CN1590445A - 包含腈聚合物的丁基合成橡胶组合物 - Google Patents
包含腈聚合物的丁基合成橡胶组合物 Download PDFInfo
- Publication number
- CN1590445A CN1590445A CNA2004100566665A CN200410056666A CN1590445A CN 1590445 A CN1590445 A CN 1590445A CN A2004100566665 A CNA2004100566665 A CN A2004100566665A CN 200410056666 A CN200410056666 A CN 200410056666A CN 1590445 A CN1590445 A CN 1590445A
- Authority
- CN
- China
- Prior art keywords
- rubber
- carboxylated nitrile
- isoprene
- halogenated
- nitrile rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920000642 polymer Polymers 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims description 41
- 150000002825 nitriles Chemical class 0.000 title description 15
- 229920005549 butyl rubber Polymers 0.000 title description 8
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 37
- 239000000945 filler Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims description 41
- 239000005060 rubber Substances 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 27
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229920005557 bromobutyl Polymers 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 4
- 229920005555 halobutyl Polymers 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 10
- 230000031709 bromination Effects 0.000 description 9
- 238000005893 bromination reaction Methods 0.000 description 9
- -1 bromobutyl Chemical group 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 238000005987 sulfurization reaction Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005502 peroxidation Methods 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 229920013649 Paracril Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 125000004968 halobutyl group Chemical group 0.000 description 3
- 239000012764 mineral filler Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920002449 FKM Polymers 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
- 241001441571 Hiodontidae Species 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- AEUZJPHUNWZRCJ-UHFFFAOYSA-N 1-butyl-2-propan-2-ylbenzene Chemical compound CCCCC1=CC=CC=C1C(C)C AEUZJPHUNWZRCJ-UHFFFAOYSA-N 0.000 description 1
