶。
发明描述
如贯穿本说明书使用的，术语“腈聚合物”用意是具有宽泛的含义并表示包括从至少一种共轭二烯、至少一种α，β-不饱和腈和任选另外的一种或多种可共聚单体衍生的重复单元的共聚物。
共轭二烯可以为任何已知的共轭二烯，特别是C4-C6共轭二烯。优选的共轭二烯为丁二烯、异戊二烯、间戊二烯、2，3-二甲基丁二烯及其混合物。更优选的C4-C6共轭二烯为丁二烯、异戊二烯及其混合物。最优选的C4-C6共轭二烯为丁二烯。
不饱和α，β-不饱和腈可以为任何已知的α，β-不饱和腈，特别是C3-C5 α，β-不饱和腈。优选的C3-C5 α，β-不饱和腈为丙烯腈、甲基丙烯腈、乙基丙烯腈及其混合物。最优选的C3-C5 α，β-不饱和腈为丙烯腈。
优选地，该共聚物包括40到85wt％的衍生自一种或多种共轭二烯的重复单元和15到60wt％的衍生自一种或多种不饱和腈的重复单元。更优选地，共聚物包括60到75wt％的衍生自一种或多种共轭二烯的重复单元和25到40wt％的衍生自一种或多种不饱和腈的重复单元。最优选地，共聚物包括60到70wt％的衍生自一种或多种共轭二烯的重复单元和30到40wt％的衍生自一种或多种不饱和腈的重复单元。
任选地，共聚物可以进一步包括衍生自一种或多种可共聚单体，例如不饱和羧酸的重复单元。适合的不饱和羧酸的非限制实例为富马酸、马来酸、丙烯酸、甲基丙烯酸及其混合物。从一种或多种可共聚单体衍生的重复单元将替代丁腈橡胶的腈或二烯烃部分，并且对于本领域技术人员显而易见的是上述数值必须被调整到结果为100wt％。在所述不饱和羧酸的情况下，丁腈橡胶优选包括占橡胶1到10wt％的衍生自一种或多种不饱和羧酸的重复单元，该量替代共轭二烯的对应量。这些共聚单体的存在似乎增强了复分解反应并使所述反应在0-50℃进行。
其它优选的任选另外的单体为不饱和单或二羧酸或其衍生物(例如酯、酰胺等)，包括其混合物。
根据本发明，使底物同时发生复分解反应和氢化反应。
本发明的方法在一种或多种以下通式I的化合物存在下进行，
结构式I
其中
M为Os或Ru，
R和R1独立地为氢或选自以下的烃基：C2-C20烯基、C2-C20炔基、C1-C20烷基、芳基、C1-C20羧酸根、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、芳氧基、C2-C20烷氧基羰基、C1-C20烷硫基、C1-C20烷基磺酰基和C1-C20烷基亚磺酰基，
X和X1独立地为任何阴离子配位体，
L为任何中性配位体，例如膦、胺、硫醚，
L1为咪唑烷亚基或咪唑烷或任何中性卡宾(carbine)，任选地L和L1可以彼此连接形成二齿中性配位体；
已知作为第二代格鲁布斯(Grubb)催化剂的结构式I的化合物，例如1，3-双-(2，4，6-三甲基苯基)-2-咪唑烷亚基)-(三环己基-膦)钌(苯基亚甲基)二氯化物是优选的。
催化剂化合物的量将取决于所述的化合物的性质和催化活性。典型地，化合物与NBR的比率为0.005到5，优选为0.025到1，以及更优选为0.1到0.5。
该方法可以在任何合适的溶剂中进行，所述溶剂不使催化剂钝化或以其它方式干涉反应。优选的溶剂包括但不限于二氯甲烷、苯、甲苯、四氢呋喃、甲基乙基酮、环己烷等。最优选的溶剂为一氯苯(MCB)。
反应混合物中NBR的浓度并非关键，但是显然，例如如果混合物过于粘稠以至不能被有效地搅拌，则应使得反应不被阻碍。优选地，NBR的浓度为1到40wt％，最优选为6到15wt％。
氢气的浓度通常为500psi到2000psi，优选为1000psi到1400
psi。
该方法优选在0到140℃；优选20到100℃的温度下进行。
反应时间将取决于许多因素，包括胶的浓度、使用的催化剂量和进行反应的温度。反应进程可以通过标准的分析技术，例如使用GPC或溶液粘度进行监测。贯穿说明书任何时候引用的聚合物的分子量分布是通过凝胶渗透色谱法(GPC)，使用Waters 2690分离模块和Waters410差示折光计，运行Waters Millenium软件版本3.05.01测定的。将试样溶于四氢呋喃(THF)，用0.025％ BHT稳定。用于测量的柱为三个顺序的来自Polymer Labs的混合-B凝胶柱。使用的参照标准为来自American Polymer Standards Corp.的聚苯乙烯标准样品。
本发明中的氢化优选被理解为，存在于起始腈聚合物中的大于50％的残余双键(RDB)被氢化，优选大于90％的RDB被氢化，更优选大于95％的RDB被氢化，以及最优选大于99％的RDB被氢化。
橡胶的门尼粘度可以使用ASTM测试D1646加以测定。
由于得到的HNBR的低粘度，理论上合适的是通过但不限于模塑注射技术进行加工。该聚合物也可以用于转移模塑、压缩模塑或液体注塑。
此外，本发明的聚合物很好地适合于制造成型制品，例如通过注塑技术制造的密封件、软管、轴承垫、定子、井口密封件、阀片、电缆护套、轮子、辊、管封件、就位衬垫或鞋衬部件。
实施例
实施例1-2
