CN1116633A - 有机硅烷和有机多分子硅醚自由基引发剂及其应用 - Google Patents
有机硅烷和有机多分子硅醚自由基引发剂及其应用 Download PDFInfo
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- CN1116633A CN1116633A CN95108617A CN95108617A CN1116633A CN 1116633 A CN1116633 A CN 1116633A CN 95108617 A CN95108617 A CN 95108617A CN 95108617 A CN95108617 A CN 95108617A CN 1116633 A CN1116633 A CN 1116633A
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- organosilane
- organopolysiloxane
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- 150000003254 radicals Chemical class 0.000 title claims abstract description 55
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 52
- 150000001282 organosilanes Chemical class 0.000 title claims abstract description 38
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 28
- 239000003999 initiator Substances 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- -1 amino, hydroxyl Chemical group 0.000 claims description 76
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 239000012815 thermoplastic material Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 229920000620 organic polymer Polymers 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 229920001519 homopolymer Polymers 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- OJZQOQNSUZLSMV-UHFFFAOYSA-N (3-aminophenyl)methanol Chemical compound NC1=CC=CC(CO)=C1 OJZQOQNSUZLSMV-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- 125000006043 5-hexenyl group Chemical group 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- VGUXWSJVGWCTEC-UHFFFAOYSA-N bicyclo[2.2.1]hept-3-ene Chemical compound C1C(C2)CCC2=C1 VGUXWSJVGWCTEC-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- PEJQKHLWXHKKGS-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octachloro-1,3,5,7-tetraza-2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraphosphacycloocta-1,3,5,7-tetraene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 PEJQKHLWXHKKGS-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 125000005826 2-chloro-1,4-phenylene group Chemical group [H]C1=C([*:2])C([H])=C(Cl)C([*:1])=C1[H] 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- CWUGIPSBHFLNTE-UHFFFAOYSA-N 2-hydroxy-2-methylbutanedinitrile Chemical compound N#CC(O)(C)CC#N CWUGIPSBHFLNTE-UHFFFAOYSA-N 0.000 description 1
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- 125000001188 haloalkyl group Chemical group 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
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- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000005358 mercaptoalkyl group Chemical group 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 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 1
- 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 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