- OGUOSVCZUXJHJQ-UHFFFAOYSA-N 2-butyl-4-[(dimethylamino)methyl]phenol Chemical group CCCCC1=CC(CN(C)C)=CC=C1O OGUOSVCZUXJHJQ-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical group CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 239000006237 Intermediate SAF Substances 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
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920006170 Therban® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
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- OQIOVJHINWLQCM-UHFFFAOYSA-J dizinc prop-2-enoate Chemical compound [Zn++].[Zn++].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C OQIOVJHINWLQCM-UHFFFAOYSA-J 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 229920002313 fluoropolymer Polymers 0.000 description 1
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- 239000003365 glass fiber Substances 0.000 description 1
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- 229910052602 gypsum Inorganic materials 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
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- 230000036571 hydration Effects 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- 229960001708 magnesium carbonate Drugs 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
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- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 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
- 238000011089 mechanical engineering Methods 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种聚合物复合物,所述复合物包括至少一种任选氢化的羧化丁腈橡胶聚合物和至少卤化的丁基橡胶;一种制备所述聚合物复合物的方法,其中至少一种任选氢化的羧化丁腈橡胶和至少卤化的丁基橡胶相混合;一种成型制品,其包括至少一种任选氢化的羧化丁腈橡胶和至少卤化的丁基橡胶;还有一种提高卤化的丁基橡胶交联密度的方法,该方法通过将所述卤化的丁基橡胶与至少一种任选氢化的羧化丁腈橡胶聚合物,任选的至少一种交联剂和任选的一种填料相混合,然后硫化该复合物。
Description
技术领域
本发明涉及一种聚合物复合物,其包括至少一种任选氢化的羧化丁腈橡胶聚合物,和至少卤化的丁基橡胶;一种制备所述聚合物复合物的方法,其中将至少一种任选氢化的羧化丁腈橡胶聚合物和至少卤化的丁基橡胶混合;一种成型制品包括至少一种任选氢化的羧化丁腈橡胶聚合物和至少卤化的丁基橡胶。
背景技术