氯化三(三苯基膦)合铑(Wilkinson′s氢化催化剂)、二氯化[(苯基亚甲基)·(1，3-双-(2，4，6-三甲基苯基)-2-咪唑烷亚基)·(三环己基-膦)合钌](格鲁布斯第二代复分解催化剂)。三苯基膦(TPP)和一氯苯(MCB)分别购自JMI，Materia Inc.，Elf Atochem和PPG，并直接使用。
反应在2美制加仑高压帕尔(Parr)反应器中在以下条件下进行：
胶浓度 12wt.％
反应温度 参见表A
催化剂类型和填充量 参见表A
溶剂 一氯苯
底物 统计上的丁二烯-丙烯腈共聚物，
丙烯腈含量为34wt％和门尼粘度
ML(1+4)在100℃时为29单位
H2(g)压力 1200psi
搅拌器速率 600rpm
反应器温度 138℃
将胶在充分搅拌下用H2(100psi)脱气3次。使反应器温度升高到130℃，并将含有催化剂和三苯基膦(如果需要)的60mL一氯苯溶液加入反应器。使温度升高到138℃并在反应期间内保持恒定。通过在各种间隔下使用IR光谱测定残余双键(RDB)水平对氢化反应进行监测。
实施例1-2：细节
表1 氢化历程的对比
表2 HNBR性能概述
实施例3-4：过氧化物配方中的配混和物理测试
将聚合物复合材料在开口磨上混合。在分离的混合步骤中将固化剂添加到冷的开口磨上。该评价中使用的配方基于简化的过氧化物配方。
炭黑N 660 Sterling-V，购自Cabot Tire Blacks
D为MgO，购自C.P.Hall。
Plasthall TOTM为偏苯三甲酸三辛酯，购自C.P.Hall。
DIAK #7为三烯丙基异氰脲酸酯，购自DuPont Dow Elastomers。
Vulcup 40KE为2，2′-二(叔丁基过氧基二异丙基苯)，购自HarwickStandard。
表3 过氧化物硫化配方
聚合物复合材料性能的概要
表4表示实施例3和4的聚合物复合材料性能的概述。实施例4用于对比。MDR硫化特性为1.7Hz，1°弧，180℃，30分钟，100dNm。
表4 聚合物复合材料性能的概述
从表4，很清楚，虽然在聚合物复合材料3中使用的低门尼粘度的HNBR的分子量(Mw)仅为
A3406的分子量的66％，但是物理性能仍然很好。
Claims (4)
1.一种制备氢化丁腈橡胶的方法，包括在氢气存在下、在没有任何共烯烃存在下，以及在至少一种选自通式I的化合物存在下使丁腈橡胶反应，
结构式I
其中
M为Ru，
R和R1独立地为氢或选自以下的基团：C2-C20烯基、C2-C20炔基、C1-C20烷基、芳基、C1-C20羧酸根、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、芳氧基、C2-C20烷氧基羰基、C1-C20烷硫基、C1-C20烷基磺酰基和C1-C20烷基亚磺酰基，
X和X1为氯离子，
L为三烷基膦，
L1选自任何1，3-二取代的咪唑烷亚基或1，3-二取代的咪唑烷基配位体；
其中所述方法在一步中进行。
2.根据权利要求1的方法，其中L1为所述的咪唑烷亚基。
3.根据权利要求1或2的方法，其中式I的化合物与丁腈橡胶的比率为0.005至5。
4.根据权利要求1或2的方法，其中该方法在选自一氯苯、二氯甲烷、苯、甲苯、四氢呋喃和环己烷的惰性溶剂中进行。
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| CA002462005A CA2462005A1 (en) | 2004-02-23 | 2004-02-23 | Process for the preparation of low molecular weight hydrogenated nitrile rubber |
| CA2,462,005 | 2004-02-23 |
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| EP (1) | EP1720920B1 (zh) |
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| KR (1) | KR101236031B1 (zh) |
| CN (1) | CN100526353C (zh) |
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| CA (1) | CA2462005A1 (zh) |
| MX (1) | MXPA06009368A (zh) |
| PL (1) | PL1720920T3 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2350280A1 (en) | 2001-06-12 | 2002-12-12 | Bayer Inc. | Low molecular weight hydrogenated nitrile rubber |
| US6841623B2 (en) | 2001-06-29 | 2005-01-11 | Bayer Inc. | Low molecular weight nitrile rubber |