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- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical group O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 1
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- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
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- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- ZMYXZXUHYAGGKG-UHFFFAOYSA-N propoxysilane Chemical compound CCCO[SiH3] ZMYXZXUHYAGGKG-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silicon Polymers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerization Catalysts (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
本发明涉及含有能形成自由基的基团并且可溶于有机溶剂的有机硅烷和有机多分子硅醚及其制备方法,以及按照本发明,以有机硅烷和有机多分子硅醚作为自由基引发剂,从可进行自由基聚合的有机单体所得到的大分子单体和接枝共聚物,制备大分子单体和接枝共聚物的方法,以及它们的应用。
制备接枝共聚物的一种可能是包括将活性单体接枝于带有可反应官能末端基团的高聚物上,该方法称之为“接枝其上(grafting onto)”法。例如EP-A-539,901所述,通过乳液聚合法,将乙烯单体接枝于经乳化的含接合点的有机多分子硅醚上。该接合点由共缩合成有机多分子硅醚的二烷氧基硅烷生成,并含有能形成自由基的基团。该“接枝其上”法中,有机单体的均聚反应通过外部氧化还原引发剂体系引发,并且,生长的有机聚合物链接合于有机多分子硅醚接枝基础物的接合点上。
该方法的明显缺点是有机高聚物与有机多分子硅醚相连接并不一定能实现,因此相当一部分有机高聚物不能接枝于多分子硅醚上,而以非接合的均聚物存在。该“接枝其上”法的另一个缺点是,由于分子内连接,特别是有机高聚物链多重接合于有机硅高聚物核而形成环状物,形成的失控状态构建的接枝共聚物,正如由此类接枝共聚物的结构特征(例如借助态和动态静光散射测得)所证明的一样。
本发明的目的是提供含有能形成自由基之基团的有机硅烷和有机多分子硅醚,它们可以简单的,容易再制得的方法制备,利用它们,通过自由基聚合,可以合成大分子单体和接枝共聚物,这些产物不具有上面所述已知接枝共聚物的缺点,即高含有机高聚物均聚物及失控构建的弊病。
本发明涉及含有能够形成自由基之基团的有机硅烷和有机多分子硅醚,而其组成如下:
含0.1-100.0%(重量)的下述通式的单元[RaSi(O(3-a)/2)-R1-C6H4-xR5 x-N=N-Sy-R1-R2] (1)
含0-80.0%(重量)的下述通式的单元
[R2 3SiO1/2] (2)
含0-99.9%(重量)的下述通式的单元
[R2 2SiO2/2] (3)
含0-80.0%(重量)的下述通式的单元
[R2SiO3/2] (4)以及,
含0-80.0%(重量)的下述通式的单元
[SiO4/2] (5)其中:
R是相同的或不相同的氯或溴原子,羟基,C1-至C18-烷氧基,或者由卤原子、氨基、羟基、环氧烷基或者氰基取代或未取代的的C1-至C18-单价烃基;
R1是一化学键,或者相同或不同的C1-至C18-二价烃基,该烃基可被卤原子,氨基,羟基,酰氧基、环氧烷基、氰基取代或未取代,还可由两端键合于碳原子上的,选自-O-,-S-,-COO-,-OOC-,-CONR2-,-NR2CO-,-NR2-和-CO-的二价基团所隔断;
R5是相同的或不同的卤原子,氰基,硝基,或者-R、-OR或-C(O)R基团;
R2是氢原子或基团R;
a是数值0,1,2或3;
x是数值0,1,2,3或4;
y是数值0或1;
其先决条件是,若出现100%(重量)式(1)单元的话,a值为3。
未取代的R基团的典型例是烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基和叔戊基、己基(如正己基)、庚基(如正庚基)、辛基(如正辛基,异辛基如2,2,4-三甲基戊基)、壬基(如正壬基)、癸基(如正癸基)、十二烷基(如正十二烷基)、十八烷基(如正十八烷基);烯基,例如乙烯基,烯丙基,正-5-己烯基,4-乙烯基环己基及3-降冰片烯基(3-norbornenyl);环烷基,例如环戊基、环己基、4-乙基环己基和环庚基、降冰片基(norbornyl)和甲基环己基;芳基,例如苯基,联苯基,
基,葸基及菲基;烷芳基,例如邻-,间-和对-甲苯基,二甲苯基和乙基苯基;是芳烷基,例如苄基及α及β苯乙基。
R基为取代的烃基,其典型例是卤代烃基,例如氯甲基、3-氯丙基、3-溴丙基、3,3,3-三氟丙基、5,5,5,4,4,3,3-七氟戊基、氯苯基、二氯苯基及三氟甲苯基;是巯烷基,例如2-巯乙基和3-巯丙基;是氰烷基,例如2-氰乙基及3-氰丙基;是氨烷基,例如3-氨丙基,N-(2-氨乙基)-3-氨丙基-和N-(2-氨乙基)-3-氨基-(2-甲基)丙基;是氨芳基,例如氨苯基;是酰氧烷基,例如3-丙烯酰氧丙基和3-甲基丙烯酰氧丙基;是羟烷基,例如羟丙基及下式的基团:和
HOCH2CH(OH)CH2SCH2CH2-。
基团R特别优选甲基、乙基、正丙基、乙烯基、3-降冰片烯基、正-5-己烯基、甲苯基和苯基、尤其是甲基和乙烯基。假如通式(1)为有机硅烷,基团R还优选氯原子、甲氧基及乙氧基。
在通式(1)中,偶氮基可于邻位,间位或对位连于芳香基上。
二价烃基R1的取代基典型例是卤原子,氰基和C1-C6酰氧基。二价烃基R1的典型例是饱和的,支链或直链亚烷基,例如亚甲基、亚乙基以及亚丙基、亚丁基、亚戊基、1-甲基亚戊基、亚己基、环亚己基及亚十八烷基;或者不饱和亚烷基或亚芳基,例如亚己烯基、亚苯基(如2-氯-1,4-亚苯基,以及特别是通式(6)-(13)的基团:-(CH2)b- (6)-(CH2)bN(R3)-C(O)-(CH2)b- (7)-(CH2)b-OC(O)-(CH2)b- (8)-(CH2)b-O-CH2-CH(OH)-(CH2)-O-(CH2)b (9)-(CH2)b-(CO)O-(CH2)b (10)-(CH2)b-NH-C(O)O-(CH2)b (12)-(CH2)b-S-C(O)-(CH2)b- (13)