硫化橡胶的物理性能极大地受交联密度的影响。
氢化丁腈橡胶(HNBR),其由选择性氢化的丙烯腈-丁二烯橡胶制备(丁腈橡胶;NBR,是一种共聚物,其包括至少一种共轭二烯,至少一种不饱和腈和任选的其他共聚单体),是一种特种橡胶,其具有很好耐热性、出色的耐臭氧和耐化学性能,以及出色的耐油性。伴随着该橡胶的高水平的机械性能(特别是高耐磨性),不令人惊讶的是,已经发现NBR和HNBR在汽车(密封件、软管、轴承垫)、石油(挡板、井口密封件、阀片)、电气(电缆包皮)、机械工程(轮、辊)和造船(管密封件、联轴器)工业及其他工业中有广泛应用。氢化的羧化丁腈橡胶聚合物(HXNBR)已经被WO-01/77185-A1披露。
卤化的丁基橡胶可由Bayer Inc(拜耳公司)市售获得。
发明内容
本发明的一个方面,涉及一种聚合物复合物,其包括至少一种任选氢化的羧化丁腈橡胶聚合物和至少卤化的丁基橡胶。优选任选氢化的羧化丁腈橡胶聚合物是一种统计分布的共聚物。进一步优选卤化的丁基橡胶是一种溴化丁基橡胶或″溴丁基″橡胶。优选羧化丁腈橡胶聚合物(″XNBH″)完全或部分氢化(″HXNBR″)。
本发明的另一方面,涉及一种制备所述聚合物复合物的方法,该复合物包括至少一种任选氢化的羧化丁腈橡胶聚合物和至少卤化的丁基橡胶,其中所述的至少一种任选氢化的羧化丁腈橡胶聚合物和至少卤化的丁基橡胶相混合。
本发明的再一方面,涉及一种成型制品,其包括至少一种任选氢化的羧化丁腈橡胶聚合物和至少卤化的丁基橡胶。
本发明还有一方面,涉及一种增加卤化的丁基橡胶交联密度的方法,该方法通过将所述的卤化的丁基橡胶与至少一种任选氢化的羧化丁腈橡胶聚合物、任选的至少一种交联剂和任选的一种填料混合,然后硫化该复合物。
附图说明
图1表示实施例1-3的混合物硫化第一小时后在扭转1弧度和170℃下的扭矩(MH),单位是dN.m。
具体实施方式
整个说明书中所使用的术语″腈聚合物″或XNBR具有广泛的含义,其意味着包括具有来源于至少一种共轭二烯、至少一种α-β-不饱和腈、至少一种具有羧基单体和任选的一种或以上的其他可共聚单体的重复单元的共聚物。
共轭二烯可以是任何已知的共轭二烯,特别是C4-C6的共轭二烯。优选的共轭二烯是丁二烯、异戊二烯、1,3-戊二烯、2,3-二甲基丁二烯及其混合物。更优选的C4-C6共轭二烯是丁二烯、异戊二烯及其混合物。最优选的C4-C6共轭二烯是丁二烯。
α-β-不饱和腈可以是任何已知的α-β-不饱和腈,特别是C3-C5的α-β-不饱和腈。优选的C3-C5的α-β-不饱和腈是丙烯腈、甲基丙烯腈、乙基丙烯腈及其混合物。最优选的C3-C5的α-β-不饱和腈是丙烯腈。
具有至少一个羧基的单体可以是任何已知的具有至少一个羧基并且可以与腈和二烯共聚合的单体。
优选具有至少一种羧基的单体是不饱和羧酸。适用于不饱和羧酸的非限定性例子是富马酸、马来酸、丙烯酸、甲基丙烯酸和其混合物。其他优选单体是不饱和单或二羧酸类或其衍生物(例如酯、酰胺等等)包括其混合物。优选共聚物包括40至85wt%的源自一种或以上共轭二烯烃重复单元、15至60wt%的源自一种或以上的不饱和腈重复单元和0.1至15wt%的源自具有至少一个羧基的一种或以上单体的重复单元。更优选共聚物包括55至75wt%的源自一种或以上共轭二烯烃重复单元、25至40wt%的源自一种或以上的不饱和腈重复单元和1至7wt%的源自具有至少一个羧基的一种或以上单体的重复单元。
共聚物可以任选进一步包括源自一种或以上可共聚单体的重复单元,例如烷基丙烯酸酯,苯乙烯。源自一种或以上可共聚单体的重复单元可替换丁腈橡胶中的腈或二烯部分,并且对于本领域的技术人员明显的是,调整上述数字使其满足100wt%。
本发明中氢化优选被理解为在起始腈聚合物/NBR中超过50%的残余双键(RDB)被氢化,优选超过90%的RDB被氢化,更优选超过95%的RDB被氢化,而最优选超过99%的RDB被氢化。
本发明并非限定于制备氢化的羧化丁腈橡胶的特定方法。然而,本发明中优选的HXNBR已经可以由WO-01/77185-A1所披露的获得。由于许可这一过程的管辖范围,WO-01/77185-A1在此处被引用以作参考。
XNBR和HXNBR形成本发明聚合物复合物的优选成分,其可以由现有技术中已知标准技术表征。例如聚合物的分子量分布可以通过使用Waters 2690分离模块(Waters 2690 Seperation Module)的凝胶渗透色谱法(GPC)和运行Waters Millennium软件3.05.01版本的Waters 410差示折光计测定。样品溶于用0.025%BHT(丁基羟基甲苯)稳定的四氢呋喃(THF)中。用于测定的柱为三个连续的来自Polymer Labs.的混合-B凝胶柱。而所用的参照标准物是来自American Polymer StandardsCorp.的聚苯乙烯标准物。
