CA2458741A1 - Peroxide curable butyl formulations containing high-isoprene butyl rubber - Google Patents
Peroxide curable butyl formulations containing high-isoprene butyl rubber Download PDFInfo
- Publication number
- CA2458741A1 CA2458741A1 CA 2458741 CA2458741A CA2458741A1 CA 2458741 A1 CA2458741 A1 CA 2458741A1 CA 2458741 CA2458741 CA 2458741 CA 2458741 A CA2458741 A CA 2458741A CA 2458741 A1 CA2458741 A1 CA 2458741A1
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- CA
- Canada
- Prior art keywords
- mol
- multiolefin
- repeating units
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- compound according
- 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.)
- Abandoned
Links
- 150000002978 peroxides Chemical class 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 title description 33
- 229920005549 butyl rubber Polymers 0.000 title description 20
- 238000009472 formulation Methods 0.000 title description 17
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 title description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 229920001971 elastomer Polymers 0.000 claims abstract description 20
- 239000005060 rubber Substances 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 6
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 25
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 16
- JTEJPPKMYBDEMY-UHFFFAOYSA-N 5-methoxytryptamine Chemical compound COC1=CC=C2NC=C(CCN)C2=C1 JTEJPPKMYBDEMY-UHFFFAOYSA-N 0.000 claims 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 41
- 238000000034 method Methods 0.000 description 15
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- 230000009257 reactivity Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- -1 vinyl aromatic compound Chemical class 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001451 organic peroxides Chemical class 0.000 description 5
- XJBOZKOSICCONT-UHFFFAOYSA-N 4,6,6-trimethylbicyclo[3.1.1]hept-2-ene Chemical compound CC1C=CC2C(C)(C)C1C2 XJBOZKOSICCONT-UHFFFAOYSA-N 0.000 description 4
- 229920002367 Polyisobutene Polymers 0.000 description 4
- 150000001348 alkyl chlorides Chemical class 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- HIACAHMKXQESOV-UHFFFAOYSA-N 1,2-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC=C1C(C)=C HIACAHMKXQESOV-UHFFFAOYSA-N 0.000 description 3
- 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 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- ZJQIXGGEADDPQB-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4-dimethylbenzene Chemical group CC1=CC=C(C=C)C(C=C)=C1C ZJQIXGGEADDPQB-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012668 chain scission Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 2
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 2
- 229940038597 peroxide anti-acne preparations for topical use Drugs 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- BOGRNZQRTNVZCZ-AATRIKPKSA-N (3e)-3-methylpenta-1,3-diene Chemical compound C\C=C(/C)C=C BOGRNZQRTNVZCZ-AATRIKPKSA-N 0.000 description 1
- AFVDZBIIBXWASR-AATRIKPKSA-N (E)-1,3,5-hexatriene Chemical compound C=C\C=C\C=C AFVDZBIIBXWASR-AATRIKPKSA-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
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- BOGRNZQRTNVZCZ-UHFFFAOYSA-N 1,2-dimethyl-butadiene Natural products CC=C(C)C=C BOGRNZQRTNVZCZ-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- JLSUFZZPRVNDIW-UHFFFAOYSA-N 1-ethenylcyclohexa-1,3-diene Chemical compound C=CC1=CC=CCC1 JLSUFZZPRVNDIW-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- DZPCYXCBXGQBRN-UHFFFAOYSA-N 2,5-Dimethyl-2,4-hexadiene Chemical compound CC(C)=CC=C(C)C DZPCYXCBXGQBRN-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- XNUNYHQZMMREQD-UHFFFAOYSA-N 2-methylhepta-1,6-diene Chemical compound CC(=C)CCCC=C XNUNYHQZMMREQD-UHFFFAOYSA-N 0.000 description 1
- SLQMKNPIYMOEGB-UHFFFAOYSA-N 2-methylhexa-1,5-diene Chemical compound CC(=C)CCC=C SLQMKNPIYMOEGB-UHFFFAOYSA-N 0.000 description 1
- DRWYRROCDFQZQF-UHFFFAOYSA-N 2-methylpenta-1,4-diene Chemical compound CC(=C)CC=C DRWYRROCDFQZQF-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-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
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- BEAVVRNWAHFHLW-UHFFFAOYSA-N 3-prop-1-en-2-ylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C(C(=C)C)=CC1C2 BEAVVRNWAHFHLW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- AQYKIROTAGYYQK-UHFFFAOYSA-N 5,5-dimethyl-3-methylidenehex-1-ene Chemical compound CC(C)(C)CC(=C)C=C AQYKIROTAGYYQK-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 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
- 239000004604 Blowing Agent Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QAIOLDOTSOHBJD-UHFFFAOYSA-N [ClH]1C(CCCC1)=O Chemical compound [ClH]1C(CCCC1)=O QAIOLDOTSOHBJD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229960003328 benzoyl peroxide Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- IMJGQTCMUZMLRZ-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C=CC(=C)C1=CC=CC=C1 IMJGQTCMUZMLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
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- 239000004088 foaming agent Substances 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
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- 229920001194 natural rubber Polymers 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 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
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- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- GQIJYUMTOUBHSH-IJIVKGSJSA-N piperyline Chemical compound C=1C=C2OCOC2=CC=1/C=C/C=C/C(=O)N1CCCC1 GQIJYUMTOUBHSH-IJIVKGSJSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- FQLQNUZHYYPPBT-UHFFFAOYSA-N potassium;azane Chemical class N.[K+] FQLQNUZHYYPPBT-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- 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
- C08F236/08—Isoprene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
- C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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Abstract
The present invention relates to a peroxide curable rubber compound containing polymers with a Mooney viscosity of at least 25 Mooney-units and a gel content of less than 15 wt.% comprising repeating units derived from at least one isoolefin monomer, more than 4.1 mol% of repeating units derived from at least one multiolefin monomer, as well as optionally further copolymerizable monomers, and repeating units derived from at least one multiolefin cross-linking agent containing no transition metal compounds and no organic nitro compounds.
Description
PEROXIDE CURABLE RUBBER COMPOUND CONTAINING HIGH
ISOPRENE BUTYL RUBBER
FIELD OF THE INVENTION
The present invention relates to a peroxide curable rubber compound containing polymers with a Mooney viscosity of at least 25 Mooney-units and a gel content of less than 15 wt.% comprising repeating units derived from at least one isoolefin monomer, more than 4.1 mol% of repeating units derived from at least one multiolefm monomer, as well as optionally further copolymerizable monomers, and repeating units derived from at least one multiolefin cross-linking agent containing no transition metal compounds and no organic nitro compounds.
Preferably the polymers have a multiolefin content of greater than 4.1 mol%, and a gel content of less than 10 wt.% and have been produced at conversions ranging from 70 % to 95%. Preferably, the polymers have a Mooney viscosity in the range of from 25-70 MU, more preferably 30-60 MU, even more preferably 30-55 MU.
BACKGROUND OF THE INVENTION
Butyl rubber is understood to be a copolymer of an isoolefin and one or more, preferably conjugated, multiolefins as comonomers. Commercial butyl comprise a major portion of isoolefin and a minor amount, not more than 2.5 mol %, of a conjugated multiolefin. The preferred isoolefin is isobutylene. However, this invention also covers polymers optionally comprising additional copolymerizable co-monomers.
Butyl rubber or butyl polymer is generally prepared in a slurry process using methyl chloride as a vehicle and a Friedel-Crafts catalyst as part of the polymerization initiator. The methyl chloride offers the advantage that AlCl3, a relatively inexpensive Friedel-Crafts catalyst, is soluble in it, as are the isobutylene and isoprene comonomers.
Additionally, the butyl rubber polymer is insoluble in the methyl chloride and precipitates out of solution as fine particles. The polymerization is generally earned out at temperatures of about -90°C to -100°C. See U.S. Patent No.
ISOPRENE BUTYL RUBBER
FIELD OF THE INVENTION
The present invention relates to a peroxide curable rubber compound containing polymers with a Mooney viscosity of at least 25 Mooney-units and a gel content of less than 15 wt.% comprising repeating units derived from at least one isoolefin monomer, more than 4.1 mol% of repeating units derived from at least one multiolefm monomer, as well as optionally further copolymerizable monomers, and repeating units derived from at least one multiolefin cross-linking agent containing no transition metal compounds and no organic nitro compounds.