R3是氢原子或相同或不同的单价SiC-键合的,取代或未取代的C1-C6烃基,
b是各自出现,相互无关的0-6整数。
端基-R1-R2优选典型例是式
-C(CN)2CH3,
-C(CH3)2CN,
-C(C6H5)2Cl,
-C(C6H5)2OAc,
-C(C6H5)CH3Cl,
-C(C6H5)CH3OAc,
-C6H5,及
-S-C6H5的基团。
x优选0、1或2。
含能生成自由基之基团的有机多分子硅醚优选含有0.5-20.0%(重量),特别优选1.0-10.0%(重量)的通式(1)单元。
如果有机多分子硅醚为环状化合物,那么该含可生成自由基之基团的有机多分子硅醚可以包括例如高达90.0%(重量)的通式(3)单元。该含有能生成自由基之基团的有机多分子硅醚一般包含20.0-99.0%(重量),特别是50.0-99.0%(重量)的通式(3)单元。
一优选实施方案中,含有可形成自由基之基团的有机多分子硅醚包括至少90.0%(重量),特别是95.0%(重量)的通式(3)单元,而其余单元为通式(2)和(1)单元,其中a为1。这些有机多分子硅醚有线性的,梳状(comb-like)结构。就与可通过自由基聚合的有机单体反应而言,通式(1)单元上的接合点特别容易接近。
含有可形成自由基之基团的有机多分子硅醚可以含有,例如至少90.0%(重量)的通式(2),(4)和(5)的单元,在这种情况下它们是树脂。含有可形成自由基之基团的有机多分子硅醚优选含有不超过80.0%(重量)、尤其是50.0%(重量),特别优选不超过20.0%(重量)的通式(4)或(5)单元。
优选的含有能形成自由基之基团的有机多分子硅醚为优选含有氢原子和甲基或乙烯基(正如基团R2的某些基)的线性有机多分子硅醚或高弹体。
优选于20℃,含有可形成自由基之基团的有机多分子硅醚在100ml甲苯中可溶解至少15g,特别是溶解30g。该含有能形成自由基之基团的有机多分子硅醚也很容易溶于其它有机溶剂,例如二噁烷、四氢呋喃(THF),因此它特别适用于溶液接枝聚合法中,作为自由基大分子引发剂。
该含有能形成自由基之基团的有机多分子硅醚的平均分子量优选103-105g/mol,尤其是5×103-5×104g/mol。
本发明也涉及制备含有可形成自由基之基团的有机硅烷和有机多分子硅醚的方法。方法1):
该方法中,I)由含0.1-100.0%(重量)的下述通式单元,
[RaSi(O(3-a)/2)-A] (14)以及在上面所作的有关含有可形成自由基之基团的有机硅烷及有机多分子硅醚介绍时,述及的含通式(2)-(5)单元的有关量,所形成的有机硅烷和有机多分子硅醚,与下述通式的化合物反应
B-C6H4-xR5 x-N=N-Sy-R1-R2 (15)其中,A是相同或不同的C1-C17单价烃基,该烃基含有羧酸酐或环氧基团,或基团-COCl或-NCO,该烃基可由卤原子、氨基、羟基、环氧烷基或氰基取代或未取代,并可由两端连于碳原子的,选自-O-,-S-,-COO-,-OOC-,-CONR2-,-NR2CO-,-NR2-和-CO-的两价基团所隔断,
B是
-(CH2)cOH,
-(CH2)cNHR1,
-(CH2)cCOOH,
-(CH2)cSH基团,
c各自独立,相互无关,是0-10的整数,
R、R5、a、x、y、R1和R2与上面所述定义相同,
其先决条件是A和B中的碳原子总数不超过18。
本发明又涉及II)制备含有能形成自由基之基团的有机硅烷和有机多分子硅醚的相应方法,其中,在上述通式(14)和(15)中:
B是羧酸酐或环氧基团,基团-COCl,-COOH或-NCO,或者是含有羧酸酐或环氧基团,或基团-COCl,或-NCO的相同或不同的单价C1-C17烃基,该烃基可被卤原子,氨基、羟基、环氧烷基或氰基取代或未取代的,并可由两端与碳原子相连的、选自-O-、-S-、-COO-、-OOC-、-CONR2-、-NR2CO-,-NR2及-CO-的二价基团所隔断,
A是
-(CH2)cOH,
-(CH2)cCH2NHR1,
-(CH2)cCH2COOH,或
-(CH2)cCH2SH基团,以及,
R、a、c、R1和R2与上面所述定义相同,
其先决条件是A和B中的碳原子总数不超过18。
方法1优选在下述方法2中所述有机溶剂中进行。
假如方法1中,其A或B中有-COCl基团存在,那么该反应优选在有例如三乙胺或吡啶之类的碱存在下进行,以便捕获氯化氢。方法2):
该方法中,由
含0.1-100.0%(重量)的下述通式单元,
[RaSiH(O(3-a)/2)] (16)以及正如前面在介绍有关含有能形成自由基之基团的有机硅烷和有机多分子硅醚时所述及的通式(2)-(5)单元的量,所构成的有机硅烷和有机多分子硅醚,
在铂、铑或其化合物的存在下,与下述通式化合物反应,
R4-C6H4-xR5 x-N=N-Sy-R1-R2 (17)其中:
R4是相同的或不同的含有烯双键或者炔三键的C1-C18烃基,该烃基可被卤原子、氨基、羟基、酰氧基、环氧烷基或氰基取代或未取代的,并可由两端连碳原子的、选自-O-、-S-、-COO-、-OOC-、-CONR2-、-NR2CO-、-NR2-和-CO-的二价基团所隔断,
R、R5、a、x、y、R1和R2与上面所定义的意义相同。
所有目前为止,能用于将直接键合于Si上的氢加成到脂肪族不饱和的化合物上的催化剂,均可用于上述反应。这些催化剂的典型例,如,金属细粉铂(可载于二氧化硅、氧化铝或活性炭之类的载体上),铂的化合物或配合物,例如卤化铂(PtCl4,H2PtCl6*6H2O及Na2PtCl4*4H2O之类)、铂-烯烃配合物、铂-醇配合物、铂-醇化物配合物、铂-醚配合物、铂-醛配合物、铂-酮配合物(包括H2PtCl6*6H2O和环己酮的反应产物)、铂-乙烯基硅氧烷配合物,尤其是铂-二乙烯基四甲基二硅氧烷配合物(带有或不带有可检测出的无机键合囟素)、二氯·双(γ-甲基吡啶)合铂、二氯·三亚甲基二吡啶合铂、二氯·二环戊二烯合铂、二氯·二甲基亚砜亚乙基合铂(II),以及四氯化铂与烯烃和伯胺、或仲胺、或者伯胺和仲胺的反应产物,例如溶于1-辛烯的四氯化铂与仲丁胺的反应产物或铵-铂配合物。
催化剂的优选用量为0.5-500ppm(重量)(每百万份重量中所占重量份数),尤其是2-400ppm重量。各情况下,是作为元素金属来计算的,并且基于在混合物中并含直接键合于硅原子上的氢原子的硅烷和/或硅醚的总重量。
上述反应(以下称之为氢化硅烷化反应)可在有溶剂或无溶剂存在下进行,优选有溶剂存在。