本发明的聚合物复合物进一步包括至少卤化的丁基橡胶。此处所用的术语″卤化的丁基橡胶″涉及一种氯化和/或溴化丁基弹性体。优选溴化丁基弹性体,本发明通过实施例的方式参照这种溴丁基弹性体来加以阐述。然而,应当理解本发明可扩展到氯化丁基弹性体的使用。
因而,在本发明的实践中适宜使用的卤化弹性体包括但并非限定于溴化丁基弹性体。这种弹性体可以通过丁基橡胶(其为异丁烯和一种通常为C4至C6的共轭二烯优选异戊二烯的共聚单体的一种共聚物)的溴化获得。然而,可以使用除了共轭二烯以外的共聚单体,并且所述及的是由烷基取代的乙烯基芳族共聚单体例如C1至C4的烷基取代苯乙烯。这种市售弹性体的例子是溴化异丁烯甲基苯乙烯共聚物(BIMS),其中共聚单体是对-甲基苯乙烯。
溴化丁基弹性体典型地包含1至3wt%的异戊二烯和97至99wt%的异丁烯(基于聚合物的烃含量)和1至4wt%的溴(基于溴丁基聚合物)。典型的溴丁基聚合物具有一种以门尼粘度(ML 1+8,在25℃)表示的数值范围为28至55的分子量。
本发明中所用的溴化丁基弹性体优选包含1至5wt%的二烯,例如异戊二烯,95至99wt%的异烯烃,例如异丁烯(基于聚合物的烃含量),以及0.5至2.5wt%,优选0.75至2.3wt%的溴(基于溴化丁基聚合物)。
稳定剂可以加入到溴化丁基弹性体中。适宜的稳定剂包括硬脂酸钙和环氧化大豆油,优选所用的数量为每100重量份溴化丁基橡胶0.5至5重量份。
适宜的溴化丁基弹性体的例子包括BayerBromobutyl 2030、BayerBromobutyl 2040(BB2040),以及BayerBromobutyl X2,这些可以由Bayer Inc.市售获得。BayerBB2040具有39±4的门尼粘度(RPML 1+8125℃按照ASTM D 52-89),2.0±0.3wt%的溴含量,以及大约分子量Mw为500,000g/mol。
本发明聚合物复合物的组成取决于所需用途,并且通过调整丁腈橡胶和卤丁基的含量,可以满足最终复合物和所得制品的特性。然而,优选本发明的聚合物复合物包括每一百重量份的卤丁基橡胶0.01至20重量份的至少一种任选氢化的羧化丁腈橡胶聚合物,更优选0.1到5重量份。
本发明聚合物复合物进一步任选地包括至少一种填料。填料可以是一种活性或惰性填料或其混合物。填料特别可以是:
-高度分散的二氧化硅,其例如由硅酸盐溶液沉淀或卤化硅的火焰水解反应制备,其具有5至1000m2/g的比表面积,并且其初级颗粒尺寸为10至400nm;该二氧化硅任选也可与其他金属氧化物以混合氧化物的形式提供,金属氧化物例如是Al、Mg、Ca、Ba、Zn、Zr和Ti的氧化物。
-合成的硅酸盐,比如硅酸铝和碱土金属硅酸盐(比如硅酸镁或硅酸钙),其具有20至400m2/g的BET比表面积和10-400nm的初级颗粒直径;
-天然硅酸盐,例如高岭土及其他天然产生的二氧化硅;
-玻璃纤维和玻璃纤维制品(编织品、挤出产品)或玻璃微球;金属氧化物,例如氧化锌、氧化钙、氧化镁和氧化铝;
-金属碳酸盐,例如碳酸镁、碳酸钙和碳酸锌;
-金属氢氧化物,例如氢氧化铝和氢氧化镁;
-炭黑;这里所用的炭黑可以由灯黑、炉法炭黑或气黑工艺制备,并优选具有20至200m2/g的BET比表面积(DIN 66 131),其例如为SAF、ISAF、HAF、FEF或GPF炭黑;
-橡胶凝胶,尤其是那些基于聚丁二烯、丁二烯/苯乙烯共聚物、丁二烯/丙烯腈共聚物和氯丁橡胶的橡胶凝胶;或其混合物。
优选矿物填料的例子包括二氧化硅、硅酸盐、粘土例如膨润土、石膏、矾土、二氧化钛、滑石其混合物以及诸如此类。这些矿物颗粒在其表面具有羟基,从而使其具有亲水性和疏油性。这使得难以在填料颗粒和橡胶之间获得优良的相互作用。对于多种目的,优选的矿物是二氧化硅,尤其是通过由硅酸钠的二氧化碳沉淀所制备的二氧化硅。按照本发明适宜使用的干燥无定形二氧化硅颗粒可以具有1至100μm的平均附聚物粒度,优选在10-50μm之间,最优选10-25μm之间。优选体积百分数小于10%的附聚物颗粒粒径低于5μm或大于50μm。此外适宜的无定形干燥二氧化硅通常具有50至450m2/g的BET比表面积,每100克二氧化硅150至400克的DBP吸收以及0至10wt%的干燥失重,BET比表面积按照DIN(德国工业标准)66131测定,DBP吸收按照DIN 53601测定,干燥失重按照ISO 787/11测定。适宜的二氧化硅填料可以由PPGIndustries Inc.提供的商标为HiSil210,HiSil233和HiSil243获得。由Bayer AG提供的VulkasilS和VulkasilN也是适宜的。
