CN1264404A - 可通过去醇以制成弹性体的可交联有机聚硅氧烷材料 - Google Patents
可通过去醇以制成弹性体的可交联有机聚硅氧烷材料 Download PDFInfo
- Publication number
- CN1264404A CN1264404A CN98807401A CN98807401A CN1264404A CN 1264404 A CN1264404 A CN 1264404A CN 98807401 A CN98807401 A CN 98807401A CN 98807401 A CN98807401 A CN 98807401A CN 1264404 A CN1264404 A CN 1264404A
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- CN
- China
- Prior art keywords
- acid
- group
- organopolysiloxane
- weight part
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 38
- 229920001971 elastomer Polymers 0.000 title description 2
- 239000000806 elastomer Substances 0.000 title description 2
- 150000001298 alcohols Chemical class 0.000 title 1
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 30
- 239000007848 Bronsted acid Substances 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 239000002841 Lewis acid Substances 0.000 claims abstract description 10
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 10
- -1 siloxanes Chemical class 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052794 bromium Inorganic materials 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- 239000011737 fluorine Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 229910000765 intermetallic Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 125000003110 organyloxy group Chemical group 0.000 abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 abstract 1
- 125000001302 tertiary amino group Chemical group 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 35
- 239000002585 base Substances 0.000 description 26
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 21
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 21