如果使用溶剂,那么优选反应条件下极为惰性的溶剂或混合溶剂,特别是0.1MPa下沸点或沸点范围高至120℃的溶剂。溶剂的典型例,如二噁烷、四氢呋喃、***、乙二醇二甲醚之类的醚类;二氯甲烷、氯仿、四氯化碳、1,2-二氯乙烷及三氯乙烯之类的氯化烃;戊烷、正己烷、己烷异构体混合物、庚烷、辛烷、洗涤汽油、石油醚、苯、甲苯、二甲苯之类的烃;丙酮、甲乙酮、甲基异丁基酮之类的酮、二硫化碳、硝基苯、二甲基乙酰胺、二甲基甲酰胺、二甲基亚砜、N-甲基吡咯烷酮,或以上溶剂的混合物。
所谓溶剂,并不意味着所有反应成分必需溶于其中。该反应也可在一种或多种反应物处于悬浮液或乳液的状态下进行。该反应也可在有混溶性区的混合溶剂中进行,各种情况下,在混合物的各相中至少有一种反应成分是可溶的。
该氢化硅烷化反应可在大气压下进行,这就是说约0.1MPa(绝对)压力下,但也可在较高或较低压力下反应,优选0.01MPa-1.0MPa(绝对压力),特别是0.09MPa(绝对压力)-0.11MPa(绝对压力)。方法3):
在该方法中,将下述各成分的混合物进行反应,A)下述通式的有机硅烷[RaSi(O(3-a)/2)-R1-C6H4-xR5 x-N=N-Sy-R1-R2] (1)B)从下面挑选出的有机硅化合物
B1)下述通式的有机硅烷
R2 dSi(R6)(4-d) (18)以及,
B2)下述通式单元的有机硅醚
R2 e(R6)fSiO(4-e-f)/2 (19)
假如适宜还包括:C)在组分A和B中的按每摩尔烷氧基团、氯原子或溴原子至少加有0.5mol水,以及,假如适宜D)可与水混溶的溶剂,
其中,通式(18)和(19)中:
R6表示氯或溴原子或者被卤原子取代或未取代的C1-C10烷氧基团,
d、e和f在任何情况下分别为数值0、1、2或3,R、R1、R2和a与前面所定义的相同,
其先决条件是成分B中,每摩尔硅原子至少要含0.01摩尔烷氧基团,或氯、或溴原子。
基团R5优选C1-C6烷基,特别是甲基、乙基、正丙基、异丙基和己基,尤其是甲基和乙基。
本发明方法中所采用的通式(18)之有机硅烷B1的典型例是四甲氧基硅烷、四乙氧基硅烷、四正丙氧基硅烷、甲基三甲氧基硅烷、乙烯基三甲氧基硅烷、3-巯丙基三甲氧基硅烷、3-氯代丙基三甲氧基硅烷、苯基三甲氧基硅烷、邻-、间-和对-甲苯基三甲氧基硅烷、丙基三甲氧基硅烷、甲基三乙氧基硅烷、乙烯基三乙氧基硅烷、乙烯基二甲基乙氧基硅烷、3-巯丙基三乙氧基硅烷、丙基三甲氧基硅烷、二甲基二乙氧基硅烷、二甲基二甲氧基硅烷和三甲基乙氧基硅烷,其中优选四乙氧基硅烷、甲基三甲氧基硅烷、二甲基二乙氧基硅烷、乙烯基二甲基乙氧基硅烷、甲基三乙氧基硅烷、苯基三乙氧基硅烷、邻-、间-和对-甲苯基三乙氧基硅烷和丙基三乙氧基硅烷,特别优选四乙氧基硅烷。
本发明方法中所采用的有机硅醚B2优选含不超过100个通式(19)单元。有机硅醚B2的典型例是直链的有机硅醚,例如乙硅醚,如六甲基乙硅醚,1,3-二苯基甲基乙硅醚,1,3-双)正-5-己烯基)四甲基乙硅醚、1,3-二乙烯基四甲基乙硅醚、聚二甲基硅氧烷、聚苯基甲基硅氧烷、α、ω-羟基聚二甲基硅氧烷、优选六甲基乙硅醚,和1,3-二乙烯基四甲基乙硅醚。B2典型例还包括含3-8(优选4-5)个通式(19)单元的环状有机多分子硅醚,例如六甲基环三硅氧烷,八甲基环四硅氧烷和十甲基环五硅氧烷,还包括聚硅氧烷,例如聚二甲基硅氧烷和α,ω-羟基聚二甲基硅氧烷。
组分B也可包括单体或高聚物硅酸酯。该情况具体为制备树脂所用。优选硅酸酯为原硅酸甲酯、原硅酸乙酯、聚硅酸甲酯和聚硅酸乙酯、含有烷氧基的硅酸酯。
烷氧基团、或氯或溴原子在组分B中的含量优选每摩尔硅原子0.5-2mol,特别是0.65-1.5mol。
组分A和B的每摩尔烷氧基和氯或溴原子,采用作为C成分的水时,优选至少0.5mol,特别是0.5-0.8mol。
组分D优选采用20℃时,按体积比1∶1与水均匀混合的有机溶剂。作为组分D适用的溶剂典型例是单羟基或多羟基醇、如甲醇、乙醇、正丙醇、异丙醇、和乙二醇;是醚类如二噁烷、四氢呋喃;是酰胺、如二甲基甲酰胺、二甲基亚砜和环丁砜,或以上溶剂的混合物。
特别优选于0.1MPa下,沸点或沸点范围高达120℃的溶剂,尤其是上述单羟基醇。
方法3优选在有本身已知的催化剂存在下进行。具体说来,催化剂的典型例是硫酸、磷酸、三氟甲基磺酸、氯化铁(II)、氯化铝、三氟化硼、氯化锌、高岭土、酸性沸石、磺化活性炭、碱金属氢氧化物(优选氢氧化钾和氢氧化铯),碱金属醇化物、季铵氢氧化物(如四甲基氢氧化铵、苄基三甲基氢氧化铵和苄基三乙基氢氧化铵)、丁醇苄基三甲基铵(benzyltrimethylammo-nium butylate)、2-乙基己酸β-羟基乙基三甲基铵、氢氧化季鏻(如氢氧化四正丁基季鏻和氢氧化三正丁基-3-[三(三甲基-甲硅烷氧基)甲硅烷基]-正丙基季鏻)、碱金属硅氧烷化物(siloxanolate)和铵有机硅氧烷化物(如苄基三甲基铵乙基硅氧烷化物以及氮磷化合物(如氯化磷腈(phosphonitrile chloride))。
催化剂优选用量为通式(1)、(18)和(19)化合物总重量的0.1-10%。
上述制备方法1-3优选于-10℃至80℃温度下进行,特别是0°至60℃。上述制备方法于避光下进行较好。上述各方法中,优选合成之后除去挥发性成分和盐。
含有能形成自由基之基团的有机硅烷和有机多分子硅醚,优选用作制备烯类不饱和有机单体的大分子单体和接枝共聚物的自由基引发剂。
本发明还涉及制备大分子单体和接枝共聚物的方法,该方法即将95-1%(重量)的上述含有能形成自由基之基团的有机硅烷和有机多分子硅醚与1-95%(重量)的烯类不饱和单体反应。
大分子单体(macromonomer)系其末端至少有活性单官能团的高聚物。本文中大分子单体由有机硅烷组成,可以缩合或平衡反应得到接枝共聚物。
在接枝共聚方法中,欲行接枝的接枝基础物带有能与加入接枝的单体反应的活性基团。该方法称之为“由此接枝(grafting from)法”。当聚合反应开始,接出的分枝直接在接枝基础物上生长,以便有一定结构的接枝共聚物和大分子单体可以按特定的可控方式构建。
可以通过加热或光辐照使带有能形成自由基之基团的有机硅烷和有机多分子硅醚活化。该过程中氮被消去(eliminate)并形成一对自由基。连于有机多分子硅醚的芳基便成为烯类不饱和单体的活性接合点。在该活化作用期间,要从有机硅烷和有机多分子硅醚中***开第二个自由基是很慢的,使它仅能聚合极少单体。因此,比起通过“接枝其上法”进行接枝过程来说,上述方法得到的游离有机高分子均聚物是非常低的。
该制备大分子单体和接枝共聚物的方法,可采用本体聚合,或有机溶液聚合,或乳液聚合,可能是该含有能形成自由基之基团的有机硅烷和有机多分子硅醚能部分或全部溶解。优选采用的溶剂是四氢呋喃和二噁烷之类的醚及甲苯之类的烃。有机溶剂用量优选为该含有能形成自由基之基团的有机硅烷和有机多分子硅醚重量的0-10倍,特别是1-3倍。