通常炭黑作为填料使用是有利的。在聚合物复合物中所存在的炭黑数量通常为20至200重量份,优选30至150重量份,更优选40至100重量份。此外在本发明的聚合物复合物中炭黑和矿物填料的结合使用可能是有利的。矿物填料和炭黑的组合比率通常为0.05至20,优选0.1至10。
聚合物复合物进一步包含其他天然或合成橡胶是有利的,例如BR(聚丁二烯)、ABR(丁二烯/丙烯酸-C1-C4-烷基酯-共聚物)、CR(聚氯丁二烯)、IR(聚异戊二烯)、苯乙烯含量为1至60wt%的SBR(苯乙烯/丁烯-共聚物)、丙烯腈含量为5至60wt%的NBR(丁二烯/丙烯腈-共聚物)、具有门尼粘度(ML 1+4在100℃按照ASTM test D1646)至少为30(部分或完全氢化NBR-橡胶)的HNBR、EPDM(乙烯/丙烯/二烯-共聚物)、FKM(含氟聚合物或氟橡胶),以及所获得聚合物的混合物。仔细混合常规的HNBR经常可以减少聚合物复合物的成本而不会降低可加工性。常规HNBR和/或其他天然或合成橡胶的数量将取决于在制造成型制品中所应用的加工条件,并且可以通过很少的初步试验而容易获得。
聚合物复合物此外任选的包括一种或以上的交联剂或硫化体系。尽管本发明并不限定特定的硫化体系,然而优选过氧化物硫化体系。此外,本发明并不限于特定的过氧化物硫化体系。例如无机或有机过氧化物是适宜的。优选的有机过氧化物例如是二烷基过氧化物、酮缩醇过氧化物、芳烷基过氧化物、醚类过氧化物、酯类过氧化物例如二-叔-丁基过氧化物、二-(叔-丁基过氧化异丙基)-苯、双枯基过氧化物、2,5-二甲基-2,5-二(叔-过氧化丁基)-己烷、2,5-二甲基-2,5-二(叔-过氧化丁基)-己烯-(3)、1,1-二-(叔-过氧化丁基)-3,3,5-三甲基环己烷、过氧化苯甲酰、叔-丁基枯基过氧化物和叔-丁基过氧化苯甲酸盐。通常聚合物复合物中过氧化物的数量为1至10phr(=每一百份橡胶),优选为4至8phr。接着的硫化在温度范围为100至200℃下进行,优选为130至180℃。过氧化物可以聚合物结合剂的形式被方便的应用。市售适宜的体系例如为Rhein Chemie Rheinau GmbH D提供的Polydispersion T(VC)D-40P(=聚合物结合剂二-叔-过氧化丁基-异丙苯)。交联也受辐射例如α-、β-、γ-辐射的影响。
按照本发明的橡胶组合物可以进一步包括用于橡胶的辅助材料,例如反应加速剂、硫化加速剂、硫化加速助剂、抗氧剂、起泡剂、防老剂、热稳定剂、光稳定剂、臭氧稳定剂、加工助剂、增塑剂、增稠剂、发泡剂、染料、颜料、石蜡、膨胀剂、有机酸、抑制剂、金属氧化物,和活化剂例如三乙醇胺、聚乙二醇、己烷三醇等等,这些为橡胶工业所熟知。橡胶助剂所用量为常规数量,其尤其取决于所需的用途。常规数量例如是基于橡胶的0.1至50wt%。优选组合物包含0.1至20phr的有机脂肪酸作为辅助材料,优选分子中具有一个、两个或更多碳碳双键的不饱和脂肪酸,其更优选包括10wt%或以上的分子中具有至少一个共轭碳-碳双键的共轭二烯酸。那些脂肪酸优选具有8至22个碳原子,更优选12至18个碳原子。例子包括硬脂酸、棕榈酸和油酸以及它们的钙盐、锌盐、镁盐、钾盐和铵盐。优选组合物包含5至50phr的丙烯酸盐作为辅助材料。适宜的丙烯酸盐已经由EP-A1-0319320所得知,特别是第3段第16-35行,也可由US5208294所得知,特别是第2栏第25-40行,还可以由US4983678得知,特别是第2栏第45-62行。特别参考丙烯酸锌、二丙烯酸锌或二甲基丙烯酸锌,或液体丙烯酸酯例如三羟甲基丙烷三甲基丙烯酸酯(TRIM)、丁二醇二甲基丙烯酸酯(BDMA)和乙二醇二甲基丙烯酸酯(EDMA)。结合使用不同的丙烯酸酯和/或其金属盐是有利的。特别有利的是经常在使用丙烯酸金属盐时结合使用防焦剂例如空间位阻酚(例如甲基取代氨基烷基苯酚、特别是2,6-二-叔丁基-4-二甲基氨基甲基苯酚)。
本发明的另一方面涉及一种制备所述聚合物复合物的方法,该复合物包括至少一种任选氢化的羧化丁腈橡胶聚合物和至少卤化的丁基橡胶,其中所述的至少一种任选氢化的羧化丁腈橡胶聚合物和至少卤化的丁基橡胶相混合。
最终聚合物复合物的成分适宜在升温状态下混合在一起,升温的温度变化范围可以是25至200℃。通常混合时间不超过一个小时并且混合时间为2至30分钟通常是足够的。混合适宜在密炼机里进行,例如班伯里密炼机,或Hakke或Brabender小型密炼机。两辊辊炼机也提供在弹性体中的优良的添加剂分散体。挤出机也可在较短的混合时间提供优良的混合。混合可以在两个或两个以上步骤进行,并且混合可以在不同的装置中进行,例如一阶段在密炼机内以及一阶段在挤压机内进行。然而,应当注意在混合阶段不希望发生不需要的预交联(=过早硫化)。对于混炼和硫化也可参见:Encyclopedia of PolymerScience and Engineering,第4卷,66页及其后各页(混炼)以及第17卷,666页及其后各页(硫化)。在固化/硫化过程中,卤丁基和XNBR/HXNBR间发生所需要的交联,并且因而增加了复合物的交联密度。