- 239000004205 dimethyl polysiloxane Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 14
- 239000011593 sulfur Substances 0.000 description 14
- 239000000945 filler Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000002209 hydrophobic effect Effects 0.000 description 11
- 238000000197 pyrolysis Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- ZRXHQNQYIKVKNQ-UHFFFAOYSA-N 2-ethylhexanoic acid;zinc Chemical compound [Zn].CCCCC(CC)C(O)=O ZRXHQNQYIKVKNQ-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- 208000034189 Sclerosis Diseases 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 210000000981 epithelium Anatomy 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
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- 230000009849 deactivation Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- UOBRDZDWGZDBST-UHFFFAOYSA-N dibutyltin;oxalic acid Chemical compound OC(=O)C(O)=O.CCCC[Sn]CCCC UOBRDZDWGZDBST-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
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- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000206 moulding compound Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 229920002239 polyacrylonitrile Polymers 0.000 description 1
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- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
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Abstract
本发明涉及一种生产由有机基氧基封端的有机聚硅氧烷的方法,其中,(A)羟基封端的有机聚硅氧烷与(B)具有至少两个烷氧基硅烷及含有至少一个通过二价C1-C12烃基连接到硅原子上的仲或叔氨基的基团,在有(C)布朗斯台德酸或路易斯酸存在的情况下进行反应,还涉及包含该反应产物并以带有有机基氧基端基的有机聚硅氧烷作为主要成分的烷氧基室温硫化-1材料。
Description
本发明涉及通过含有端羟基的有机聚硅氧烷与一种含仲或叔氨基的烷氧基硅烷在酸存在的情况下反应而制备含有有机基氧基的有机聚硅氧烷的方法,并涉及该反应产物作为烷氧基室温硫化-1组合物的用途。
在本发明的正文中,有机聚硅氧烷一词包含二聚、低聚及多聚硅氧烷。
