CN102781969A - 氨基硅烷引发剂及由其制备的官能化聚合物 - Google Patents
氨基硅烷引发剂及由其制备的官能化聚合物 Download PDFInfo
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- CN102781969A CN102781969A CN2010800649981A CN201080064998A CN102781969A CN 102781969 A CN102781969 A CN 102781969A CN 2010800649981 A CN2010800649981 A CN 2010800649981A CN 201080064998 A CN201080064998 A CN 201080064998A CN 102781969 A CN102781969 A CN 102781969A
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- Prior art keywords
- compound
- alkyl
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- component
- metallization
- Prior art date
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000003999 initiator Substances 0.000 title claims abstract description 42
- 229920000642 polymer Polymers 0.000 title abstract description 15
- 229920001971 elastomer Polymers 0.000 claims abstract description 69
- 239000005060 rubber Substances 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 23
- -1 alkylamino silane compound Chemical class 0.000 claims description 69
- 238000006116 polymerization reaction Methods 0.000 claims description 51
- 239000003795 chemical substances by application Substances 0.000 claims description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000001465 metallisation Methods 0.000 claims description 36
- 239000000126 substance Substances 0.000 claims description 33
- 239000000945 filler Substances 0.000 claims description 20
- 239000002585 base Substances 0.000 claims description 18
- 229910000077 silane Inorganic materials 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- 229960001866 silicon dioxide Drugs 0.000 claims description 11
- 125000000746 allylic group Chemical group 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 9
- QRLBICHXRCOJDU-UHFFFAOYSA-N methyl(phenyl)silane Chemical compound C[SiH2]C1=CC=CC=C1 QRLBICHXRCOJDU-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000002879 Lewis base Substances 0.000 claims description 5
- 150000007527 lewis bases Chemical class 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 150000003818 basic metals Chemical class 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 46
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 25
- 239000000047 product Substances 0.000 description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 19
- 239000004568 cement Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000006229 carbon black Substances 0.000 description 12
- 235000019241 carbon black Nutrition 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007822 coupling agent Substances 0.000 description 10
- 238000012856 packing Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 230000009466 transformation Effects 0.000 description 10
- 238000004073 vulcanization Methods 0.000 description 10
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000004594 Masterbatch (MB) Substances 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 150000001343 alkyl silanes Chemical class 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 239000000806 elastomer Substances 0.000 description 7
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 5
- 230000005595 deprotonation Effects 0.000 description 5
- 238000010537 deprotonation reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000006231 channel black Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000006138 lithiation reaction Methods 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- ONJMNXFNTYIEEA-UHFFFAOYSA-N benzene ethene Chemical compound C1=CC=CC=C1.C=C.C=C.C=C ONJMNXFNTYIEEA-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 229910052752 metalloid Inorganic materials 0.000 description 3
- 150000002738 metalloids Chemical class 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 229920013730 reactive polymer Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000008247 solid mixture Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000004646 arylidenes Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 2
- 229910000080 stannane Inorganic materials 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- UYJHFNNLKCQMOX-UHFFFAOYSA-L 1,1'-biphenyl dichlorotin Chemical compound Cl[Sn]Cl.C1=CC=CC=C1C1=CC=CC=C1 UYJHFNNLKCQMOX-UHFFFAOYSA-L 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- LRKYLKBLUJXTFL-UHFFFAOYSA-N 1-(piperidin-1-ylmethyl)piperidine Chemical compound C1CCCCN1CN1CCCCC1 LRKYLKBLUJXTFL-UHFFFAOYSA-N 0.000 description 1
- DMYOHQBLOZMDLP-UHFFFAOYSA-N 1-[2-(2-hydroxy-3-piperidin-1-ylpropoxy)phenyl]-3-phenylpropan-1-one Chemical compound C1CCCCN1CC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 DMYOHQBLOZMDLP-UHFFFAOYSA-N 0.000 description 1
- ATYRWKGHNCIOGX-UHFFFAOYSA-N 1-chlorohexane silane Chemical compound [SiH4].C(CCCCC)Cl ATYRWKGHNCIOGX-UHFFFAOYSA-N 0.000 description 1
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- POWLNZLBDWXMTR-UHFFFAOYSA-N CCCO[Sn] Chemical compound CCCO[Sn] POWLNZLBDWXMTR-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- FQEKAFQSVPLXON-UHFFFAOYSA-N butyl(trichloro)silane Chemical compound CCCC[Si](Cl)(Cl)Cl FQEKAFQSVPLXON-UHFFFAOYSA-N 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- ONQMBYVVEVFYRP-UHFFFAOYSA-N chloro(triphenyl)germane Chemical compound C=1C=CC=CC=1[Ge](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ONQMBYVVEVFYRP-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- WENLKAKVZDPNQX-UHFFFAOYSA-N methanetetrol silicic acid Chemical compound C(O)(O)(O)O.[Si](O)(O)(O)O WENLKAKVZDPNQX-UHFFFAOYSA-N 0.000 description 1