如果适宜的话,本发明的有机硅烷和有机多分子硅醚可以一开始就与溶剂一起引入反应容器中。但是也可以在自由基大分子引发剂活化前,将该方法的所有组分混合在一起。
该反应优选在排除湿气和氧的条件下进行。自由基引发剂活化前,优选将反应混合物以氮或氩气之类的惰性气体充填10-90分钟使之饱和,并且使其pH值优选为7-9。
优选提高温度到40-100℃(优选60-85℃)开始在自由剂引发剂上以接枝。也可以用汞灯或汞/氙灯进行长达24小时的照射,借助紫外线加速接枝。
将烯类不饱和有机单体,按接枝共聚物总重的20-80%计量加入混合物中较为有利。有机高聚物组分优选的单体是丙烯酸、甲基丙烯酸、具有1-10个碳原子的脂肪醇或二醇的丙烯酸酯或甲基丙烯酸酯、丙烯腈、苯乙烯、对甲基苯乙烯、醋酸乙烯酯、丙酸乙烯酯、马来酰亚胺、乙烯基吡咯烷酮、氯代乙烯、乙烯、丁二烯、异戊二烯和氯丁二烯。特别优选的单体是苯乙烯及具有1-4个碳原子的脂肪醇的丙烯酸酯和甲基丙烯酸酯,例如(甲基)丙烯酸甲酯,(甲基)丙烯酸乙酯或(甲基)丙烯酸丁酯、乙二醇二(甲基)丙烯酸酯以及乙烯、丁二烯。上面提及的单体的均聚物和共聚物均适合作为有机高聚物成分。含有两个烯双键的单体进行接枝聚合反应可导致生成交联接枝聚合物。
当聚合反应完全,保持初温30分钟-8小时,优选1-2小时。然后可以通过蒸馏,除去剩余的未反应单体,假如适宜,则优选与溶剂一起蒸出。优选采用极性溶剂中进行沉淀,来从溶剂中分离大分子单体和接枝共聚物,并除去残余未反应的有机单体,所述极性溶剂例如乙醇,甲醇或水,或者采用其它已知提纯方法来分离之。大分子单体和接枝共聚物实质上是无色油状物或固体。
本发明还涉及由上述方法所获得的大分子单体和接枝共聚物。
根据本发明的接枝共聚物的分子量优选104-107g/mol,特别是5×104-5×105g/mol。
由于有机高聚链特异性连接于硅接枝基础物上,因此由上述方法制备的大分子单体和接枝共聚物有一定的构成。该大分子单体和接枝共聚物易溶于有机溶剂(特别是适宜于接枝聚合的溶剂),可作为热塑性材料加工。
本发明的上述所有大分子单体和接枝共聚物适于作为改性热塑性材料使用,并可作为含硅高聚物混合料的相容性介体,或作为高聚物混合料中的硅成份。上面所述单体的均聚物和共聚物均宜于作为热塑性材料中的有机高聚物含量,以及作为高聚物配料中的有机高聚物成份。
为制备混合料,将本发明的接枝共聚物,均按混合料总重占0.5-50%(优选3-10%)的(重量),与两种相应的均聚物一起经挤出,或者熔融模压加工。根据需要,此处均聚物的相互比例可以改变。特别优选不饱和乙烯/丙烯共聚物(EPDM)和硅高聚物的混合物。若用硅高聚物改性橡胶,则硅的良好抗热性及低温柔软性与橡胶的良好机械性质正好结合起来。
除非另外说明,下述实施例中有如下规定:
a)所有量均以重量计;
b)所有压力均为0.10PMa(绝对压力);
c)所有温度为20℃。
还使用下述简写:
of th.=理论(产率)
A.G=分析纯
conc.=浓缩
GPC=凝胶渗透色谱
RI=折射率
THF=四氢呋喃
MMA=甲基丙烯酸甲酯
PMMA=聚甲基丙烯酸甲酯
Mn=数均(分子量)(number average)
Mw=重均(分子量)(weight average)
实施例
有机多分子硅醚自由基大分子引发剂
实施例1
合成3-酰氯苯基二乙基偶氮-1,1-二腈(3-acylchlorophenylazoethane-1,1-dinitrile,Azo I)
将60g冰加入6.31g(4.6×10-2mol)3-氨基苯甲酸中,将其溶于100ml水和13ml conc.盐酸的混合物中并冷却至0℃(L1)。将溶于50ml水的3.22g(4.6×10-2mol)亚硝酸钠冷却至0℃(L2)。将60ml乙醇中的3.55g(4.4×10-2mol)甲基丙二腈(methylmalonitrile)与43.9g(0.54mol)乙酸钠于100ml水中的浓液混合,冷却至0℃(L4)。将L1滴入L2中,其间温度不高于0℃。将悬浮液滴(L3)加入L4中,同时用冰冷却。将混合物0℃搅拌1小时,然后于室温搅拌30分钟。将该混合物置于分液漏中上面覆盖一层***,用浓盐酸酸化水相并振荡混合物。加入酸直至偶氮化合物在醚相中完全溶解为止。分离出有机相,以水洗涤并以硫酸镁干燥。将溶剂蒸出,其产物3-羧苯基二乙基偶氮-1,1-二腈(3-carboxyphenylazoethane-1,1-dinitrile)于真空干燥之。
产率:5.63g(56%of th.)3-羧苯基二乙基偶氮-1,1-二腈。
将15.0g(6.6×10-2mol)3-羧苯基二乙基偶氮-1,1-二腈溶于500ml无水甲苯中,并将该溶液冷却至0℃。将13.7g(6.6×10-2mol)溶于20ml二氯甲烷中的五氯化磷慢慢滴加入上述混合物中,以使反应温度不超过4℃。然后将该反应混合物于室温下搅拌3小时。加入2升已烷,于-20℃放置过夜产物结晶析出,将其在惰性气体下用烧结滤器过滤并真空干燥之。
产率:10.3g(63%)(Azo I)
实施例2
合成4-羟基甲基苯基二乙基偶氮-1,1-二腈(4-hydroxymethylphenylazoethane-1,1-dinitrile,Azo II)
将11.31g(0.092mol)3-氨基苄基醇(L1)溶于加有13mlHCl(conc.)的100ml水中,并冷却至0℃。将6.44g(0.092mol)亚硝酸钠溶于50ml水中(L2)并用冰冷却。将L2慢慢滴加入L1中,以使反应温度不超过0℃(L3)。同时,将7.1g(0.091mol)甲基丙二腈和87.7g(1.07mol)乙酸钠溶于100ml水中(L4)。将L3很快加入L4中。将反应溶液于室温下搅拌45分钟,然后用***振荡萃取5次。将各次所得醚相合并用氧化铝过滤并经硫酸镁干燥,蒸出溶剂。将产物溶于少量二氯甲烷(1份)中并加入4-5份戊烷。弃去油状副产物,浓缩溶液,将剩余之黄色产物于真空干燥。产率:6g(3%)
实施例3
由Azo I和N-环己基氨基-丙基二甲氧基甲基硅烷合成酰胺(Azo III)
先引入12.3g(0.05mol)N-环己基氨基-丙基二甲氧基甲基硅烷和13g(0.11mol)三甲基甲氧基硅烷。将22mg(5.5×10-4mol)氢氧化钠于4ml水中的溶液滴加入进去,同时不断搅拌。将得到的乳液于60℃控温1小时,由此形成清澈溶液。常压下于100℃,将所有高挥发性化合物蒸出。残余物与6ml 20%浓度的盐酸水溶液一起加热回流4小时,将非水相分出。用水洗两次,并于1mbar下蒸馏(沸点120-121℃)。产率:5.53g(31%of th.)