因此,本发明涉及一种增加卤化的丁基橡胶交联密度的方法,该方法通过将所述的卤化的丁基橡胶与至少一种任选氢化的羧化丁腈橡胶聚合物、任选的至少一种交联剂和任选的一种填料相混合,然后硫化该复合物。
相对于比较例,本发明的复合物组合物导致改善最终部件的硫化状态,这导致改善最终部件的物理性能,其可以通过多种拉伸模量和混合物硬度来测定。
此外,本发明提供了一种成型制品,其包括所述的本发明的聚合物复合物,该复合物包括至少一种任选氢化的羧化丁腈橡胶聚合物和至少卤化的丁基橡胶。优选的成型制品是轮胎,轮胎部件例如内衬、胎面和侧壁,密封件,粘合剂和密封复合物,涂料,粘固剂和包覆管子的带。
实施例
实施例1-3
聚合物复合物在开炼机上混合(6×12英寸开炼机,容量1000),而开炼机的温度设定为30℃。然后将炭黑、硬脂酸和油在分离的混合步骤加到相同的设定为30℃的开炼机上。然后,将固化剂和VulkacittDM/C在分开的混合步骤分别加到相同的设定为30℃的开炼机上。配方按照表1。
TherbanXT VP KA 8889为由Bayer Inc.市售的HXNBR。
BayerBromobutyl 2030为由Bayer Inc.市售的溴丁基合成橡胶。
炭黑N 660 Sterling-V购自Cabot Tire Blacks。
硬脂酸购自C.P.Hall。
Sunpar2280是由Sun Oil生产的石蜡油。
StruktolZP 1014是由Struktol市售的过氧化锌制备的。
VulkacitDM/C是二苯并噻唑基-二硫化物,购自Bayer AG。
表1 复合物配方
实施例 | 1(比较例) | 2 | 3 |
TherbanXT VP KA 8889 | 0 | 4 | 8 |
BayerBromobutyl2030 | 100 | 100 | 100 |
炭黑N 660 | 60 | 60 | 60 |
硬脂酸 | 1 | 1 | 1 |
Sunpar2280 | 7 | 7 | 7 |
VulkacitDM/C | 1.3 | 1.3 | 1.3 |
固化剂 | |||
Spider Sulfur | 0.5 | 0.5 | 0.5 |
StruktolZP 1014 | 6 | 6 | 6 |
聚合物复合物性能
表2表示实施例1-3的聚合物复合物的性能总结。实施例1用于比较。
复合物门尼粘度:测定是在100℃下使用大转子进行的。
硫化流变测定法:ASTM D 52-89 MDR2000E Rheometer(流变仪)在1弧度和1.7Hz下进行。
复合物门尼过早硫化:测定是在135℃使用大转子进行的。
应力-应变:通过在170℃硫化大片材tc90+5分钟,此后对适当的样品染色制得样品。测试在23℃下进行。
实施例 | 1 | 2 | 3 |
复合物门尼粘度 | |||
ML 1+4在100℃ | 63.7 | 67.5 | 67.8 |
衰变时间80%(min) | 0.09 | 0.11 | 0.11 |
斜率(1gM/1gs) | -0.5341 | -0.5011 | -0.4867 |
截距(MU) | 30.557 | 32.9044 | 32.9654 |
曲线下面积 | 777.3 | 949.7 | 1002.4 |
复合物门尼过早硫化 | |||
t5在135℃(min) | 10.9 | 12.2 | 14.2 |
MDR硫化特性1.7Hz;1°弧度;170℃:60分钟 | |||
MH(dN.m) | 8.78 | 13.52 | 15.92 |
ML(dN.m) | 2.76 | 3.50 | 3.71 |
ΔMH-ML(dN.m) | 6.02 | 10.02 | 12.21 |
ts 1(min) | 1.32 | 1.50 | 1.62 |
ts 2(min) | 1.62 | 1.92 | 2.16 |
ts 10(min) | 1.21 | 1.50 | 1.74 |
ts 25(min) | 1.45 | 2.08 | 2.69 |
ts 50(min) | 2.11 | 3.40 | 4.50 |
ts 90(min) | 8.45 | 9.62 | 9.69 |
ts 95(min) | 12.53 | 12.78 | 12.24 |
Δt’50-t’10(min) | 0.90 | 1.90 | 2.76 |
实施例 | 1 | 2 | 3 |
应力-应变(哑铃) | |||
在170℃下硫化时间(min) | 15 | 17 | 17 |
应力在10(MPa) | 0.56 | 1.27 | 1.60 |