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- VJHDVMPJLLGYBL-UHFFFAOYSA-N tetrabromogermane Chemical compound Br[Ge](Br)(Br)Br VJHDVMPJLLGYBL-UHFFFAOYSA-N 0.000 description 1
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- FPADWGFFPCNGDD-UHFFFAOYSA-N tetraethoxystannane Chemical compound [Sn+4].CC[O-].CC[O-].CC[O-].CC[O-] FPADWGFFPCNGDD-UHFFFAOYSA-N 0.000 description 1
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- DDFYIVSQEDKSGY-UHFFFAOYSA-M tri(propan-2-yl)stannanylium;chloride Chemical compound CC(C)[Sn](Cl)(C(C)C)C(C)C DDFYIVSQEDKSGY-UHFFFAOYSA-M 0.000 description 1
- JSQJUDVTRRCSRU-UHFFFAOYSA-N tributyl(chloro)silane Chemical compound CCCC[Si](Cl)(CCCC)CCCC JSQJUDVTRRCSRU-UHFFFAOYSA-N 0.000 description 1
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- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
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- YSCVYRUCAPMZFG-UHFFFAOYSA-K trichlorotin Chemical compound Cl[Sn](Cl)Cl YSCVYRUCAPMZFG-UHFFFAOYSA-K 0.000 description 1
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- 150000003673 urethanes Chemical class 0.000 description 1
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Classifications
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- C08F4/486—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkali metals selected from lithium, rubidium, caesium or francium at least two metal atoms in the same molecule
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Abstract
用作阴离子聚合中的官能化引发剂的金属化氨基硅烷化合物，以及使用所述金属化氨基硅烷化合物引发至少一种阴离子可聚合单体的阴离子聚合来生产氨基硅烷官能化聚合物的方法。所述金属化氨基硅烷化合物的优选用途为产生用于包括氨基硅烷官能化聚合物的轮胎用橡胶组合物。
Description
本申请要求2009年12月31日递交的美国临时申请61/291635号的优先权，在此以其整体将其引入以作参考。
技术领域
本申请涉及硅烷官能化聚合物和由其制备的橡胶硫化产品。
背景技术
在轮胎制造领域中，期望采用显示降低的滞后损失(即机械能至热的损失较少)的橡胶硫化产品。滞后损失通常归因于交联橡胶网络内的聚合物自由端，以及填料附聚物的离解。
官能化聚合物已被用于降低滞后损失并增加结合橡胶。官能化聚合物的官能团被认为降低聚合物自由端的数量。另外，官能团与填料颗粒之间的相互作用减少填料附聚，从而降低归因于填料附聚物的离解的滞后损失。本申请源自以下认知：已发现橡胶硫化产品的聚合物部分中的氨基硅烷(“硅氮烷”)官能团改进了橡胶硫化产品的物理性质。可推测聚合物中的氨基硅烷官能度改进聚合物与附加组分如二氧化硅填料的相互作用。该改进的相互作用通常理解为改进的混炼和成分的更好分散。
发明内容
本发明提供用于引发阴离子聚合的金属化氨基硅烷化合物。
本申请还提供用于生产氨基硅烷官能化聚合物的方法，所述方法包括以下步骤：通过制备预先形成的或原位的金属化氨基硅烷化合物来提供引发剂，并使用所述金属化氨基硅烷化合物引发聚合来使至少一种阴离子可聚合单体聚合。
本申请还提供轮胎用橡胶组合物，所述橡胶组合物包括已根据本申请所公开的方法制备的氨基硅烷官能化聚合物。
具体实施方式
本申请以用于阴离子聚合的特定的金属化氨基硅烷化合物的形式提供官能化引发剂。使用这些引发剂制备的聚合物在聚合物链的头部含有官能团，并且已发现基于此类官能化聚合物的可硫化弹性体化合物及其制品显示有用的性质。通常，聚合物的“头”为引发剂残基所位于的链端，而“尾”是最接近最后单体单元添加到聚合物的位置的链端。如本文所使用的，术语“在头部”和“在尾部”分别意指位于或接近头和尾的位置。
使用本文所公开的金属化氨基硅烷化合物来引发阴离子加成聚合(或共聚合)允许产生具有氨基硅烷基团的硅的氨基硅烷官能化聚合物，所述硅通过一个或多个碳原子直接键合至聚合物链端。通过一个或多个碳原子将氨基硅烷的硅直接键合至聚合物链的头部使得以下的可能性增加：在整个聚合反应以及任何随后的聚合物与橡胶硫化产品材料的加工中，硅都将保持键合至聚合物链。不希望受理论的束缚，认为氨基硅烷官能化聚合物可通过水解来反应并与橡胶硫化产品配混物中的填料缩合以给出改进的填料微分散，产生降低滞后的橡胶硫化产品配混物，该配混物在改进由其制备的轮胎的燃料经济中是有用的。
在一个实施方案中，本申请公开了一种用于引发阴离子聚合的金属化氨基硅烷化合物，所述化合物包括至少一种金属化剂与至少一种具有式(IA)或(IB)的烷氨基硅烷化合物的反应产物
其中n为选自由0-2组成的组的整数，m为选自由1-3组成的组的整数，条件是m和n的和等于3；其中T为甲基、乙基、丙基或烯丙型基团(allylic group)；其中各R4和R5独立地为烃基；其中各R6独立地为亚烃基(hydrocarbylene)；和其中当m大于1时，一个或多个R5可在两个氮原子之间形成桥。
通常，本申请的氨基硅烷化合物可为含有1至3个直接键合至硅原子的二烃基氨基的任何化合物。氨基硅烷化合物可含有除二烃基氨基以外的各种其他烃基或苯基。
本申请所述的烷氨基硅烷化合物为具有至少一个直接键合至硅原子的烷基或烯丙型基团(“T”或“接合(tether)”基团)的氨基硅烷化合物。如本文所使用的，术语“烯丙型基团”是指任何键合至硅原子的取代或未取代的烯丙型基团烯丙型基团可含有一个或多个氢、烷基或芳基取代基(B)。通常，以使金属化试剂可提取质子并且所产生的金属-烷基键引发聚合这样的方式来选择T。T的非限制性实例为甲基、乙基、丙基和烯丙基(allyl group)。
在一个实施方案中，烷氨基硅烷化合物选自由亚烷基亚氨基二烃基烷基硅烷、双-(亚烷基亚氨基)烃基烷基硅烷、三-(亚烷基亚氨基)烷基硅烷、亚芳基亚氨基二烃基烷基硅烷、双-(亚芳基亚氨基)烃基烷基硅烷、三-(亚芳基亚氨基)烷基硅烷、二烷氨基二烃基烷基硅烷、双-(二烷氨基)烃基烷基硅烷、三-(二烷氨基)烷基硅烷、二芳基氨基二烃基烷基硅烷、双-(二芳基氨基)烃基烷基硅烷、三-(二芳基氨基)烷基硅烷及其组合组成的组。在另一实施方案中，烷氨基硅烷化合物选自由亚烷基亚氨基二烃基烯丙基硅烷、双-(亚烷基亚氨基)烃基烯丙基硅烷、三-(亚烷基亚氨基)烯丙基硅烷、亚芳基亚氨基二烃基烯丙基硅烷、双-(亚芳基亚氨基)烃基烯丙基硅烷、三-(亚芳基亚氨基)烯丙基硅烷、二烷氨基二烃基烯丙基硅烷、双-(二烷氨基)烃基烯丙基硅烷、三-(二烷氨基)烯丙基硅烷、二芳基氨基二烃基烯丙基硅烷、双-(二芳基氨基)烃基烯丙基硅烷、三-(二芳基氨基)烯丙基硅烷及其组合组成的组。优选地，烷氨基硅烷化合物选自由双(二烷氨基)苯基甲基硅烷、双(六亚甲基亚胺基)苯基甲基硅烷、三(二烷氨基)烯丙基硅烷及其组合组成的组。特别考虑到可利用其他烷氨基硅烷化合物。
如本领域所公知的，金属化典型地涉及有机化合物的质子被金属取代的过程。所述金属通常源自有机金属化合物。如本文所述，使氨基硅烷化合物金属化以形成引发剂可以用各种方式完成。
通常，金属化剂为任何能够使烷氨基硅烷金属化的化合物。金属化剂通过使氨基硅烷的有机取代基(典型地烷基或烯丙型接合基团T)去质子化来起作用。经去质子化的金属化可需要比经加成的金属化所需的更高的碱溶液。就这一点而言，通过适当的选择金属化剂可促进去质子化。例如，仲或叔丁基锂的使用典型地促进烷氨基硅烷化合物的金属化。此外，可通过使用与路易斯碱结合的金属化剂来促进去质子化。有机路易斯碱的非限制性实例包括醚、胺、膦、亚砜、磷酰胺和格氏试剂。可使用任意这些(或其他)的混合物。
在另一实施方案中，可通过使用与以下试剂结合的金属化剂来促进去质子化，所述试剂选自由碱金属醇盐(如，洛氏碱(Lochmann’s base))、碱金属芳基磺酸盐及其组合组成的组。
金属化剂的非限制性实例包括有机金属化合物如烃基锂化合物、烃基钠化合物、烃基钾化合物、烃基镁化合物及其组合。优选地，金属化剂为烃基锂或烃基钠化合物，或其组合。典型地，金属化剂为具有通式C-Li的烃基锂化合物，其中C选自由具有1至20个碳原子的烷基、环烷基、烯基、芳基和芳烷基组成的组。典型的烷基包括但不限于异丙基、丁基异构体和戊基异构体。
金属化氨基硅烷引发剂可任选地在适当的温度(通常在-20℃至80℃之间)下，在不存在待聚合的单体的情况下，通过预先混合金属化剂和烷氨基硅烷化合物(统称为“成分”)来预先形成，可将所得反应产物老化一段时间(几秒至几天的范围)，然后与单体溶液混合。如果使用路易斯碱或其他碱性试剂，还可在此时将其添加至混合物。在预先形成引发剂时，可采用可起到溶解成分的作用的有机溶剂或载体。任选地，溶剂可仅充当载体。任何所采用的有机溶剂优选对金属化氨基硅烷化合物和其他成分是惰性的。有用的溶剂包括极性和非极性烃溶剂如芳族烃、脂族烃和环脂族烃。还可使用此类烃的混合物。
在另一实施方案中，可任选地原位形成金属化氨基硅烷引发剂。通常，阴离子引发剂的原位制备通过以下实施：制备包括聚合溶剂的溶液，如有的话，该溶液还包括一种或多种待聚合的单体，并将氨基硅烷化合物和金属化剂与该溶液混合。调整工艺条件以便使得形成含有期望的官能化聚合物的溶液(胶浆)。工艺条件如反应时间和温度可根据需要而变化以使氨基硅烷化合物和金属化剂反应，随后聚合单体溶液。
在本申请的一个实施方案中，用于生产氨基硅烷官能化聚合物的方法包括以下步骤：(a)通过制备金属化氨基硅烷化合物来提供预先形成的阴离子引发剂，所述化合物包括至少一种金属化剂与至少一种具有式(IA)或(IB)的化合物的反应产物，和(b)通过使用所述金属化氨基硅烷化合物引发聚合来使至少一种阴离子可聚合单体聚合。
