CN101289564A - 改性丁基橡胶组合物 - Google Patents
改性丁基橡胶组合物 Download PDFInfo
- Publication number
- CN101289564A CN101289564A CNA2008100925454A CN200810092545A CN101289564A CN 101289564 A CN101289564 A CN 101289564A CN A2008100925454 A CNA2008100925454 A CN A2008100925454A CN 200810092545 A CN200810092545 A CN 200810092545A CN 101289564 A CN101289564 A CN 101289564A
- Authority
- CN
- China
- Prior art keywords
- butyl rubber
- modified butyl
- butyl
- rubber
- rubber composition
- 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
Links
- 229920005549 butyl rubber Polymers 0.000 title claims abstract description 38
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001971 elastomer Polymers 0.000 claims description 41
- 239000005060 rubber Substances 0.000 claims description 41
- -1 nitroxid Chemical class 0.000 claims description 34
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000012763 reinforcing filler Substances 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 abstract description 13
- 238000006011 modification reaction Methods 0.000 abstract 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 21
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 20
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 14
- 238000005502 peroxidation Methods 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000126 substance Substances 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
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 4
- 230000001404 mediated effect Effects 0.000 description 4
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 3
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229960003328 benzoyl peroxide Drugs 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 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
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-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
- 239000002253 acid Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001723 carbon free-radicals Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 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
