CN101010355A - Functional siloxanes and silanes and their vinyl co-polymers - Google Patents
Functional siloxanes and silanes and their vinyl co-polymers Download PDFInfo
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- CN101010355A CN101010355A CN 200580029346 CN200580029346A CN101010355A CN 101010355 A CN101010355 A CN 101010355A CN 200580029346 CN200580029346 CN 200580029346 CN 200580029346 A CN200580029346 A CN 200580029346A CN 101010355 A CN101010355 A CN 101010355A
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- group
- radical
- integer
- phenyl
- siloxane
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- -1 siloxanes Chemical class 0.000 title claims description 94
- 150000004756 silanes Chemical class 0.000 title claims description 21
- 229920006163 vinyl copolymer Polymers 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 66
- 239000012966 redox initiator Substances 0.000 claims abstract description 52
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 150000003254 radicals Chemical class 0.000 claims description 80
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 42
- 229910000077 silane Inorganic materials 0.000 claims description 40
- 229920000642 polymer Polymers 0.000 claims description 32
- 229920002554 vinyl polymer Polymers 0.000 claims description 30
- 150000001299 aldehydes Chemical class 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- 229920001577 copolymer Polymers 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 19
- PBWQZEMADHTUIF-UHFFFAOYSA-N 2-phenylpent-4-enal Chemical compound C=CCC(C=O)C1=CC=CC=C1 PBWQZEMADHTUIF-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- 229920000578 graft copolymer Polymers 0.000 claims description 15
- 229920001400 block copolymer Polymers 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- 150000001721 carbon Chemical group 0.000 claims description 10
- 150000002825 nitriles Chemical class 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004104 aryloxy group Chemical group 0.000 claims description 9
- 230000000087 stabilizing effect Effects 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 150000001345 alkine derivatives Chemical class 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- RCQKLWAPRHHRNN-UHFFFAOYSA-N 2-Methyl-4-pentenal Chemical compound O=CC(C)CC=C RCQKLWAPRHHRNN-UHFFFAOYSA-N 0.000 claims description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 125000003367 polycyclic group Chemical group 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
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- OUVFWIHVZPQHJF-UHFFFAOYSA-N 5-ethenyl-5-methylcyclohexa-1,3-diene Chemical compound C=CC1(C)CC=CC=C1 OUVFWIHVZPQHJF-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- PNWJILFKWURCIR-UHFFFAOYSA-N 1-chloro-1,3,3,3-tetrafluoroprop-1-ene Chemical compound FC(Cl)=CC(F)(F)F PNWJILFKWURCIR-UHFFFAOYSA-N 0.000 claims description 2
- FPBWSPZHCJXUBL-UHFFFAOYSA-N 1-chloro-1-fluoroethene Chemical group FC(Cl)=C FPBWSPZHCJXUBL-UHFFFAOYSA-N 0.000 claims description 2
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims description 2
- PUKZNBXCVBLXNF-UHFFFAOYSA-N 2-bromo-2-ethylpent-4-enal Chemical compound CCC(Br)(C=O)CC=C PUKZNBXCVBLXNF-UHFFFAOYSA-N 0.000 claims description 2
- UGXDVWMHCZFWGE-UHFFFAOYSA-N 2-bromo-2-methylpent-4-enal Chemical compound O=CC(Br)(C)CC=C UGXDVWMHCZFWGE-UHFFFAOYSA-N 0.000 claims description 2
- CSQLZPHFKWHVMI-UHFFFAOYSA-N 2-bromo-2-phenylpent-4-enal Chemical compound C=CCC(Br)(C=O)C1=CC=CC=C1 CSQLZPHFKWHVMI-UHFFFAOYSA-N 0.000 claims description 2
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 claims description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical class [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims 16
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims 16
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims 8
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 229910052731 fluorine Inorganic materials 0.000 claims 2
- 239000011737 fluorine Substances 0.000 claims 2
- NJLPMHLSZDVUMV-UHFFFAOYSA-N 1-chloro-1,2,3,3,3-pentafluoroprop-1-ene Chemical compound FC(Cl)=C(F)C(F)(F)F NJLPMHLSZDVUMV-UHFFFAOYSA-N 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 150000002334 glycols Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 13
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 description 12
- 229920001296 polysiloxane Polymers 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 10
- 150000001336 alkenes Chemical group 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 125000005265 dialkylamine group Chemical group 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 5
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 5
- YPAJRUMMODCONM-UHFFFAOYSA-N 2-Phenyl-2-pentenal Chemical compound CCC=C(C=O)C1=CC=CC=C1 YPAJRUMMODCONM-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- DEETYPHYGZQVKD-UHFFFAOYSA-N copper ethyl hexanoate Chemical compound [Cu+2].CCCCCC(=O)OCC DEETYPHYGZQVKD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005691 oxidative coupling reaction Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical group CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 125000005466 alkylenyl group Chemical group 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical group C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229920005684 linear copolymer Polymers 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- WURFKUQACINBSI-UHFFFAOYSA-M ozonide Chemical compound [O]O[O-] WURFKUQACINBSI-UHFFFAOYSA-M 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- DTCCTIQRPGSLPT-ONEGZZNKSA-N (E)-2-pentenal Chemical compound CC\C=C\C=O DTCCTIQRPGSLPT-ONEGZZNKSA-N 0.000 description 1
- CDOOAUSHHFGWSA-UHFFFAOYSA-N 1,3,3,3-tetrafluoropropene Chemical compound FC=CC(F)(F)F CDOOAUSHHFGWSA-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 239000004614 Process Aid Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- DTCCTIQRPGSLPT-UHFFFAOYSA-N beta-Aethyl-acrolein Natural products CCC=CC=O DTCCTIQRPGSLPT-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 230000002940 repellent Effects 0.000 description 1
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Landscapes
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A method for preparing a polymerizable siloxane is provided comprising the steps of (a) synthesizing a redox initiator selected from the group consisting of aldehyde and acetal, wherein said redox initiator comprises an alpha-carbon having either a single hydrogen bond or a single halogen bond; and (b) attaching said redox initiator to a siloxane to form a polymerizable siloxane.
Description
Technical Field
The present invention relates generally to methods of producing silane and siloxane compositions. More particularly, the invention relates to a method of producing polymerizable silane and siloxane compositions containing polymerization sites that are made prior to attachment to the silane or siloxane.
Background
Silanes and siloxane compounds constitute a class of important industrial chemicals commonly found in various forms of organic copolymers, such as fluids, gels, elastomers, and resins. By modifying silanes or siloxanes with certain organofunctional groups and bonding these compounds to organic polymers, polymers and copolymers can be formed having many desirable physical and chemical properties such as increased impact resistance, flame retardancy, thermal stability, lubricity, and flow. Many such compounds have been used in a variety of applications such as wetting agents, manufacturing process aids, surfactants, foam control additives, pressure sensitive adhesives, thermoplastic elastomers, compatibilizers, water repellent materials, dry cleaning fluids, textile aids, personal and household goods, preservatives, pesticides, and electronic circuitry. In addition, many such polymers and copolymers are non-toxic and environmentally compatible.