Preferably the polymers have a multiolefin content of greater than 4.1 mol%, and a gel content of less than 10 wt.% and have been produced at conversions ranging from 70 % to 95%. Preferably, the polymers have a Mooney viscosity in the range of from 25-70 MU, more preferably 30-60 MU, even more preferably 30-55 MU.
BACKGROUND OF THE INVENTION
Butyl rubber is understood to be a copolymer of an isoolefin and one or more, preferably conjugated, multiolefins as comonomers. Commercial butyl comprise a major portion of isoolefin and a minor amount, not more than 2.5 mol %, of a conjugated multiolefin. The preferred isoolefin is isobutylene. However, this invention also covers polymers optionally comprising additional copolymerizable co-monomers.
Butyl rubber or butyl polymer is generally prepared in a slurry process using methyl chloride as a vehicle and a Friedel-Crafts catalyst as part of the polymerization initiator. The methyl chloride offers the advantage that AlCl3, a relatively inexpensive Friedel-Crafts catalyst, is soluble in it, as are the isobutylene and isoprene comonomers.
Additionally, the butyl rubber polymer is insoluble in the methyl chloride and precipitates out of solution as fine particles. The polymerization is generally earned out at temperatures of about -90°C to -100°C. See U.S. Patent No.
2,356,128 and Ullmanns Encyclopedia of Industrial Chemistry, volume A 23, 1993, pages 288-295.
The low polymerization temperatures are required in order to achieve molecular weights which are sufficiently high for rubber applications.
Peroxide curable butyl rubber compounds offer several advantages over conventional, sulfur-curing, systems. Typically, these compounds display extremely fast cure rates and the resulting cured articles tend to possess excellent heat resistance.
In addition, peroxide-curable formulations are considered to be "clean" in that they do not contain any extractable inorganic impurities (e.g. sulfur). The clean rubber articles can therefore be used, for example, in condenser caps, biomedical devices, pharmaceutical devices (stoppers in medicine-containing vials, plungers in syringes) and possibly in seals for fuel cells.
It is well accepted that polyisobutylene and butyl rubber decompose under the action of organic peroxides. Furthermore, US 3,862,265 and US 4,749,505 teach us that copolymers of a Cø to C~ isomonoolefin with up to 10 wt. % isoprene or up to 20 wt. % para-alkylstyrene undergo a molecular weight decrease when subjected to high shear mixing. This effect is enhanced in the presence of free radical initiators.
One approach to obtaining a peroxide-curable butyl-based formulation lies in the use of conventional butyl rubber in conjunction with a vinyl aromatic compound like DVB and an organic peroxide (see JP-A-107738/1994). In place of DVB, an electron-withdrawing group-containing polyfunctional monomer (ethylene dimethacrylate, trimethylolpropane triacrylate, N,N'-m-phenylene dimaleimide) can also be used (see JP-A-172547/1994).
A commercially available terpolymer based on IB, IP, and DVB, Bayer XL-10000, is curable with peroxides alone. However, this material does possess some significant disadvantages. For example, the presence of significant levels of free DVB
can present serious safety concerns. In addition, since the DVB is incorporated during the polymerization process a significant amount of crosslinking occurs during manufacturing. The resulting high Mooney (ca. 60-75 MU, M~,1+8 @ 125 °C) and presence of gel particles make this material extremely difficult to process.
For these reasons, it would be desirable to have an isobutylene based polymer which is peroxide curable, completely soluble (i.e. gel free) and contains no, or trace amounts of, divinylbenzene in its composition.
White et al. (US 5,578.682) have previously claimed a process for obtaining a polymer with a bimodal molecular weight distribution derived from a polymer that originally possessed a monomodal molecular weight distribution. The polymer, e.g., polyisobutylene, a butyl rubber or a copolymer of isobutylene and para-rnethylstyrene, was mixed with a polyunsaturated crosslinking agent (and, optionally, a free radical initiator) and subjected to high shearing mixing conditions in the presence of organic peroxide. This bimodalization was a consequence of the coupling of some of the free-s radical degraded polymer chains at the unsaturation present in the crosslinking co-agent. It is important to note that this patent was silent about any filled compounds of such modified polymers or the cure state of such compounds.
Sudo et. al. (US 5,994,465) have claimed a method for curing regular butyl, with isoprene contents ranging from 0.5 to 2.5 moI %, by treatment with a peroxide and a bismaleimide species. In essence, this patent blankets all commercially available grades of butyl rubber. As will be shown by our comparative examples, the cure states (delta torques) achieved for formulations based on RB301 or RB402 (both of which are materials which fall under the specification window described in 5994465) are significantly inferior to those observed for the inventive high IP butyl analogues of this invention.
Co-Pending application CA-2,418;884 discloses a continuos process for producing polymers having a Mooney viscosity of at least 25 Mooney-units and a gel content of less than 15 wt. % comprising repeating units derived from at least one isoolefin monomer, more than 4.1 mol % of repeating units derived from at least one multiolefin monomer and optionally further copolymerizable monomers in the presence of AIC13 and a proton source and/or cationogen capable of initiating the polymerization process and at least one multiolefin cross-linking agent wherein the process is conducted in the absence of transition metal compounds. These polymers are well suited for the inventive rubber formulations of this invention and with regards to jurisdictions allowing for this method are enclosed by reference herein.
SUMMARY OF THE INVENTION
The present invention provides a peroxide curable rubber compound containing polymers with a Mooney viscosity of at least 25 Mooney-units and a gel content of less than 15 wt.% comprising repeating units derived from at least one isoolefin monomer, more than 4.1 moI% of repeating units derived fram at least one multiolefin monomer, as well as optionally further copolymerizable monomers, and repeating units derived from at least one multiolefin cross-linking agent containing no transition metal compounds and no organic nitro compounds.
SHORT DESCRIPTION OF THE DRAWINGS
Fig. 1 shows the MDR cure characteristics of Examples 3-9 DETAILED DESCRIPTION OF THE INVENTION
The Mooney viscosity of the polymer is determined using ASTM test D1646 using a large rotor at 125 °C, a preheat phase of 1 min, and an analysis phase of 8 min (MLl+8 @ 125 °C) The invention is not limited to a special isoolefin. However, isoolefins within the range of from 4 to 16 carbon atoms, in particular 4-7 carbon atoms, such as isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1-pentene and mixtures thereof are preferred. Most preferred is isobutene.
The invention is not limited to a special multiolefin. Every multiolefin copolymerizable with the isoolefin known by the skilled in the art can be used.
However, multiolefins within the range of from 4-14 carbon atoms, such as isoprene, butadiene, 2-methylbutadiene, 2,4-dimethylbutadiene, piperyline, 3-methyl-1,3-pentadiene, 2,4-hexadiene, 2-neopentylbutadiene, 2-methyl-1,5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-1,4-pentadiene, 2-methyl-1,6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclohexadiene and mixtures thereof, in particular conjugated dimes, are preferably used.
Isoprene is particularly preferably used.
In the present invention, (3-pinene can also be used as a co-monomer for the isoolefin.
As optional monomers every monomer copolymerizable with the isoolefins and/or dimes known by the skilled in the art can be used. oc-methyl styrene, p-methyl styrene, chlorostyrene, cyclopentadiene and methylcyclopentadiene are preferably used.
Indene and other styrene derivatives may also be used in this invention The multiolefin content is at least greater than 4.1 mol%, more preferably greater than 5.0 mol%, even more preferably greater than 6.0 mol%, yet even more preferably greater than 7.0 mol%.
The low polymerization temperatures are required in order to achieve molecular weights which are sufficiently high for rubber applications.
Peroxide curable butyl rubber compounds offer several advantages over conventional, sulfur-curing, systems. Typically, these compounds display extremely fast cure rates and the resulting cured articles tend to possess excellent heat resistance.
In addition, peroxide-curable formulations are considered to be "clean" in that they do not contain any extractable inorganic impurities (e.g. sulfur). The clean rubber articles can therefore be used, for example, in condenser caps, biomedical devices, pharmaceutical devices (stoppers in medicine-containing vials, plungers in syringes) and possibly in seals for fuel cells.
