CN101456935A - 改性丁基橡胶组合物 - Google Patents
改性丁基橡胶组合物 Download PDFInfo
- Publication number
- CN101456935A CN101456935A CNA2008101871220A CN200810187122A CN101456935A CN 101456935 A CN101456935 A CN 101456935A CN A2008101871220 A CNA2008101871220 A CN A2008101871220A CN 200810187122 A CN200810187122 A CN 200810187122A CN 101456935 A CN101456935 A CN 101456935A
- Authority
- CN
- China
- Prior art keywords
- butyl rubber
- composition
- modified butyl
- rubber
- group
- 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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- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 37
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 title claims abstract description 33
- 229920001971 elastomer Polymers 0.000 claims abstract description 44
- 239000005060 rubber Substances 0.000 claims abstract description 44
- 150000003254 radicals Chemical class 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- -1 nitroxyl free radical Chemical class 0.000 claims description 57
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 claims description 18
- 239000000470 constituent Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000012763 reinforcing filler Substances 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 150000001451 organic peroxides Chemical class 0.000 abstract 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 22
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 230000001404 mediated effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000005502 peroxidation Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229940059574 pentaerithrityl Drugs 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 4
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000012264 purified product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229960003328 benzoyl peroxide Drugs 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- GOAHRBQLKIZLKG-UHFFFAOYSA-N 1-tert-butylperoxybutane Chemical compound CCCCOOC(C)(C)C