Of particular interest in the above applications are silane-vinyl and siloxane-vinyl block and graft copolymers. Methods of producing such polymers and copolymers are known in the art, for example, U.S. patent No. 5,708,115 (graver et al); 5,789,503(Graiver et al); 5,789,516(Graiver et al); and "Silicones and Siliconemoodified Materials" (polysiloxanes and polysiloxane modified Materials), ACS symposium series, 729, p.445-59, by Graiver et al. The physical and chemical properties of the individual polymer blocks, their relative concentrations and molecular weights, and their methods of manufacture are reported to affect the overall morphology and overall performance of such copolymers. See D.Graiver et al, Graft and Block Copolymers with polysiloxane and Vinyl Polymer Segments, Silicon Chemistry, Vol.1, PP.107-120 (2002).
The preparation of silane-or siloxane-vinyl copolymers generally involves a polymerization reaction in which a vinyl group reacts with a functional silane or siloxane, respectively. Desirable functionalized silanes and siloxanes particularly suitable for use in these processes are those with aldehyde functionality, since aldehydes can readily participate in the polymerization reaction. Methods of preparing aldehyde-functionalized siloxanes are known in the art. For example, U.S. patent No. 5,739,246 (graver et al) discloses a method of making carbonyl-functional polysiloxanes and U.S. patent No. 5,880,304 (graver et al) discloses a method of making organosilicon carbonyl compounds. In addition, U.S. Pat. No. 4,609,574(Keryk et al) discloses a method of hydrolyzing chlorosilanes to produce aldehyde-bearing polysiloxanes.
However, the methods known in the art for preparing silanes and siloxanes with aldehyde functionality do not allow precise control over the molecular architecture design and molecular weight of the molecule. Such processes are not generally useful for industrial applications because of the low yields of the process, the occurrence of severe side reactions and/or the high costs associated with the starting materials or the processing itself.
For example, the process described by Gravier involves the formation of aldehyde-functionalized siloxanes as follows: ozonolysis of a terminal olefin-containing siloxane to an intermediate ozonide followed by reaction of the resulting ozonide with acetic acid in the presence of a zinc catalyst to form an aldehyde-functionalized siloxane of the general formula (I):
wherein n is 2 or 3.
Aldehyde-functional siloxanes synthesized by the Gravier method suffer from severe limitations: the 2 hydrogen bonds on the alpha carbon atom that are active polymerization sites are functionally indistinguishable and can generate a large amount of by-product upon copolymerization of the siloxane. These unwanted side reactions destabilize the process (as used herein, the term "stability" refers to the speed and selectivity of the reaction, rather than to the tendency to readily participate in the reaction).
The result of the lack of control over the copolymerization reaction is the formation of many high viscosity crosslinked polymers, and the copolymer products therefore have very different molecular weights, rather than a better narrow molecular weight distribution. This also inherently leads to low yields of the desired product.
Furthermore, the nature of the aldehyde functionality is determined by the olefin reactants in the Gravier process. The reactivity cannot be tailored to alter the behavior of the resulting polymer or polymerization reaction. Furthermore, the compounds formed by this method are limited to those with only aldehyde functionality (i.e., the method is not capable of synthesizing compounds with multiple functional groups). The aldehyde functional siloxanes produced by methods known in the art are therefore of limited flexibility.
Summary of The Invention
The applicant has found that among the problems mentioned above, the following can be solved by synthesis: redox initiators with specific functionality are formed and then attached to silanes or siloxanes to form polymerizable silanes and siloxanes, respectively. The redox initiator can then act to tailor the polymerization site to the compound. The tailored copolymerization site allows for better control of the overall kinetics of the copolymerization reaction and greatly reduces unwanted side chain reactions. For example, redox initiators may be tailored to limit the effectiveness and accessibility of silane or siloxane copolymerization sites. In general, fewer copolymerization points result in fewer undesirable side chain reactions. In addition, stabilizing substituents, such as resonance radical stabilizing functional groups, may be added near the copolymerization reaction point of the redox initiator to stabilize the point during the copolymerization reaction, resulting in better control of the overall reaction.
Accordingly, one aspect of the present invention is a method of making a polymerizable silane or siloxane, the method comprising a first step of synthesizing a redox initiator and a second step of attaching the redox initiator to the silane or siloxane to form a polymerizable compound. Since the redox initiator can be selected to control the copolymerization reaction, the specific redox initiator synthesized will depend on the desired polymer and copolymer, but will generally have the following general formula (II):
wherein:
z is a free radical initiator;
Cαis a first carbon atom adjacent to Z;
x is an abstraction moiety;
R1is a stabilizing component; and
a is a group capable of being hydrosilylated, preferably an alkene or alkyne.
Another aspect of the invention is a polymerizable siloxane and silane formed by the above method. In certain preferred embodiments, the polymerizable silane or siloxane has the general formula (III)
Wherein R is1、X、CαAnd Z is as previously defined, A' is a linking group formed by hydrosilylation, d is an integer from about 1 to about 40, and "Sil" is a silane or siloxane moiety.
In accordance with another aspect of the present invention, there is provided a method of forming a silane and siloxane copolymer in which at least one vinyl monomer or polymer is reacted with at least one of the aforementioned polymerizable silanes or siloxanes to form a block or graft copolymer.
Still another aspect of the present invention is the silicone-vinyl block and graft copolymers formed by the above-described process. A preferred embodiment of this aspect of the invention is a block siloxane-vinyl copolymer having the general formula (V):
wherein R is11Independently methyl, ethyl, phenyl, and the like;
R12、R13、R14and R15Independently H, alkyl, aryl, heterocycle, fluoro, fluoroalkyl, acetate, acrylic, anhydride, and the like;
R21independently methyl, ethyl, phenyl, etc.;
b is an integer of 10 to 200; and
c is an integer of 10 to 200.
Detailed Description
The present invention provides methods for producing polymerizable silanes and siloxanes having customizable polymerization or copolymerization sites to efficiently produce a variety of block and graft copolymers, respectively. Specifically, methods are provided for producing polymerizable silanes and siloxanes in which a redox initiator containing functionality designed to facilitate a particular copolymer is synthesized and then attached to the silane or siloxane to form a polymerizable silane or siloxane product. During the copolymerization, a copolymeric bond is formed on the redox initiator, which serves to customize the copolymerization site, since the functionality of the redox initiator can be tailored to favor a particular copolymerization product.
According to a first aspect of the present invention, there is provided a method for synthesizing polymerizable silanes and siloxanes, comprising the steps of: (a) synthesizing a redox initiator functionality that facilitates the formulation of a particular copolymer; and (b) attaching the redox initiator to the silane or siloxane to form a polymerizable siloxane.