| EP1883658B2 (en) * | 2005-05-20 | 2016-01-27 | Bridgestone Corporation | Method for preparing low molecular weight polymers |
| DE102006008521A1 (de) * | 2006-02-22 | 2007-08-23 | Lanxess Deutschland Gmbh | Verwendung von Katalysatoren mit erhöhter Aktivität für die NBR-Metathese |
| DE102006040569A1 (de) * | 2006-08-30 | 2008-03-06 | Lanxess Deutschland Gmbh | Verfahren zum Metathese-Abbau von Nitrilkautschuken |
| DE102007039525A1 (de) * | 2007-08-21 | 2009-02-26 | Lanxess Deutschland Gmbh | Verfahren zum Metathese-Abbau von Nitrilkautschuk |
| EP2143489A1 (de) * | 2008-07-08 | 2010-01-13 | Lanxess Deutschland GmbH | Katalysator-Systeme und deren Verwendung für Metathese-Reaktionen |
| EP2147721A1 (de) * | 2008-07-08 | 2010-01-27 | Lanxess Deutschland GmbH | Katalysator-Systeme und deren Verwendung für Metathese-Reaktionen |
| EP2289620A1 (en) | 2009-08-31 | 2011-03-02 | LANXESS Deutschland GmbH | Process for the preparation of hydrogenated nitrile rubber |
| EP2289621A1 (en) * | 2009-08-31 | 2011-03-02 | LANXESS Deutschland GmbH | Process for the preparation of low molecular weight hydrogenated nitrile rubber |
| SG178464A1 (en) | 2009-08-31 | 2012-04-27 | Lanxess Deutschland Gmbh | Vulcanizable polymer composition comprising a low molecular weight optionally hydrogenated nitrile rubber |
| EP2289623A1 (en) | 2009-08-31 | 2011-03-02 | LANXESS Deutschland GmbH | Metathesis of nitrile rubbers in the presence of transition metal catalysts |
| WO2011079439A1 (en) * | 2009-12-30 | 2011-07-07 | Zannan Scitech Co., Ltd. | Highly active metathesis catalysts selective for romp and rcm reactions |
| WO2013056463A1 (en) | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
| WO2013056461A1 (en) * | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
| WO2013056400A1 (en) | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
| WO2013056459A1 (en) * | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
| CN104271607B (zh) * | 2012-04-28 | 2017-05-24 | 阿朗新科德国有限责任公司 | 丁腈橡胶的氢化 |
| WO2013159365A1 (en) | 2012-04-28 | 2013-10-31 | Lanxess Deutschland Gmbh | Hydrogenation of nitrile rubber |