- 238000002360 preparation method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 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
- 238000012360 testing method Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- YKYIFUROKBDHCY-ONEGZZNKSA-N (e)-4-ethoxy-1,1,1-trifluorobut-3-en-2-one Chemical group CCO\C=C\C(=O)C(F)(F)F YKYIFUROKBDHCY-ONEGZZNKSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- UFFVWIGGYXLXPC-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1N1C(=O)C=CC1=O UFFVWIGGYXLXPC-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YHCVYAHUIMOIGE-UHFFFAOYSA-N 2,3-dihydroxypropyl but-2-enoate Chemical compound CC=CC(=O)OCC(O)CO YHCVYAHUIMOIGE-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
- IQQVCMQJDJSRFU-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO IQQVCMQJDJSRFU-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- KJTSSZOXUOZDSR-UHFFFAOYSA-N 2-imino-1-$l^{1}-oxidanyl-5,5-dimethylimidazol-4-amine Chemical compound CC1(C)N([O])C(=N)N=C1N KJTSSZOXUOZDSR-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004156 Azodicarbonamide Substances 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
- 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
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- 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
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- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
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- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
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- 235000010290 biphenyl Nutrition 0.000 description 1
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- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
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- 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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- YOQPJXKVVLAWRU-UHFFFAOYSA-N ethyl carbamate;methyl prop-2-enoate Chemical compound CCOC(N)=O.COC(=O)C=C YOQPJXKVVLAWRU-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- KVWOTUDBCFBGFJ-UHFFFAOYSA-N tert-butyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC(C)(C)C KVWOTUDBCFBGFJ-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