长久以来,已公知,能在无水分条件下储存的有机聚硅氧烷组合物,当有水分浸入其中时,能在室温下去醇交联以得到所谓的烷氧基室温硫化-1组合物。它们主要包含一种带有有机基氧基端基的有机聚硅氧烷和作为其它组分的带有至少三个可水解基团的交联剂、催化剂以及选择性地含有添加剂。这些烷氧基室温硫化-1体系的优势是,在交联过程中,它们产生无味、中性的生态醇作为解离产物。
带有有机基氧基端基的有机聚硅氧烷是通过带有端羟基的有机聚硅氧烷与烷氧基硅烷反应而制得的。这已经在例如US-A-4942211中提及。这种方法的缺点在于该反应在室温下需几小时。该反应时间在升高温度下明显缩短,但仍是太长以致于必须等到烷氧基室温硫化-1组合物能够用所制得的具有有机基氧基端基的有机聚硅氧烷和其它组分制得。
带HO端基的有机聚硅氧烷与烷氧基硅烷在各种催化剂存在下的反应是公知的。例如在US-A-5196497中,该反应在碱金属氢氧化物存在的情况下实施。然而,该催化剂的去活化作用还需要其它的反应步骤。
本发明是以用尽可能简单的方法制备烷氧基室温硫化-1组合物为目的。
本发明涉及带有有机基氧基端基的有机聚硅氧烷的制备方法,其中,
(A)带有端羟基的有机聚硅氧烷与
(B)具有至少两个烷氧基及含有至少一个通过二价C1-C12烃基连接到硅原子上的仲或叔氨基的基团的烷氧基硅烷,在有
(C)布朗斯台德酸或路易斯酸存在的情况下进行反应。
该方法即使在室温下也选择性地以极高的反应速率进行,以致于组分(A)、(B)和(C)刚混合后,就立即得到带有有机基氧基端基的有机聚硅氧烷,选择性地混入其它组分后,其就可用作烷氧基室温硫化-1组合物。
本方法的另一个优点在于没有副反应发生,例如,在线型有机聚硅氧烷上没有发现有T和Q单元形成。所生成的氨盐不必从反应产物中除去,因为它们在烷氧基室温硫化-1组合物中不会引起麻烦且甚至对硫化速率有加速作用。多余的布朗斯台德或路易斯酸(C)在所制得的带有有机基氧基端基的有机聚硅氧烷中或在烷氧基室温硫化-1组合物中均不会引起麻烦。
具有端羟基的有机聚硅氧烷(A)优选是具有通式(I)的线型α,ω-二羟基聚(二有机硅氧烷)
HO-[R2SiO]m-H (I)
其中,R为一个选择性地由氟、氯、溴、C1-C4烷氧基烷基或氰基取代的单价C1-C8羟基,及
m的值对应于使具有端羟基的有机聚硅氧烷(A)的粘度为0.05至1000Pa.s。
烃基R的实例是:线型及环状的饱和及不饱和烷基,例如:甲基,芳基,例如苯基,烷芳基,例如甲苯基,及芳烷基,例如苄基。
R基优选为具有1至6个碳原子、未经取代的烃基,更优选为甲基。
有机聚硅氧烷(A)在23℃温度下的粘度优选为100至1000000mPa.,更优选为20000至350000mPa.s。
具有通式(II)的烷氧基硅烷优选用作烷氧基硅烷(B),
(R1O)nSiR2 (3-n)R3 (II)
其中,R1和R2分别表示选择性地由氟、氯、溴、C1-C4烷氧基烷基或氰基取代的单价C1-C10烷基,n为2或3,
R3表示具有通式(III)的单价基团,
HpR4 (2-p)N[-R5-NR6]q(CH2)-R5- (III)
R4表示选择性地由氟、氯、溴、C1-C4烷氧基烷基或氰基取代的单价C1-C10烷基,
R5表示选择性地由氟、氯、溴、C1-C4烷氧基烷基或氰基取代的二价C1-C12亚烷基,
R6表示氢基或选择性地由氟、氯、溴、C1-C4烷氧基烷基或氰基取代的单价C1-C10烷基,
P为0或1的值,和
q为0,1,2或3。
R1和R2各自优选为未经取代的C1-C6的烃基,更优选为甲基、乙基及丙基。
R4优选为直链或环状的饱和C1-C10烷基,更优选为C1-C8烷基。
R5优选为直链和支化的饱和C1-C10烷基,更优选为C1-C8烷基。更优选,R5基是未经取代的。
R6优选为氢基并具有R4的优选范围。氢基是特别优选的。
P优选为1。