GOAHRBQLKIZLKG-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- ZPMCCZKDFLIVHD-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane;1,2-di(propan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C.CC(C)C1=CC=CC=C1C(C)C ZPMCCZKDFLIVHD-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical compound CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 150000001723 carbon free-radicals Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 1
- UFFVWIGGYXLXPC-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical class O=C1C=CC(=O)N1C1=CC=CC=C1N1C(=O)C=CC1=O UFFVWIGGYXLXPC-UHFFFAOYSA-N 0.000 description 1
- ARJFNIGGXQKXBD-UHFFFAOYSA-N 1-ethenyl-4-methylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CC1=CC=C(C=C)C=C1 ARJFNIGGXQKXBD-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- NICLKHGIKDZZGV-UHFFFAOYSA-N 2-cyanopentanoic acid Chemical class CCCC(C#N)C(O)=O NICLKHGIKDZZGV-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- DGBFOBNYTYHFPN-UHFFFAOYSA-N 3-[ethoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(C)CCCOC(=O)C=C DGBFOBNYTYHFPN-UHFFFAOYSA-N 0.000 description 1
- MJEDTBDGYVATPI-UHFFFAOYSA-N 4-hydroxy-TEMPO benzoate Chemical compound C1C(C)(C)N([O])C(C)(C)CC1OC(=O)C1=CC=CC=C1 MJEDTBDGYVATPI-UHFFFAOYSA-N 0.000 description 1
- WSGDRFHJFJRSFY-UHFFFAOYSA-N 4-oxo-TEMPO Chemical compound CC1(C)CC(=O)CC(C)(C)N1[O] WSGDRFHJFJRSFY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NGMNTLCQDNNBNT-UHFFFAOYSA-N C(C=C)(=O)OC.C(CS)(=O)OCCOC(CS)=O Chemical compound C(C=C)(=O)OC.C(CS)(=O)OCCOC(CS)=O NGMNTLCQDNNBNT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 241000238367 Mya arenaria Species 0.000 description 1
- NMOJAXCSURVGEY-UHFFFAOYSA-N N#CC#N.[S] Chemical compound N#CC#N.[S] NMOJAXCSURVGEY-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 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
- 239000007983 Tris buffer Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000033 alkoxyamino group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