预先形成的金属化氨基硅烷引发剂可通过以上所讨论的方式使金属化剂与至少一种具有式(IA)或(IB)的化合物反应来制备。然后如下所讨论的，在典型的聚合条件下，在金属化氨基硅烷化合物的存在下聚合至少一种阴离子可聚合单体。
阴离子加成聚合及活性聚合的原理对于本领域技术人员是已知的。阴离子聚合的聚合物可通过间歇法、半间歇法或连续法制备。通常，通过将单体与溶剂的共混物装入适当的反应容器，随后添加极性配位剂(如果采用)和引发化合物来起始间歇聚合。将反应物加热到适当的温度(通常约20℃至约130℃)，并使聚合在充分时间(通常约0.1至约24小时)内进行。反应产生具有反应性端或活性端的聚合物。与连续聚合不同，不向反应器连续添加引发剂，也不连续除去反应产物。
在半间歇聚合中，将反应介质和引发剂添加到反应容器，并以依赖于温度、单体/引发剂/改性剂的浓度等的速度随时间连续添加单体。与连续聚合不同，不从反应器连续除去产物。
通常，在连续聚合反应中，将单体、引发剂和溶剂作为原料流同时装入适当的反应容器。其后，接着是在适当的停留时间后除去产物的连续步骤。在某些实施方案中，可存在附加原料流以将附加组分装入反应容器，所述附加组分包括但不限于反应改性剂、官能化剂和终止剂等。在某些实施方案中，一种或多种原料流可在装入反应容器前结合，以便预先成形包括但不限于引发剂的组分。在其他实施方案中，一个或多个反应可在从连续聚合反应器中除去活性聚合物后完成，所述反应包括但不限于聚合物的官能终止。涉及连续聚合和连续聚合反应器的原理的附加信息公开于美国专利5,231,152；5,610,227；6,362,282；6,451,935；6,881,795；6,897,270和7,442,748，将其公开内容引入于此以作参考。
本文所描述的聚合方法涉及至少一种阴离子可聚合单体和任选的附加共聚单体。通常，可使用所有已知的阴离子可聚合单体。阴离子可聚合单体的非限制性实例包括共轭二烯和乙烯基芳族化合物，优选具有4至12个碳原子的共轭二烯和具有8至18个碳原子的单乙烯基芳族化合物，更优选共轭的丁二烯和戊二烯、异戊二烯、月桂烯和苯乙烯。
典型地在极性溶剂如四氢呋喃(THF)或非极性烃如各种环状和无环的己烷、庚烷、辛烷、戊烷、它们的烷基化衍生物及其混合物，以及苯中进行阴离子聚合。
为了促进共聚中的无规化并控制乙烯基含量，可将极性配位剂(改性剂)添加到聚合成分中。极性配位剂的使用对于本领域熟练技术人员是已知的，适当的极性配位剂的使用在本申请的范围内。是否使用极性配位剂以及要使用的改性剂的量依赖于许多因素，包括但不限于期望的乙烯基含量的量和聚合温度，以及所采用的特定极性配位剂的性质。典型地，有用的极性配位剂包括具有氧或氮杂原子以及非键合电子对的化合物。非限制性实例包括单和低聚亚烷基(oligo alkylene)二醇的二烷基醚；“冠”醚；叔胺如四甲基亚乙基二胺(TMEDA)；和线形THF低聚物。优选的极性配位剂包括但不限于四氢呋喃(THF)、线形和环状低聚四氢呋喃基(oxolanyl)烷如2,2-双(2′-四氢呋喃基)丙烷、二哌啶基乙烷、二哌啶基甲烷、六甲基磷酰胺、N,N′-二甲基哌嗪、二氮杂二环辛烷、二甲醚、二乙醚和三丁基胺等。线形和环状低聚四氢呋喃基烷改性剂记载于美国专利4,429,091号，将其引入于此以作参考。
进行本文所述的阴离子聚合时所采用的金属化氨基硅烷引发剂的量可基于所期望的聚合物性质而广泛变化。在一个实施方案中，金属与单体的摩尔比可为1:10至1:20,000。金属意指金属化氨基硅烷化合物中或金属化剂中的金属。同样地，在一个实施方案中，金属与烷氨基硅烷化合物的摩尔比可为0.8至1.2。
如上所述为通过使用本文所述的金属化氨基硅烷引发剂的至少一种阴离子可聚合单体的引发聚合和使聚合继续进行。通常，一旦实现期望的转化率，可通过终止或偶联来停止聚合。一种终止聚合的方式为通过添加为活性端贡献质子的化合物来使活性聚合物质子化。非限制性实例包括水、异丙醇和甲醇及其任意混合物。
在一个或多个实施方案中，可使活性聚合物偶联以将两个或多个活性聚合物链连接在一起。本领域熟练技术人员理解偶联聚合物链的能力依赖于与聚合物链反应的偶联剂的量。例如，以引发剂上锂的当量与偶联剂上离去基团(leaving group)(如卤原子)的当量之间为1:1的比例来添加偶联剂可实现有利的偶联。偶联剂的非限制性实例包括金属卤化物、准金属卤化物、烷氧基硅烷和烷氧基锡烷。
在一个或多个实施方案中，金属卤化物或准金属卤化物可选自包括由式(1)R*nM1Y(4-n)、式(2)M1Y4和式(3)M2Y3表示的化合物的组，其中各R*独立地为具有1至20个碳原子的单价有机基团，M1为锡原子、硅原子或锗原子，M2为磷原子，Y为卤原子和n为0-3的整数。
由式(1)表示的示例性化合物包括卤代有机金属化合物，由式(2)和(3)表示的化合物包括卤代金属化合物。
在M1表示锡原子的情况下，由式(1)表示的化合物可为例如，三苯基氯化锡、三丁基氯化锡、三异丙基氯化锡、三己基氯化锡、三辛基氯化锡、二苯基二氯化锡、二丁基二氯化锡、二己基二氯化锡、二辛基二氯化锡、苯基三氯化锡、丁基三氯化锡和辛基三氯化锡等。此外，四氯化锡和四溴化锡等可示例为由式(2)表示的化合物。
在M1表示硅原子的情况下，由式(1)表示的化合物可为例如，三苯基氯硅烷、三己基氯硅烷、三辛基氯硅烷、三丁基氯硅烷、三甲基氯硅烷、二苯基二氯硅烷、二己基二氯硅烷、二辛基二氯硅烷、二丁基二氯硅烷、二甲基二氯硅烷、甲基三氯硅烷、苯基三氯硅烷、己基三氯硅烷、辛基三氯硅烷、丁基三氯硅烷和甲基三氯硅烷等。此外，四氯化硅和四溴化硅等可示例为由式(2)表示的化合物。在M1表示锗原子的情况下，由式(1)表示的化合物可为例如，三苯基氯化锗、二丁基二氯化锗、二苯基二氯化锗和丁基三氯化锗等。此外，四氯化锗和四溴化锗等可示例为由式(2)表示的化合物。三氯化磷和三溴化磷等可示例为由式(3)表示的化合物。在一个或多个实施方案中，可使用金属卤化物和/或准金属卤化物的混合物。
在一个或多个实施方案中，烷氧基硅烷或烷氧基锡烷可选自包括由式(4)R*nM1(OR^)4-n表示的化合物的组，其中各R*独立地为具有1至20个碳原子的单价有机基团，M1为锡原子、硅原子或锗原子，OR^为烷氧基，其中R^为单价有机基团和n为0-3的整数。
由式(4)表示的示例性化合物包括原硅酸四乙酯、原硅酸四甲酯、原硅酸四丙酯、四乙氧基锡、四甲氧基锡和四丙氧基锡。
抗氧化剂可在终止剂添加的同时、之前或之后添加。当聚合停止时，可利用脱溶剂和干燥的常规步骤从聚合混合物中回收聚合物。例如，聚合物可通过如下方法从溶液中分离：用醇如甲醇、乙醇或异丙醇使聚合混合物凝固，随后分离，或者使溶剂和未反应单体蒸汽蒸馏，随后分离。然后，干燥所分离的聚合物以除去残量的溶剂和水。可选地，聚合物可通过蒸发溶剂，例如通过直接鼓风干燥聚合物胶浆而从聚合混合物中分离。
在本申请的另一实施方案中，提供轮胎用橡胶组合物，所述组合物包括通过前述方法制备的氨基硅烷官能化聚合物、至少一种橡胶状聚合物和至少一种填料。
如本申请所述，氨基硅烷官能化聚合物，以及含有此类官能化聚合物的橡胶组合物特别用于制备轮胎组件。这些轮胎组件可通过单独使用或与其他橡胶状聚合物一起使用本申请中所述的氨基硅烷官能化聚合物来制备。氨基硅烷官能化聚合物通过使用预先形成的阴离子引发剂来引发至少一种阴离子可聚合单体所形成，所述预先形成的阴离子引发剂如上所述包括至少一种金属化剂和至少一种具有式(IA)或(IB)的化合物的反应产物。在另一实施方案中，如上所述，氨基硅烷官能化聚合物通过使用原位形成的金属化氨基硅烷化合物来引发至少一种阴离子可聚合单体所形成。
其他可使用的橡胶状聚合物包括天然和合成弹性体。有用的橡胶状弹性体的非限制性实例包括天然橡胶、合成聚异戊二烯、聚丁二烯、聚(异丁烯-co-异戊二烯)、氯丁橡胶、聚(乙烯-co-丙烯)、聚(苯乙烯-co-丁二烯)、聚(苯乙烯-co-异戊二烯)、聚(苯乙烯-co-异戊二烯-co-丁二烯)，聚(异戊二烯-co-丁二烯)、聚(乙烯-co-丙烯-co-二烯)、聚硫橡胶、丙烯酸类橡胶、聚氨酯橡胶、硅橡胶、表氯醇橡胶及其混合物。这些弹性体可具有大量包括线形、支化和星形的大分子结构。由于弹性体在轮胎工业中的常规用途，优选的弹性体包括天然橡胶、聚丁二烯、聚异戊二烯以及苯乙烯、丁二烯和异戊二烯的各种共聚物。
典型地，在本文公开的橡胶组合物中，氨基硅烷官能化聚合物以10至100phr范围内的量存在，而其他橡胶状聚合物以0至90phr范围内的量存在。
橡胶组合物可包括填料如无机和有机填料，及其混合物。有机填料的非限制性实例包括炭黑和淀粉，及其混合物。无机填料的非限制性实例包括二氧化硅、氢氧化铝、氢氧化镁、粘土(水合硅酸铝)，及其混合物。
在一个或多个实施方案中，二氧化硅包括通过在水中的化学反应生产，并沉淀为超细球形颗粒的湿法水合二氧化硅。在一个实施方案中，二氧化硅具有约32至约400m2/g，在另一实施方案中约100至约250m2/g，还在另一实施方案中约150至约220m2/g的表面积。在一个实施方案中，二氧化硅填料的pH约5.5至约7，在另一实施方案中约5.5至约6.8。商购可得的二氧化硅包括Hi-SilTM215、Hi-SilTM233、Hi-SilTM255LD和Hi-SilTM190(PPG Industries;Pittsburgh,Pennsylvania)，ZeosilTM 1165MP和175GRPlus(Rhodia)，VulkasilTM(Bary AG)，UltrasilTMVN2、VN3(Degussa)以及HuberSilTM8745(Huber)。
在一个或多个实施方案中，炭黑可包括任何通常可得、商业生产的炭黑。这些包括具有至少20m2/克的表面积(EMSA)，和在其他实施方案中为至少35m2/克至多达200m2/克或更高的表面积的那些炭黑。表面积值包括通过使用十六烷基三甲基溴化铵(CTAB)技术的ASTM试验D-1765所测定的那些。有用的炭黑为炉黑、槽黑和灯黑。更具体地，炭黑的实例包括超耐磨炉(SAF)黑、高耐磨炉(HAF)黑、快压出炉(FEF)黑、细炉(FF)黑、中等超耐磨炉(ISAF)黑、半补强炉(SRF)黑、中等加工槽黑、难加工槽黑和导电槽黑。其他可利用的炭黑包括乙炔黑。两种或多种上述炭黑的混合物可用于制备本发明的炭黑产品。示例性炭黑包括带有ASTM命名(D-1765-82a)N-110、N-220、N-339、N-330、N-351、N-550和N-660的那些炭黑。在一个或多个实施方案中，炭黑可包括氧化炭黑。
在一个实施方案中，二氧化硅可以以如下的量使用：基于每百分橡胶的约5至约200重量份(phr)、在其他实施方案中为约10至约150phr、还在另一实施方案中为约15至约80phr和还在另一实施方案中为约25至约75phr。
在一个实施方案中，炭黑可以以约1至约200phr的量、以约5至约100phr的量，或可选地以约30至约80phr的量使用。
可采用许多橡胶固化剂，包括硫或过氧化物类固化体系。固化剂描述于Kirk-Othmer，ENCYCLOPEDIA OF CHEMICALTECHNOLOGY,第20卷,第365-468页,(第三版，1982),特别是Vulcanization Agents and Auxiliary Materials,第390-402页，和A.Y.Coran,Vulcanization,ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING,(第二版，1989),在此将其引入以作参考。硫化剂可单独或组合使用。在一个或多个实施方案中，可硫化组合物的制备以及轮胎的结构和固化不受本发明实施的影响。
可采用的其它成分包括促进剂、油、蜡、焦化抑制剂、加工助剂、氧化锌、增粘树脂、补强树脂、脂肪酸如硬脂酸、塑解剂，以及一种或多种附加橡胶。油的实例包括石蜡油、芳香油、环烷油、除蓖麻油之外的植物油，和包括MES、TDAE、SRAE和重环烷油的低PCA油。
这些胶料(stocks)对于形成轮胎组件特别有用：如胎面、胎面基部、黑胎侧、胎体隔离胶和胎圈填胶等。优选地，官能化聚合物用于胎面配方。在一个或多个实施方案中，这些胎面配方可包括约10重量%至约100重量%，在另一些实施方案中约35重量%至约90重量%，和在其他实施方案中约50重量%至80重量%的官能化聚合物，基于配方中橡胶的总重量。