将0.68g(2.8×10-3mol)实施例1所述Azo I和0.28g(2.8×10-3mol)三乙胺滴加入溶于20ml THF的上面制得的1g(2.8×10-3mol)双[三甲基甲硅烷氧基]-N-环己基氨基-丙基-甲基硅烷中,并冷却至0℃。将反应混合物搅拌1小时。滤除固体物,并真空浓缩滤液。将残余物倒入50ml***中,用30ml水洗涤混合物二次,分离出有机相,经硫酸钠干燥。于室温高真空下除去溶剂至产物恒重。获得1.19g(70%of th.)黄色油状物。
实施例4
由Azo I合成自由基大分子引发剂(RM/1)
将5.0g含N-甲基氨基丙基官能团的聚二甲基硅氧烷(2.6×10-3mol -NHCH3,分子量Mn=15300)溶于30ml无水THF中,将0.36ml(0.26g,2.6×10-3mol)三乙胺和0.64g(2.6×10-3mol)AzoI的无水THF溶液滴加入其中。该混合物被搅拌过夜。于真空中35℃汽提出溶剂,使其降至一半量,并将剩余物滴加入甲醇和水的2∶1混合物中。所得乳液被搅拌1小时,并每次用100ml醚振荡萃取二次。合并***相,用100ml 3%浓度的NaOH溶液和100ml水洗涤、干燥,于35℃用旋转蒸发器蒸出***。高真空下,进一步从***中游离出粘稠黄色油状产物。产率:4.7g(85%of th.)
实施例5
由Azo I合成自由基大分子引发剂(RM/2)
将20g含N-环己基氨基丙基官能团的聚二甲基硅氧烷(1.3×10-2mol NH-环己基官能团,分子量Mn=15800g/mol)和Azo I酰氯(3.21g,1.3×10-2mol)各溶于50mo1无水THF中。将1.33g(1.3×10-2mol)三乙胺加入硅氧烷溶液中,该混合物被冷却至约10℃,再将酰氯溶液滴加进去,同时搅拌。混合物于10℃再搅拌一小时,真空汽提出溶剂直至降为一半量为止,将剩余物滴加入800ml甲醇中。搅拌该乳液1小时,产物沉降过夜,倒入THF,用MgSO4干燥混合物,并从溶剂中经真空游离出。产率:14.3g(62%)
实施例6
由Azo I合成自由基大分子引发剂(RM/3)
将8g含N-环己基氨基丙基官能团的聚二甲基硅氧烷(2×10-3molNH-环己基官能团,分子量Mn=15500g/mol)和0.5g AzoI酰氯(2×10-3mol)分别溶于50ml无水THF中。将0.21g(2×10-3mol)三乙胺加入该硅氧烷溶液中,冷却该混合物至约10℃,再将酰氯溶液慢慢滴加进去,同时搅拌。于10℃再搅拌混合物1小时,真空下汽提溶剂至一半量为止,剩余物滴加入800ml甲醇中。该乳液被搅拌1小时,将产物沉降过夜,倒入THF中,用MgSO4干燥混合物,真空下从溶剂中游离出产物。
产物:5.3g(62%);分子量(GPC测定,以THF为洗脱液,聚苯乙烯校准,RI检测器)Mn=28300,Mw=33700g/ml
实施例7
由Azo II合成自由基大分子引发剂(RM/3)
将5.25g未经处理的氧化铝粉末(颗粒大小为150目,58A)与20ml无水***及0.21g(1mmol)AzoII一起搅拌10分钟。加入含缩水甘油基(glycidyloxy)官能团的3.88g聚二甲基硅氧烷(1mmol环氧官能团,分子量=12600g/mol),再搅拌该混合物16小时。过滤反应溶液,真空蒸出溶剂。获得浅黄色油状产物。产率:1.1g(27%)
实施例8
合成3-乙烯基苯基二乙基偶氮-1,1-二腈(3-vinylphenylazoethane-1,1-dinitrile,Azo IV)
将1.19g(0.01mol)3-氨基苯乙烯溶于30ml水和5ml浓盐酸中,并加入30g冰。于0℃,用冰冷却的0.7g(0.01mol)NaNO2的20ml水溶液进行重氮化反应。然后将经过滤的重氮盐溶液,于0-5℃滴加入0.8g(0.01mol)甲基丙二腈和10g(0.12mol)溶于15ml乙醇及25ml水的乙酸钠溶液中。室温下搅拌混合物30分钟,用***萃取偶氮化合物。用柱色谱(70g SiO2+10%水、石油醚(100ml)/***(3ml))提纯后,获得黄色固体物。产率:1.8g(85%of th.)
实施例9
合成自由基大分子引发剂RM/5
将2.0g(9.5mmol)3-乙烯基苯基二乙基偶氮-1,1-二腈和2.88g含氢量1.6%(重量)(相当于4.75×10-2mol HSi单元)、25℃下粘度为83mPas的聚氢化甲基硅氧烷相混合,然后将含有17%(重量)铂的1.44mg二乙烯基四甲基二硅氧烷-铂配合物加入,以使总混合物含50ppm铂(以纯金属计)。尔后加入5m1甲苯,45℃下搅拌该反应溶液16小时。反应2小时后,再加入1.44mg上述催化剂。反应结束后,将溶液慢慢滴加入甲醇中,沉淀出黄色产物。过滤出固体、高真空下干燥至恒重。获得4.7g(产率96%of th.)黄色粉末。
实施例10
合成自由基大分子引发剂RM/6
将2.47gα,ω-羟基聚二甲基硅氧烷(其粘度25℃时为100mPas)和10mg(3.9×10-5mol)四丁基氢氧化铵,加入到0.5g(9.5×10-4mol)实施例3所述Azo III中。于45℃搅拌混合物24小时,冷却至室温后将产物溶于50ml醚中,每次用水30ml振荡萃取该混合物二次,分出有机相,用硫酸钠干燥,并于30℃高真空下浓缩至恒重。得到2.4g(产率:80%ofth.)透明黄色油状物。
实施例11a
通过热分解,按RM/1∶MMA为1∶3.9的比例进行接枝共聚合反应(PC1)。
将1g RM/1(4.6×10-4mol偶氮官能团)和3.9g(1.8×10-3mol)MMA溶于50ml甲苯中。将反应混合物彻底脱气,并加热至70℃16小时。冷却后将溶液于800ml甲醇中沉淀。过滤出沉淀的接枝共聚物并真空干燥之。产率:3.5g(61%)分子量(GPC测定,THF作洗脱液,聚苯乙烯校准,RI检测):Mn=65300,Mw=179100g/mol
实施例11b
按RM/2∶MMA为1∶1的比例进行接枝共聚反应(PC1b)
将7.5g RM/2(4.9×10-3mol偶氮官能团)和7.5g MMA(7.5×10-2mol)溶于70ml甲苯中。将反应混合物彻底脱气,然后加热至75℃16小时。冷却之后,该溶液于800ml甲醇中沉淀。滤出沉淀的产物并真空干燥之。产率:5.3g(35%)分子量(GPC测定,THF作洗脱液,聚苯乙烯校准,RI检测):Mn=19100,Mw=30300g/mol
实施例11c
按RM/2∶MMA为1∶10的比例进行接枝共聚反应(CP1c)
将1.36g RM/2(8.9×10-4mol偶氮官能团)和13.64g MMA(1.36×10-2mol)溶于70ml甲苯中。将反应混合物彻底脱气,然后加热75℃16小时。冷却之后,溶液于800ml甲醇中沉淀。滤出沉淀之产物并真空干燥之。产率:11.5g(76%)分子量(GPC测定,THF作洗脱液,聚苯乙烯校准,RI检测):Mn=61700,Mw=114700g/mol
实施例11d
按RM/4∶MMA为1∶5的比例进行接枝共聚反应(PC1d)
将1g RM/4(2.4×10-4mol偶氮官能团)和5g MMA(5×10-2mol)溶于70ml甲苯中。将反应混合物彻底脱气,然后加热至75℃16小时。冷却之后,溶液于800ml甲醇中沉淀,滤出沉淀产物并真空干燥之。产率:4.81g(80%)分子量(GPC测定,THF作洗脱液,聚苯乙烯校准,RI检测):Mn=77200,Mw=137100g/mol