The term "redox initiator", as used herein, refers to a system that causes free radical polymerization of monomers. In particular, redox initiators, when attached to silanes and siloxanes, promote oxidative coupling between the silane or siloxane and one or more vinyl monomers or polymers to form silane polymers or block or graft siloxane copolymers. Such oxidative coupling, also referred to as "redox polymerization," generally involves the transfer of electrons between a redox initiator attached to a silane or siloxane and at least one other monomer or polymer during a polymerization or copolymerization reaction. Without being bound by any particular theory, it is believed that redox initiators suitable for use in the present invention accept electrons during the redox reaction, thereby generating polysilane or polysiloxane radicals. The polymer radicals in turn react with vinyl monomers and/or polymers to form, for example, siloxane-vinyl block or graft copolymers.
Several redox initiators are known in the art. Those suitable for use in the present invention include: (1) a free radical initiator that functions to facilitate reduction of the silane monomer or polysiloxane, (2) an abstraction moiety that can be isolated from the redox initiator to provide a pair of free electrons, (3) a tertiary alpha carbon atom that functions as a copolymerization site, (4) a stabilizing component that controls the kinetics of copolymerization, and (5) a group that can be hydrosilylated to function to attach the redox initiator to a silane or siloxane. The redox initiators of the present invention generally have the following general formula (II):
wherein,
z is a free radical initiator, preferably an aldehyde;
Cαis a first carbon atom adjacent to Z;
x is an abstraction moiety;
R1is a stabilizing component; and
a is a group capable of being hydrosilylated, preferably an alkene or alkyne.
As regards the free-radical initiator Z, it is the agent used to cause the redox reaction of the polymerizable silane or siloxane. The redox initiator, when attached to the siloxane, must be reducible to facilitate the formation of polymer radicals. The polymer radical has an unpaired electron formed upon cleavage of a molecular bond. That is, the free radical has at least one bonding orbital occupied by a single electron. Once formed, the polymer radical is capable of undergoing oxidative coupling with another monomer and/or polymer. This action causes a chain-lock reaction in which the radicals consumed by the formation of the polymer or copolymer bonds are regenerated, resulting in the formation of a polymer or copolymer. Examples of preferred free radical initiators include, but are not limited to, aldehydes.
With respect to the abstraction moiety X, it is that portion that leaves the molecule for the generation of polymer radicals. The abstraction sites generally become polymeric bonding sites. According to the invention, these abstracting moieties are hydrogen or highly electronegative atoms, such as halogen atoms. Preferred abstraction moieties include, but are not limited to, hydrogen, chlorine, bromine, and iodine.
With respect to the stabilizing component R1It is a moiety that preferably stabilizes the free radicals formed during the polymerization reaction by resonance forces. It is known that the more stable the free radical is, the more easily it is formed. That is, the ease of radical formation (i.e., electron accepting and corresponding hydrogen or halogen abstraction) increases with increasing stability of the radical formed. Dissociation of the abstracted moiety bond can generally provide a measure of the relative intrinsic stability of the free radical. With respect to carbon-based radicals, the order of stability is as follows:
tertiary > secondary > primary > CH4> vinyl radical
Increasing the number of alkyl substituents on the radical center generally leads to improved stability, which is believed to be a hyperThe result of conjugation. Therefore, redox initiators having a radical on a tertiary carbon atom (i.e., having only one abstracted moiety carbon) are more preferred over redox initiators having a radical on a secondary carbon atom because of the more prominent resonance stabilization of the free gene centered around the "tertiary-carbon". Such radicals having tertiary carbon atoms as the centre consisting of R1Alkyl or phenyl, and the like.
The stability of the radicals of the invention can also be increased by the presence of electron donating groups or electron withdrawing groups in the center of the radical. The improvement in stability is believed to result from a further increase in resonance. R as electron donating group1Examples of (d) include, but are not limited to, alkoxy, aryloxy, thioether, dialkylamine or phenyl preferably substituted on the fourth carbon with alkoxy, aryloxy, thioether or dialkylamine. Particularly preferred alkoxides include those of the formula-O-R2Wherein R is2Is C1～C3An alkyl group. Particularly preferred aryloxides include those having the formula-O- (C)6H6) Those of (a). Particularly preferred thioethers include those of the formula-S-R3Wherein R is3Is C1～C3Alkyl or phenyl. Particularly preferred dialkylamines include those of the formula-N (R)4)2Wherein R is4Is methyl, ethyl or phenyl. R as an electron-withdrawing group1Examples of (B) include, but are not limited to, nitro, nitrile, aldehyde, C, preferably on the fourth carbon atom1～C3Ketones or C1～C3Aryl substituted by ester.
Specific R for addition of redox initiators1Will depend on the desired reaction kinetics and can be readily determined by one skilled in the art without undue experimentation. Thus, for copolymerization reactions requiring a slower rate but improved selectivity, redox initiators with substituents such as aromatic rings that can resonance stabilize free radicals are synthesized. In contrast, for copolymerization reactions requiring increased speed but reduced selectivity, redox initiators with groups such as methyl groups having less resonance stabilizing properties are synthesized. In the selectionSelecting specific R1Also consider R1The functionality of the substituent.
Redox initiators containing a tertiary carbon atom are also preferred because polymerization occurs at a hydrogen abstraction site, in the case of a tertiary carbon atom, there is only one abstraction site. The polymerization reaction is limited in one point to reduce uncontrolled side chain reactions and undesirably crosslinked polymers formed.
With respect to the group a capable of being hydrosilylated, which is a functional moiety capable of bonding to a silane or siloxane, the hydrosilylation reaction is preferably carried out, but any chemical method known in the art may be used. Such hydrosilylation reactions occur on silicon-hydrogen bonds and involve the addition of silanes or siloxanes to the terminal carbon-carbon double or triple bonds of redox initiators. Thus, preferably A is an alkene or alkyne, more preferably C with a double or triple bond, respectively, at the redox initiator remote from the end of the terminal aldehyde group3An alkene or an alkyne.
The hydrosilylation process is generally carried out in the presence of a catalyst, such as platinum. In certain preferred embodiments, a redox initiator containing carbon-carbon double and triple bonds capable of being hydrosilylated is attached to the silane, either terminally located at one or both ends of the siloxane or pendant from the siloxane backbone. Preferred groups capable of being hydrosilylated include ethylene moieties such as 1-propene, 1-butene, 1-pentene, and the like.
In certain preferred embodiments, the redox initiator of formula (II) can be further defined, wherein:
a is 3-vinyl or 3-allyl;
x is hydrogen, chlorine, bromine or iodine;
z is an aldehyde, more preferably formaldehyde or an aldehyde derived from an acetal such as dimethyl acetal; and
R1is C1～C3Alkyl, alkoxy, aryloxy, thioether, dialkylamine or quilt alkoxy, aryloxy, thioether, dialkylamine, nitro, nitrile, aldehyde, C1～C3Ketones or C1～C3An ester-substituted aryl group.