在一个或多个实施方案中，可硫化橡胶组合物可通过形成包括橡胶组分和填料的初始母炼胶来制备(橡胶组分任选包括本发明的官能化聚合物)。可将初始母炼胶在约25℃至约125℃的起始温度、约135℃至约180℃的排料温度下混合。为了防止过早硫化(也称为焦化)，该初始母炼胶可包括硫化剂。一旦处理初始母炼胶，则可将硫化剂在最后混合阶段在低温下引入并混入初始母炼胶(其优选不引发硫化过程)中。任选地，可在母炼胶混合阶段和最后混合阶段之间采用另外的混合阶段，有时也称为再炼。在这些再炼期间，可添加包括本发明的官能化聚合物在内的各种成分。这里采用的橡胶配混技术和添加剂一般公开于Rubber Technology(第二版，1973)中的The Compoundingand Vulcanization of Rubber。
如美国专利5,227,425、5,719,207和5,717,022，以及欧洲专利890,606(在此将其全部引入以作参考)中所描述的，适用于二氧化硅填充的轮胎配方的混合条件和方法是公知的。在一个或多个实施方案中，在二氧化硅用作填料(单独或与其它填料组合)时，可以将偶联剂和/或保护剂在混合期间添加至橡胶配方。有用的偶联剂和保护剂公开于美国专利3,842,111、3,873,489、3,978,103、3,997,581、4,002,594、5,580,919、5,583,245、5,663,396、5,674,932、5,684,171、5,684,172、5,696,197、6,608,145、6,667,362、6,579,949、6,590,017、6,525,118、6,342,552和6,683,135中，在此将其引入以作参考。在一个实施方案中，通过在基本上不存在偶联剂和保护剂下将本发明的官能化聚合物和二氧化硅包括在内来制备初始母炼胶。认为该方法将增加官能化聚合物在与偶联剂或保护剂竞争前同二氧化硅反应或相互作用的机会，所述偶联剂或保护剂可在后期的固化再炼(latercuring remills)中添加。
在可硫化橡胶组合物用于制造轮胎的情况下，这些组合物可以按照包括标准橡胶成型、模塑和固化技术的一般轮胎制造技术加工成轮胎组件。可制造任何各种橡胶轮胎组件，包括但不限于，胎面、胎侧、带束层隔离胶(belt skims)和胎体。典型地，硫化是通过在模具中加热硫化组合物，例如可将其加热到约140至约180℃来产生。固化或交联的橡胶组合物可称为硫化产品，其通常包含热固化的三维聚合物网络。也可将其它成分如加工助剂和填料均匀地分散在整个硫化网络中。充气轮胎可以如美国专利5,866,171、5,876,527、5,931,211和5,971,046所讨论的那样制造，在此将其引入以作参考。
涉及使用用于轮胎组件的橡胶组合物中的填料(包括炭黑和二氧化硅填料)和附加成分的附加信息，以及涉及配混这些配方的信息公开于美国专利7,612,144、6,221,943、6,342,552、6,348,531、5,916,961、6,252,007、6,369,138、5,872,176、6,180,710、5,866,650、6,228,908和6,313,210，在此将其公开内容引入以作参考。
通过以下实施例进一步说明本发明的实施，这些实施例不应理解为是对权利要求书中所述的本发明的范围的限制。
一般实验测试方法
分子量测定：使用装配有Model 2414折射计和Model 996光电二极管阵列检测器(UV)的Waters Model 150-C仪，通过凝胶渗透/尺寸排阻色谱法(SEC)来测量分子量。由基于聚苯乙烯标准物并使用以下SBR用Mark-Houwink常量校正的通用校正曲线来计算分子量：k=0.000269，α=0.73。
NMR：在300MHz Gemini 300NMR分光光度计体系(Varian)上使用1H-NMR(CDCl3)和13C NMR测量来确定苯乙烯和乙烯基含量，以及小分子结构的证实。
玻璃化转变温度(Tg)：使用DSC2910差示扫描热量计(TAInstruments)测定玻璃化转变温度。将Tg测量为热容量(Cp)变化时发生的拐点的温度。
动态机械性质：使用两种技术测量动态机械性质。使用带有15mm厚、9.27mm直径的按钮的平行板模式中的流变动态分析仪RDAII(Rheometric Scientific)。在1Hz和50℃下，在0.25-14.5%γ的变形下测量损耗模量G″、储能模量G′和tanδ。通过计算G′(0.25%γ)-G′(14.0%γ)的差来预估潘恩(Payne)效应。还使用带有具31.7mm×12.7mm×2.0mm尺寸的样品的扭力矩形模式中的RDA700(Rheometric Scientific)。以5℃min-1的速度从-80℃升温至100℃。使用5Hz的频率以及-80℃至-10℃的0.5%γ和-10℃至100℃的2%γ的变形来获得模量(G′和G″)。
门尼粘度：根据ASTM-D 1646-89进行门尼粘度的测量。
实施例
代表性的烷氨基硅烷化合物
实施例1
用仲丁基锂(s-BuLi)处理双-(二甲氨基)苯基甲基硅烷以进行锂化，用以下方式提供具有结构A的化合物：
将以下成分装入300mL干燥的氮气净化的、用冠封盖和腈类盖衬垫(cap liner)固定的瓶中：双-(二甲氨基)苯基甲基硅烷，9.23mmol(2.0mL,1.92g)；三乙胺，5.0mL；仲丁基锂，10.1mmol(7.2mL环己烷中的1.4M溶液)。将所得溶液在50℃下搅拌2.5hr，并预估为大约0.65M化合物A。
实施例2
在密封瓶中使用实施例1的新制金属化试剂以聚合1,3-丁二烯。目标为Mn=25kg/mol的聚合物。800mL的瓶(如实施例1的干燥、净化并固定)装有31.4g在261g无水己烷中的1,3-丁二烯，然后将2.0mL(约1.3mmol)实施例1的试剂注入瓶中。将瓶在50℃下搅拌75min，然后使其冷却至室温过夜。用2mL 2-丙醇(i-PrOH)猝灭所得胶浆，并用二叔丁基对甲酚(DBPC)来稳定化。从固成分中预估90%的转化率。使胶浆在乙醇中凝固，并在己烷中再溶解凝固物，然后以相同的方式再凝固两次。将凝固的聚合物在室温下在氮气流下干燥4hr，然后在约70℃下在真空下过夜。如通过SEC所测定的，聚丁二烯(PBD)产物具有Mn=26.9kg/mol。产物的NMR(13C)分析显示甲硅烷基几乎定量的引入((Si-CH2区中的碳(11.6-12.04ppm)与来自末端CH3的那些(反式，18.0ppm；顺式，13.0ppm)之比接近1:1)。
实施例3-5
如实施例1制备另一新制金属化试剂并用于在密封瓶中使1,3-丁二烯与苯乙烯与1,3-丁二烯的混合物聚合。随后，除了聚合时间为120min以外，进行实施例2的聚合步骤和加工(workup)。这些聚合的目标为125kg/mol PBD(实施例3：发现Mn=139.2kg/mol)，以及25和125kg/mol苯乙烯-丁二烯共聚物(SBR)(发现实施例4和5分别为Mn=35.6和211.2kg/mol)。实施例3、4和5的聚合分别以80%、97%和96%的转化率进行。
实施例6(预先混合，间歇)
如实施例1制备浓度约0.65M的双-(二甲氨基)苯基甲基硅烷的新制锂化试剂在己烷中的溶液。根据以下步骤，在无水氮气气氛下，在间歇反应器中将其用于引发苯乙烯与1,3-丁二烯的共聚，目的为Mn=120kg/mol。搅拌的7.6L高压釜型反应器装有3755g无水己烷、551.1g无水1,3-丁二烯、129.3g无水苯乙烯和1.2mL己烷中的1.60M低聚四氢呋喃基丙烷溶液。使混合物保持在49℃的稳定温度下，并添加8.72mL(5.67mmol)锂化的双-(二甲氨基)苯基甲基硅烷溶液。在达到55.2℃的峰顶温度后，使聚合继续另外60min，如从胶浆的固成分预估达到92%的转化率。通过针状物(needle)将产物胶浆的样品收集到干燥、净化、密封的800mL瓶中。用2mL喷氮气的2-丙醇猝灭各产物胶浆的样品并用DBPC来稳定化，其后在含有添加了DBPC的2-丙醇中凝固。在110℃下，在双辊磨机上鼓风干燥所结合的凝固物，产生6号样品。性质总结与下表1中。
实施例7(预先混合，半间歇)
根据以下步骤，在计量的半间歇条件下在无水氮气气氛的搅拌间歇反应器中进行苯乙烯与1,3-丁二烯的共聚，目的为Mn=140kg/mol。搅拌的7.6L高压釜型反应器装有1710g无水己烷和0.27mL己烷中的1.60M低聚四氢呋喃基丙烷溶液。加热混合物至并保持于85℃。然后通过使用计量器以约36g/min向反应器添加2063.4g无水己烷中的217.7g无水苯乙烯和462.7g无水1,3-丁二烯的混合物。计量约十分钟后，添加7.48mL的0.65M锂化的双-(二甲氨基)苯基甲基硅烷溶液(4.86mmol)(根据实施例1新制备的)。在装入引发剂后继续单体的计量添加62min。然后，通过针状物将产物胶浆的样品收集到干燥、净化、密封的800mL瓶中。从胶浆的固成分预估聚合中的转化率为87.4%。如实施例6猝灭、稳定、凝固并干燥五个瓶中的胶浆，产生实施例7。性质总结与下表1中。
实施例8(预先混合，半间歇)
以每Li的Sn-Cl当量为0.6将在实施例7的剩余五瓶中的胶浆各自用0.2M SnCl4的溶液处理，然后在50℃下搅拌35min。搅拌后，如上述实施例猝灭、稳定、凝固并干燥胶浆，产生实施例8。性质总结与下表1中。
实施例9(预先混合，间歇)
重复实施例6的步骤。在93.4%的转化率下进行聚合。如实施例6加工产物，产生实施例9，其性质包括在下表1中。
比较例A(间歇对照)
除了正丁基锂为唯一的引发剂以外，按照实施例6的步骤进行。在96.6%的转化率下进行聚合。如实施例6加工产物，产生样品10，其性质包括在下表1中。样品A用作比较例用对照间歇聚合物。
比较例A′(间歇对照)
按照比较例A的步骤进行，产生具有非常相似性质的聚合物，定为样品A′，其性质包括在下表1中。样品A′也用作比较例用对照间歇聚合物。
比较例B(半间歇对照)
除了正丁基锂为唯一的引发剂以外，按照实施例7的计量的半间歇聚合步骤进行。未测量转化的程度。如实施例6加工产物，产生样品B，其性质包括在下表1中。样品B用作比较例用对照半间歇聚合物。
表1
尽管以上示出的实施例使用引发剂A，但由其他底物以类似的方式可产生具有类似效果的试剂。例如，将通过用仲丁基锂处理双-(六亚己基亚胺基)辛基甲基硅烷所产生的锂化物用于引发1,3-丁二烯的聚合和1,3-丁二烯与苯乙烯的共聚(如上述实施例2和4)，分别产生转化率为86%和97.6%的聚合物。在各情况中目标为25kg/mol的分子量，所获得的产物分别具有通过SEC测量的Mn为30.5和33.2kg/mol。因此，其他结构的范围也有效。
总之，采用A作为引发剂的1,3-丁二烯与苯乙烯的阴离子共聚在高转化率下进行，以产生高分子量弹性体。获得在目标分子量处或附近的分子量的产物。聚合物包含在头部基团的硅，Si通过碳原子键合至聚合物链。
随后使用“全硅”配方将聚合物与其他成分配混以制备可硫化弹性体化合物。基于每100份橡胶的组分的重量份(phr)示于下表2。
表2
首先，将聚合物置于65-g班伯里混炼机中，0.5分钟后，加入除硬脂酸以外的剩余成分。然后在3分钟后加入硬脂酸。混合初始组分5.5分钟。在混炼结束时，温度约为165℃。将各样品转移至60℃的温度下操作的磨机，此时切片，随后冷却至室温。130℃下再炼混炼胶3.5分钟，借此在比母炼胶阶段更温和的条件下加入偶联剂。将各样品再次转移至60℃的磨机、切片并冷却至室温。通过加入再炼物料来混炼终组分，同时将固化材料加入混炼机中。初始混炼机温度为65℃，同时在45rpm下操作。当材料温度在100℃至105℃之间时，2.5分钟后从混炼机中除去终材料。将终产物切片成Dynastat按钮和15×15×0.1875cm的片。在置于热压机中的标准模具中，在171℃下将样品固化15分钟。
试验样品和比较样品的配混评价结果总结于下表3。
表3
表3中的数据显示当相对于使用正丁基锂引发剂的比较例评判时，对于使用引发剂A用弹性体制备的化合物具有相当可观的60℃下的滞后降低。在间歇聚合条件下(样品6和9)、而不是半间歇条件下(样品7和8)制备的聚合物中，滞后降低较大。
比较样品C(对照半间歇)