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Abstract
改性丁基橡胶组合物,其包含通过分子中具有寻常温度下在氧存在下稳定的硝基氧自由基的化合物(a)和自由基引发剂(b)的改性反应而获得的改性丁基橡胶,和至少两种双官能或更多官能的可自由基聚合的单体(c)。
Description
技术领域
本发明涉及改性丁基橡胶组合物,更特别涉及能够以自由基引发剂交联和能够廉价地改善改性丁基橡胶组合物的拉伸性能的改性橡胶组合物。
背景技术
丁基橡胶具有极低的不饱和度,因此其耐候性、耐热性、耐臭氧性等优异,并且透气性低。因此,丁基橡胶被用作密封剂、粘合剂等。作为丁基橡胶交联的方法,已知硫磺交联、醌型交联、树脂交联等,但是很难说目前通过任何方法都得到实践上令人满意的结果。也就是说,硫磺交联需要在高温下长时间交联。此外,醌型交联通常使用有害的铅丹作为用于活化醌的氧化剂,因此存在环境问题。此外,树脂交联的反应速度非常低,需要在高温下长时间加热。所述产物倾向于以不完全交联的状态形成,因此在使用中存在倾向于进行交联反应和物理性能容易被显著改变的问题。此外,在这些交联基于二烯的橡胶等的方法中,根本不常使用通过耐热性非常优良的有机过氧化物进行交联作为交联丁基橡胶的方法。这是因为,如果将该交联方式应用于丁基橡胶,容易主要地发生主链的降解反应,橡胶容易被相反地软化而不是交联。另一方面,部分交联的丁基橡胶可以作为对其可进行过氧化物交联的丁基橡胶而商购得到,但是这存在可加工性能不够的问题。此外,专利文献1公开了用于使得未交联的丁基橡胶在机过氧化物和具有电子受体基团的多官能单体存在下进行交联的方法,但是,根据该方法容易发生严重的逆反应。
在这些情况下,本发明人先前提出了改性丁基橡胶组合物,其耐候性、耐热性、耐臭氧性等优良,和能够使气体透过性低的普通丁基橡胶与有机过氧化物进行交联(参见专利文献2)。
专利文献1:日本专利公开(A)号6-172547
专利文献2:日本专利公开号2006-131780
发明内容
因此,本发明的一个目的在于廉价获得能够与有机过氧化物交联和能够进一步改善所述改性橡胶组合物的拉伸性能的改性橡胶组合物。
根据本发明,提供了一种改性丁基橡胶组合物,其包含通过分子中具有寻常温度下在氧存在下稳定的硝基氧自由基的化合物(a)和自由基引发剂(b)的改性反应而获得的(I)改性丁基橡胶,和至少两种双官能或更多官能的可自由基聚合的单体(c)。
根据本发明,向普通丁基橡胶中,通过添加和使得分子中具有硝基氧自由基(其在寻常温度下是稳定的,例如在室温下,甚至在氧存在下也是稳定的)的化合物(a)例如TEMPO衍生物和自由基引发剂反应,然后向其上接枝有上述分子中具有硝基氧自由基的化合物的改性丁基橡胶中添加和使得双官能或更多官能的可自由基聚合的单体和有机过氧化物反应,进行相同的交联反应,可以得到高拉伸性能的交联产物,即使所述可自由基聚合的单体的总重量被降低。
发明的最佳实施方式
本发明人之前进行了深入的研究以使普通丁基橡胶与有机过氧化物交联,结果提出了包含改性丁基橡胶的改性丁基橡胶组合物,所述改性丁基橡胶通过添加和使得分子中具有在寻常温度下甚至在氧存在下是稳定的硝基氧自由基的化合物(a)例如TEMPO衍生物和自由基引发剂(b)与所述普通丁基橡胶反应、然后添加和使得一种双官能或更多官能的可自由基聚合的单体(c)反应而获得,并且另外提出了含有改性丁基橡胶的改性丁基橡胶组合物,所述改性丁基橡胶通过化合物(a)、自由基引发剂(b)和一种双官能或更多官能的可自由基聚合的单体(c)与丁基橡胶反应而获得,但进行进一步研究,结果发现通过使用所述两种或更多种可自由基聚合的单体(c),可以改善交联产物的拉伸性能,即使使用少量的可自由基聚合的单体(c)。
根据本发明改性的丁基橡胶是异丁烯(其通常称为“丁基橡胶(IIR)”)和少量的异戊二烯(例如占所述整个橡胶的0.6-2.5mlo%)或其衍生物(例如氯化丁基橡胶、溴化丁基橡胶)的共聚物橡胶。这些是本领域公知的。还有很多可商购得到的产品。
本发明中使用的分子中具有寻常温度下在氧存在下稳定的硝基氧自由基的化合物(a)并不限于以下化合物,但可以例举以下化合物:
式1
式2
通式
在式(1)-(6)中,R表示含有官能团的有机基团,例如C1-C30烷基、烯丙基、氨基、异氰酸酯基、羟基、硫醇基、乙烯基、环氧基、硫杂丙环基(thirane group)、羧基、含有羰基的基团(例如无水琥珀酸、无水马来酸、无水戊二酸、无水酞酸、和其它环状酸酐)、酰胺基、酯基、酰亚胺基、腈基、硫氰基、C1-C20烷氧基、甲硅烷基、烷氧基甲硅烷基、硝基。
式3