In certain preferred embodiments, these redox initiators are pendant or terminal attached to the siloxane.
Particularly preferred redox initiators include 2-methyl-4-pentenal, 2-methyl-2-bromo-4-pentenal, 2-ethyl-2-bromo-4-pentenal, 2-phenyl-4-pentenal and 2-phenyl-2-bromo-4-pentenal. Among the particularly preferred redox initiators wherein Z is an aldehyde derived from an acetal include aldehydes derived from 2-methyl- (1, 1 '-dimethoxy) -4-pentene, 2-ethyl- (1, 1' -dimethoxy) -4-pentene, 2-phenyl- (1, 1 '-dimethoxy) -4-pentene, 2-methyl-2-bromo- (1, 1' -dimethoxy) -4-pentene, 2-ethyl-2-bromo- (1, 1 '-dimethoxy) -4-pentene or 2-phenyl-2-bromo- (1, 1' -dimethoxy) -4-pentene.
Alternatively, the above and other aldehydes can be synthesized by methods well known in the art. For example, substituted-4-pentenals suitable for use in the present invention can be synthesized as described in U.S. patent 3,928,644, wherein 2-phenyl-4-pentenal is synthesized from benzaldehyde.
After the redox initiator is synthesized, it is attached to the silane or siloxane as described above.
As used herein, the term "silane" refers to a compound containing a single silicon atom bonded to at least one hydrogen, wherein the silicon-hydrogen bond can function as a redox initiator attachment point. Preferred silanes have the general formula (VI)
Wherein: r5Is a straight-chain or branched, substituted or unsubstituted C1～C20Alkyl radical, C6～C8Aryl or C1～C10A heterocycle;
R6is hydrogen, straight-chain or branched, substituted or unsubstituted C1～C20Alkyl radical, C6～C8Aryl or C1～C10A heterocycle; and
q is an integer of 0 to 3.
As used herein, the term "siloxane" refers to straight chain, cyclic, and polycyclic compounds containing silicon atoms singly bonded to oxygen atoms and arranged in such a way that each silicon atom is bonded to at least one oxygen atom. Preferably the siloxane of the present invention will be a polysiloxane (i.e., a siloxane polymer based on the structure of which the silicon and oxygen atoms alternate, and various organic radicals are attached to the silicon atom). In addition, the siloxanes suitable for use in the present invention have at least one silicon-hydrogen bond that serves as a point of attachment for a redox initiator. Thus, preferred siloxanes include halide-terminated siloxanes, monohalide-terminated siloxanes, and pendent or "rake" halide siloxanes. Preferred siloxanes for use in the present invention will have the following general formula (VII):
wherein: r7Is H, C1～C50Straight-chain or branched alkyl, C3～C12Substituted or unsubstituted ring, C1～C11Heterocycle, C6～C8Aryl radical, C6～C8Aryloxy radical, C1～C12Alkoxy radical, C2～C12Dialkylamino radical, C1～C12Alkyl sulfur, C1～C12Fluoroalkyl, C1～C12Epoxy group, C1～C6Acrylic or methacryloxy radical, C6～C50A polyether or some combination thereof;
R8independently is H, -O-R9O, C bonded to Si to produce therein a cyclic or polycyclic form1～C50Straight-chain or branchedAlkyl radical, C3～C12Substituted or unsubstituted ring, C1～C11Heterocycle, C6～C8Aryl radical, C6～C8Aryloxy radical, C1～C12Alkoxy radical, C2～C12Dialkylamino radical, C1～C12Alkyl sulfur, C1～C12Fluoroalkyl, C1～C12Epoxy group, C1～C6Acrylic or methacryloxy radical, C6～C50A polyether or some combination thereof;
R9is that
And
p is an integer of 3 to 40,
with the following conditions: for acyclic siloxanes, R7For monohydrogen terminal siloxanes, R8Not equal to H; for hydride terminated siloxanes, R7H and terminal R8H; and for the Rake hydride siloxanes, R7H, terminal R8Not equal to H, and at least one R8＝H。
In certain preferred embodiments, the hydride terminated siloxane, monohydroxide siloxane, and rake hydride siloxane have one of the following general formulas:
wherein R is16And R17Independently of each other is a methyl group or a phenyl group,
x is an integer of 0 to 80,
y is an integer of 0 to 80,
x+y≠0，
w + z is an integer of 3 to 40, and
z is an integer of 1 to 40.
Siloxanes according to the present invention are available from a number of commercial sources including, for example, dimethyl siloxane-hydrogen terminations from dow corning (CAS number 70900-21-9) and dimethyl, methylhydrogensiloxane-trimethylsiloxy terminations also from dow corning (CAS number 68037-59-2).
Alternatively, the above and other silicones can be made by any method known in the art. For example, Polydimethylsiloxane (PDMS) with terminal silicon-hydride functionality can be prepared from octamethylcyclotetrasiloxane and dimethylsilane in the presence of CF3SO3H is reacted in the presence of H. The polydimethylsiloxanes with pendant silicon-hydride functionality can be prepared from octamethylcyclotetrasiloxane and 1, 3, 5, 7-tetramethylcyclotetrasiloxane and Tetramethyldisiloxane (TMDS) in the presence of CF3SO3H is reacted in the presence of H.
Once the redox initiator has been attached to the silane or siloxane, the compound can participate in a redox copolymerization reaction with the vinyl monomer or polymer. The term "polymerizable silane", as used herein, refers to a silane that contains functional groups that convert silane monomers to polymer radicals during polymerization. The term "polymerizable siloxane", as used herein, refers to a siloxane compound that contains functional groups that convert the siloxane compound to polymer radicals during copolymerization. Thus, in accordance with another aspect of the present invention, there are provided novel silanes or siloxanes containing terminal or pendant functionality, preferably aldehyde functionality.
The polymerizable silanes and polysiloxanes of the present invention can be formed by any chemical method known in the art in which a redox initiator is attached to a silicon atom of a silane or siloxane. As indicated above, the preferred method of attaching the redox initiator to the silicon atom is a hydrosilylation process. Such hydrosilylation reactions occur on silicon-hydrogen bonds and involve the addition of a silane or siloxane to a carbon-carbon double bond of a redox initiator. The hydrosilylation process is generally carried out in the presence of a catalyst, such as a platinum catalyst.
In certain preferred embodiments, the polymerizable silanes and siloxanes of the present invention will have the general formula III:
wherein R is1、X、CαAnd Z is as defined above, A' is a linker formed by hydrosilylation, d is an integer from about 1 to about 40, and "Sil" is a silane or siloxane moiety. Since hydrosilylation involves addition of siloxane to the carbon-carbon double bond of the moiety a ', a' will generally be an alkyl group derived from the alkene a. For example, if A is 2-propenyl, the corresponding hydrogenated form A' will be propyl, and the rest.