应力在25(MPa) | 0.71 | 1.62 | 2.18 |
应力在50(MPa) | 0.86 | 2.01 | 2.81 |
应力在100(MPa) | 1.29 | 2.85 | 3.84 |
应力在200(MPa) | 2.92 | 5.21 | 6.09 |
应力在300(MPa) | 5.09 | 7.92 | 8.60 |
极限抗张(MPa) | 10.55 | 10.94 | 10.18 |
极限伸长率(%) | 671 | 443 | 370 |
硬度Shore A2(Pts.) | 44 | 63 | 68 |
ΔMH-ML表示交联密度。从实施例2-3(表2和图1)可以清楚的看到,少量氢化的羧化丁腈橡胶加入到溴丁基合成橡胶配制物从而导致复合物硫化状态的显著改善。这导致复合物具有改善的硬度和在设定伸长下增加的模量。
Claims (12)
1.一种聚合物复合物,所述复合物包括至少一种任选氢化的羧化丁腈橡胶聚合物和至少卤化的丁基橡胶。
2.如权利要求1所述的复合物,其中羧化丁腈橡胶聚合物是一种氢化的羧化丁腈橡胶。
3.如权利要求1或2所述的复合物,其中卤化的丁基橡胶是一种溴化丁基橡胶。
4.如权利要求1-3任何一项所述的复合物,其中羧化丁腈橡胶是一种统计分布的共聚物。
5.如权利要求1-4任何一项所述的复合物,其中聚合物复合物进一步包含至少一种交联剂。
6.如权利要求1-5任何一项所述的复合物,其中聚合物复合物进一步包含至少一种填料。
7.一种制备如权利要求1-6任何一项所述聚合物复合物的方法,其中将至少一种任选氢化的羧化丁腈橡胶聚合物,至少卤化的丁基橡胶,任选的至少一种填料和任选至少一种交联剂相混合。
8.一种成型制品,其包括至少一种任选氢化的羧化丁腈橡胶聚合物和至少卤化的丁基橡胶。
9.按照权利要求8的成型制品,其形式为轮胎或轮胎部件。
10.一种提高卤化的丁基橡胶交联密度的方法,通过将卤化的丁基橡胶与至少一种任选氢化的羧化丁腈橡胶聚合物,任选的至少一种交联剂和任选的一种填料相混合,然后硫化该复合物。
11.按照权利要求9的方法,其中羧化丁腈橡胶是一种统计分布的共聚物。
12.在按照权利要求9或10的方法中,其中卤化的丁基橡胶是一种溴化丁基橡胶。
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CN103554571A (zh) * | 2013-10-25 | 2014-02-05 | 安徽文峰电子科技集团有限公司 | 一种耐油耐臭氧丁腈橡胶电缆料 |
CN105037849A (zh) * | 2015-07-20 | 2015-11-11 | 安徽华宇电缆集团有限公司 | 一种海上石油平台专用耐磨耐热电缆 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US7906600B2 (en) * | 2004-12-29 | 2011-03-15 | Exxonmobil Chemical Patents Inc. | Processable filled, curable halogenated isoolefin elastomers |
FR2919613B1 (fr) * | 2007-07-30 | 2009-10-09 | Inergy Automotive Systems Res | Objet a base d'une composition contenant un melange reticule d'elastomeres |
US7994257B2 (en) * | 2008-02-15 | 2011-08-09 | Stowe Woodward, Llc | Downwell system with swellable packer element and composition for same |
JP5301236B2 (ja) * | 2008-10-01 | 2013-09-25 | 東洋ゴム工業株式会社 | ゴム組成物及びその製造方法、並びにカーボンブラックマスターバッチ |
KR102222870B1 (ko) * | 2019-11-22 | 2021-03-03 | 이창열 | 슬립저항성이 우수한 모노 펌프 고정자용 부틸계 고무 조성물 및 이를 이용하여 제조되는 모노 펌프 고정자 |
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Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3061883A (en) * | 1959-12-07 | 1962-11-06 | Du Pont | Polymers of carboxylic modified copolymers of butadiene-1, 3 hydrocarbons and acrylic nitriles |