It is well accepted that polyisobutylene and butyl rubber decompose under the action of organic peroxides. Furthermore, US 3,862,265 and US 4,749,505 teach us that copolymers of a Cø to C~ isomonoolefin with up to 10 wt. % isoprene or up to 20 wt. % para-alkylstyrene undergo a molecular weight decrease when subjected to high shear mixing. This effect is enhanced in the presence of free radical initiators.
One approach to obtaining a peroxide-curable butyl-based formulation lies in the use of conventional butyl rubber in conjunction with a vinyl aromatic compound like DVB and an organic peroxide (see JP-A-107738/1994). In place of DVB, an electron-withdrawing group-containing polyfunctional monomer (ethylene dimethacrylate, trimethylolpropane triacrylate, N,N'-m-phenylene dimaleimide) can also be used (see JP-A-172547/1994).
A commercially available terpolymer based on IB, IP, and DVB, Bayer XL-10000, is curable with peroxides alone. However, this material does possess some significant disadvantages. For example, the presence of significant levels of free DVB
can present serious safety concerns. In addition, since the DVB is incorporated during the polymerization process a significant amount of crosslinking occurs during manufacturing. The resulting high Mooney (ca. 60-75 MU, M~,1+8 @ 125 °C) and presence of gel particles make this material extremely difficult to process.
For these reasons, it would be desirable to have an isobutylene based polymer which is peroxide curable, completely soluble (i.e. gel free) and contains no, or trace amounts of, divinylbenzene in its composition.
White et al. (US 5,578.682) have previously claimed a process for obtaining a polymer with a bimodal molecular weight distribution derived from a polymer that originally possessed a monomodal molecular weight distribution. The polymer, e.g., polyisobutylene, a butyl rubber or a copolymer of isobutylene and para-rnethylstyrene, was mixed with a polyunsaturated crosslinking agent (and, optionally, a free radical initiator) and subjected to high shearing mixing conditions in the presence of organic peroxide. This bimodalization was a consequence of the coupling of some of the free-s radical degraded polymer chains at the unsaturation present in the crosslinking co-agent. It is important to note that this patent was silent about any filled compounds of such modified polymers or the cure state of such compounds.
Sudo et. al. (US 5,994,465) have claimed a method for curing regular butyl, with isoprene contents ranging from 0.5 to 2.5 moI %, by treatment with a peroxide and a bismaleimide species. In essence, this patent blankets all commercially available grades of butyl rubber. As will be shown by our comparative examples, the cure states (delta torques) achieved for formulations based on RB301 or RB402 (both of which are materials which fall under the specification window described in 5994465) are significantly inferior to those observed for the inventive high IP butyl analogues of this invention.
Co-Pending application CA-2,418;884 discloses a continuos process for producing polymers having a Mooney viscosity of at least 25 Mooney-units and a gel content of less than 15 wt. % comprising repeating units derived from at least one isoolefin monomer, more than 4.1 mol % of repeating units derived from at least one multiolefin monomer and optionally further copolymerizable monomers in the presence of AIC13 and a proton source and/or cationogen capable of initiating the polymerization process and at least one multiolefin cross-linking agent wherein the process is conducted in the absence of transition metal compounds. These polymers are well suited for the inventive rubber formulations of this invention and with regards to jurisdictions allowing for this method are enclosed by reference herein.
SUMMARY OF THE INVENTION
The present invention provides a peroxide curable rubber compound containing polymers with a Mooney viscosity of at least 25 Mooney-units and a gel content of less than 15 wt.% comprising repeating units derived from at least one isoolefin monomer, more than 4.1 moI% of repeating units derived fram at least one multiolefin monomer, as well as optionally further copolymerizable monomers, and repeating units derived from at least one multiolefin cross-linking agent containing no transition metal compounds and no organic nitro compounds.
SHORT DESCRIPTION OF THE DRAWINGS
Fig. 1 shows the MDR cure characteristics of Examples 3-9 DETAILED DESCRIPTION OF THE INVENTION
The Mooney viscosity of the polymer is determined using ASTM test D1646 using a large rotor at 125 °C, a preheat phase of 1 min, and an analysis phase of 8 min (MLl+8 @ 125 °C) The invention is not limited to a special isoolefin. However, isoolefins within the range of from 4 to 16 carbon atoms, in particular 4-7 carbon atoms, such as isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1-pentene and mixtures thereof are preferred. Most preferred is isobutene.
The invention is not limited to a special multiolefin. Every multiolefin copolymerizable with the isoolefin known by the skilled in the art can be used.
However, multiolefins within the range of from 4-14 carbon atoms, such as isoprene, butadiene, 2-methylbutadiene, 2,4-dimethylbutadiene, piperyline, 3-methyl-1,3-pentadiene, 2,4-hexadiene, 2-neopentylbutadiene, 2-methyl-1,5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-1,4-pentadiene, 2-methyl-1,6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclohexadiene and mixtures thereof, in particular conjugated dimes, are preferably used.
Isoprene is particularly preferably used.
In the present invention, (3-pinene can also be used as a co-monomer for the isoolefin.
As optional monomers every monomer copolymerizable with the isoolefins and/or dimes known by the skilled in the art can be used. oc-methyl styrene, p-methyl styrene, chlorostyrene, cyclopentadiene and methylcyclopentadiene are preferably used.
Indene and other styrene derivatives may also be used in this invention The multiolefin content is at least greater than 4.1 mol%, more preferably greater than 5.0 mol%, even more preferably greater than 6.0 mol%, yet even more preferably greater than 7.0 mol%.
Preferably, the monomer mixture comprises in the range of from 80% to 95% by weight of at least one isoolefin monomer and in the range of from 4.0% to 20%
by weight of at least one multiolefin monomer including (3-pinene and in the range of from 0.01 % to 1 % by weight of at least one multiolefin cross-linking agent. More preferably, the monomer mixture comprises in the range of from 83% to 94% by weight of at least one isoolefin monomer and in the range of from 5.0% to 17% by weight of a multiolefin monomer or (3-pinene and in the range of from 0.01% to 1% by weight of at least one multiolefin cross-linking agent. Most preferably, the monomer mixture comprises in the range of from 85% to 93% by weight of at least one isoolefin monomer and in the range of from 6.0% to 15% by weight of at least one multiolefin monomer, including (3-pinene and in the range of from 0.01 % to 1 % by weight of at least one multiolefin cross-linking agent.
The weight average molecular weight, MW, is preferably greater than 240 kg/mol, more preferably greater than 300 kg/mol, even more preferably greater than 500 kg/mol, yet even more preferably greater than 600 kg/mol.
In connection with this invention the term "gel" is understood to denote a fraction of the polymer insoluble for 60 min in cyclohexane boiling under reflux. The gel content is preferably less than 10 wt.%, more preferably less than 5 wt%, even more preferably less than 3 wt%, yet even more preferably less than 1 wt%.
There are no organic nitro compounds or transition metals present.
The butyl polymer further comprises unites derived from one or more multiolefin cross-linking agents. The term cross-linking agent is known to those skilled in the art and is understood to denote a compound that causes chemical cross-linking between the polymer chains in opposition to a monomer that will add to the chain.
Some easy preliminary tests will reveal if a compound will act as a monomer or a cross-linking agent. The choice of the cross-linking agent is not particularly restricted.
Preferably, the cross-linking comprises a multiolefinic hydrocarbon compound.
Examples of these are norbornadiene, 2-isopropenylnorbornene, 2-vinyl-norbornene, 1,3,5-hexatriene, 2-phenyl-1,3-butadiene, divinylbenzene, diisopropenylbenzene, divinyltoluene, divinylxylene and C1 to C2o alkyl-substituted derivatives thereof. More preferably, the multiolefin crosslinking agent is divinylbenzene, diisopropenylbenzene, divinyltoluene, divinyl-xylene and C1 to C2o alkyl substituted derivatives thereof, and or mixtures of the compounds given. Most preferably the multiolefin crosslinking agent comprises divinylbenzene and diisopropenylbenzene.