In certain other preferred embodiments, hydrosilylation can also be used to add other functionalized olefins to silanes or siloxanes to form novel polymerizable silanes and siloxanes. That is, the terminal carbon double bonds of functional groups, such as ethylene, propylene, styrene, epoxy, acrylic, acryloxy, and polyether, can be hydrosilylated in the presence of a catalyst, such as platinum, in which the functional groups are attached to the silicon atoms of the silane or siloxane. For example, the polyfunctional rake siloxane may be formed from a trimethylsiloxy-terminated polyalkylhydrosiloxane as shown below:
wherein R is10Is, for example, methyl or phenyl;
R18is, for example, alkyl, aryl, alkoxy, aryloxy, dialkylamino, alkylthio orA fluoroalkyl group;
d is, for example, ethylene, propylene, C2～C50Alkyl, styrene or 1-methylstyrene;
b is, for example,
an epoxy compound of the formula:
an acrylic or methacryloxy compound of the formula:
wherein R is19Is H or CH3And R20Is CH3、C2H5Or CH2CH2OH or
A polyether of the formula:
wherein j is an integer of 2 to 20;
k is an integer of 3 to 40; and
i + h + g ═ k, where g ≠ 0.
Other preferred polymerizable siloxanes according to the present invention include, but are not limited to, those having one of the following general formulas (XII) to (XV):
wherein R is16、R17X, y and z are as defined above; and
R20is methyl, ethyl or phenyl.
It is to be understood that the polymerizable siloxanes mentioned above are merely exemplary and that many other embodiments of the present invention are contemplated, including, but not limited to, cyclic siloxanes, polycyclic siloxanes and siloxanes having different functional groups attached to the silicon atom.
According to another aspect of the present invention, there is provided a process for preparing block and graft copolymers in which a polymerizable silane or siloxane, such as those mentioned above, is reacted with a vinyl monomer and/or polymer in the presence of a catalyst to form a silane-or siloxane-vinyl copolymer.
As used herein, the term "vinyl" means containing or derived from at least a functional group CH2CH-moiety. The term "vinyl monomer", as used herein, generally refers to vinyl compounds (i.e., compounds containing vinyl functionality) which include, but are not limited to, vinyl chloride, vinyl acetate and similar esters, styrene, methacrylates, acrylonitrile, and the like. Preferably, the copolymerization reaction involves the formation of polysiloxane radicals, which react with vinyl monomers or polymers to form siloxane-vinyl copolymers.
In a particularly preferred embodiment, the copolymerization process comprises the steps of: aldehyde-functional polymerizable siloxanes are mixed with vinyl monomers and copper (II) redox system in a suitable solvent such as benzene, toluene, xylene, ethylene glycol, etc., and heated to 60 c to 125 c for about 5 to about 24 hours. To prepare the siloxane-polyfluoroalkenes, fluorinated solvents may be used. Once the polymerization reaction is complete, the reaction mixture is cooled to room temperature and mixed with an aprotic solvent, such as methanol or the like, to precipitate the copolymer product. The solid product is then washed with a solvent, dried, and purified by typical polymerization methods known in the art.
The choice of vinyl monomer to participate in the copolymerization reaction depends on the desired copolymer product. Examples of vinyl monomers that can be used in the present invention include, but are not limited to, ethylene, propylene, styrene, N-vinyl pyrrolidone, vinylidene fluoride, chlorofluoroethylene, methyl methacrylate, ethyl methacrylate, acrylonitrile, hydroxyethyl methacrylate, vinyl acetate, and maleic anhydride. Other examples of vinyl monomers include fluoroolefin monomers, such as 3, 3, 3-trifluoro-1-propene; 2, 3, 3, 3-tetrafluoro-1-propene; 1, 3, 3, 3-tetrafluoro-1-propene; 1-chloro-1, 3, 3, 3-tetrafluoro-1-propene; 2, 2, 3, 3, 3-pentafluoro-1-propene; 4-vinyl-pyridine; and so on.
Depending on the starting materials selected for use in the above-described process, a number of novel siloxane-vinyl block and graft copolymers can be efficiently obtained. As used herein, the term "block copolymer" refers to the following linear copolymers: in which several monomers of a first type are linked together and then to another chain segment of another monomer different from the first type. The term "graft copolymer", as used herein, refers to the following non-linear copolymers: in which one or more chains consisting of one monomer are attached as side chains to different polymer main chains. Thus, in accordance with another aspect of the present invention, there are provided novel siloxane-vinyl block and graft copolymers. In certain preferred embodiments, the siloxane-vinyl block polymer will have the general formula (X):
wherein: r11Is methyl, ethyl, phenyl, etc.;
R12、R13、R14and R15Independently H, alkyl, aryl, heterocycle, fluoro, fluoroalkyl, acetate, acrylic, anhydride, and the like;
b is an integer of 10 to 200; and
c is an integer of 10 to 200.
In certain other preferred embodiments, the siloxane-vinyl group is a graft copolymer. It is understood that the graft copolymers according to the invention may have siloxane moieties as backbone moieties of the copolymer, as in the following structure:
or as a side chain moiety of a copolymer, as in the following structure:
in addition, by tailoring the redox initiator, the copolymerization reaction occurs more selectively, resulting in higher yields and better process control of the desired product stream and fewer by-products therein. As used herein, the term "product stream" refers to the process in which siloxane and vinyl monomers react to form a block or graft copolymer. Although the term "flow" is used, it is to be understood that the present invention can be applied to either batch or continuous processes. The term "yield" refers to the weight percent of the target copolymer formed by the product stream relative to the reactants.
Examples
The invention is further described with reference to the following examples which are intended to be illustrative and in no way limiting.
Example 1:
hydrosilylation of 2-phenyl-pentenal with Tetramethyldimethylsiloxane (TMDS):
reagent:
1.4g Tetramethyldimethylsiloxane (TMDS) (0.01mol)
60ppm (platinum) Karstedt-catalyst in xylene
3.5g 2-phenyl-4-pentenal (about 92%, 0.02mol), CAS number: [24401-36-3]
The reagents were mixed, degassed with nitrogen and heated to 85 ℃ for 24 h. The mixture darkened. After filtration through activated carbon, IR showed complete disappearance of Si-H groups, GC showed no TMDS, some residual pentenal and disubstituted products, which were also analyzed by GC-MS. Excess 2-phenyl-4-pentenal can be removed by distillation.
Example 2:
hydrosilylation of 2-phenyl-pentenal with Polydimethylsiloxane (PDMS):
reagent:
5g Polydimethylsiloxane (PDMS) (Gelest, MW 400-500, active H0.5%)
60ppm (platinum) Karstedt-catalyst in xylene
3.5g 2-phenyl-4-pentenal
The reagents were mixed, degassed with nitrogen and heated to 85 ℃ for 24 h. After filtration through activated carbon, IR showed that the Si-H groups had all disappeared,1H-NMR showed that the Si-H groups had disappeared completely and that some residual 2-phenyl-4-pentenal and a new group of compounds were present together with the signal. Excess 2-phenyl-4-pentenal can be removed by distillation.