JPS5839436A (ja) * | 1981-09-03 | 1983-03-08 | Showa Gomme Kk | ゴムせん |
US4626568A (en) * | 1985-08-08 | 1986-12-02 | Polysar Limited | Vibration and noise insulating rubber compositions |
US5005625A (en) * | 1989-04-24 | 1991-04-09 | The Goodyear Tire & Rubber Company | Pneumatic tire having air retention innerliner |
US4987192A (en) * | 1989-05-19 | 1991-01-22 | Oberster Arthur E | Colored tire stocks having improved abrasion resistance, color and color stability |
JP2956344B2 (ja) * | 1992-02-08 | 1999-10-04 | 日本ゼオン株式会社 | ゴム組成物 |
US5397837A (en) * | 1993-05-11 | 1995-03-14 | Exxon Chemical Patents Inc. | Compatibilized blends containing halogenated copolymers of isobutylene and para-methyl styrene and carboxy modified elastomers |
JP3601569B2 (ja) * | 1997-03-26 | 2004-12-15 | 株式会社ブリヂストン | 樹脂強化エラストマー、その製造方法、及びそれを用いた空気入りタイヤ |
CA2304501A1 (en) * | 2000-04-10 | 2001-10-10 | Bayer Inc. | Process for hydrogenating carboxylated nitrile rubber, the hydrogenated rubber and its uses |
DE10061543A1 (de) * | 2000-12-11 | 2002-06-13 | Bayer Ag | Gelhaltige Kautschukmischungen mit multifunktionellen Isocyanaten und Polyolen |
CA2357089A1 (en) * | 2001-09-07 | 2003-03-07 | Bayer Inc. | Elastomeric compositions |
US20030204008A1 (en) * | 2002-04-24 | 2003-10-30 | Campion Robert Paget | Elastomers |
US7029598B2 (en) * | 2002-06-19 | 2006-04-18 | Fuji Photo Film Co., Ltd. | Composite material for piezoelectric transduction |
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CN103554571A (zh) * | 2013-10-25 | 2014-02-05 | 安徽文峰电子科技集团有限公司 | 一种耐油耐臭氧丁腈橡胶电缆料 |
CN105037849A (zh) * | 2015-07-20 | 2015-11-11 | 安徽华宇电缆集团有限公司 | 一种海上石油平台专用耐磨耐热电缆 |
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US20050113516A1 (en) | 2005-05-26 |
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BRPI0403245A (pt) | 2005-05-31 |
CA2437406A1 (en) | 2005-02-14 |
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