The polymerization preferably is performed in a continuous process in slurry (suspension), in a suitable diluent, such as chloroalkanes as described in US
5,417,930.
The monomers are generally polymerized canonically, preferably at temperatures in the range from -120°C to +20°C, preferably in the range from -100°C
to -20°C, and pressures in the range from 0.1 to 4 bar.
The use of a continuous reactor as opposed to a batch reactor seems to have a positive effect on the polymer. Preferably, the process is conducted in at least one continuos reactor having a volume of between O.I m3 and 100 m3, more preferable between 1 m3 and 10 m3.
Inert solvents or diluents known to the person skilled in the art for butyl polymerization may be considered as the solvents or diluents (reaction medium). These comprise alkanes, chloroalkanes, cycloalkanes or aromatics, which are frequently also mono- or polysubstituted with halogens. Hexane/chloroalkane mixtures, methyl chlo-ride, dichloromethane or the mixtures thereof may be mentioned in particular.
Chlo-roalkanes are preferably used in the process according to the present invention.
Said polymers with a Mooney viscosity of at least 25 Mooney-units and a gel content of less than 15 wt.% comprising repeating units derived from at least one isoolefin monomer, more than 4.1 mol% of repeating units derived from at least one multiolefin monomer, as well as optionally further copolymerizable monomers, and repeating units derived from at least one multiolefin cross-linking agent containing no transition metal compounds and no organic nitro compounds may be partially or fully chlorinated or brominated.
Bromination or chlorinanon can be performed according to the procedures described in Rubber Technology, 3'~ Ed., Edited by Maurice Morton, HIuwer Academic Publishers, pp. 297 - 300 and references cited within this reference.
The rubber compounds presented in this invention are ideally suitable for the production of moldings of all kinds, in particular tyre components and industrial rubber articles, such as bungs, damping elements, profiles, films, coatings. The polymers are used to this end in pure form or as a mixture with other rubbers, such as NR, BR, HNBR, NBR, SBR, EPDM or fluororubbers. The preparation of these compounds is known to those skilled in the art. In most cases carbon black is added as filler and a peroxide based curing system is used. For the compounding and vulcanization it is referred to Encyclopedia of Polymer Science and Engineering, Vol. 4, S. 66 et seq.
(Compounding) and Vol. 17, S. 666 et seq. (Vulcanization).
The invention is not limited to a special peroxide curing system. For example, inorganic or organic peroxides are suitable. Preferred are organic peroxides such as dialkylperoxides, ketalperoxides, aralkylperoxides, peroxide ethers, peroxide esters, such as di-tert.-butylperoxide, bis-(tert.-butylperoxyisopropyl)-benzol, dicumylperoxide, 2,5-dimethyl-2,5-di(tert.-butylperoxy)-hexane, 2,5-dimethyl-2,5-di(tert.-butylperoxy)-hexene-(3), 1,1-bis-(tert.-butylperoxy)-3,3,5-trimethyl-cyclohexane, benzoylperoxide, tert.-butylcumylperoxide and tert.-butylperbenzoate.
Usually the amount of peroxide in the compound is in the range of from 1 to 10 phr (_ per hundred rubber), preferably from 1 to 5 phr. Subsequent curing is usually performed at a temperature in the range of from 100 to 200°C, preferably 130 to 180°C.
Peroxides might be applied advantageously in a polymer-bound form. Suitable systems are commercially available, such as Polydispersion T(VC) D-40 P from Rhein Chemie Rheinau GmbH, D (= polymerbound di-tert.-butylperoxy-isopropylbenzene).
Even if it is not preferred, the compound may further comprise other natural or synthetic rubbers such as BR (polybutadiene), ABR (butadiene/acrylic acid-C1-Cq, alkylester-copolymers), CR (polychloroprene), IR (polyisoprene), SBR
(styrene/butadiene-copolymers) with styrene contents in the range of 1 to 60 wt%, NBR
(butadiene/acrylonitrile-copolymers with acrylonitrile contents of 5 to 60 wt%, HNBR
(partially or totally hydrogenated NBR-rubber), EPDM (ethylene/propylene/diene copolymers), FKM (fluoropolymers or fluororubbers), and mixtures of the given polymers.
The rubber composition according to the invention can contain further auxiliary products for rubbers, such as reaction accelerators, vulcanizing accelerators, vulcanizing acceleration auxiliaries, antioxidants, foaming agents, anti-aging agents, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, tackifiers, blowing agents, dyestuffs, pigments, waxes, extenders, organic acids, inhibitors, metal oxides, and activators such as triethanolamine, polyethylene glycol, hexanetriol, etc., which are known to the rubber industry. The rubber aids are used in conventional amounts, which depend inter alia on the intended use.
Conventional amounts are e.g. from 0.1 to 50 wt.%, based on rubber. Preferably the composition furthermore comprises in the range of O.I to 20 phr of an organic fatty acid, preferably a unsaturated fatty acid having one, two or more carbon double bonds in the molecule which more preferably includes 10% by weight or more of a conjugated dime acid having at least one conjugated carbon-carbon double bond in its molecule.
Preferably those fatty acids have in the range of from 8- 22 carbon atoms, more preferably 12-18.
Examples include stearic acid, palmic acid and oleic acid and their calcium-, zinc-, magnesium-, potassium- and ammonium salts.
The ingredients of the final compound are mixed together, suitably at an elevated temperature that may range from 25 °C to 200 °C.
Normally the mixing time does not exceed one hour and a time in the range from 2 to 30 minutes is usually adequate. The mixing is suitably carried out in an internal mixer such as a Banbury mixer, or a Haake or Brabender miniature internal mixer. A two roll mill mixer also provides a good dispersion of the additives within the elastomer. An extruder also provides good mixing, and permits shorter mixing times. It is possible to carry out the mixing in two or more stages, and the mixing can be done in different apparatus, for example one stage in an internal mixer and one stage in an extruder. However, it should be taken care that no unwanted pre-crosslinking (= scorch) occurs during the mixing stage.
The inventive compounds are very well suited for the manufacture of shaped articles, especially shaped articles for high-purity applications such as fuel cell components (e.g. condenser caps), medical devices, The following Examples are provided to illustrate the present invention:
by weight of at least one multiolefin monomer including (3-pinene and in the range of from 0.01 % to 1 % by weight of at least one multiolefin cross-linking agent. More preferably, the monomer mixture comprises in the range of from 83% to 94% by weight of at least one isoolefin monomer and in the range of from 5.0% to 17% by weight of a multiolefin monomer or (3-pinene and in the range of from 0.01% to 1% by weight of at least one multiolefin cross-linking agent. Most preferably, the monomer mixture comprises in the range of from 85% to 93% by weight of at least one isoolefin monomer and in the range of from 6.0% to 15% by weight of at least one multiolefin monomer, including (3-pinene and in the range of from 0.01 % to 1 % by weight of at least one multiolefin cross-linking agent.
The weight average molecular weight, MW, is preferably greater than 240 kg/mol, more preferably greater than 300 kg/mol, even more preferably greater than 500 kg/mol, yet even more preferably greater than 600 kg/mol.
In connection with this invention the term "gel" is understood to denote a fraction of the polymer insoluble for 60 min in cyclohexane boiling under reflux. The gel content is preferably less than 10 wt.%, more preferably less than 5 wt%, even more preferably less than 3 wt%, yet even more preferably less than 1 wt%.
There are no organic nitro compounds or transition metals present.
The butyl polymer further comprises unites derived from one or more multiolefin cross-linking agents. The term cross-linking agent is known to those skilled in the art and is understood to denote a compound that causes chemical cross-linking between the polymer chains in opposition to a monomer that will add to the chain.
Some easy preliminary tests will reveal if a compound will act as a monomer or a cross-linking agent. The choice of the cross-linking agent is not particularly restricted.
Preferably, the cross-linking comprises a multiolefinic hydrocarbon compound.