根据以下步骤，在无水氮气气氛的搅拌间歇反应器中，在计量的半间歇条件下进行苯乙烯与1,3-丁二烯的共聚，目标Mn=140kg/mol。搅拌的7.6L高压釜型反应器装有1710g无水己烷和0.27mL己烷中的1.60M低聚四氢呋喃基丙烷溶液。加热混合物至并保持在93.3℃。然后通过使用计量器，以约36g/min向反应器添加2063.4g无水己烷中的217.7g无水苯乙烯和462.7g无水1,3-丁二烯的混合物。计量约十分钟后，将用25mL无水己烷稀释的2.86mL的1.6M n-BuLi(4.86mmol)装入反应器。在装入引发剂后继续单体的计量添加62min，然后，通过针状物将产物胶浆的样品收集到干燥、净化、密封的800mL瓶中。将瓶中的胶浆如样品A各自猝灭、稳定、凝固并干燥，产生样品C。性质总结与下表4中。
表4
使用金属化氨基硅烷引发剂的附加实施例
实施例19A(锂化引发剂加工)
用仲丁基锂(s-BuLi)处理三-(二甲氨基)甲基硅烷(上述结构B)以进行锂化。将以下成分装入300mL干燥的氮气净化的瓶(用冠封盖和腈类盖衬垫(cap liner)固定该瓶)中：三-(二甲氨基)甲基硅烷，9.7mmol(2.0mL,1.92g)；三乙胺，4.0mL；仲丁基锂，10.1mmol(7.8mL环己烷中的1.3M溶液)。将所得溶液在50℃下搅拌2hr，并预估为大约0.73M锂化试剂。
实施例19B(预先混合，间歇)
利用样品A的步骤以产生苯乙烯-丁二烯共聚物。然而，这次通过如实施例19A制备锂化试剂，其后立即将其装入反应器，来将锂化的三-(二甲氨基)甲基硅烷(结构B)用作引发剂。温度在56.7℃下达到峰顶，并且之后进行聚合另外的60min，达到88%的转化率。将胶浆收集到800mL瓶中，用2mL喷氮气的乙醇猝灭各胶浆并用DBPC稳定化，其后在含有添加了DBPC的2-丙醇中凝固。在110℃下，在双辊磨机上鼓风干燥所结合的凝固物，产生样品19，其性质包括在下表5中。
实施例20(预先混合，间歇)
利用样品A的步骤以产生苯乙烯-丁二烯共聚物。然而，这次将1.21mL纯三-(二甲氨基)烯丙基硅烷(以上结构C)与3.34mL1.6Mn-BuLi混合并用无水己烷稀释至50mL，并将所得混合物立即装入反应器。温度在58.9℃达到峰顶，并之后进行聚合另外的60min，达到大于90%的转化率。将胶浆收集到800mL瓶中，各胶浆用2mL喷氮气的乙醇并用DBPC稳定，其后在含有添加了DBPC的2-丙醇中凝固。在110℃下，在双辊磨机上鼓风干燥所结合的凝固物，产生样品20，其性质包括在下表5中。
实施例21(预先混合，半间歇)
利用样品C的步骤以产生苯乙烯-丁二烯共聚物。然而，在该情况下所使用的引发剂由2.0mL 9.7M三-(二甲氨基)甲基硅烷(上述结构B)、4mL纯三乙胺和7.8mL环己烷中的1.3M仲丁基锂的混合物组成，将其在50℃下搅拌2.5hr(~0.73M，锂化试剂中)，其后将其装入反应器。聚合温度保持在约85℃至约95℃之间，计量在约120分钟后停止。如上所述，将产物胶浆收集到800mL瓶中，并如样品C各自猝灭、稳定、凝固并干燥，产生样品21。性质总结与下表5中。
实施例22(预先混合，半间歇)
利用样品C的步骤以产生苯乙烯-丁二烯共聚物。然而，在该情况下所使用的引发剂由0.96mL己烷中的4.44M三-(二甲氨基)烯丙基硅烷(上述结构C)和用无水己烷稀释至25mL的2.65mL 1.6M n-BuLi的混合物组成。混合后立即将引发剂装入反应器。聚合温度保持在约85℃至约95℃之间，计量在约120分钟后停止。如上所述，将产物胶浆收集到800mL瓶中，并如样品C各自猝灭、稳定、凝固并干燥，产生样品22。性质总结与下表5中。
表5
如上述表2中所公开的，其后将共聚物配混以制备可硫化弹性体配混物。配混橡胶的试验结果列于下表6。
表6
对于本文所述各方法的包括金属化氨基硅烷引发剂的聚合物，表6中的数据示出一致的滞后性质的改进。
术语“包括(includes或including)”在本说明书或权利要求书中所使用的范围，旨在将以下囊括在内，该方式类似于当在权利要求中将术语“包含(comprising)”作为过度词使用时所解释的该术语的方式。此外，术语“或”所使用的范围(例如，A或B)，意指“A或B或二者”。当本申请人旨在表示“仅A或B但不是二者”时，将采用术语“仅A或B但不是二者”。因此，本文中术语“或”的使用是包含性，而不是排它性使用。参见，Bryan A.Garner,A Dictionary of Modern Legal Usage 624(第2版，1995)。此外，术语“在…中(in或into)”在本说明书或权利要求书中所使用的范围，旨在另外还指“在…上(on或onto)”。此外，术语“连接”在本说明书或权利要求书中所使用的范围，不仅意指“直接连接至”，还意指“间接连接至”，例如通过另一个或多个组件连接。
虽然通过描述本申请的实施方案说明本申请，并且虽然非常详细地描述实施方案，但本申请人并非意欲将所附权利要求的范围限定为或以任何方式限制为此详细说明。另外的优势和修改对于本领域熟练技术人员将是显而易见的。因此，在更广泛的方面，本申请不局限于具体细节、代表性的设备和方法，以及所示出和述及的示例性实施例。因此，在不脱离本申请人总的发明构思的精神和范围内可从该细节产生差异。
Claims (20)
1.一种用于引发阴离子聚合的金属化氨基硅烷化合物，其包括如下(1)和(2)的反应产物：
(1)至少一种金属化剂，和
(2)至少一种具有式(IA)或(IB)的烷氨基硅烷化合物
其中n为选自由0-2组成的组的整数，m为选自由1-3组成的组的整数，条件是m和n的和等于3；其中T为甲基、乙基、丙基或烯丙型基团；其中各R4和R5独立地为烃基；其中各R6独立地为亚烃基；和其中当m大于1时，一个或多个R5可在两个氮原子之间形成桥。
2.根据权利要求2所述的金属化氨基硅烷化合物，其中所述至少一种金属化剂选自由烃基锂化合物、烃基钠化合物、烃基钾化合物和烃基镁化合物及其组合组成的组。
3.根据权利要求1所述的金属化氨基硅烷化合物，其中所述至少一种金属化剂包括第一组分和第二组分，其中所述第一组分为路易斯碱，和所述第二组分选自由烃基锂化合物、烃基钠化合物、烃基钾化合物、烃基镁化合物及其组合组成的组。
4.根据权利要求1所述的金属化氨基硅烷化合物，其中所述至少一种金属化剂包括第一组分和第二组分，其中所述第一组分选自由碱金属醇盐、碱金属芳基磺酸盐及其组合组成的组，和其中所述第二组分选自由烃基锂化合物、烃基钠化合物、烃基钾化合物、烃基镁化合物及其组合组成的组。
5.根据权利要求1所述的金属化氨基硅烷化合物，其中所述至少一种烷氨基硅烷化合物选自由双(二烷氨基)苯基甲基硅烷、双(六亚甲基亚胺基)苯基甲基硅烷、三(二烷氨基)烯丙基硅烷及其组合组成的组。
6.根据权利要求1所述的金属化氨基硅烷化合物，其中在不存在选自由共轭二烯单体、单乙烯基芳族单体及其组合组成的组的任何单体下产生所述反应产物。
7.一种生产氨基硅烷官能化聚合物的方法，其包括以下步骤：
(a)通过制备权利要求1所述的金属化氨基硅烷化合物来提供预先形成的引发剂，和
(b)通过使用所述金属化氨基硅烷化合物引发聚合来使至少一种阴离子可聚合单体聚合。
8.根据权利要求7所述的方法，其中所述至少一种阴离子可聚合单体选自由共轭二烯单体和单乙烯基芳族单体组成的组。
9.根据权利要求7所述的方法，其中所述金属与氨基硅烷化合物的比在0.8至1.2之间。
10.一种包括来自引发剂的残基的聚合物，其中所述引发剂包括如下(1)和(2)的反应产物：
(1)至少一种金属化剂，和
(2)至少一种具有式(IA)或(IB)的烷氨基硅烷化合物
其中n为选自由0-2组成的组的整数，m为选自由1-3组成的组的整数，条件是m和n的和等于3；其中T为甲基、乙基、丙基或烯丙型基团；其中各R4和R5独立地为烃基；其中各R6独立地为亚烃基；和其中当m大于1时，一个或多个R5可在两个氮原子之间形成桥。
11.根据权利要求10所述的聚合物，其中所述至少一种金属化剂选自由烃基锂化合物、烃基钠化合物、烃基钾化合物和烃基镁化合物及其组合组成的组。
12.根据权利要求10所述的聚合物，其中所述至少一种金属化剂包括第一组分和第二组分，其中所述第一组分为路易斯碱，和所述第二组分选自由烃基锂化合物、烃基钠化合物、烃基钾化合物、烃基镁化合物及其组合组成的组。
13.根据权利要求10所述的聚合物，其中所述至少一种金属化剂包括第一组分和第二组分，其中所述第一组分选自由碱金属醇盐、碱金属芳基磺酸盐及其组合组成的组，和其中所述第二组分选自由烃基锂化合物、烃基钠化合物、烃基钾化合物、烃基镁化合物及其组合组成的组。
14.根据权利要求10所述的聚合物，其中所述至少一种烷氨基硅烷化合物选自由双(二烷氨基)苯基甲基硅烷、双(六亚甲基亚胺基)苯基甲基硅烷、三(二烷氨基)烯丙基硅烷及其组合组成的组。
15.一种轮胎用橡胶组合物，其包括：
(a)10至100phr的通过权利要求7所述的方法形成的聚合物，其中所述至少一种阴离子可聚合单体选自由共轭二烯单体、单乙烯基芳族单体及其组合组成的组；
(b)90至0phr的至少一种橡胶状聚合物；和
(c)5至200phr的至少一种填料。
16.根据权利要求15所述的橡胶组合物，其中所述至少一种填料包括二氧化硅。
17.根据权利要求15所述的橡胶组合物，其中所述二氧化硅以10至150phr的量存在。
18.一种轮胎用橡胶组合物，其包括：
(a)10至100phr的根据权利要求10所述的聚合物；
(b)90至0phr的至少一种橡胶状聚合物；和
(c)5至200phr的至少一种填料。
19.根据权利要求18所述的橡胶组合物，其中所述至少一种填料包括二氧化硅。
20.根据权利要求18所述的橡胶组合物，其中所述二氧化硅以10至150phr的量存在。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103313863A (zh) * | 2010-12-30 | 2013-09-18 | 株式会社普利司通 | 氨基硅烷引发剂及由其制备的官能化聚合物 |
| CN109563195A (zh) * | 2016-07-22 | 2019-04-02 | 公共型股份公司希布尔控股 | 用于生产支化改性橡胶的方法和包含通过所述方法制备的支化改性橡胶的橡胶组合物及其用途 |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101909756B1 (ko) | 2009-12-31 | 2018-10-18 | 가부시키가이샤 브리지스톤 | 아미노실란 개시제 및 이로부터 제조된 관능화된 중합체 |
| RU2609166C2 (ru) * | 2012-09-14 | 2017-01-30 | ТРИНСЕО ЮРОП ГмбХ | Полимеры, модифицированные аминосиланом |
| PL3169712T3 (pl) * | 2014-07-14 | 2019-04-30 | Trinseo Europe Gmbh | Związki diaryloetenowe podstawione grupą aminosilylową do polimeryzacji anionowej |
| KR101705947B1 (ko) * | 2014-11-12 | 2017-02-10 | 한화토탈 주식회사 | 실릴음이온 개시제를 이용한 변성공액디엔계 중합체의 중합 |
| KR20160079323A (ko) | 2014-12-26 | 2016-07-06 | 한화토탈 주식회사 | 변성 공액디엔계 중합체 및 그를 포함하는 조성물 |
| EP3133093A1 (en) * | 2015-08-20 | 2017-02-22 | Trinseo Europe GmbH | Elastomeric polymer |
| EP3363804A1 (en) | 2017-02-20 | 2018-08-22 | Trinseo Europe GmbH | Metallated benzylsilanes and their use as polymerization initiators |