实施例12
RM/2与苯乙烯按1∶5的比例进行接枝共聚反应(PC2)
将1g RM/2(6.5×10-4mol偶氮官能团)和5g苯乙烯(4.8×10-2mol)溶于70ml甲苯中。将反应混合物彻底脱气,然后加热至90℃16小时。冷却之后,溶液于800ml甲醇中沉淀。滤出沉淀产物并真空干燥之。产率:3.9g(65%)分子量(GPC测定,THF作洗脱液、聚苯乙烯校准,RI检测:Mn=7600,Mw=19300g/mol
实施例13
通过光分解,按RM/2与MMA为1∶5的比例进行接枝共聚反应(PC3)
将0.19g RM/2(1.2×10-4mol偶氮官能团)和0.94g MMA(9.4×10-3mol)溶于3ml甲苯中。将反应混合物彻底脱气,然后于25℃,充惰性气体条件下,在石英池中于Hg-Xe高压灯光中(灯输出功率=200W,对样品的输出功率为100W/cm2)暴露6小时。曝光之后,将溶液于20ml甲醇中沉淀。滤出沉淀产物并真空干燥之。产率:0.4g(35%)分子量(GPC测定,THF作洗脱液、聚苯乙烯校准,RI检测):Mn=16100,Mw=23800g/mol
实施例14
PMMA/硅油与加入PC1的混合料
将1g聚二甲基硅氧烷(Mn=312000,Mw=540000),9g PMMA(Mn=30200,Mw=50000)和0.3g PC1c溶于30ml甲苯中,从溶液形成膜,将其于室温干燥10天,然后于40℃干燥2天。与未加PC1c的10%聚二甲基硅氧烷和90%PMMA膜相比,该膜机械性能得到改善。
Claims (8)
1、含有能形成自由基之基团的有机硅烷和有机多分子硅醚,其组成如下:
0.1-100.0%(重量)的下述通式单元
[RaSi(O(3-a)/2)-R1-C6H4-xR5 x-N=N-Sy-R1-R2] (1)
0-80.0%(重量)的下述通式单元
[R2 3SiO1/2] (2)
0-99.9%(重量)的下述通式单元
[R2 2SiO2/2] (3)
0-80.0%(重量)的下述通式单元
[R2SiO3/2] (4)以及,
0-80.0%(重量)的下述通式单元
[SiO4/2] (5)其中:
R是相同的或不同的氯或溴原子、羟基、C1-C18烷氧基,或由卤原子,氨基、羟基、环氧烷基或氰基取代或未取代的C1-C18单价烃基,
R1是一条化学键,或者相同或不同的C1-C18二价烃基,该烃基可由卤原子,氨基,羟基、酰氧基、环氧烷基或氰基取代或未取代,并可被两端连于碳原子,选自-O-,-S-,-COO-,-OOC-,-CONR2-,-NR2CO-,-NR2-及-CO-的二价基团所隔断,
R5是相同或不同的卤原子、氰基、硝基、或基团-R,-OR或-C(O)R,
R2是氢原子或基团R,
a是数值0、1、2或3,
x是数值0、1、2、3或4,
y上数值0或1,
其先决条件是,如果式(1)单元占100%(重量),那么a的值为3。
2、如权利要求1的制备含有能形成自由基之基团的有机硅烷或有机多分子硅醚的方法,该方法包括:
由0.1-100,0%(重量)的下述通式单元
[RaSi(O(3-a)/2)-A] (14)和一定量通式(2)-(5)单元,该量正如上述含有能形成自由基之基团的有机硅烷和有机多分子硅醚所述及的量,所组成的有机硅烷和有机多分子硅醚,与下述通式的化合物反应,
B-C6H4-xR5 x-N=N-Sy-R1-R2 (15)其中:
A是相同的或不同的,含有羧酸酐或环氧基,或-COCl、或-NCO基团的C1-C17单价烃基,该烃基可由卤素原子、氨基、羟基、环氧烷基、或氰基取代或未取代,并可被两端连于碳原子的,选自-O-,-S-、-COO-,-OOC-,-CONR2-,-NR2CO-,-NR2-和-CO-的二价基团所隔断,
B是
-(CH2)cOH、
-(CH2)cNHR1、
-(CH2)cCOOH、
-(CH2)cSH基团,
c在每种情况下均相互无关,分别为0-10的整数,
R、R5、a、x、y、R1和R2的定义与前面相同,
其先决条件是A和B中碳原子总数不超过18。
3、如权利要求1的制备含有能形成自由基之基团的有机硅烷或有机多分子硅醚的方法,其中,所述通式(14)和(15)中:
B是羧酸酐或环氧基团、-COCl、-COOH或-NCO基团,或者相同或不同的含有羧酸酐或环氧基,或-COCl或-NCO基团的C1-C17单价烃基,该烃基可由卤原子,氨基、羟基、环氧烷基或氰基取代或未取代的,并可被两端连于碳原子的,选自-O-,-S-,-COO-,-OOC-,-CONR2-,-NR2CO-,-NR2-和-CO-的二价基团所隔断,
A是
-(CH2)cOH,
-(CH2)cCH2NHR1,
-(CH2)cCH2COOH,或
-(CH2)cCH2SH基团,
R、a、c、R1和R2与上面定义相同,
其先决条件是A和B中的碳原子总数不超过18。
4、如权利要求1的制备含有能形成自由基之基团的有机硅烷和有机多分子硅醚的方法,该方法包括将由
0.1-100.0%(重量)的下述通式单元
[RaSiH(O(3-a)/2)] (16)和一定量通式(2)和(5)单元,该量正如上述含有能形成自由基之基团的有机硅烷和有机多分子硅醚所述及的量,所组成的有机硅烷或有机多分子硅醚,
在铂,铑或其化合物存在下,与下述通式化合物反应,
R4-C6H4-xR5 x-N=N-Sy-R1-R2 (17)其中:
R4是相同的或不同的,含有烯双键或炔三键的C1-C18价烃基,该烃基可由卤原子、氨基、羟基、酰氧基、环氧烷基或氰基取代或未取代,并可被两端连于碳原子的,选自-O-,-S-,-COO-,-OOC-、-CONR2-,-NR2CO-,-NR2-和-CO-的二价基团隔断,
R、R5、a、x、y、R1和R2与上面定义相同。
5、如权利要求1的制备含有能形成自由基之基团的有机硅烷和有机多分子硅醚的方法,该方法是将下述各成份的混合物进行反应,
A)下述通式的有机硅烷[RaSi(O(3-a)/2)-R1-C6H4-xR5 x-N=N-Sy-R1-R2] (1)
B)从下面挑选的有机硅化合物
B1)下述通式的有机硅烷
R2 dSi(R6)(4-d) (18)以及,
B2)下述通式单元的有机硅醚
R2 e(R6)fSiO(4-e-f)/2 (19)假如适宜,还包括:
c)在组分A和B中的按每摩尔烷氧基团、氯原子或溴原子至少加有0.5mol水,以及,假如适宜,
D)与水混溶的溶剂
其中,通式(18)和(19)中:
R6表示氯或溴原子,或者被卤原子取代或未取代的C1-C10烷氧基团,
d、e和f在任何情况下分别为数值0、1、2或3,以及,
R、R1、R2和a与前面所定义的相同,
其先决条件是组分B中,每摩尔硅原子至少要含0.01mol烷氧基团,或氯、或溴原子。
6、制备大分子单体和接枝共聚物的方法,该方法是将95-1%(重量)的上述有机硅烷和有机多分子硅醚,与1-95%(重量)的烯类不饱和单体反应。
7、根据权利要求6的方法所获得的大分子单体和接枝共聚物。
8、权利要求7的大分子单体和接枝共聚物作为改性热塑材料,含硅高聚物混合料的相容性介体、或在高聚物混合料中的硅成份中的应用。
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DEP4426832.7 | 1994-07-28 | ||