| EP2676971B1 (en) | 2012-06-22 | 2015-04-08 | University Of Waterloo | Hydrogenation of a diene-based polymer latex |
| EP2676969B1 (en) | 2012-06-22 | 2016-06-01 | University Of Waterloo | Tandem metathesis and hydrogenation of diene-based polymers in latex |
| CN105542037B (zh) * | 2014-10-29 | 2017-08-25 | 中国石油化工股份有限公司 | 一种不饱和共聚物的加氢方法 |
| TWI566835B (zh) | 2014-12-25 | 2017-01-21 | 財團法人工業技術研究院 | 烯烴複分解觸媒及低分子量丁腈橡膠之製備方法 |
| CN107540765B (zh) * | 2016-06-24 | 2020-06-09 | 中国石油天然气股份有限公司 | 一种丁腈橡胶用阻燃型增塑剂的制备方法 |
| EP3827029A1 (en) | 2018-07-23 | 2021-06-02 | ARLANXEO Deutschland GmbH | Method for producing hydrogenated nitrile rubber and hnbr compositions thereof |
| CN114262394B (zh) * | 2020-09-16 | 2023-08-18 | 浙江赞昇新材料有限公司 | 液体氢化丁腈橡胶及其制备方法和应用 |
| JP2022131899A (ja) * | 2021-02-26 | 2022-09-07 | 横浜ゴム株式会社 | ホース用ゴム組成物及びホース |
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| DE19907519A1 (de) * | 1999-02-22 | 2000-08-31 | Basf Ag | Verfahren zur Herstellung von substituierten Olefinen |
| TW593386B (en) * | 2001-06-12 | 2004-06-21 | Bayer Inc | Process for the preparation of low molecular weight hydrogenated nitrile rubber |
| CA2350280A1 (en) * | 2001-06-12 | 2002-12-12 | Bayer Inc. | Low molecular weight hydrogenated nitrile rubber |
| CA2413636A1 (en) * | 2002-12-05 | 2004-06-05 | Bayer Inc. | Adhesive compositions |
| CA2413607A1 (en) * | 2002-12-05 | 2004-06-05 | Bayer Inc. | Process for the preparation of low molecular weight hydrogenated nitrile rubber |
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| PL1720920T3 (pl) | 2012-11-30 |
| JP2007534797A (ja) | 2007-11-29 |
| US20080214741A1 (en) | 2008-09-04 |
| EP1720920B1 (en) | 2012-06-13 |
| TW200604222A (en) | 2006-02-01 |
| WO2005080456A1 (en) | 2005-09-01 |
| EP1720920A4 (en) | 2010-07-28 |
| EP1720920A1 (en) | 2006-11-15 |
| JP4611371B2 (ja) | 2011-01-12 |
| TWI347328B (en) | 2011-08-21 |
| BRPI0507938B1 (pt) | 2016-01-12 |
| CA2462005A1 (en) | 2005-08-23 |
| CN1922224A (zh) | 2007-02-28 |
| BRPI0507938A (pt) | 2007-07-17 |
| KR20070032278A (ko) | 2007-03-21 |
| MXPA06009368A (es) | 2007-01-26 |
| US7585920B2 (en) | 2009-09-08 |
| KR101236031B1 (ko) | 2013-02-21 |
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