| EA202190668A1 (ru) * | 2018-09-03 | 2021-05-27 | Синтос С.А. | Аминосилил-функционализованные сопряженные диены, их получение и их использование при производстве каучуков |
| US11661500B2 (en) | 2018-09-21 | 2023-05-30 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition containing a multi-functional group functionalized elastomer and tire with tread |
| EP4011921A1 (en) | 2020-12-09 | 2022-06-15 | The Goodyear Tire & Rubber Company | Rubber with backbone and end-group functionalization and its method of manufacturing and use in a tire |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000050478A1 (en) * | 1999-02-25 | 2000-08-31 | Fmc Corporation | Novel formulations of alkyllithiums with improved thermal stability, processes to produce these formulations and processes for using the same to improve stability of living polymer chain ends |
| CN1961011A (zh) * | 2004-04-05 | 2007-05-09 | 株式会社普利司通 | 改性共轭二烯类聚合物、聚合引发剂及其制备方法和橡胶组合物 |
Family Cites Families (92)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL134835C (zh) * | 1966-12-05 | |||
| US3485857A (en) * | 1966-12-05 | 1969-12-23 | Dow Corning | Organometallic aminosilicon compounds |
| FR1600009A (zh) | 1968-01-31 | 1970-07-20 | ||
| US3607846A (en) | 1969-01-21 | 1971-09-21 | Firestone Tire & Rubber Co | Process of joining lithiated polymers or copolymers |
| US3873489A (en) | 1971-08-17 | 1975-03-25 | Degussa | Rubber compositions containing silica and an organosilane |
| US3978103A (en) | 1971-08-17 | 1976-08-31 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Sulfur containing organosilicon compounds |
| BE787691A (fr) | 1971-08-17 | 1973-02-19 | Degussa | Composes organosiliciques contenant du soufre |
| SU580840A3 (ru) | 1974-02-07 | 1977-11-15 | Дегусса (Фирма) | Способ получени серосодержащих кремнийорганических соединений |
| US4002594A (en) | 1975-07-08 | 1977-01-11 | Ppg Industries, Inc. | Scorch retardants for rubber reinforced with siliceous pigment and mercapto-type coupling agent |
| JPS5251106A (en) | 1975-10-22 | 1977-04-23 | Kawasaki Heavy Ind Ltd | Construction of interlocking section of base plate and side plate used for a flat-bottomed cylinderical tank |
| US4429091A (en) | 1983-03-09 | 1984-01-31 | The Firestone Tire & Rubber Company | Oligomeric oxolanyl alkanes as modifiers for polymerization of dienes using lithium-based initiators |
| US4616069A (en) | 1984-10-26 | 1986-10-07 | Nippon Zeon Co., Ltd. | Process for making diene polymer rubbers |
| DE3538576A1 (de) * | 1985-10-30 | 1987-05-07 | Basf Ag | Verfahren zum herstellen von homo- und copolymerisaten des ethylens mittels eines ziegler-katalysatorsystems |
| FR2601001B1 (fr) * | 1986-07-02 | 1988-11-10 | Rhone Poulenc Chim Base | Procede de chloration de composes phenoliques |
| US4771116A (en) | 1987-04-30 | 1988-09-13 | E. I. Du Pont De Nemours And Company | Silylamines as additives in group transfer polymerization |
| US4771117A (en) | 1987-04-30 | 1988-09-13 | E. I. Du Pont De Nemours And Company | Polymerization of acrylic esters |
| US5189109A (en) * | 1988-02-25 | 1993-02-23 | Sumitomo Chemical Company, Limited | Modified diene polymer rubbers |
| JPH01278529A (ja) | 1988-04-30 | 1989-11-08 | Cemedine Co Ltd | 複素環式化合物の開環方法及び重合方法 |
| US5219938A (en) | 1988-05-02 | 1993-06-15 | Sumitomo Chemical Company, Limited | Modified diene polymer rubbers |
| EP0341496B1 (en) * | 1988-05-02 | 1993-10-20 | Sumitomo Chemical Company, Limited | Modified diene polymer rubbers |
| JPH0768249B2 (ja) * | 1989-03-13 | 1995-07-26 | 信越化学工業株式会社 | オルトリチオ置換フェニルシラン化合物の製造方法 |
| GB9002804D0 (en) | 1990-02-08 | 1990-04-04 | Secr Defence | Anionic polymerisation |
| US5153159A (en) | 1990-04-09 | 1992-10-06 | Bridgestone/Firestone, Inc. | Elastomers and products having reduced hysteresis |
| US5231152A (en) | 1990-12-18 | 1993-07-27 | Bridgestone Corporation | Continuous process for preparing copolymers of conjugated dienes and aromatic vinyl compounds |
| FR2673187B1 (fr) | 1991-02-25 | 1994-07-01 | Michelin & Cie | Composition de caoutchouc et enveloppes de pneumatiques a base de ladite composition. |
| US5332810A (en) | 1992-10-02 | 1994-07-26 | Bridgestone Corporation | Solubilized anionic polymerization initiator and preparation thereof |
| US5565526A (en) | 1994-05-13 | 1996-10-15 | Fmc Corporation | Functionalized initiators for anionic polymerization |
| US5527753A (en) | 1994-12-13 | 1996-06-18 | Fmc Corporation | Functionalized amine initiators for anionic polymerization |
| US5521309A (en) | 1994-12-23 | 1996-05-28 | Bridgestone Corporation | Tertiary-amino allyl-or xylyl-lithium initiators and method of preparing same |
| US6080835A (en) | 1995-02-01 | 2000-06-27 | Bridgestone Corporation | Aminoalkyllithium compounds containing cyclic amines and polymers therefrom |
| US5496940A (en) | 1995-02-01 | 1996-03-05 | Bridgestone Corporation | Alkyllithium compounds containing cyclic amines and their use in polymerization |
| US5574109A (en) | 1995-02-01 | 1996-11-12 | Bridgestone Corporation | Aminoalkyllithium compounds containing cyclic amines and polymers therefrom |
| US5674932A (en) | 1995-03-14 | 1997-10-07 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and use in tires |