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- 239000011324 bead Substances 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 description 1
- RLDQYSHDFVSAPL-UHFFFAOYSA-L calcium;dithiocyanate Chemical group [Ca+2].[S-]C#N.[S-]C#N RLDQYSHDFVSAPL-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
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- 238000013016 damping Methods 0.000 description 1
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- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
- MASNVFNHVJIXLL-UHFFFAOYSA-N ethenyl(ethoxy)silicon Chemical compound CCO[Si]C=C MASNVFNHVJIXLL-UHFFFAOYSA-N 0.000 description 1
- IBKNSIPMTGYUNZ-UHFFFAOYSA-N ethenyl(methoxy)silane Chemical compound CO[SiH2]C=C IBKNSIPMTGYUNZ-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- ZHFOZEBDSIVYQP-UHFFFAOYSA-N hydrogen peroxide;methane Chemical compound C.OO ZHFOZEBDSIVYQP-UHFFFAOYSA-N 0.000 description 1
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
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Abstract
本发明提供了一种能交联有机过氧化物并具有改进模量和抗张强度的改性丁基橡胶组合物。一种改性丁基橡胶组合物,其包含(i)包含丁基橡胶的橡胶成分与(ii)(a)其分子具有常温下甚至在氧气存在下稳定的氮氧自由基的化合物、(b)自由基引发剂、(c)双官能或更高官能的可自由基聚合单体和(d)具有烷氧基甲硅烷基团的可自由基聚合单体的反应产物。
Description
技术领域
本发明涉及一种改性丁基橡胶组合物,具体而言涉及一种具有显著改进模量和抗张强度的改性丁基橡胶组合物。
背景技术
发明人以前发现(1)在丁基橡胶中加入过氧化物,将多官能可自由基聚合的单体接枝到该橡胶上而由此用过氧化物进行交联和(2)在改性丁基橡胶中加入可自由基聚合的单体和过氧化物,将2,2,6,6-四甲基-1-哌啶基氧自由基(即TEMPO)化合物接枝到该橡胶上而由此用过氧化物进行交联(参见日本专利申请(A)号2007-231244)以及在日本专利申请号2007-110605(2007年4月19日提交)的说明书中进一步发现可以通过将两种或更多种类型单体用作可自由基聚合的单体来提高交联产物的拉伸性能。
发明内容
本发明目的为显著改进通过发明人以前开发的方法获得的可过氧化物交联的改性丁基橡胶的模量和抗张强度,其中将TEMPO化合物接枝到丁基橡胶上,然后使多官能丙烯酸酯与之反应。
本发明提供一种改性丁基橡胶组合物,其包含(i)包含丁基橡胶的橡胶成分与(ii)(a)其分子具有常温下甚至在氧气存在下稳定的氮氧自由基的化合物、(b)自由基引发剂、(c)双官能或更高官能的可自由基聚合单体和(d)具有烷氧基甲硅烷基团的可自由基聚合单体的反应产物。
根据本发明,可以通过将其分子具有常温下甚至在氧气存在下稳定的氮氧自由基的化合物如4-羟基-2,2,6,6-四甲基哌啶基-1-氧自由基(即OH-TEMPO)接枝到丁基橡胶上并进一步使该接枝产物与双官能或更高官能的可自由基聚合单体如多官能丙烯酸酯反应而得到可过氧化物交联的改性丁基橡胶并使所得产物不只与多官能丙烯酸酯还与具有烷氧基甲硅烷基团如烷氧基硅烷的(甲基)丙烯酸酯反应来显著改进该改性丁基橡胶的模量和抗张强度。
具体实施方式
在本发明说明书和权利要求书中,单数形式除非在正文中显示为单数形式,否则还包括复数形式。