Examples of these are norbornadiene, 2-isopropenylnorbornene, 2-vinyl-norbornene, 1,3,5-hexatriene, 2-phenyl-1,3-butadiene, divinylbenzene, diisopropenylbenzene, divinyltoluene, divinylxylene and C1 to C2o alkyl-substituted derivatives thereof. More preferably, the multiolefin crosslinking agent is divinylbenzene, diisopropenylbenzene, divinyltoluene, divinyl-xylene and C1 to C2o alkyl substituted derivatives thereof, and or mixtures of the compounds given. Most preferably the multiolefin crosslinking agent comprises divinylbenzene and diisopropenylbenzene.
The polymerization preferably is performed in a continuous process in slurry (suspension), in a suitable diluent, such as chloroalkanes as described in US
5,417,930.
The monomers are generally polymerized canonically, preferably at temperatures in the range from -120°C to +20°C, preferably in the range from -100°C
to -20°C, and pressures in the range from 0.1 to 4 bar.
The use of a continuous reactor as opposed to a batch reactor seems to have a positive effect on the polymer. Preferably, the process is conducted in at least one continuos reactor having a volume of between O.I m3 and 100 m3, more preferable between 1 m3 and 10 m3.
Inert solvents or diluents known to the person skilled in the art for butyl polymerization may be considered as the solvents or diluents (reaction medium). These comprise alkanes, chloroalkanes, cycloalkanes or aromatics, which are frequently also mono- or polysubstituted with halogens. Hexane/chloroalkane mixtures, methyl chlo-ride, dichloromethane or the mixtures thereof may be mentioned in particular.
Chlo-roalkanes are preferably used in the process according to the present invention.
Said polymers with a Mooney viscosity of at least 25 Mooney-units and a gel content of less than 15 wt.% comprising repeating units derived from at least one isoolefin monomer, more than 4.1 mol% of repeating units derived from at least one multiolefin monomer, as well as optionally further copolymerizable monomers, and repeating units derived from at least one multiolefin cross-linking agent containing no transition metal compounds and no organic nitro compounds may be partially or fully chlorinated or brominated.
Bromination or chlorinanon can be performed according to the procedures described in Rubber Technology, 3'~ Ed., Edited by Maurice Morton, HIuwer Academic Publishers, pp. 297 - 300 and references cited within this reference.
The rubber compounds presented in this invention are ideally suitable for the production of moldings of all kinds, in particular tyre components and industrial rubber articles, such as bungs, damping elements, profiles, films, coatings. The polymers are used to this end in pure form or as a mixture with other rubbers, such as NR, BR, HNBR, NBR, SBR, EPDM or fluororubbers. The preparation of these compounds is known to those skilled in the art. In most cases carbon black is added as filler and a peroxide based curing system is used. For the compounding and vulcanization it is referred to Encyclopedia of Polymer Science and Engineering, Vol. 4, S. 66 et seq.
(Compounding) and Vol. 17, S. 666 et seq. (Vulcanization).
The invention is not limited to a special peroxide curing system. For example, inorganic or organic peroxides are suitable. Preferred are organic peroxides such as dialkylperoxides, ketalperoxides, aralkylperoxides, peroxide ethers, peroxide esters, such as di-tert.-butylperoxide, bis-(tert.-butylperoxyisopropyl)-benzol, dicumylperoxide, 2,5-dimethyl-2,5-di(tert.-butylperoxy)-hexane, 2,5-dimethyl-2,5-di(tert.-butylperoxy)-hexene-(3), 1,1-bis-(tert.-butylperoxy)-3,3,5-trimethyl-cyclohexane, benzoylperoxide, tert.-butylcumylperoxide and tert.-butylperbenzoate.
Usually the amount of peroxide in the compound is in the range of from 1 to 10 phr (_ per hundred rubber), preferably from 1 to 5 phr. Subsequent curing is usually performed at a temperature in the range of from 100 to 200°C, preferably 130 to 180°C.
Peroxides might be applied advantageously in a polymer-bound form. Suitable systems are commercially available, such as Polydispersion T(VC) D-40 P from Rhein Chemie Rheinau GmbH, D (= polymerbound di-tert.-butylperoxy-isopropylbenzene).
Even if it is not preferred, the compound may further comprise other natural or synthetic rubbers such as BR (polybutadiene), ABR (butadiene/acrylic acid-C1-Cq, alkylester-copolymers), CR (polychloroprene), IR (polyisoprene), SBR
(styrene/butadiene-copolymers) with styrene contents in the range of 1 to 60 wt%, NBR
(butadiene/acrylonitrile-copolymers with acrylonitrile contents of 5 to 60 wt%, HNBR
(partially or totally hydrogenated NBR-rubber), EPDM (ethylene/propylene/diene copolymers), FKM (fluoropolymers or fluororubbers), and mixtures of the given polymers.
The rubber composition according to the invention can contain further auxiliary products for rubbers, such as reaction accelerators, vulcanizing accelerators, vulcanizing acceleration auxiliaries, antioxidants, foaming agents, anti-aging agents, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, tackifiers, blowing agents, dyestuffs, pigments, waxes, extenders, organic acids, inhibitors, metal oxides, and activators such as triethanolamine, polyethylene glycol, hexanetriol, etc., which are known to the rubber industry. The rubber aids are used in conventional amounts, which depend inter alia on the intended use.
Conventional amounts are e.g. from 0.1 to 50 wt.%, based on rubber. Preferably the composition furthermore comprises in the range of O.I to 20 phr of an organic fatty acid, preferably a unsaturated fatty acid having one, two or more carbon double bonds in the molecule which more preferably includes 10% by weight or more of a conjugated dime acid having at least one conjugated carbon-carbon double bond in its molecule.
Preferably those fatty acids have in the range of from 8- 22 carbon atoms, more preferably 12-18.
Examples include stearic acid, palmic acid and oleic acid and their calcium-, zinc-, magnesium-, potassium- and ammonium salts.
The ingredients of the final compound are mixed together, suitably at an elevated temperature that may range from 25 °C to 200 °C.
Normally the mixing time does not exceed one hour and a time in the range from 2 to 30 minutes is usually adequate. The mixing is suitably carried out in an internal mixer such as a Banbury mixer, or a Haake or Brabender miniature internal mixer. A two roll mill mixer also provides a good dispersion of the additives within the elastomer. An extruder also provides good mixing, and permits shorter mixing times. It is possible to carry out the mixing in two or more stages, and the mixing can be done in different apparatus, for example one stage in an internal mixer and one stage in an extruder. However, it should be taken care that no unwanted pre-crosslinking (= scorch) occurs during the mixing stage.
The inventive compounds are very well suited for the manufacture of shaped articles, especially shaped articles for high-purity applications such as fuel cell components (e.g. condenser caps), medical devices, The following Examples are provided to illustrate the present invention:
Examples Equipment Polymer unsaturation was determined through 1H NMR spectroscopy with the use of a Bruker 500 MHz NMR Spectrometer. NMR samples used to determine isoprene content were prepared in CDCl3. NMR samples used to determine DVB
content were prepared in THF-d8. Microstructure information was calculated with the use of previously established integration methods. Peak shifts were referenced to a TMS internal standard.
GPC analysis was performed with the use of a Waters Alliance 2690 Separations Module and Viscotek Model 300 Triple Detector Array. GPC samples were prepared by dissolution in THF.
Polymer gel content was determined through conventional gravimetric analysis of the dry, hydrocarbon-insoluble fraction (insoluble in boiling cyclohexane, under agitation for a period of 60 minutes).
Mixing was accomplished with the use of a miniature internal mixer (Brabender MIM) from C. W. Brabender, consisting of a drive unit (Plasticorder °
Type PL-V 151) and a data interface module.
Cure characteristics were determined with a Moving Die Rheometer (MDR) test carried out according to ASTM standard D-5289 on a Monsanto MDR 200 (E). The upper disc oscillated though a small arc of 1 degree.
Curing was achieved with the use of an Electric Press equipped with an Allan-Bradley Programmable Controller.
Stress-strain tests were carried out using an Instron Testmaster Automation System, Mode14464.
The compounds presented in these examples employed the use of carbon black (IRB #7), a peroxide (DI-CUP 40C, Struktol Canada Ltd.) and a co-agent (HVA-2).
content were prepared in THF-d8. Microstructure information was calculated with the use of previously established integration methods. Peak shifts were referenced to a TMS internal standard.