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-乙氧基羰基TEMPO
式4
4-(N-苯基氨基甲酰基氧基)TEMPO 4-(N-甲基氨基甲酰基氧基)TEMPO
4-(N-乙基氨基甲酰基氧基)TEMPO
(6)
苯基(4-TEMPO)硫酸酯 甲基(4-TEMPO)硫酸酯
乙基(4-TEMPO)硫酸酯
其它实例如下:
式5
式6
2,2,6,6-四-甲基哌啶-1-基氧
X:Br或Cl
X:Br或Cl
式7
4-TEMPO-缩水甘油醚
式8
式9
式10
3-羟基-PRYXYL
3-异氰酸酯-PRYXYL
式11
3-PRYXYL-硫代缩水甘油醚
式12
二苯基硝酰
ON(SO3K)2 Fermi盐
式13
对本发明中可用的化合物(a)的用量没有特别的限定,但是优选0.001~0.5mol,更优选0.005~0.1mol,基于100g待改性的丁基橡胶。如果该量小的话,则丁基橡胶的改性量容易变低,但反过来如果大的话,则随后的交联容易停止进行。
作为在本发明中可用的自由基引发剂(b),可以使用能够将化合物(a)引入到丁基橡胶分子链中的任何自由基引发剂。具体而言,可以列举例如过氧化苯甲酰、过氧化苯甲酸叔丁酯、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、过氧化2,4-二氯苯甲酰、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、正丁基-4,4-二(叔丁基过氧)戊酸酯、2,2-二(叔丁基过氧)丁烷、过氧化二异丁基、过氧化新癸酸枯基酯、过氧化二碳酸-二正丙基酯、过氧化二碳酸二异丙基酯、过氧化二碳酸二仲丁基酯、过氧化新癸酸1,1,3,3-四甲基丁基酯、过氧化二碳酸二(4-叔丁基环己基)酯、过氧化新癸酸1-环己基-1-甲基乙基酯、过氧化二碳酸-二(2-乙氧基乙基)酯、过氧化二碳酸-二(2-乙氧基己基)酯、过氧化新癸酸叔己酯、过氧化二碳酸二甲氧基丁基酯、过氧化新癸酸叔丁酯、过氧化新戊酸叔己基酯、过氧化新戊酸叔丁基酯、过氧化-二(3,3,5-三甲基己酰)、过氧化-二-正辛酰、过氧化二月桂酰、过氧化二硬脂酰、过氧化-2-乙基己酸1,1,3,3-四甲基丁基酯、过氧化二琥珀酸酯、2,5-二甲基-2,5-二(2-乙基己酰基过氧)己烷、过氧化-2-乙基己酸叔己酯、过氧化二(4-甲基苯甲酰)、过氧化-2-乙基己酸叔丁酯、过氧化二(3-甲基苯甲酰)和过氧化苯甲酰基(3-甲基苯甲酰)和过氧化二苯甲酰的混合物、过氧化二苯甲酰、过氧化异丁酸叔丁酯。另外,关于能在低温下由氧化还原催化剂的作用引起分解的引发剂的典型实例,可以提及过氧化二苯甲酰、对孟烷氢过氧化物(paramethane hydroperoxide)、氢过氧化二异丙基苯、氢过氧化1,1,3,3-四甲基丁基、氢过氧化枯烯、氢过氧化叔丁基等。通过将这些引发剂加入反应体系内(即混合物体系和催化剂体系),可以在所述丁基橡胶中产生碳自由基,通过使在具有稳定自由基的化合物(a)与所述碳自由基反应而形成所希望的改性丁基橡胶。
对本发明中自由基引发剂(b)的添加量没有特别的限定,但优选是0.001~0.5mol,更优选0.005~0.2mol,基于100g待改性的丁基橡胶。如果该量过小的话,从所述丁基橡胶链离开的氢原子的量容易降低,而反之如果该量过大的话,所述丁基橡胶的主链容易分解,其分子量容易被大大降低。
对可用于本发明的两种或更多种双官能或更多官能的可自由基聚合的单体(c)没有特别的限定,但是可以提及例如二(甲基)丙烯酸亚乙基酯(这里,措词二(甲基)丙烯酸亚乙基酯包括二甲基丙烯酸亚乙基酯和二丙烯酸亚乙基醇酯,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)异氰酸酯三(甲基)丙烯酸酯、乙氧基化的三羟甲基丙烷三(甲基)丙烯酸酯、三(甲基)丙烯酸季戊四醇酯、乙氧基化的三羟甲基丙烷三(甲基)丙烯酸酯、丙氧基化的三羟甲基丙烷三(甲基)丙烯酸酯、丙氧基化的(甲基)丙烯酸甘油酯、四(甲基)丙烯酸季戊四醇酯、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、乙氧基化的四(甲基)丙烯酸季戊四醇酯、聚硅氧烷二(甲基)丙烯酸酯、各种类型的聚氨酯(甲基)丙烯酸酯、各种类型的(甲基)丙烯酸金属盐、聚丙二醇二(甲基)丙烯酸酯、N,N’-亚苯基二马来酰亚胺、双马来酰亚胺二苯基甲烷、N,N’-亚苯基二丙烯酰胺、二乙烯基苯、三烯丙基异氰脲酸酯等。其中,从提高改性率来看,分子内包含电子受体单元(例如,羰基(酮、醛、酯、羧酸、羧酸酯、酰胺)、硝基、氰基等)的单体是优选的。
对所述至少两种双官能或更多官能的可自由基聚合的单体(c)的用量没有特别的限定,但是优选0.001~0.5mol,更优选0.005~0.2mol,基于100g待改性的丁基橡胶。如果该量过小,则后来的交联不容易进行,而如果反之该量过大,则交联产物的物理性能容易恶化。