发明人致力于解决上述问题并发现可以通过将TEMPO化合物接枝到丁基橡胶上并进一步使所得产物与双官能或更高官能的可自由基聚合单体如多官能丙烯酸酯反应而得到可过氧化物交联的改性丁基橡胶并使所得产物不只与多官能丙烯酸酯还与其他具有烷氧基甲硅烷基团的可自由基聚合单体如具有烷氧基硅烷的(甲基)丙烯酸酯反应来显著改进该改性丁基橡胶的模量和抗张强度。
通过本发明改性的丁基橡胶为称作“丁基橡胶(IIR)”的异丁烯与少量(例如全部橡胶的0.6-2.5摩尔%)异戊二烯的共聚物橡胶或氯化丁基橡胶、溴化丁基橡胶或它们的其他衍生物。这些在现有技术中众所周知。还有很多市售产品。
本发明中所用的其分子具有常温下甚至在氧气存在下稳定的氮氧自由基的化合物(a)可由下列化合物说明但不限于下列化合物:
2,2,6,6-四甲基-1-哌啶基氧自由基(TEMPO)
4-氧代TEMPO
在式(1)-(6)中,R为C1-C30烷基、烯丙基、氨基、异氰酸酯基团、羟基、硫羟基、乙烯基、环氧基团、硫杂丙环基团、羧基、含羰基的基团(如琥珀酸酐、马来酸酐、戊二酸酐、邻苯二甲酸酐和其他环状酸酐)、酰胺基团、酯基、酰亚胺基团、腈基、硫氰(thiocyan)基团、C1-C20烷氧基、甲硅烷基团、烷氧基甲硅烷基团、硝基或含其他官能团的有机基团。
4-苯基TEMPO 4-甲基TEMPO 4-乙基TEMPO 4-氯TEMPO
4-苯氧基TEMPO 4-甲氧基TEMPO 4-乙氧基TEMPO
4-苯甲酰基TEMPO 4-甲基羰基TEMPO 4-乙基羰基TEMPO
4-苯甲酰氧基TEMPO 4-乙酰氧基TEMPO 4-乙氧羰基TEMPO
4-(N-苯氨基甲酰氧基)TEMPO 4-(N-甲基氨基甲酰氧基)TEMPO
4-(N-乙基氨基甲酰氧基)TEMPO
苯基(4-TEMPO)硫酸酯 甲基(4-TEMPO)硫酸酯
乙基(4-TEMPO)硫酸酯
在下面给出其他实例:
2,2,6,6-四甲基哌啶-1-基氧自由基
X:Br或C1
X:Br或Cl
4-氨基-2,2,6,6-四甲基哌啶基氧自由基-TEMPO
4-异氰酸酯-TEMPO
4-TEMPO-缩水硫甘油醚
3-氨基甲酰基-PROXYL
3-异氰酸酯-PRYXYL
ON(SO3K)2 Fermi盐
本发明中所使用的化合物(ii)(a)的用量不作特别限制,但基于100g待改性丁基橡胶优选为0.001-0.5摩尔,更优选0.005-0.1摩尔。如果该用量小,则丁基橡胶的改性量倾向于较低,但相反如果该用量大,则随后的交联倾向于阻止加工。
可以将任何能够将化合物(ii)(a)引入丁基橡胶分子链的自由基引发剂用作可在本发明中使用的自由基引发剂(ii)(b)。具体而言,可以阐述为过氧化苯甲酰、过苯甲酸叔丁基酯、过氧化二枯基、过氧化叔丁基枯基、过氧化二叔丁基、2,5-二甲基-2,5-二叔丁基过氧己烷、2,5-二甲基-2,5-二叔丁基过氧-3-己炔、2,4-二环过氧化苯甲酰、二叔丁基过氧-二异丙基苯、1,1-二(叔丁基过氧)-3,3,5-三甲基环己烷、4,4-二(叔丁基过氧)戊酸正丁基酯、2,2-二(叔丁基过氧)丁烷、过氧化二异丁基、过新癸酸枯基酯、过二碳酸二正丙基酯、过二碳酸二异丙基酯、过二碳酸二仲丁基酯、过新癸酸1,1,3,3-四甲基丁基酯、过二碳酸二(4-叔丁基环己基)酯、过新癸酸1-环己基-1-甲基乙基酯、过二碳酸二(2-乙氧基乙基)酯、过二碳酸二(2-乙氧基己基)酯、过新癸酸叔己基酯、过二碳酸二甲氧基丁基酯、过新癸酸叔丁基酯、过新戊酸叔己基酯、过新戊酸叔丁基酯、过氧化二(3,5,5-三甲基己酰)、过氧化二正辛酰、过氧化二月桂酰、过氧化二硬脂酰、过2-乙基己酸1,1,3,3-四甲基丁基酯、过氧化二琥珀酸、2,5-二甲基-2,5-二(2-乙基己酰基过氧)己烷、过氧2-乙基己酸叔己基酯、过氧化二(4-甲基苯甲酰)、过氧2-乙基己酸叔丁基酯,过氧化二(3-甲基苯甲酰)和过氧化苯甲酰(3-甲基苯甲酰)以及过氧化二苯甲酰的混合物、过氧化二苯甲酰、过异丁酸叔丁基酯等。另外因氧化还原催化剂的作用可以在低温下断裂的引发剂的典型实例可以阐述为过氧化二苯甲酰、对位甲烷过氧化氢(paramethane hydroperoxide)、二异丙基苯过氧化氢、1,1,3,3-四甲基丁基过氧化氢、氢过氧化枯烯、叔丁基过氧化氢等。可以通过在反应体系(如混合体系和接触体系)中加入这些自由基引发剂而在丁基橡胶中形成碳自由基,并通过使具有稳定自由基的化合物(ii)(a)与碳自由基反应而获得改性丁基橡胶。
本发明中所使用的自由基引发剂(ii)(b)的加入量不作特别限制,但基于100g待改性丁基橡胶优选为0.001-0.5摩尔,更优选0.005-0.2摩尔。如果该量太小,则从丁基橡胶链中抽出的氢原子的量倾向于降低,但相反如果该量太大,则丁基橡胶主链倾向于断裂并且分子量倾向于显著降低。