GPC analysis was performed with the use of a Waters Alliance 2690 Separations Module and Viscotek Model 300 Triple Detector Array. GPC samples were prepared by dissolution in THF.
Polymer gel content was determined through conventional gravimetric analysis of the dry, hydrocarbon-insoluble fraction (insoluble in boiling cyclohexane, under agitation for a period of 60 minutes).
Mixing was accomplished with the use of a miniature internal mixer (Brabender MIM) from C. W. Brabender, consisting of a drive unit (Plasticorder °
Type PL-V 151) and a data interface module.
Cure characteristics were determined with a Moving Die Rheometer (MDR) test carried out according to ASTM standard D-5289 on a Monsanto MDR 200 (E). The upper disc oscillated though a small arc of 1 degree.
Curing was achieved with the use of an Electric Press equipped with an Allan-Bradley Programmable Controller.
Stress-strain tests were carried out using an Instron Testmaster Automation System, Mode14464.
The compounds presented in these examples employed the use of carbon black (IRB #7), a peroxide (DI-CUP 40C, Struktol Canada Ltd.) and a co-agent (HVA-2).
All of the compounds studied were composed of:
Polymer: 100 phr Carbon black (IRB #7; N330): 50 phr Peroxide (DI-CUP 40 C): 4 phr Optionally, 2.5 phr of HVA-2 was also used.
Mixing was achieved with the use of a Brabender internal mixer (capacity ca.
g) with a starting temperature of 60 °C and a mixing speed of 50 rpm according to the following sequence:
0.0 min: polymer added I.5 min: carbon black added, in increments 6.0 min: peroxide added 7.0 min: co-agent (HVA-2) added 8.0 min: mix removed In cases where no co-agent was present, the peroxide was added 7.0 min into the mixing process. The final compound was refined on a 6" x I2" mill.
Example 1 The following example illustrates our ability to produce, via a continuous process, a novel grade of IIR possessing an isoprene content of up to 5.0 mol % and Mooney viscosity (NQ, l+8 @ 125 °C) between 35 and 40 MU.
The monomer feed composition was comprised of 2.55 wt. % of isoprene (IP or IC5) and 27.5 wt. % of isobutene (IP or IC4). This mixed feed was introduced into the continuous polymerization reactor at a rate of 5900 kg/hour. In addition, DVB
was introduced into the reactor at a rate of 5.4 to 6 kg/hour. Polymerization was initiated via the introduction of an A1C13/MeCI solution (0.23 wt. % of AlCl3 in MeCI) at a rate of 204 to 227 kg/hour. The internal temperature of the continuous reaction was maintained between =95 and -100 °C through the use of an evaporative cooling process. Following sufficient residence within the reactor, the newly formed polymer crumb was separated from the MeCI diluent with the use of an aqueous flash tank. At this point, ca. 1 wt. % of stearic acid was introduced into the polymer crumb.
Prior to drying, 0.1 wt. % of Irganox~ 1010 was added to the polymer. Drying of the resulting material was accomplished with the use of a conveyor oven. Table 1 details the characteristics of the final material.
Example 2 The following example illustrates our ability to produce, via a continuous process, a novel grade of IIR possessing an isoprene content of up to 8.0 mol % and Mooney viscosity (ML 1+8 @ 125 °C) between 35 and 40 MU.
The monomer feed composition was comprised of 4.40 wt. % of isoprene (IP or IC5) and 25.7 wt. % of isobutene (IP or IC4). This mixed feed was introduced into the continuous polymerization reactor at a rate of 5900 kg/hour. In addition, DVB
was introduced into the reactor at a rate of 5.4 to 6 kg/hour. Polymerization was initiated via the introduction of an A1C13/MeC1 solution (0.23 wt. % of A1C13 in MeCI) at a rate of 204 to 227 kg/hour. The internal temperature of the continuous reaction was maintained between -95 and -100 °C through the use of an evaporative cooling process. Following sufficient residence within the reactor, the newly formed polymer crumb was separated from the MeCI diluent with the use of an aqueous flash tank. At this point, ca. 1 wt. % of stearic acid was introduced into the polymer crumb.
Prior to drying, 0.1 wt. % of Irganox~ 1010 was added to the polymer. Drying of the resulting material was accomplished with the use of a conveyor oven. Table 2 details the characteristics of the final material.
It is important to note that although the experimental high IP IIR elastomers described in Examples 1 and 2 contain trace amounts of DVB, (ca. 0.07 - 0.11 mol %) this level is less than 10 % of that found in commercial XL-10000 (ca. 1.2 -1.3 mol %).
Examtple 3 - Comparative This compound was based on a commercial butyl rubber (Bayer Butyl 301, isobutylene content = 98.4 mol %, isoprene content = 1.6 mol %) according to the recipe presented above. In this case, 2.5 phr of HVA-2 was employed in the formulation. As can be seen from Figure 1 and Table 3, moderate cure reactivity is observed for this system. This suggests that the presence of IP in the polymer main chain is an important factor in determining the peroxide-curability of polyisobutylene based copolymers. It is also important to note that a significant degree of reversion is seen for this system. This suggests that a chain degradation mechanism may be acting in conjunction with the crosslinking reaction.
Example 4 - Comparative This compound was based on a commercial butyl rubber (Bayer Butyl 402, isobutylene content = 97.9 moI %, isoprene content = 2.1 mol %) according to the recipe presented above. In this case, 2.5 phr of HVA-2 was employed in the formulation. As can be seen from Figure 1 and Table 3, moderate cure reactivity is observed for this system. This suggests that the presence of IP in the polymer main chain is an important factor in determining the peroxide-curability of polyisobutylene based copolymers. It is also important to note that a significant degree of reversion is seen for this system. This suggests that a chain degradation mechanism may be acting in conjunction with the crosslinking reaction.
Example 5 - Comparative This compound was based on a commercial butyl rubber (Bayer XL-10000, isoprene content = 1.6 mol %, DVB content = 1.2 - 1.3 mol %, gel content 70 -85 wt.
%) according to the recipe presented above. In this case, a traditional XL-formulation was used in which HVA-2 was omitted from the formulation. As can be seen from Figure 1 and Table 3, significant cure reactivity is observed for this system.
Example 6 - Invention This compound was based on the experimental high IP IIR described in Example 1 (isoprene content = 5.0 mol %, DVB content = 0.07 - 0.11 mol %, gel content < 5 wt. %) according to the recipe presented above. In this case, HVA-2 was omitted from the formulation. As can be seen from Figure 1 and Table 3, evidence of cure reactivity with no reversion is observed for this system.
Example 7 - Invention This compound was based on the experimental high IP IIR described in Example 2 (isoprene content = 7.5 mol %, DVB content = 0.07 - 0.11 mol %, gel content < 5 wt. %) according to the recipe presented above. In this case, HVA-2 was omitted from the formulation. As can be seen from Figure 1 and Table 3, evidence of cure reactivity with no reversion is observed for this system.
Example 8 - Invention This compound was based on the experimental high Il' TIK described in Example 2 (isoprene content = 5.0 mol %, DVB content = 0.07 - 0.11 rnol %, gel content < 5 wt. %) according to the recipe presented above. In this case, 2.5 phr of HVA-2 was added to the formulation. As can be seen from Figure 1 and Table 3, evidence of significant cure reactivity is observed for this system.
Example 9 - Invention This compound was based on the experimental high IP TIR described in Example 2 (isoprene content = 7.5 mol %, DVB content = 0.07 - 0.11 mol %, gel content < 5 wt. %) according to the recipe presented above. In this case, 2.5 phr of HVA-2 was added to the formulation. As can be seen from Figure 1 and Table 3, evidence of significant cure reactivity is observed for this system.
The preceding examples clearly demonstrate that both RB301 (Example 3) and RB402 (Example 4) undergo some cure reactivity on thermal treatment in the presence of HVA-2. However, following an initial rise in torque a rapid decrease in the elastic modules is observed (Figure 1). This suggests that chain scission is the dominant mechanism operating in this system. On elevation of the IP content to 5.0 and 7.5 mol % (Examples 6 and 7 respectively), no reversion process was detected by rheometric analysis even in the absence of the HVA-2 co-agent. This suggests that the presence of elevated levels (cf. RB301 and RB402) of IP in the polymer backbones of these samples acts to stabilize these materials against free-radical mediated chain scission.