能够使用的布朗斯台德或路易斯酸(C)的实例是无机酸、羧酸和磺酸,和能够起路易斯酸作用的金属化合物、金属盐、和金属络合盐。路易斯酸的实例是BF3、AlCl3、TiCl3、SnCl4、SO3、PCl5、POCl3、FeCl3和它们的水合物以及ZnCl2。布朗斯台德酸的实例是硼酸、四氟硼酸和硝酸、亚硝酸、磷酸、亚磷酸、次磷酸、酸式磷酸酯、酸式多磷酸酯、硫酸、亚硫酸、过氧化硫酸、盐酸、氢氟酸、氢碘酸、氢溴酸、高氯酸、六氯化磷酸、苯磺酸、对甲苯磺酸、甲磺酸、三氟甲磺酸、和羧酸、例如氯乙酸、三氯乙酸、乙酸、丙烯酸、苯甲酸、三氟乙酸、柠檬酸、丁烯酸、甲酸、富马酸、马来酸、丙二酸、滑食子酸、衣康酸、乳酸、酒石酸、草酸、苯二酸和丁二酸。
与水水解并生成布朗斯台德酸或路易斯酸的化合物也可用在本方法中。在这种情况下,制取布朗斯台德酸所需的水必须在同一时间加入。例如,可使用易水解的羧基硅烷如甲基三乙氧基硅烷或硅氧烷。该水解过程所需的水也可被吸附在固体如填料上。
特别优选的布朗斯台德酸(C)是通式(IV)的酸式磷酸酯
(HO)aOP(-O-R7)(3-a) (IV)
其中,R7表示C3-C50的单价烃基,该单价烃基可选择性由羟基、氟、氯、溴、C1-C10烷氧基烷基或氰基取代并能被一种基团中断、该基团能够从两边键接到碳原子上并选自由-O-,-COO-,-OOC-,-CONR2-,-NR2CO-和-CO-组成的组,
a表示1或2的值。
该通式(IV)的酸式磷酸酯的反应产物对所制得的带有机基氧基端基的有机聚硅氧烷和由它制备的烷氧基室温硫化组合物在储存期间起稳定作用。更具体地说,该烷氧基室温硫化-1组合物的皮膜形成时间实际上保持恒稳定并且抑制了脱色作用。通式(IV)的酸式磷酸酯优选具有表面活性。
烃基R7可以是直链和环状、饱和的及不饱和的、支化和非支链化烷基,芳香基,烷芳基和芳烷基。
优选的烃基R7具有通式(V)
[(CR8 2)b-O]c[(CR9 2)d]o-L-M (V)
其中,R8及R9为一氢基、甲基或羟基,
b及d为2或3,
c为1至15的整数,
o为0或1,
L是一个选自由-O-、-COO-、-OOC-、-CONR2-及-CO-组成的组的基团,且
M是一个选择性地由羟基、氟、氯、溴、C1-C10烷氧基烷基或氰基取代的单价C1-C20烃基,但在任一碳原子上仅有一个R8和R9基可以是一羟基。
c优选表示1至10的整数值。L优选表示-O-基。
M优选表示选择性地由C1-C10烷氧基烷基取代的C1-C20烃基。
通式(V)的具有如下特点的烃基R7是特别优选的,其中R8和R9为一氢基、b和d为2,C为2,3,4或5,L代表-O-基且M代表未经取代的C5-C18烃基。
在通式(I)至(V)中,R1-R9的所有基团和所有指数a,b,c,d,m,n,o,p和q各自独立,可相同或不同。
在所有通式中,硅原子是四价的,例如n+o最多为4。
基于酸基和带有端羟基的有机聚硅氧烷(A)中的羟基,所述布朗斯台德或路易斯酸(C)优选以等当量使用,更优选稍微过量。
相反,烷氧基硅烷(B)优选以相对于化学计量比过量的量添加至带有端羟基的有机聚硅氧烷(A)中。为了使带有端羟基的有机聚硅氧烷(A)与烷氧基硅烷(C)的反应进行得尽可能地完全,相对于每500重量份带有端羟基的有机聚硅氧烷(A)可优选使用1-50重量份烷氧基硅烷(B)。反应中没有反应掉的过量烷氧基硅烷(B)并不是带有机基氧基端基的有机聚硅氧烷和烷氧基室温硫化-1组合物的不利因素,所以可以保留在反应产物中。过量的烷氧基硅烷(B)能够在烷氧基室温硫化-1组合物中作为粘结促进剂。
该反应优选在20-50℃的温度下,更优选在室温下进行。根据使用的烷氧基硅烷(B),反应时间是1-10分钟。
在反应过程中反应速率一方面依赖于所用烷氧基硅烷(B)的反应活性,且另一方面依赖于布朗斯台德或路易斯酸(C)的酸度。
室温下特别优选的反应时间是1-5分钟,这对于以单罐法制备室温硫化-1组合物是特别有利的。
本发明也涉及包含有由上述方法制备的反应产物并以带有有机基氧端基的有机聚硅氧烷为主要成分的室温硫化-1组合物。本发明具体地涉及包含使用通式(IV)的酸式磷酸酯制备的反应产物的烷氧基室温硫化-1组合物。
为了使最终组合物达到改善的储存稳定性,带有有机基氧基端基的有机聚硅氧烷和由其制备的烷氧基室温硫化-1组合物能够被支化羧酸的金属盐稳定,如US-A-4942211中所述。
除了上述的组分外,该烷氧基室温硫化-1组合物还能够包含其它公知组分。