可在本发明中使用的双官能或更高官能的可自由基聚合单体(ii)(c)不作特别限制,但例如可以提到二(甲基)丙烯酸乙二酯(表述“二(甲基)丙烯酸乙二酯”在这里指二甲基丙烯酸乙二酯和二丙烯酸乙二酯,下文相同)、三羟甲基丙烷三(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、四羟甲基甲烷三(甲基)丙烯酸酯、四羟甲基甲烷四(甲基)丙烯酸酯、三(2-羟乙基)异氰脲酸酯三(甲基)丙烯酸酯、乙氧基化三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、乙氧基化三羟甲基丙烷三(甲基)丙烯酸酯、丙氧基化三羟甲基丙烷(甲基)丙烯酸酯、丙氧基化甘油(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二(三羟甲基丙烷)四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯、聚硅氧烷二(甲基)丙烯酸酯、各种类型的尿烷(甲基)丙烯酸酯、各种类型的金属(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、N,N’-亚苯基双马来酰亚胺、双马来酰亚胺二苯甲烷、N,N’-亚苯基双丙烯酰胺、二乙烯基苯、三烯丙基异氰脲酸酯等。其中,从提高改性率的观点出发,优选分子中含有电子受体基团(例如羰基(酮、醛、酯、羧酸、羧酸酯和酰胺)、硝基、氰基等)的单体。
双官能或更高官能的可自由基聚合单体(ii)(c)的用量不作特别限制,但基于100g待改性丁基橡胶优选为0.001-0.5摩尔,更优选0.005-0.2摩尔。如果该用量太小,则后面的交联不易进行,但相反如果该用量太大,则交联产物的物理性能易恶化。
在本发明中,具有烷氧基甲硅烷基团的可自由基聚合单体的成分(ii)(d)优选由式(I)表示:
Si(OR1)4-n(R-A)n(I)
其中,在(I)中,R和R1独立地为烃基并且A为可自由基聚合的基团,n为1-3的整数,但n为2或3时,R可以相同或不同,作为这种基团R,例如可优选提及甲基、乙基、丙基、己基、十二烷基、十八烷基或其他烷基,环丙基、环己基或其他环烷基,苯基、苄基或其他芳基等。另外,n为2或3时,R1可以相同或不同,作为这种基团R1,例如可优选提及甲基、乙基、丙基、己基、十二烷基、十八烷基或其他烷基,环丙基、环己基或其他环烷基,苯基、苄基或其他芳基或基于聚乙二醇、聚丙二醇或其他聚氧化烯的基团等。
另外,n为2或3时,可自由基聚合的基团A可以相同或不同。作为这种基团A,例如可优选提及乙烯基、烯丙基、苯乙烯基、(甲基)丙烯酰氧基团、(甲基)丙烯酰胺基团、卤化乙烯基、丙烯腈基团等。其中优选包括电子受体基团(例如羰基、卤素、氰基等)的基团。此外,其中特别优选具有(甲基)丙烯酰氧基团的基团。
可在本发明中使用的具有烷氧基甲硅烷基团的可自由基聚合单体不作特别限制,但例如优选可以提到乙烯基甲氧基硅烷、乙烯基三甲氧基硅烷、乙烯基乙氧基硅烷、乙烯基三乙氧基硅烷、γ-甲基丙烯酰氧丙基三甲氧基硅烷、γ-甲基丙烯酰氧丙基甲基二甲氧基硅烷、γ-甲基丙烯酰氧丙基二甲基甲氧基硅烷、γ-丙烯酰氧丙基甲基二乙氧基硅烷、γ-丙烯酰氧丙基二甲基乙氧基硅烷、γ-丙烯酰氧丙基三乙氧基硅烷、N-(丙基三乙氧基硅烷)马来酰亚胺等。
另外,可以使用呈水解和缩合形式的具有烷氧基甲硅烷基团的可自由基聚合单体。还可以使用具有两个或更多个硅氧烷键重复单元并具有烷氧基甲硅烷基团等的硅油类型偶联剂,即具有可自由基聚合基团的低聚物。
在本发明中成分(ii)(d)的用量不作特别限制,但基于100g待改性丁基橡胶优选为0.0001-0.5摩尔,更优选0.0003-0.2摩尔。如果该用量太小,则对交联产物的模量和抗张强度的改进没有作用,因此不优选。相反如果该用量太大,则过量(d)易对交联产物的压缩形变具有不利影响,因此不优选。
在本发明中,丁基橡胶改性的方法和双官能或更高官能的可自由基聚合单体(ii)(c)与具有烷氧基甲硅烷基团的可自由基聚合单体(ii)(d)混合的方法在这里不作特别限制,但例如丁基橡胶可以做如下改性。即将丁基橡胶(i)和化合物(ii)(a)和引发剂(ii)(b)预混合的混合物在150-220℃的温度下在氮气置换的内捏合机中反应。优选氮气置换,但该反应还可以在贫氧条件下进行。可自由基聚合的单体(ii)(c)和/或(ii)(d)可以通过捏合以通常方法混合。也可以同时捏合各种类型的添加剂、增强填料和交联剂。这些可通过使用内捏合机、双螺杆挤出类型捏合机、单螺杆捏合机、辊、班伯里密炼机、捏合机等改性和混合。