DE4426832A DE4426832A1 (de) | 1994-07-28 | 1994-07-28 | Organosilan- und Organopolysiloxan-Radikalinitiatoren und damit herstellbare Makromonomere und Pfropfcopolymerisate |
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CN1116633A true CN1116633A (zh) | 1996-02-14 |
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US (1) | US5705589A (zh) |
EP (1) | EP0696608B1 (zh) |
JP (1) | JP2793149B2 (zh) |
CN (1) | CN1116633A (zh) |
AT (1) | ATE146202T1 (zh) |
CA (1) | CA2154331A1 (zh) |
DE (2) | DE4426832A1 (zh) |
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CN115558419A (zh) * | 2022-10-28 | 2023-01-03 | 西安长峰机电研究所 | 一种光固化复合型环氧氟硅树脂涂料及其制备和涂层制备方法 |
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DE10232993A1 (de) * | 2002-07-19 | 2004-02-05 | Wacker Polymer Systems Gmbh & Co. Kg | Silicon-haltige Polymerisate von ehtylenisch ungesättigten Monomeren |
DE102006037270A1 (de) * | 2006-08-09 | 2008-02-14 | Wacker Chemie Ag | Selbstdispergierbare Silikoncopolymerisate und Verfahren zu deren Herstellung und deren Verwendung |
DE102006037271A1 (de) * | 2006-08-09 | 2008-02-14 | Wacker Chemie Ag | Vernetzbare reaktive Silikonorganocopolymere sowie Verfahren zu deren Herstellung und deren Verwendung |
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US4316041A (en) * | 1980-02-19 | 1982-02-16 | Union Carbide Corporation | Liquid crystal silanes |
DE3226091C2 (de) * | 1982-07-13 | 1986-11-20 | Degussa Ag, 6000 Frankfurt | Polymere Di-, Tri- oder Tetrasulfide, Verfahren zu ihrer Herstellung und Verwendung |
JPH0647620B2 (ja) * | 1987-02-02 | 1994-06-22 | 東レ・ダウコーニング・シリコーン株式会社 | ジオルガノポリシロキサン・アゾベンゼン交互共重合体およびその製造方法 |
GB2209169B (en) * | 1987-04-07 | 1991-04-24 | Plessey Co Plc | Siloxane polymers exibiting non-linear optical properties |
DE3808430A1 (de) * | 1988-03-14 | 1989-09-28 | Consortium Elektrochem Ind | Fluessigkristalline polymere mit chromophoren seitengruppen |
JP3126772B2 (ja) * | 1991-10-29 | 2001-01-22 | ジェイエスアール株式会社 | 熱可塑性樹脂の製造方法 |
-
1994
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1995
- 1995-07-12 US US08/501,750 patent/US5705589A/en not_active Expired - Fee Related
- 1995-07-20 CA CA002154331A patent/CA2154331A1/en not_active Abandoned
- 1995-07-25 JP JP7189332A patent/JP2793149B2/ja not_active Expired - Lifetime
- 1995-07-27 AT AT95111817T patent/ATE146202T1/de not_active IP Right Cessation
- 1995-07-27 EP EP95111817A patent/EP0696608B1/de not_active Expired - Lifetime
- 1995-07-27 DE DE59500063T patent/DE59500063D1/de not_active Expired - Fee Related
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CN115558419A (zh) * | 2022-10-28 | 2023-01-03 | 西安长峰机电研究所 | 一种光固化复合型环氧氟硅树脂涂料及其制备和涂层制备方法 |
CN115558419B (zh) * | 2022-10-28 | 2023-07-21 | 西安长峰机电研究所 | 一种光固化复合型环氧氟硅树脂涂料及其制备和涂层制备方法 |
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JPH0859836A (ja) | 1996-03-05 |
DE59500063D1 (de) | 1997-01-23 |
DE4426832A1 (de) | 1996-02-01 |
JP2793149B2 (ja) | 1998-09-03 |
ATE146202T1 (de) | 1996-12-15 |
EP0696608A1 (de) | 1996-02-14 |
US5705589A (en) | 1998-01-06 |
EP0696608B1 (de) | 1996-12-11 |
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