本发明中,对用于改性丁基橡胶的方法和用于将所述可自由基聚合的单体(c)与其混合的方法没有特别的限定,但是例如丁基橡胶可以例如如下进行改性。将所述丁基橡胶、化合物(a)和引发剂(b)的预混合物在用氮置换的内部捏合机中在150~220℃的温度下进行反应。优选氮置换,但是所述反应也可以在贫氧条件下进行。可以通过一般方法进行两种或更多种单体(c)的混合。各种添加剂、增强填料和交联剂可以被同时捏合。它们可以通过使用内部捏合机、双螺杆挤出型捏合机、单螺杆捏合机、辊、班伯里密炼机、捏合机等来改性和混合。
根据本发明的橡胶组合物优选进一步包含:基于100重量份含有所述改性丁基橡胶的橡胶组分计,其量为5~300重量份、优选30~200重量份的增强填料(e),如碳黑和/或二氧化硅,和其量优选为0.05~15重量份、更优选0.1~10重量份的交联剂(d)(例如过氧化苯甲酰、过氧化苯甲酸叔丁酯、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、过氧化2,4-二氯苯甲酰、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、正丁基-4,4-二(叔丁基过氧)戊酸酯、2,2-二(叔丁基过氧)丁烷,或其它有机过氧化物和偶氮二酰胺、偶氮二异丁腈、2,2’-偶氮二-(2-脒基丙烷)二盐酸盐、2,2’-偶氮二(异丁酸)二甲酯、偶氮二-氰基戊酸、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)或其它偶氮型自由基引发剂等)。
根据本发明的改性丁基橡胶组合物可以含有作为其它橡胶组分的苯乙烯-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、聚芳族乙烯基化合物、聚烯烃、聚异戊二烯、各种苯乙烯-丁二烯共聚物、各种聚丁二烯、丙烯腈-丁二烯共聚物、氢化丙烯腈-丁二烯共聚物、丙烯酸酯橡胶、硅氧烷橡胶、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,但是所述改性丁基橡胶在所述橡胶组分中的量优选为至少10wt%。
除了上述组分之外,根据本发明的橡胶组合物还可以包含其它填料、硫化或交联剂、硫化或交联促进剂、各种油、抗氧化剂、增塑剂、和通常被混入轮胎和其它橡胶产品用的橡胶组合物中的其它各种添加剂。这些添加剂可以通过一般方法混合,以得到用于硫化或交联的组合物。这些添加剂的量可以是常规的一般用量,只要对本发明的目的没有不利影响。
实施例
现在使用实施例来进一步说明本发明,但本发明的范围决不限于这些实施例。
以下实施例中所用的物料如下:
IIR:丁基橡胶(由Bayer生产,BUTYL301)
1,3-双-(叔丁基过氧异丙基)苯:[由Kayaku Akzo Corporation生产,Parkadox 14-G]
OH-TEMPO:4-羟基-2,2,6,6-四甲基哌啶基-1-氧基[由Adenka生产,LA7RD]
制备改性IIR组合物(OHT-IIR)的实施例
将IIR 350.0g、1,3-双-(叔丁基过氧异丙基)苯24.2g和OH-TEMPO32.2g装入温度设置为60℃的密闭式班伯里密炼机中,并混合10分钟。由此获得的混合物在温度设置为100℃的密闭式班伯里密炼机中进行捏合,同时用氮置换该密炼机的内部5分钟。捏合的同时,升高温度至165℃,连续捏合20分钟。将由此获得的聚合物的一部分溶解于甲苯中,然后通过沉淀操作分离和纯化所述聚合物。纯化的产物被用于通过1H-NMR的分析,确定TEMPO(烷氧基氨基)位点的引入。引入率是0.317mol%。
实施例1~6、比较实施例1和参考实施例1~11
将表I中所示的各配方(重量份)在150cc捏合机中捏合6分钟。加入丙烯酸酯,并通过8英寸的开放辊进一步捏合,以获得橡胶组合物。将由此获得的橡胶组合物在180℃压紧硫化20分钟,以形成2mm厚的片状物。从该片状物打孔出编号为3的哑铃体测试片,然后根据JIS K 6251对其进行张力测试,以获得50%的模量、断裂拉伸强度和断裂伸长率。结果示于表I中。
表I的注释
*1)参见制备实施例
*2)Asahi#50:由Asahi Carbon生产
*3)Talc F:由Nippon Talc生产
*4)珠状硬脂酸YR:由NOF Corporation生产
*5)过氧化二枯基:由NOF Corporation生产,Percumyl D
*6)锌白型号3:由Seido Chemical Industrial生产
*7)三羟甲基丙烷三甲基丙烯酸酯:由Shin-Nakamura Chemical生产,NK酯A-AMPT
*8)二三羟甲基丙烷四丙烯酸酯:由Startomer生产,SR-355
*9)二季戊四醇六丙烯酸酯:由Shin-Nakamura Chemical生产,A-DPH
工业应用性