The cure reactivity as detected for Examples 6 and 7 is significantly less than that observed for XL-10000 (Example 5). However, the inclusion of 2.5 phr HVA-into formulations containing the high IP IIR samples (Example 8 and 9) resulted in a dramatic increase in cure reactivity. As can be seen from Figure l, the cure state achieved for Examples 8 and 9 is significantly higher than that observed for the XL-10000 comparative formulation. Importantly, the stress-strain properties associated with the formulations described in Examples 8 and 9 are consistent with those observed for the standard XL-10000 formulation. However, the ultimate tensile strength measured for Examples 8 and 9 is superior to that determined for the XL-10000 control.
In summary, the use of IIR with elevated levels of IP (5.0 and 7.5 mol % in this case) in conjunction with a co-agent such as HVA-2 allows for the preparation of peroxide curable butyl formulations with similar or better tensile properties as that observed for the XL-10000 control compound. In addition, the processability of compounds based on experimental high IP IZR is far superior as a result of the significantly reduced gel content (cf. XL-1000) present in these polymers.
Table 1.
Isoprene Content (mol %) 4.5 - 5.0 DVB Content (mol %) 0.07 - 0.11 Mooney Viscosity (MU, MLl+8 @ 125 35 - 40 C) Gel Content (wt. %) < 5.0 MW (kg/mol) 450 - 550 Mn (kg/mol) 200 - 220 MZ (kg/mol) 900 1400 -Conversion (%) 77 - 84 Table 2.
Isoprene Content (mol %) 7.0 8.0 -DVB Content (mol %) 0.07 0.11 -Mooney Viscosity (MU, MLl+8 @ 35 - 40 125 C) Gel Content (wt. %) < 5.0 _ __ MW (kg~mol) 700 900 -M" (kg/mol) 100 -105 _ _ MZ (kg~mol) 3200 5500 -Conversion (%) 77 - 84 N Z ~ N Cc~O
N
N
x W
h Cr0 M
'~' ~t x cc 00t~
O~N c~p~
O
M ~
x W
r W N Q QO~
r _ Z ~ r x r - CEOO ~ N
N
d' ' . N Cfld d' x W
M
N r r pp M r CO00 ~
N f~
Eaao z~~ ~a ~Q
o °' ~ a~
cc cM ~_c~°
H a~ H
a ~n.~'~
c ~
ca H
___
Polymer: 100 phr Carbon black (IRB #7; N330): 50 phr Peroxide (DI-CUP 40 C): 4 phr Optionally, 2.5 phr of HVA-2 was also used.
Mixing was achieved with the use of a Brabender internal mixer (capacity ca.
g) with a starting temperature of 60 °C and a mixing speed of 50 rpm according to the following sequence:
0.0 min: polymer added I.5 min: carbon black added, in increments 6.0 min: peroxide added 7.0 min: co-agent (HVA-2) added 8.0 min: mix removed In cases where no co-agent was present, the peroxide was added 7.0 min into the mixing process. The final compound was refined on a 6" x I2" mill.
Example 1 The following example illustrates our ability to produce, via a continuous process, a novel grade of IIR possessing an isoprene content of up to 5.0 mol % and Mooney viscosity (NQ, l+8 @ 125 °C) between 35 and 40 MU.
The monomer feed composition was comprised of 2.55 wt. % of isoprene (IP or IC5) and 27.5 wt. % of isobutene (IP or IC4). This mixed feed was introduced into the continuous polymerization reactor at a rate of 5900 kg/hour. In addition, DVB
was introduced into the reactor at a rate of 5.4 to 6 kg/hour. Polymerization was initiated via the introduction of an A1C13/MeCI solution (0.23 wt. % of AlCl3 in MeCI) at a rate of 204 to 227 kg/hour. The internal temperature of the continuous reaction was maintained between =95 and -100 °C through the use of an evaporative cooling process. Following sufficient residence within the reactor, the newly formed polymer crumb was separated from the MeCI diluent with the use of an aqueous flash tank. At this point, ca. 1 wt. % of stearic acid was introduced into the polymer crumb.
Prior to drying, 0.1 wt. % of Irganox~ 1010 was added to the polymer. Drying of the resulting material was accomplished with the use of a conveyor oven. Table 1 details the characteristics of the final material.
Example 2 The following example illustrates our ability to produce, via a continuous process, a novel grade of IIR possessing an isoprene content of up to 8.0 mol % and Mooney viscosity (ML 1+8 @ 125 °C) between 35 and 40 MU.
The monomer feed composition was comprised of 4.40 wt. % of isoprene (IP or IC5) and 25.7 wt. % of isobutene (IP or IC4). This mixed feed was introduced into the continuous polymerization reactor at a rate of 5900 kg/hour. In addition, DVB
was introduced into the reactor at a rate of 5.4 to 6 kg/hour. Polymerization was initiated via the introduction of an A1C13/MeC1 solution (0.23 wt. % of A1C13 in MeCI) at a rate of 204 to 227 kg/hour. The internal temperature of the continuous reaction was maintained between -95 and -100 °C through the use of an evaporative cooling process. Following sufficient residence within the reactor, the newly formed polymer crumb was separated from the MeCI diluent with the use of an aqueous flash tank. At this point, ca. 1 wt. % of stearic acid was introduced into the polymer crumb.
Prior to drying, 0.1 wt. % of Irganox~ 1010 was added to the polymer. Drying of the resulting material was accomplished with the use of a conveyor oven. Table 2 details the characteristics of the final material.
It is important to note that although the experimental high IP IIR elastomers described in Examples 1 and 2 contain trace amounts of DVB, (ca. 0.07 - 0.11 mol %) this level is less than 10 % of that found in commercial XL-10000 (ca. 1.2 -1.3 mol %).
Examtple 3 - Comparative This compound was based on a commercial butyl rubber (Bayer Butyl 301, isobutylene content = 98.4 mol %, isoprene content = 1.6 mol %) according to the recipe presented above. In this case, 2.5 phr of HVA-2 was employed in the formulation. As can be seen from Figure 1 and Table 3, moderate cure reactivity is observed for this system. This suggests that the presence of IP in the polymer main chain is an important factor in determining the peroxide-curability of polyisobutylene based copolymers. It is also important to note that a significant degree of reversion is seen for this system. This suggests that a chain degradation mechanism may be acting in conjunction with the crosslinking reaction.
Example 4 - Comparative This compound was based on a commercial butyl rubber (Bayer Butyl 402, isobutylene content = 97.9 moI %, isoprene content = 2.1 mol %) according to the recipe presented above. In this case, 2.5 phr of HVA-2 was employed in the formulation. As can be seen from Figure 1 and Table 3, moderate cure reactivity is observed for this system. This suggests that the presence of IP in the polymer main chain is an important factor in determining the peroxide-curability of polyisobutylene based copolymers. It is also important to note that a significant degree of reversion is seen for this system. This suggests that a chain degradation mechanism may be acting in conjunction with the crosslinking reaction.
Example 5 - Comparative This compound was based on a commercial butyl rubber (Bayer XL-10000, isoprene content = 1.6 mol %, DVB content = 1.2 - 1.3 mol %, gel content 70 -85 wt.
%) according to the recipe presented above. In this case, a traditional XL-formulation was used in which HVA-2 was omitted from the formulation. As can be seen from Figure 1 and Table 3, significant cure reactivity is observed for this system.
Example 6 - Invention This compound was based on the experimental high IP IIR described in Example 1 (isoprene content = 5.0 mol %, DVB content = 0.07 - 0.11 mol %, gel content < 5 wt. %) according to the recipe presented above. In this case, HVA-2 was omitted from the formulation. As can be seen from Figure 1 and Table 3, evidence of cure reactivity with no reversion is observed for this system.
Example 7 - Invention This compound was based on the experimental high IP IIR described in Example 2 (isoprene content = 7.5 mol %, DVB content = 0.07 - 0.11 mol %, gel content < 5 wt. %) according to the recipe presented above. In this case, HVA-2 was omitted from the formulation. As can be seen from Figure 1 and Table 3, evidence of cure reactivity with no reversion is observed for this system.