Example 3:
cu (ii) -catalyzed copolymerization of styrene with 2-phenylpentenal modified PDMS:
reagent:
10ml of chlorobenzene (dry)
0.1g(2.68×10-4mol of Cu (II) -ethyl hexanoate
0.5g pyridine
0.3g of triphenylphosphine (0.3g, 1.14X 10)-3mol)
0.1g triethylamine (1X 10)-3mol)
5mL of styrene
2-Phenylpentenal-modified PDMS (3.1X 10) was added to chlorobenzene-4mol acetaldehyde function), copper (II) -ethyl hexanoate, pyridine, triphenylphosphine and triethylamine, the mixture turned green. Adding styrene and 2-phenyl pentenal to modify PDMS and adding N2The mixture was degassed for 5min. Heating the mixture at 70 ℃ for about 20-24 h. The color became less green and the mixture was more viscous. After allowing the mixture to cool to room temperature, quench into 20mL of MeOH with vigorous stirring. A polymer precipitate formed. The precipitate was filtered and washed with MeOH, then dried under vacuum at room temperature.
Example 4:
this example illustrates the hydrosilylation of H-terminated PDMS MW 1100 and 2-phenyl-4-pentenal.
250g (0.238mol) of DMS-H11(Gelest, Inc., Morrisville, PA 19067, USA) and 83g of 2-phenyl-4-pentenal (0.5mol) were heated to 85 ℃ under stirring under an inert atmosphere. Karstedt's catalyst (Aldrich, 0.1m in xylene) was added in 4 portions in a total amount of 0.96 mL. The reaction was carried out for 2h between each addition. After the addition of the first portion of catalyst, the temperature rose from 85 ℃ to 110 ℃. After the catalyst addition had been completed, the mixture was stirred at 85 ℃ overnight. IR of the sample indicated complete conversion of Si-H. The mixture was filtered on a charcoal filter and the excess 2-phenyl-4-pentenal was distilled off.
Example 5:
this example illustrates the hydrosilylation of H-terminated PDMS MW 6000 and 2-phenyl-4-pentenal.
9g (1.5mmol) of DMS-H21(Gelest, Inc), 1.88. mu.l of Karstedt's catalyst solution (Johnson Matthey, 4% in isopropanol) and 0.53g of 2-phenyl-4-pentenal (3.3mmol) are stirred under inert atmosphere in 45mL of isopropanol and heated to 83 ℃ for 48H. IR analysis indicated complete conversion of the SiH bonds.
Example 6:
this example illustrates the hydrosilylation of H-terminated PDMS MW 550 and 2-phenyl-4-pentenal.
The procedure of example 4 was followed, but DMS-H11(Gelest, Inc.) was replaced by an equimolar amount of DMS-H03(Gelest, Inc.). IR analysis indicated complete conversion of the SiH bonds.
Example 7:
this example illustrates the copolymerization of styrene with 2-phenyl-4-pentenal modified PDMS-H03.
5mL of styrene, 5mL of copper-catalyst solution (44mL of chlorobenzene, 5mL of pyridine, 1g of copper (II) -ethylhexanoate, 1.36mL of triethylamine and 1.5g of triphenylphosphine) and 150mg of the hydrosilylated product from example 6 (as macroinitiator) are degassed with nitrogen and heated to 80 ℃ under nitrogen with stirring for 21 h. The thick mixture was diluted with another 15mL of chlorobenzene and added to 150mL of methanol while stirring with an Ultraturrax homogenizer. The white solid was filtered and washed with 75mL of methanol and then dried. The yield was 2.3g, and the average molecular weight was 300000 as determined by GPC.
Example 8:
this example illustrates the copolymerization of 4-vinylpyridine with 2-phenyl-4-pentenal modified PDMS-H03.
5mL of 4-vinylpyridine, 5mL of copper-catalyst solution (44mL of chlorobenzene, 5mL of pyridine, 1g of copper (II) -ethylhexanoate, 1.36mL of triethylamine and 1.5g of triphenylphosphine) and 150mg of the hydrosilylated product from example 6 (as macroinitiator) were degassed with nitrogen and heated to 70 ℃ under nitrogen with stirring for 21 h. As a result, a completely polymerized product was obtained in which a gel-like mass was formed.
Example 9:
this example illustrates the copolymerization of ethyl methacrylate with 2-phenyl-4-pentenal modified PDMS-H03.
5mL (4.6g) of ethyl methacrylate, 5mL of a copper-catalyst solution (44mL of chlorobenzene, 5mL of pyridine, 1g of copper (II) -ethylhexanoate, 1.36mL of triethylamine and 1.5g of triphenylphosphine) and 150mg of the hydrosilylated product from example 6 (as macroinitiator) are degassed with nitrogen and heated to 70 ℃ under nitrogen with stirring and thermostatted for 21 h. The thick mixture was diluted with 3 parts of 5 mL-chlorobenzene and added to 150mL of methanol at 15-20 ℃ while stirring with an Ultraturrax homogenizer. After stirring for a further 15min, the waxy product is filtered off, 100mL of methanol are added and the mixture is stirred with an Ultraturrax homogenizer at-5 to 0 ℃. The product is then filtered, washed with methanol and dried at 30 mbar and 30 ℃. The yield was 3.1g of a slightly viscous white solid. Average molecular weight by GPC was 295000.
Example 10:
the procedure of example 9 was repeated, but without adding the hydrosilylation product from example 6 as a macroinitiator. No polymerization was observed.
Having thus described several embodiments of the invention, various alterations, modifications, and improvements will readily occur to those skilled in the art. Such alterations, modifications, and improvements as are made obvious by this disclosure are intended to be part of this invention, though not expressly stated herein, and are intended to be within the scope of the invention. Accordingly, the foregoing description is by way of example only and is not intended as limiting. The invention is limited only as defined in the following claims and equivalents thereto.
Claims (35)
1. A method for preparing polymerizable silanes and siloxanes comprising the steps of:
(a) providing a redox initiator, and
(b) the redox initiator is attached to a silane or siloxane to form a polymerizable compound.
2. The method of claim 1, wherein the redox initiator has the general formula:
wherein:
z is a free radical initiator;
Cαis a first carbon atom adjacent to Z;
x is an abstraction moiety;
R1is a stabilizing component; and
a is C2-C6Olefins or C2～C6An alkyne.