在本发明优选实施方案中,首先在橡胶成分(i)中加入成分(ii)(a)和成分(ii)(b),然后将它加热到优选150-220℃并在氮气气氛或贫氧状态下反应,再后进一步加入成分(ii)(c)和成分(ii)(d)并将所得混合物加热到优选120-220℃并在氮气气氛或贫氧状态下反应。可以通过采用该反应顺序提高成分(c)和(d)在丁基橡胶上的接枝量。
本发明橡胶组合物基于100重量份含改性丁基橡胶的橡胶成分优选还含有1-300重量份,优选30-200重量份的炭黑和/或硅石、滑石、各种类型的粘土或其他增强填料和优选0.05-15重量份,更优选0.1-10重量份的交联剂(例如过氧化苯甲酰、过苯甲酸叔丁基酯、过氧化二枯基、过氧化叔丁基枯基、过氧化二叔丁基、2,5-二甲基-2,5-二叔丁基过氧己烷、2,5-二甲基-2,5-二叔丁基过氧-3-己炔、2,4-二环过氧化苯甲酰、二叔丁基过氧-二异丙基苯、1,1-二(叔丁基过氧)-3,3,5-三甲基环己烷、4,4-二(叔丁基过氧)戊酸正丁基酯、2,2-二(叔丁基过氧)丁烷或其他有机过氧化物和偶氮二碳酰胺、偶氮二异丁腈、2,2’-偶氮二(2-脒基丙烷)二氢氯化物、二甲基-2,2’-偶氮二(异丁酸酯)、偶氮二氰戊酸、1,1’-偶氮二(2,4-二甲基戊腈)、偶氮二甲基丁腈、2,2’-偶氮二(4-甲氧基-2,4-二甲基戊腈)和其他偶氮基自由基引发剂等)。
本发明改性丁基橡胶组合物可以含有作为其他橡胶成分的苯乙烯-异戊二烯-丁二烯共聚物、氯丁二烯橡胶、乙烯-丙烯-二烯三元共聚物橡胶、乙烯-丙烯共聚物、乙烯-丙烯-丁烯三元共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、苯乙烯-乙烯-丙烯-苯乙烯共聚物、聚乙烯、聚丙烯、聚苯乙烯、聚芳族乙烯基类(polyaromatic vinyl)、聚烯烃、聚异戊二烯、各种类型的苯乙烯-丁二烯共聚物、各种类型的聚丁二烯、丙烯腈-丁二烯共聚物、氢化丙烯腈-丁二烯共聚物、聚异丁烯、聚丁烯、丁基橡胶、卤化丁基橡胶、苯乙烯-对甲基苯乙烯共聚物、卤化苯乙烯-对甲基苯乙烯共聚物、丙烯酰基橡胶(acryl rubber)、硅橡胶、氟橡胶、表氯醇橡胶、各种类型的聚甲基丙烯酸酯、各种类型的聚醚、各种类型的聚硫化物、各种类型的聚乙烯基醚、各种类型的聚酯、各种类型的聚酰胺、纤维素、淀粉、各种类型的聚氨酯、各种类型的聚脲、各种类型的聚胺等,但是改性丁基橡胶在橡胶成分中的量优选为至少5重量%,更优选至少10重量%。
除了上述成分外,本发明橡胶组合物可以含有其他填料、硫化或交联剂、硫化或交联促进剂、各种类型的油、抗氧化剂、增塑剂和其他各种类型的通常在用于轮胎的橡胶组合物或其他橡胶组合物中添加的添加剂。这些添加剂可以通过通常方法配混而得到用于硫化或交联的组合物。这些添加剂的量可以为常规用量,只要对本发明目的没有不利影响。
实施例
现在用实施例来进一步解释本发明,但本发明范围决不限于这些实施例。
制备实施例
使用下列材料来制备改性丁基橡胶1和2:
IIR:丁基橡胶(BUTYL301,Bayer制造)1,3-二(叔丁基过氧异丙基)苯:(Parkadox14-G,Kayaku Akzo制造)OH-TEMPO:4-羟基-2,2,6,6-四甲基哌啶基-1-氧自由基(LA7RD,AsahiDenka制造)
二(三羟甲基丙烷)四丙烯酸酯:(SR-355,Sartomer制造)甲基丙烯酰基硅烷:γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KBM503,Shin’etsu Chemical制造)
制备实施例1(改性IIR-1)
将350.0g IIR、24.2g1,3-二(叔丁基过氧异丙基)苯和32.2g OH-TEMPO加入温度设为60℃的内班伯里密炼机中并混合10分钟。将由此得到的混合物在温度设为100℃的内班伯里密炼机中捏合,同时氮气置换5分钟。在捏合同时,将温度升至165℃并继续捏合20分钟。将由此得到的部分聚合物溶解在甲苯中,然后分离该聚合物并通过再沉淀操作纯化。通过1HNMR对该纯化产物的分析证实引入了TEMPO位点。引入率为0.360摩尔%。一旦该反应体系回到150℃,就加入11.2g二(三羟甲基丙烷)四丙烯酸酯(SR-355)并将所得混合物捏合,同时氮气置换5分钟。在捏合同时,将温度升至185℃,然后将所得混合物捏合15分钟。将由此得到的部分聚合物溶解在甲苯中,然后分离该聚合物并通过再沉淀操作纯化。对该纯化产物作IR分析和1H NMR分析。在1720cm-1附近观察到酯羰基产生的吸收。由1H NMR在6.39、6.10、5.96、4.12和3.30ppm附近观察到SR-355产生的信号。证实SR-355通过留下三个烯烃的结构引入。
制备实施例2(改性IIR-2)