Example 8 - Invention This compound was based on the experimental high Il' TIK described in Example 2 (isoprene content = 5.0 mol %, DVB content = 0.07 - 0.11 rnol %, gel content < 5 wt. %) according to the recipe presented above. In this case, 2.5 phr of HVA-2 was added to the formulation. As can be seen from Figure 1 and Table 3, evidence of significant cure reactivity is observed for this system.
Example 9 - Invention This compound was based on the experimental high IP TIR described in Example 2 (isoprene content = 7.5 mol %, DVB content = 0.07 - 0.11 mol %, gel content < 5 wt. %) according to the recipe presented above. In this case, 2.5 phr of HVA-2 was added to the formulation. As can be seen from Figure 1 and Table 3, evidence of significant cure reactivity is observed for this system.
The preceding examples clearly demonstrate that both RB301 (Example 3) and RB402 (Example 4) undergo some cure reactivity on thermal treatment in the presence of HVA-2. However, following an initial rise in torque a rapid decrease in the elastic modules is observed (Figure 1). This suggests that chain scission is the dominant mechanism operating in this system. On elevation of the IP content to 5.0 and 7.5 mol % (Examples 6 and 7 respectively), no reversion process was detected by rheometric analysis even in the absence of the HVA-2 co-agent. This suggests that the presence of elevated levels (cf. RB301 and RB402) of IP in the polymer backbones of these samples acts to stabilize these materials against free-radical mediated chain scission.
The cure reactivity as detected for Examples 6 and 7 is significantly less than that observed for XL-10000 (Example 5). However, the inclusion of 2.5 phr HVA-into formulations containing the high IP IIR samples (Example 8 and 9) resulted in a dramatic increase in cure reactivity. As can be seen from Figure l, the cure state achieved for Examples 8 and 9 is significantly higher than that observed for the XL-10000 comparative formulation. Importantly, the stress-strain properties associated with the formulations described in Examples 8 and 9 are consistent with those observed for the standard XL-10000 formulation. However, the ultimate tensile strength measured for Examples 8 and 9 is superior to that determined for the XL-10000 control.
In summary, the use of IIR with elevated levels of IP (5.0 and 7.5 mol % in this case) in conjunction with a co-agent such as HVA-2 allows for the preparation of peroxide curable butyl formulations with similar or better tensile properties as that observed for the XL-10000 control compound. In addition, the processability of compounds based on experimental high IP IZR is far superior as a result of the significantly reduced gel content (cf. XL-1000) present in these polymers.
Table 1.
Isoprene Content (mol %) 4.5 - 5.0 DVB Content (mol %) 0.07 - 0.11 Mooney Viscosity (MU, MLl+8 @ 125 35 - 40 C) Gel Content (wt. %) < 5.0 MW (kg/mol) 450 - 550 Mn (kg/mol) 200 - 220 MZ (kg/mol) 900 1400 -Conversion (%) 77 - 84 Table 2.
Isoprene Content (mol %) 7.0 8.0 -DVB Content (mol %) 0.07 0.11 -Mooney Viscosity (MU, MLl+8 @ 35 - 40 125 C) Gel Content (wt. %) < 5.0 _ __ MW (kg~mol) 700 900 -M" (kg/mol) 100 -105 _ _ MZ (kg~mol) 3200 5500 -Conversion (%) 77 - 84 N Z ~ N Cc~O
N
N
x W
h Cr0 M
'~' ~t x cc 00t~
O~N c~p~
O
M ~
x W
r W N Q QO~
r _ Z ~ r x r - CEOO ~ N
N
d' ' . N Cfld d' x W
M
N r r pp M r CO00 ~
N f~
Eaao z~~ ~a ~Q
o °' ~ a~
cc cM ~_c~°
H a~ H
a ~n.~'~
c ~
ca H
___
Claims (9)
1. A peroxide curable rubber compound containing polymers with a Mooney viscosity of at least 25 Mooney-units and a gel content of less than 15 wt.%
comprising repeating units derived from at least one isoolefin monomer, more than 4.1 mol% of repeating units derived from at least one multiolefin monomer, as well as optionally further copolymerizable monomers, and repeating units derived from at least one multiolefin cross-linking agent containing no transition metal compounds and no organic nitro compounds.
comprising repeating units derived from at least one isoolefin monomer, more than 4.1 mol% of repeating units derived from at least one multiolefin monomer, as well as optionally further copolymerizable monomers, and repeating units derived from at least one multiolefin cross-linking agent containing no transition metal compounds and no organic nitro compounds.
2. A compound according to claim l, where the polymer contains greater than 5 mot % of repeating units derived from a multiolefin and a gel content of less than 10 wt. %.
3. A compound according to claim 1, where the polymer contains greater than 7 mol % of repeating units derived from a multiolefin and a gel content of less than 5 wt. %.
4. A compound according to any of claims 1-3, wherein said isoolefin monomer is isobutene.
5. A compound according to any of the claims 1-4 wherein said multiolefin crosslinking agent is divinylbenzene.
6. A compound according to any of the claims 1-5 where the polymer is either partially or completely chlorinated or brominated.
7. A compound according to any of the claims 1-6 further comprising at least one peroxide.
8. A shaped article comprising a compound according to any of claims 1-7.
9. An article according to claim 8 in the form of a medical device or a condenser cap.
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PCT/CA2005/000254 WO2005080452A1 (en) | 2004-02-23 | 2005-02-22 | Peroxide curable rubber compound containing high-isoprene butyl rubber |
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007022643A1 (en) * | 2005-08-26 | 2007-03-01 | Lanxess Inc. | Peroxide curable rubber compound containing high multiolefin halobutyl ionomers |
WO2007022619A1 (en) * | 2005-08-26 | 2007-03-01 | Lanxess Inc. | Peroxide curable rubber compound containing high multiolefin halobutyl ionomers |
WO2007022618A1 (en) * | 2005-08-26 | 2007-03-01 | Lanxess Inc. | Process for production of peroxide curable high multiolefin halobutyl ionomers |
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WO2014094121A1 (en) | 2012-12-20 | 2014-06-26 | Lanxess Inc. | Ionomer comprising pendant vinyl groups and processes for preparing same |
US8946319B2 (en) | 2009-02-13 | 2015-02-03 | LAXNESS International S.A. | Butyl ionomers for use in reducing a population of and/or preventing accumulation of organisms and coatings made therefrom |
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CA2487906A1 (en) * | 2004-11-18 | 2006-05-18 | Lanxess Inc. | Rubber composition comprising modified filler |
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US3511821A (en) * | 1963-10-23 | 1970-05-12 | Exxon Research Engineering Co | Terpolymers of isobutylene-methylcyclopentadiene and a crosslinking agent |
US3584080A (en) * | 1968-03-07 | 1971-06-08 | Polymer Corp | Vulcanizable compositions comprising copolymers of an isoolefin and an aromatic divinyl compound |
JP2689398B2 (en) * | 1990-08-24 | 1997-12-10 | 株式会社 大協精工 | Rubber compositions and rubber products for pharmaceuticals and medical devices |
US5578682A (en) * | 1995-05-25 | 1996-11-26 | Exxon Chemical Patents Inc. | Bimodalization of polymer molecular weight distribution |
CA2316741A1 (en) * | 2000-08-24 | 2002-02-24 | Bayer Inc. | Improved processability butyl rubber and process for production thereof |
CA2420244C (en) * | 2000-08-24 | 2009-11-17 | Bayer Inc. | Improved processability butyl rubber and process for production thereof |
CA2418884C (en) * | 2003-02-14 | 2010-07-20 | Bayer Inc. | Process for production of high-isoprene butyl rubber |
-
2004
- 2004-02-23 CA CA 2458741 patent/CA2458741A1/en not_active Abandoned
-
2005
- 2005-02-22 WO PCT/CA2005/000254 patent/WO2005080452A1/en active Application Filing
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JP2009506139A (en) * | 2005-08-26 | 2009-02-12 | ランクセス・インコーポレーテッド | Peroxide curable rubber compound containing high multiolefin halobutyl ionomer |
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