其它能够在烷氧基室温硫化-1组合物的制备过程中优选一同使用的物质是通式(VI)的硅烷或它们的部分水解产物,
R10 uSi(OR11)4-u (VI)
其中,R10和R11表示选择性地由氟、氯、溴、C1-C4烷氧基烷基或氰基取代的C1-C13单价烃基,且u为0,1或2。
R10和R11的优选含义与上面R相同。
通式(VI)的硅烷的部分水解产物是,例如六甲氧基二硅氧烷和六乙氧基二硅氧烷。
能够在烷氧基室温硫化-1组合物的制备过程中优选一同使用的其它物质是双(三烷氧基硅基)C1-C13烷烃,其中烷氧基具有与OR11相同的含义,例如双(三乙氧基硅基)乙烷。
在制备烷氧基室温硫化-1组合物时,亦可使用缩合催化剂、增强型填料、非增强型填料、颜料、可溶性染料、香料、增塑剂例如以三甲基硅氧烷基封端的在室温下呈液态的聚二甲基硅氧烷或磷酸酯、杀菌剂、树脂状有机聚硅氧烷类(包含由(CH3)3SiO1/2单元及SiO4/2单元组成者),纯有机树脂,例如:丙烯腈、苯乙烯、氯乙烯或丙烯的均聚物或共聚物(其中此类纯有机树脂,尤其是苯乙烯与丙烯酸正丁基酯的共聚物,可在每个终端单元具有与Si-键结羟基的二有机聚硅氧烷存在的情况下,通过上述单体的自由基聚合作用以制得),防腐剂、聚乙二醇(可以是已被酯化或醚化)、抗氧剂、热稳定剂、溶剂、影响电学性能的品剂(例如:导电性炭黑)、阻燃剂、光稳定剂及皮膜形成时间延长剂(例如:具有SiC-键结氢硫基烷基硅烷),以及发泡剂(例如:偶氮二甲酰胺)。其他可添加的物质是:粘结促进剂,优选氨基官能硅烷。
优选使用缩合催化剂。根据本发明,该烷氧基室温硫化-1组合物可能包括任何所需的缩合催化剂,目前凡除水后即可长期储存且于室温下遇水即实施交联生成弹性体的组合物中均含有缩合催化剂。
此类缩合催化剂的实例是:锡、锌、锆、钛或铝的有机化合物。在该缩合催化剂中,优选的是:钛酸丁基酯及有机锡化合物,如二乙酸二正丁基锡、二月桂酸正丁基锡、二有机锡二有机酸盐(酯)或它们的低聚物与一种硅烷的反应产物,该硅烷的每个分子具有至少两个可水解的单价烃基,该烃基经由氧与硅键结,且必要时由烷氧基取代,该反应产物内锡原子的价位,由≡SiOSn≡基中的氧原子及/或SnC-键结的单价有机基中获得满足。
该烷氧基室温硫化-1组合物优选包含有填料。填料的实例是:非增强型填料,亦即BET表面积最高为50m2/g的填料,例如:石英、硅藻土、硅酸钙、硅酸锆、沸石、金属氧化物粉末,例如:氧化铝、氧化钛、氧化铁或氧化锌及/或该氧化物的混合物,硫酸钡、碳酸钙、石膏、氮化硅、碳化硅、氮化硼、玻璃粉及塑料粉,例如:聚丙烯腈粉;增强型填料,亦即BET表现积超过50m2/g的填料,例如:热解二氧化硅、沉淀二氧化硅、碳黑,例如:炉黑或乙炔黑,及高BET表面积的硅铝混合氧化物;及纤维型填料,例如:石棉及合成聚合物纤维。
上述填料可经疏水化处理,例如:用有机硅烷及/或硅氧烷或用硬脂酸加以处理,或将羟基加以醚化生成烷氧基。可使用单独一种填料或至少两种填料的混合物。
空气中通常含有的水分即足以使烷氧基室温硫化-1组合物实施交联作用。必要时交联作用亦可在低于或高于室温的温度下实施,例如:-5至10℃,或30至50℃。
所以本发明的烷氧基室温硫化-1组合物极适宜用作例如接缝(包含垂直接缝)、或用作类似狭缝例如建筑物、车辆、船舶或飞机等宽达10至40毫米的内部间隙的密封组合物,或例如在建造门窗、制造展示橱柜中用作粘结剂或油灰,以及用以制造保护性涂料、橡胶弹性异型制品,电机或电子设备的绝缘材料。
除另有说明外,下列实施例中所有百分比数据均系以重量计。此外,所有粘度均是在25℃温度下测得。除另有说明外,下列实施例均系在环境大气压力下(亦即约1000百帕斯卡)、室温(亦即约20℃)下或在室温下无需加热或冷却将反应物结合在一起所产生的温度下实施。实施例实施例1