3. The method of claim 2, wherein Z is an aldehyde.
4. The method of claim 2, wherein a is selected from the group consisting of: 2-vinyl, 3-allyl or 4-butenyl.
5. The method of claim 2, wherein X is selected from the group consisting of: hydrogen, chlorine, bromine and iodine.
6. The method of claim 2, wherein R1Selected from the group consisting of: c1～C3Alkyl radical, C6Aryl radical, C1～C3Alkoxy radical, C1-C3Thioether, diphenyl sulfide, nitro, nitrile, C1～C3Ketones, C1-C3Ester, dimethylamine, diethylamine, diphenylamine, C6Aryloxy, and C having a substituent on the fourth carbon ring selected from the group consisting of6Aryl: nitro, nitrile, aldehyde, C1～C3Ketones, C1～C3Esters, C1～C3Alkyl radical, C6Aryl radical, C1～C3Alkoxy radical, C1-C3Thioether, diphenyl sulfide, dimethylamine, diethylamine, diphenylamine and C6An aryloxy group.
7. The method of claim 6, wherein R1Selected from the group consisting of: methyl, ethyl, propyl and benzeneAnd (4) a base.
8. The method of claim 2, wherein the redox initiator is selected from the group consisting of: 2-methyl-4-pentenal, 2-methyl-2-bromo-4-pentenal, 2-ethyl-2-bromo-4-pentenal, 2-phenyl-4-pentenal and 2-phenyl-2-bromo-4-pentenal.
9. The process of claim 2, wherein the redox initiator is an aldehyde derived from 2-methyl- (1, 1 '-dimethoxy) -4-pentene, 2-ethyl- (1, 1' -dimethoxy) -4-pentene, 2-phenyl- (1, 1 '-dimethoxy) -4-pentene, 2-methyl-2-bromo- (1, 1' -dimethoxy) -4-pentene, 2-ethyl-2-bromo- (1, 1 '-dimethoxy) -4-pentene or 2-phenyl-2-bromo- (1, 1' -dimethoxy) -4-pentene.
10. The method of claim 2, wherein the redox initiator has the general formula:
wherein: r1Is methyl or phenyl;
x is hydrogen; and
x is 1 or 2.
11. The method of claim 1 wherein said silane has the formula:
wherein: r5Is a straight-chain or branched, substituted or unsubstituted C1～C20Alkyl radical, C6～C8Aryl or C1～C10A heterocycle;
R6is hydrogen, straight-chain or branched, substituted or unsubstituted C1～C20Alkyl radical, C6～C8Aryl or C1～C10A heterocycle; and
q is an integer of 0 to 3.
12. The method of claim 1, wherein the siloxane has the formula:
wherein: r7Selected from the group consisting of: H. c1～C50Straight-chain or branched alkyl, C3～C12Substituted or unsubstituted ring, C1～C11Heterocycle, C6～C8Aryl radical, C6～C8Aryloxy radical, C1～C12Alkoxy radical, C2～C12Dialkylamino radical, C1～C12Alkyl sulfur, C1～C12Fluoroalkyl, C1～C12Epoxy group, C1～C6Acrylic or methacrylic acyloxy, C6～C50Polyethers, and certain combinations thereof;
R8independently selected from the group consisting of: H. -O-R9O, C bonded to Si in which a cyclic or polycyclic structure is formed1～C50Straight-chain or branched alkyl, C3～C12Substituted or unsubstituted ring, C1～C11Heterocycle, C6～C8Aryl radical, C6～C8Aryloxy radical, C1～C12Alkoxy radical, C2～C12Dialkylamino radical, C1～C12Alkyl sulfur, C1～C12Fluoroalkyl, C1～C12Epoxy compound, C1～C6Acrylic or methacryloxy compound, C6～C50Polyethers, and certain combinations thereof;
R9is that
And
p is an integer of 3 to 40,
with the following conditions: for acyclic siloxanes, R7For monohydrogen terminal siloxanes, R8Not equal to H; for hydride terminated siloxanes, R7H and terminal R8H; and for the Rake hydride siloxanes, R7Not equal to H, terminal R8Not equal to H, and at least one R8＝H。
13. The method of claim 12, wherein the siloxane has a formula selected from the group consisting of:
wherein: r16And R17Independently of each other is a methyl group or a phenyl group,
x is an integer of 0 to 80,
y is an integer of 0 to 80,
x+y≠0，
w + z is an integer of 3 to 40, and
z is an integer of 1 to 40.
14. The method of claim 1, wherein the step of attaching comprises a hydrosilylation process.
15. The method of claim 14, wherein the hydrosilylation process is conducted in the presence of a platinum catalyst.
16. The method of claim 14, further comprising the steps of:
(c) attaching a vinyl compound to the polymerizable silane or siloxane, wherein the vinyl compound is selected from the group consisting of: c2～C20Olefin, styrene, epoxy, acrylic compound, acryloxy compound and C4～C20A polyether.
17. The method of claim 16, wherein the polymerizable siloxane has the formula:
wherein: r10Is methyl or phenyl;
R16and R17Independently methyl or phenyl;
R18selected from the group consisting of: c1～C3Alkyl radical, C6Aryl radical, C1～C3Alkoxy radical, C1～C3Thioether, diphenyl sulfide, nitro, nitrile, C1～C3Ketones, C1～C3Ester, dimethylamine, diethylamine, diphenylamine, C6Aryloxy and C having a substituent on the fourth carbon ring selected from the group consisting of6Aryl: nitro, nitrile, aldehyde, C1～C3Ketones, C1～C3Esters, C1～C3Alkyl radical, C6Aryl radical, C1～C3Alkoxy radical, C1～C3Thioether, diphenyl sulfide, dimethylamine, diethylamine, diphenylamine and C6An aryloxy group.
R20Is methyl, ethyl or phenyl;
d is selected from the group consisting of: ethylene, propylene, C2～C50Alkyl, styrene or 1-methylstyrene;
b is selected from the group consisting of:
an epoxy compound of the formula:
An acrylic compound, a methacryloxy compound of the general formula:
wherein R is19Is H or CH3And are and
R20selected from the group consisting of: CH (CH)3、C2H5And CH2CH2OH，
And polyethers of the general formula:
wherein j is an integer of 2 to 20,
x is an integer of 0 to 80,
y is an integer of 0 to 80,
x + y ≠ 0, and
z is an integer of 1 to 40,
k is an integer of 3 to 40, and
i + h + g ═ k, where g ≠ 0.
18. The method of claim 24, wherein the polymerizable siloxane has a cyclic or polycyclic structure.
19. A method of producing a copolymer comprising the steps of:
(a) providing a polymerizable silane or siloxane according to claim 1,
(b) providing a vinyl compound, and
(c) reacting the polymerizable siloxane with the vinyl compound to form a copolymer.