| US5580919A (en) | 1995-03-14 | 1996-12-03 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and use in tires |
| US5610227A (en) | 1995-06-07 | 1997-03-11 | Bridgestone/Firestone, Inc. | Lithium amino magnesiate polymerization initiators and elastomers having reduced hysteresis |
| JP3555809B2 (ja) | 1995-06-19 | 2004-08-18 | 株式会社ブリヂストン | ラジアルタイヤ |
| AT405285B (de) | 1995-09-07 | 1999-06-25 | Semperit Ag | Kautschukmischung |
| US5679751A (en) * | 1996-02-12 | 1997-10-21 | The Goodyear Tire & Rubber Company | Solution polymerization process for synthesis of styrene-butadiene or styrene-isoprene rubber |
| US5583245A (en) | 1996-03-06 | 1996-12-10 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
| US5719207A (en) | 1996-03-18 | 1998-02-17 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
| US5696197A (en) | 1996-06-21 | 1997-12-09 | The Goodyear Tire & Rubber Company | Heterogeneous silica carbon black-filled rubber compound |
| JP3606411B2 (ja) | 1996-07-10 | 2005-01-05 | 株式会社ブリヂストン | タイヤ加硫成型用金型およびその製造方法 |
| JP3117645B2 (ja) | 1996-09-03 | 2000-12-18 | 株式会社ブリヂストン | 空気入りラジアルタイヤ |
| US5663396A (en) | 1996-10-31 | 1997-09-02 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
| US5684171A (en) | 1997-02-11 | 1997-11-04 | The Goodyear Tire & Rubber Company | Process for the preparation of organosilicon polysulfide compounds |
| US5684172A (en) | 1997-02-11 | 1997-11-04 | The Goodyear Tire & Rubber Company | Process for the preparation of organosilicon polysulfide compounds |
| US5866650A (en) | 1997-07-11 | 1999-02-02 | Bridgestone Corporation | Composition of cyclic amine-initiated elastomers and amorphous silica and process for the production thereof |
| US6221943B1 (en) | 1997-07-11 | 2001-04-24 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
| US6252007B1 (en) | 1997-07-11 | 2001-06-26 | Bridgestone Corporation | Elastomers having a reduced hysteresis via interaction of polymer with silica surfaces |
| US6369138B2 (en) | 1997-07-11 | 2002-04-09 | Bridgestone Corporation | Processability of silica-filled rubber stocks with reduced hysteresis |
| US5872176A (en) | 1997-07-11 | 1999-02-16 | Bridgestone Corporation | Addition of salts to improve the interaction of silica with rubber |
| US6525118B2 (en) | 1997-07-11 | 2003-02-25 | Bridgestone Corporation | Processability of silica-filled rubber stocks with reduced hysteresis |
| US6228908B1 (en) | 1997-07-11 | 2001-05-08 | Bridgestone Corporation | Diene polymers and copolymers incorporating partial coupling and terminals formed from hydrocarboxysilane compounds |
| US6384117B1 (en) | 1997-07-11 | 2002-05-07 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
| US5916961A (en) | 1997-07-11 | 1999-06-29 | Bridgestone Corporation | Amine-initiated elastomers having hysteresis reducing interaction with silica |
| ES2199454T5 (es) | 1997-08-21 | 2009-03-01 | Momentive Performance Materials Inc. | Agentes de acoplamiento de mercaptosilano bloqueados para cauchos con sustancia de relleno. |
| US5971046A (en) | 1997-09-17 | 1999-10-26 | Bridgestone/Firestone, Inc. | Method and apparatus for bonding an active tag to a patch and a tire |
| FR2802542A1 (fr) | 1999-12-20 | 2001-06-22 | Michelin Soc Tech | Composition de caoutchouc vulcanisable pour la fabrication d'un pneumatique et pneumatique dont la bande de roulement comprend une telle composition |
| US6765066B2 (en) | 1999-12-30 | 2004-07-20 | Bridgestone Corporation | Copolymers prepared by using both anionic polymerization techniques and coordination catalysts |
| US6451935B1 (en) | 2000-05-10 | 2002-09-17 | Bridgestone Corporation | Highly functionalized polymers and a process for making the same |
| US6590017B1 (en) | 2000-05-15 | 2003-07-08 | Bridgestone Corporation | Processability of silica-reinforced rubber containing an amide compound |
| US6313210B1 (en) | 2000-07-31 | 2001-11-06 | Bridgestone Coporation | Silica-reinforced rubber compounds containing moisture stabilized polymers |
| US6362282B1 (en) | 2000-09-29 | 2002-03-26 | Firestone Polymers, Llc | Polymers with high vinyl end segments |
| US6608145B1 (en) | 2000-10-13 | 2003-08-19 | Bridgestone Corporation | Silica-reinforced rubber compounded with an organosilane tetrasulfide silica coupling agent at high mixing temperature |
| EP1370593B1 (en) | 2001-02-28 | 2006-07-26 | Bridgestone Corporation | Continuous process for the production of conjugated diene polymers having narrow molecular weight distribution and products therefrom |
| US6881795B2 (en) | 2001-03-28 | 2005-04-19 | Firestone Polymers, Llc | CO2 terminated rubber for plastics |
| ES2336899T3 (es) | 2001-09-27 | 2010-04-19 | Jsr Corporation | Goma polimero conjugada con diolean (co), proceso para producir goma polimero (co), composicion de la goma, composite y neumatico. |
| US6579949B1 (en) | 2001-10-30 | 2003-06-17 | Bridgestone Corporation | Preparation of low hysteresis rubber by reacting a lithium polymer with a sulfur containing reagent |
| DE10159803A1 (de) * | 2001-12-05 | 2003-07-03 | Degussa | Katalysatoren und Verfahren zur Herstellung von Isocyanuratgruppen enthaltenden Polyisocyanaten und deren Verwendung |