于23℃下,将500重量份聚二甲基硅氧烷(其每个终端单元具有一个羟基且其在22℃下的粘度为8000mPa.s)与5重量份3-环己氨基丙基三甲氧基硅烷(可从瓦克化学有限公司购得)在一带有真空设备的行星式混合器内混合。然后立即将1.3重量份乙酸(浓缩)添加至该混合物中,将各组分进行混合,并且将300g在端基单元上带有三甲基硅氧基且具有100m2/s粘度(23℃)的聚二甲基硅氧烷、10g 2-乙基己酸锌,80g BET表面积为150m2/g的热解疏水性二氧化硅,40g硅酸四乙酯和1g二正丁氧基双(三乙氧基硅氧基)锡以给定顺序加入。
在真空中实施均匀化后,将该化合物放入防水桶中。经不同时间后取样并测定由此制得的弹性体的物理性能。所得结果如表1中所示。实施例2
步骤与实施例1相似。按下列顺序将下列组分与500重量份的α,ω-二羟基聚有机硅氧烷混合:
300重量份具有-Si(CH3)3端基的聚二甲基硅氧烷,
80重量份BET表面积为150m2/g的热解疏水性二氧化硅,
5.0重量份3-环己氨基丙基三甲氧基硅烷,
3.5重量份甲基三乙氧基硅烷,
40.0重量份乙烯基三甲氧基硅烷与甲基三甲氧基硅烷的1∶1混合物,
3.0重量份二-2-乙基己酸二丁基锡。实施例3
步骤与实施例1相似。将下列组分添加至50重量份具有-Si(CH3)2-OH端基的聚二甲基硅氧烷中:
6.0重量份3-环己氨基丙基三甲氧基硅烷,
2.8重量份2-乙基己酸,
385.0重量份带有-Si(CH3)3端基的聚二甲基硅氧烷,
8.0重量份2-乙基己酸钙,
78.0重量份BET表面积为150m2/g的热解疏水性二氧化硅,
38.0重量份聚乙氧基硅氧烷。实施例4
步骤与实施例1相似。将下列组分混合:
500重量份带有-Si(CH3)2-OH端基的聚二甲基硅氧烷,
2.0重量份磷酸,
5.0重量份3-环己氨基丙基三甲氧基硅烷,
385.0重量份带有-Si(CH3)3端基的聚二甲基硅氧烷,
4.0重量份2-乙基己酸锌,
80.0重量份BET表面积为150m2/g的热解疏水性二氧化硅,
39.0重量份聚乙氧基硅氧烷与1,2-双(三乙氧基硅基)乙烷的1∶1混合物。实施例5
步骤与实施例1相似。将下列组分混合:
500.0重量份带有-Si(CH3)2-OH端基的聚二甲基硅氧烷,
3.5重量份丁氨基丙基三甲氧基硅烷,
1.0重量份乙酸(浓缩),
385.0重量份带有-Si(CH3)3端基的聚二甲基硅氧烷,
4.0重量份2-乙基己酸锌,
85.0重量份BET表面积为150m2/g的热解疏水性二氧化硅,
35.0重量份聚乙氧基硅氧烷。实施例6
步骤与实施例1相似。将下列组分混合:
500.0重量份带有-Si(CH3)2-OH端基的二甲基硅氧烷,
4.0重量份烷氧基化磷酸酯,
8.0重量份3-环己氨基丙基三甲氧基硅烷,
385.0重量份带有-Si(CH3)3端基的聚二甲基硅氧烷,
3.8重量份2-乙基己酸锌,
70.0重量份BET表面积为150m2/g的热解疏水性二氧化硅
30.0重量份聚乙氧基硅氧烷。
所述烷氧基化磷酸酯具有下列化学式:(OH)1PO[(OCH2CH2)3-4-O-(CH2)11-14-CH3]和(OH)2PO[(OCH2CH2)3-4-O-(CH2)11-14-CH3]1
表1机械性能(2mm的薄膜)
对比例1
肖氏A级硬度 | 拉伸强度 | 断裂伸长率 | 抗撕裂传播性 | 拉伸应力 | 皮膜形成时间 | 备注 | ||
实施例 | 硫化前的储存时间 | DIN53505 | DIN53504/S2N/mm2 | DIN53504/S2% | ISO 34方法CN/mm | DIN53504/S2100%伸长率 | ||
1 | 0 | 16 | 0.8 | 300 | 2.0 | 0.28 | 35 | 硫化产物是透明的 |
14天 | 16 | 0.8 | 290 | 1.9 | 0.28 | |||
28天 | 14 | 0.9 | 300 | 1.6 | 0.30 | 70 | 硫化产物是淡黄色的 | |
2 | 0 | 15 | 0.8 | 310 | 1.9 | 0.26 | 30 | 硫化产物是透明的 |
14天 | 13 | 0.8 | 320 | 1.7 | 0.25 | |||
28天 | 11 | 0.9 | 360 | 1.6 | 0.30 | 60 | 硫化产物是淡黄色的 | |