20. The method of claim 19, wherein the vinyl compound is a vinyl functional group-containing monomer or polymer.
21. The method of claim 20, wherein the vinyl compound is selected from the group consisting of: ethylene, propylene, styrene, N-vinylpyrrolidone, vinylidene fluoride, chlorofluoroethylene, methyl methacrylate, ethyl methacrylate, acrylonitrile, hydroxyethyl methacrylate, vinyl acetate, maleic anhydride, 3, 3, 3-trifluoro-1-propene, 2, 3, 3, 3-tetrafluoro-1-propene, 1-chloro-1, 3, 3, 3-tetrafluoro-1-propene, 2, 3, 3, 3-pentafluoro-1-propene and 4-vinylpyridine.
22. The method of claim 20, wherein said reacting step is carried out in the presence of a copper catalyst and in a solvent selected from the group consisting of: benzene, toluene, xylene and glycols.
23. The method of claim 19, wherein the copolymer is a block copolymer or a graft copolymer.
24. The method of claim 23, wherein the block copolymer comprises a repeat unit having the formula:
wherein: r11Selected from the group consisting of: methyl, ethyl and phenyl;
R12、R13、R14and R15Independently selected from the group consisting of: H. c1～C6Alkyl radical, C6～C8Aryl radical, C1～C10Heterocycle, fluorine, C1～C6Fluoroalkyl, acetate, acrylic, anhydride, and the like;
b is an integer of 10 to 200; and
c is an integer of 10 to 200.
25. A polymerizable composition of the formula:
wherein: z is a free radical initiator;
Cαis a first carbon atom adjacent to Z;
x is an abstraction moiety;
R1is a stabilizing component;
a' is an alkyl group derived from an olefinic substituent;
sil is a silane or siloxane moiety; and
d is an integer from about 1 to about 40.
26. The composition of claim 25 wherein Z is an aldehyde.
27. The composition of claim 25, wherein a' is selected from the group consisting of: propyl, butyl or phenyl.
28. The composition of claim 25 wherein X is selected from the group consisting of hydrogen, chlorine, bromine, and iodine.
29. The composition of claim 25, wherein R1Selected from the group consisting of: c1～C3Alkyl radical, C6Aryl radical, C1～C3Alkoxy radical, C1～C3Thioether, diphenyl sulfide, nitro, nitrile, C1～C3Ketones, C1～C3Ester, dimethylamine, diethylamine, diphenylamine, C6Aryloxy, and C having a substituent on the fourth carbon ring selected from the group consisting of6Aryl: nitro, nitrile, aldehyde, C1～C3Ketones, C1～C3Esters, C1～C3Alkyl radical, C6Aryl radical, C1～C3Alkoxy radical, C1～C3Thioether, diphenyl sulfide, dimethylamine, diethylamine, diphenylamine and C6An aryloxy group.
30. The composition of claim 29, wherein R1Selected from the group consisting of: methyl, ethyl, propyl and phenyl.
31. The composition of claim 25, wherein the composition has a formula selected from the group consisting of:
wherein: r10Is methyl or phenyl;
R16and R17Independently of each other is a methyl group or a phenyl group,
R18selected from the group consisting of: c1～C3Alkyl radical, C6Aryl radical, C1～C3Alkoxy radical, C1～C3Thioether, diphenyl sulfide, nitro, nitrile, C1～C3Ketones, C1～C3Esters, dimethylamine, diethylamine, diphenylamine,C6Aryloxy, and C having a substituent on the fourth carbon ring selected from the group consisting of6Aryl: nitro, nitrile, aldehyde, C1～C3Ketones, C1～C3Esters, C1～C3Alkyl radical, C6Aryl radical, C1～C3Alkoxy radical, C1～C3Thioether, diphenyl sulfide, dimethylamine, diethylamine, diphenylamine and C6An aryloxy group.
R20Is methyl, ethyl or phenyl;
d is selected from the group consisting of: ethylene, propylene, C2～C50Alkyl, styrene or 1-methylstyrene;
b is selected from the group consisting of:
an epoxy compound of the formula:
An acrylic compound, a methacryloxy compound of the general formula:
wherein R is19Is H or CH3And are and
R20selected from the group consisting of: CH (CH)3、C2H5、CH2CH2OH
And polyethers of the general formula:
wherein j is an integer of 2 to 20;
x is an integer of 0 to 80,
y is an integer of 0 to 80,
x + y ≠ 0, and
z is an integer of 1 to 40,
k is an integer of 3 to 40, and
i + h + g ═ k, where g ≠ 0.
32. A polymer composition comprising repeat units derived from the polymerizable composition of claim 25.
33. The polymer composition of claim 32 comprising a block or graft copolymer.
34. The polymer composition of claim 33, wherein the repeating unit has the formula:
wherein: r11Selected from the group consisting of: methyl, ethyl and phenyl;
R12、R13、R14and R15Independently selected from the group consisting of: H. c1～C6Alkyl radical, C6～C8Aryl radical, C1～C10Heterocycle, fluorine, C1～C6Fluoroalkyl, acetate, acrylic, anhydride, and the like;
b is an integer of 10 to 200; and
c is an integer of 10 to 200.
35. A method of producing a functionalized silane or siloxane comprising the steps of:
(a) preparing a compound comprising an aldehyde moiety; and
(b) the compound is attached to the silane or siloxane by a hydrosilylation reaction.
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| CN103589297A (en) * | 2013-10-24 | 2014-02-19 | 中科院广州化学有限公司 | Photocuring composite paint containing vinyl-terminated fluorosilicone graft copolymer and preparation method thereof |
| CN105536750A (en) * | 2016-01-29 | 2016-05-04 | 成都乐维斯科技有限公司 | New material with resin-coated silica gel properties |
| CN105601844A (en) * | 2016-02-29 | 2016-05-25 | 苏州印丝特纺织数码科技有限公司 | Preparation method and application of novel modified organic silicon softening agent |
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| CN103122008B (en) * | 2011-12-13 | 2016-02-24 | 曹坚林 | Silane coupling agent of a kind of cyano-containing and preparation method thereof |
| CN109529930B (en) * | 2018-10-31 | 2020-09-22 | 南京晓庄学院 | Catalyst for aromatic amine silicification reaction |
| CN111088702A (en) * | 2019-12-19 | 2020-05-01 | 广东轻工职业技术学院 | Preparation method of novel hydrophilic polyether amine modified organic silicon softening agent |
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| CN103589297A (en) * | 2013-10-24 | 2014-02-19 | 中科院广州化学有限公司 | Photocuring composite paint containing vinyl-terminated fluorosilicone graft copolymer and preparation method thereof |
| CN103589297B (en) * | 2013-10-24 | 2016-10-05 | 中科院广州化学有限公司 | A kind of containing end-vinyl fluorine silicon graft copolymer photocuring composite coating and preparation method |
| CN105536750A (en) * | 2016-01-29 | 2016-05-04 | 成都乐维斯科技有限公司 | New material with resin-coated silica gel properties |
| CN105601844A (en) * | 2016-02-29 | 2016-05-25 | 苏州印丝特纺织数码科技有限公司 | Preparation method and application of novel modified organic silicon softening agent |
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