将350.0g IIR、24.2g1,3-二(叔丁基过氧异丙基)苯和32.2g OH-TEMPO加入温度设为60℃的内班伯里密炼机中并混合10分钟。将由此得到的混合物在温度设为100℃的内班伯里密炼机中捏合,同时氮气置换5分钟。在捏合同时,将温度升至165℃并继续捏合20分钟。将由此得到的部分聚合物溶解在甲苯中,然后分离该聚合物并通过再沉淀操作纯化。通过1HNMR对该纯化产物的分析证实引入了TEMPO位点(烷氧基氨基)。引入率为0.360摩尔%。一旦该反应体系回到150℃,就加入11.2g二(三羟甲基丙烷)四丙烯酸酯(SR-355)和5.8g甲基丙烯酰基硅烷并将所得混合物捏合,同时氮气置换5分钟。在捏合同时,将温度升至185℃,然后将所得混合物捏合15分钟。将由此得到的部分聚合物溶解在甲苯中,然后分离该聚合物并通过再沉淀操作纯化。对该纯化产物作IR分析和1H NMR分析。在1720cm-1附近观察到酯羰基产生的吸收。由1H NMR在6.39、6.10、5.96、4.12和3.30ppm附近观察到SR-355产生的信号。证实SR-355通过留下三个烯烃的结构引入。引入率为0.015摩尔%。
实施例1-3、对比例1-3和参考例1-3
制备样品
在表I中所示的每个配方中,将除了硫化促进剂和硫以外的成分在150cc捏合机中捏合6分钟。加入硫化促进剂和硫并将该混合物进一步在8英寸开炼机中捏合而得到橡胶组合物。
将由此得到的橡胶组合物在180℃下在15×15×0.2cm模具中平板硫化20分钟而形成硫化橡胶片,该硫化橡胶的物理性能通过下列测试方法测量。结果示于表I中。
评价橡胶性能的测试方法
交联橡胶片的状态:在视觉上判断的预成片。
50%模量:按照JIS K6251(使用3号哑铃)在室温下进行拉伸测试而得到50%形变模量。
抗张强度:按照JIS K6251(使用3号哑铃)在室温下进行拉伸测试。
表I注释:
1]丁基橡胶:BUTYL301,Bayer制造
2-3]通过制备实施例1和2合成的:
4]滑石F:Nippon Talc制造
5]Asahi#50:Asahi Carbon制造
6]珠粒硬脂酸YR:NOF Corporation制造
7]锌白类型3:Seido Chemical Industrial制造
8]过氧化二枯基:NOF Corporation制造,Percumyl D-40(过氧化物)
9]三羟甲基丙烷三甲基丙烯酸酯:Shin-Nakamura Chemical制造,NKEster A-TMPT(交联助剂)
10]三(三羟甲基丙烷)三丙烯酸酯:Shin-Nakamura Chemical制造(交联助剂)
工业实用性
根据本发明,可以通过使丁基橡胶(i)与其分子具有常温下甚至在氧气存在下稳定的氮氧自由基的化合物(ii)(a)如TEMPO衍生物、自由基引发剂(ii)(b)、双官能或更高官能的可自由基聚合单体(ii)(c)和具有烷氧基甲硅烷基团的可自由基聚合单体(ii)(d)反应来获得能够用有机过氧化物交联的改性丁基橡胶组合物并显著提高由此获得的改性丁基橡胶组合物交联产物的模量和抗张强度,并且由此充分保留丁基橡胶的性能如耐热性、气体阻隔性能、减振等并将其用作内胎、软外壳、屋顶、传送带、软管、电缆、减振橡胶、电子部件、各种类型的工业产品等。
Claims (7)
1.一种改性丁基橡胶组合物,其包含(i)包含丁基橡胶的橡胶成分与(ii)(a)其分子具有常温下甚至在氧气存在下稳定的氮氧自由基的化合物、(b)自由基引发剂、(c)双官能或更高官能的可自由基聚合单体和(d)具有烷氧基甲硅烷基团的可自由基聚合单体的反应产物。
2.根据权利要求1的改性丁基橡胶组合物,其中首先在橡胶成分(i)中加入成分(ii)(a)和成分(ii)(b)而一起反应,然后进一步使成分(ii)(c)和成分(ii)(d)与之反应。
3.根据权利要求1或2的改性丁基橡胶组合物,其中成分(ii)(c)的可自由基聚合单体包括作为可自由基聚合基团的电子受体基团。
4.根据权利要求1或2的改性丁基橡胶组合物,其中成分(ii)(d)的可自由基聚合单体含有作为可自由基聚合基团的电子受体基团。
5.根据权利要求1或2的改性丁基橡胶组合物,其基于100重量份含改性丁基橡胶的橡胶成分还包含1-300重量份的增强填料。
6.根据权利要求1或2的改性丁基橡胶组合物,其基于100重量份含改性丁基橡胶的橡胶成分还包含0.05-15重量份的交联剂。
7.根据权利要求6的改性丁基橡胶组合物,其中所述交联剂为有机过氧化物。
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CN116478406A (zh) * | 2023-04-04 | 2023-07-25 | 浙江精一新材料科技有限公司 | 一种用于光阀的聚硅氧烷及光阀 |
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