如上所述,根据本发明,通过向使用分子中具有硝基氧自由基(其在寻常温度下甚至在氧存在下也是稳定的)的化合物(a)例如TEMPO衍生物和自由基引发剂(b)改性的丁基橡胶中加入至少两种双官能或更多官能的可自由基聚合的单体(c),可以获得能够与有机过氧化物交联的改性丁基橡胶组合物,同时使用两种或更多种可自由基聚合的单体,可以提高交联产物的拉伸性能,即使所述可聚合单体的用量被降低,因此,可以充分维持丁基橡胶的性能,例如耐热性、气体透过性、震动吸收等,并可以用作轮胎、囊、屋顶、运输带、软管、缆索、震动吸收橡胶、电子器件、各种工业制品等。
Claims (6)
1.改性丁基橡胶组合物,其包含(I)通过分子中具有寻常温度下在氧存在下稳定的硝基氧自由基的化合物(a)和自由基引发剂(b)的改性反应而获得的改性丁基橡胶,和(II)至少两种双官能或更多官能的可自由基聚合的单体(c)。
2.如权利要求1中所述的改性丁基橡胶组合物,其中所述至少两种双官能或更多官能的可自由基聚合的单体(c)是具有电子受体基团的单体。
3.如权利要求1或2中所述的橡胶组合物,其进一步包含交联剂(d)。
4.如权利要求1~3中任一项所述的改性丁基橡胶组合物,其进一步包含,基于100重量份含有所述改性丁基橡胶的橡胶组分,其量为0.05~15重量份的交联剂(d)。
5.如权利要求1~4中任一项所述的改性丁基橡胶组合物,其进一步包含,基于100重量份含有所述改性丁基橡胶的橡胶组分,其量为5~300重量份的增强填料(e)。
6.如权利要求3~5中任一项所述的改性丁基橡胶组合物,其中所述交联剂(d)是有机过氧化物。
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CN103702829A (zh) * | 2011-07-20 | 2014-04-02 | 横滨橡胶株式会社 | 橡胶叠层体 |
CN106280500A (zh) * | 2016-08-26 | 2017-01-04 | 广东省石油化工研究院 | 一种热塑性动态硫化溴化丁基橡胶/聚丙烯组合物及其制备方法 |
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JP4420095B2 (ja) | 2007-10-01 | 2010-02-24 | 横浜ゴム株式会社 | 変性ブチルゴム組成物 |
JP4442688B2 (ja) * | 2007-12-13 | 2010-03-31 | 横浜ゴム株式会社 | 変性ブチルゴム組成物 |
JP2010241915A (ja) * | 2009-04-02 | 2010-10-28 | Yokohama Rubber Co Ltd:The | 表面改質ゴム成形体の製造方法 |
JP5459042B2 (ja) * | 2010-04-23 | 2014-04-02 | 横浜ゴム株式会社 | タイヤ製造用ブラダーの製造方法 |
JP5863308B2 (ja) * | 2010-11-25 | 2016-02-16 | 横浜ゴム株式会社 | 空気入りタイヤの製造方法 |
US9745388B2 (en) * | 2012-12-18 | 2017-08-29 | Lanxess, Inc. | Butyl rubber with increased impermeability |
FR3030543B1 (fr) * | 2014-12-22 | 2017-01-13 | Michelin & Cie | Pneumatique comprenant une composition comprenant un derive d'acrylate polyfonctionnel et un peroxyde |
CN105906767A (zh) * | 2016-06-21 | 2016-08-31 | 柳州市颖航汽配有限公司 | 橡胶改性方法 |
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JP3963917B2 (ja) * | 2005-01-12 | 2007-08-22 | 横浜ゴム株式会社 | ポリマーの変性方法 |
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CN103702829B (zh) * | 2011-07-20 | 2015-09-23 | 横滨橡胶株式会社 | 橡胶叠层体 |
CN106280500A (zh) * | 2016-08-26 | 2017-01-04 | 广东省石油化工研究院 | 一种热塑性动态硫化溴化丁基橡胶/聚丙烯组合物及其制备方法 |
CN106280500B (zh) * | 2016-08-26 | 2018-08-21 | 广东省石油化工研究院 | 一种热塑性动态硫化溴化丁基橡胶/聚丙烯组合物及其制备方法 |
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