| EP1565476B1 (en) | 2002-10-30 | 2015-03-25 | Bridgestone Corporation | The use of sulfur containing initiators for anionic polymerization of monomers |
| EP1631595B1 (en) | 2003-06-09 | 2013-08-28 | Bridgestone Corporation | Improved hysteresis elastomeric compositions comprising polymers terminated with isocyanato alkoxysilanes |
| WO2005085304A1 (en) | 2004-03-01 | 2005-09-15 | Bridgestone Corporation | Continuous polymerization reactor |
| US7598322B1 (en) | 2004-07-26 | 2009-10-06 | Bridgestone Corporation | Functionalized polymers and improved tires therefrom |
| US7460716B2 (en) | 2004-09-13 | 2008-12-02 | Boston Scientific Scimed, Inc. | Systems and methods for producing a dynamic classified image |
| US7335712B2 (en) | 2005-04-21 | 2008-02-26 | Bridgestone Corporation | Process of producing a siloxy-functionalized polymer |
| US20060264590A1 (en) | 2005-05-20 | 2006-11-23 | Bridgestone Corporation | Anionic polymerization initiators and polymers therefrom |
| BRPI0611189B1 (pt) | 2005-05-31 | 2017-06-06 | Toho Titanium Co Ltd | catalisador para a polimerização de olefinas, e, processo para a produção de um polímero de olefina |
| JP4319174B2 (ja) | 2005-08-10 | 2009-08-26 | 京セラミタ株式会社 | 電子機器の冷却構造及び複写機 |
| US7732534B2 (en) | 2006-08-28 | 2010-06-08 | Bridgestone Corporation | Polymers functionalized with nitro compounds |
| US20080103261A1 (en) | 2006-10-25 | 2008-05-01 | Bridgestone Corporation | Process for producing modified conjugated diene based polymer, modified conjugated diene based polymer produced by the process, rubber composition, and tire |
| JP5391557B2 (ja) | 2007-02-28 | 2014-01-15 | 住友化学株式会社 | 共役ジエン系重合体、共役ジエン系重合体の製造方法及び共役ジエン系重合体組成物 |
| CN101835807B (zh) | 2007-06-18 | 2013-03-13 | 株式会社普利司通 | 用含氨基的卤代硅烷官能化的聚合物 |
| ES2551103T3 (es) | 2007-12-28 | 2015-11-16 | Bridgestone Corporation | Polímeros funcionalizados de hidroxiarilo |
| US9623705B2 (en) | 2008-03-10 | 2017-04-18 | Bridgestone Corporation | Method for producing modified conjugated diene polymer/copolymer, modified conjugated diene polymer/copolymer, and rubber composition and tire using the same |
| SG155871A1 (en) * | 2008-03-31 | 2009-10-29 | Sumitomo Chemical Co | Conjugated diene polymer, conjugated diene polymer composition, and process for producing conjugated diene polymer |
| KR20090104727A (ko) * | 2008-03-31 | 2009-10-06 | 스미또모 가가꾸 가부시키가이샤 | 공액 디엔계 중합체, 공액 디엔계 중합체 조성물, 및 공액 디엔계 중합체의 제조 방법 |
| TW201022301A (en) | 2008-08-27 | 2010-06-16 | Sumitomo Chemical Co | Conjugated diene polymer, conjugated diene polymer composition, and method for producing conjugated diene polymer |
| SG159473A1 (en) | 2008-08-27 | 2010-03-30 | Sumitomo Chemical Co | Conjugated diene polymer, conjugated diene polymer composition, and method for producing conjugated diene polymer |
| SG159475A1 (en) * | 2008-08-27 | 2010-03-30 | Sumitomo Chemical Co | Conjugated diene polymer and conjugated diene polymer composition |
| US8299167B2 (en) | 2008-08-27 | 2012-10-30 | Sumitomo Chemical Company, Limited | Conjugated diene polymer, conjugated diene polymer composition, and method for producing conjugated diene polymer |
| KR101909756B1 (ko) | 2009-12-31 | 2018-10-18 | 가부시키가이샤 브리지스톤 | 아미노실란 개시제 및 이로부터 제조된 관능화된 중합체 |
| KR20180078331A (ko) | 2010-12-30 | 2018-07-09 | 가부시키가이샤 브리지스톤 | 아미노실란 개시제 및 이로부터 제조된 관능화 중합체 |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000050478A1 (en) * | 1999-02-25 | 2000-08-31 | Fmc Corporation | Novel formulations of alkyllithiums with improved thermal stability, processes to produce these formulations and processes for using the same to improve stability of living polymer chain ends |
| CN1961011A (zh) * | 2004-04-05 | 2007-05-09 | 株式会社普利司通 | 改性共轭二烯类聚合物、聚合引发剂及其制备方法和橡胶组合物 |
Non-Patent Citations (2)
| Title |
|---|
| TAKEHIRO KITAURA ET AL.: ""Anionic Polymerization of (Meth)acrylates with Trialkylsilyl-protected Lithium N-Benzylamide"", 《POLYMER JOURNAL》 * |
| TATSUKI KITAYAMA ET AL.: ""Anionic Polymerization of Methyl Methacrylate with Lithium N-Benzyltrimethylsilylamide"", 《POLYMER JOURNAL》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103313863A (zh) * | 2010-12-30 | 2013-09-18 | 株式会社普利司通 | 氨基硅烷引发剂及由其制备的官能化聚合物 |
| CN103313863B (zh) * | 2010-12-30 | 2017-06-20 | 株式会社普利司通 | 氨基硅烷引发剂及由其制备的官能化聚合物 |
| CN109563195A (zh) * | 2016-07-22 | 2019-04-02 | 公共型股份公司希布尔控股 | 用于生产支化改性橡胶的方法和包含通过所述方法制备的支化改性橡胶的橡胶组合物及其用途 |
| CN109563195B (zh) * | 2016-07-22 | 2021-07-27 | 公共型股份公司希布尔控股 | 用于生产支化改性橡胶的方法和包含通过所述方法制备的支化改性橡胶的橡胶组合物及其用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2519548A1 (en) | 2012-11-07 |
| US20130066008A1 (en) | 2013-03-14 |
| BR112012016377A2 (pt) | 2017-07-04 |
| KR101909756B1 (ko) | 2018-10-18 |
| JP5551796B2 (ja) | 2014-07-16 |
| ES2797387T3 (es) | 2020-12-02 |
| EP2519548B1 (en) | 2020-04-01 |
| JP2013516421A (ja) | 2013-05-13 |
| JP2016074910A (ja) | 2016-05-12 |
| CN102781969B (zh) | 2015-06-24 |
| JP6038266B2 (ja) | 2016-12-07 |
| BR112012016377B1 (pt) | 2020-09-29 |
| KR20120101726A (ko) | 2012-09-14 |
| US10745497B2 (en) | 2020-08-18 |
| JP2014205840A (ja) | 2014-10-30 |
| WO2011082277A1 (en) | 2011-07-07 |
| US9884923B2 (en) | 2018-02-06 |
| US20180155460A1 (en) | 2018-06-07 |
| JP5841193B2 (ja) | 2016-01-13 |
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