3 | 0 | 15 | 0.9 | 300 | 1.7 | 0.28 | 40 | 硫化产物是透明的 |
14天 | 15 | 1.0 | 260 | 1.7 | 0.28 | |||
28天 | 14 | 0.8 | 240 | 1.5 | 0.30 | 120 | 硫化产物是淡黄色的 | |
4 | 0 | 17 | 1.1 | 340 | 2.3 | 0.38 | 30 | 硫化产物是透明的 |
28天 | 17 | 1.2 | 330 | 2.2 | 0.34 | 60 | 硫化产物是透明的 | |
5 | 0 | 14 | 0.7 | 290 | 1.5 | 0.29 | 45 | 硫化产物是透明的 |
28天 | 13 | 0.7 | 300 | 1.5 | 0.28 | 90 | 硫化产物是淡黄色的 | |
6 | 0 | 16 | 1.0 | 320 | 2.1 | 0.37 | 40 | 硫化产物是透明的 |
28天 | 17 | 1.0 | 330 | 2.3 | 0.37 | 35 | 硫化产物是透明的 | |
56天 | 16 | 0.9 | 305 | 2.0 | 0.35 | 52 | 硫化产物是透明的 | |
84天 | 17 | 1.1 | 280 | 2.1 | 0.34 | 55 | 硫化产物是透明的 |
步骤与实施例1相似。在真空中按下列顺序将下列组分混合:
500.0重量份带有-Si(CH3)2-OH端基的聚二甲基硅氧烷,
385.0重量份带有-Si(CH3)3端基的聚二甲基硅氧烷,
4.0重量份带有β-氨乙基-γ-氨丙基三甲氧基硅烷,
1.2重量份乙酸(浓缩),
31.0重量份聚乙氧基硅氧烷,
70.0重量份BET表面积为150m2/g的热解疏水性二氧化硅,
3.8重量份2-乙基己酸锌。对比例2
步骤与实施例1相似。在真空中按下列顺序将下列组分混合:
500.0重量份带有-Si(CH3)2-OH端基的聚二甲基硅氧烷,
385.0重量份带有-Si(CH3)3端基的聚二甲基硅氧烷,
4.0重量份带有β-氨乙基-γ-氨丙基三甲氧基硅烷,
2.5重量份乙酸(浓缩),
31.0重量份聚乙氧基硅氧烷,
70.0重量份BET表面积为150m2/g的热解疏水性二氧化硅,
3.8重量份2-乙基己酸锌。对比例3
步骤与实施例1相似。在真空中按下列顺序将下列组分混合:
500.0重量份带有-Si(CH3)2-OH端基的聚二甲基硅氧烷,
385.0重量份带有-Si(CH3)3端基的聚二甲基硅氧烷,
4.0重量份带有β-氨乙基-γ-氨丙基三甲氧基硅烷,
5.0重量份乙酸(浓缩),
31.0重量份聚乙氧基硅氧烷,
70.0重量份BET表面积为150m2/g的热解疏水性二氧化硅,
3.8重量份2-乙基己酸锌,对比例4
步骤与实施例1相似。在真空中按下列顺序将下列组分混合:
500.0重量份带有-Si(CH3)2-OH端基的聚二甲基硅氧烷,
300.0重量份带有-Si(CH3)3端基的聚二甲基硅氧烷,
4.5重量份γ-氨丙基三乙氧基硅烷,
3.5重量份甲基三乙氧基硅烷,
80.0重量份BET表面积为150m2/g的热解疏水性二氧化硅,
40.0重量份乙烯基三甲氧基硅烷与甲基三甲氧基硅烷的1∶1混合物,
3.0重量份二-2-乙基乙酸二丁基锡。对比例5
步骤与实施例1相似。在真空中按下列顺序将下列组分混合:
500.0重量份带有-Si(CH3)2-OH端基的聚二甲基硅氧烷,
385.0重量份带有-Si(CH3)3端基的聚二甲基硅氧烷,
3.0重量份γ-氨丙基三甲氧基硅烷,
1.5重量份磷酸,
80.0重量份BET表面积为150m2/g的热解疏水性二氧化硅,
31.0重量份聚乙氧基硅氧烷。
表2对比实验的结果
对比例1 1小时后化合物硬化
对比例2 3小时后化合物硬化
对比例3 22小时后化合物硬化
对比例4 4小时后化合物硬化
对比例5 13小时后化合物硬化
Claims (8)
1、一种带有有机基氧基端基的有机聚硅氧烷的制备方法,其中,
(A)带有端羟基的有机聚硅氧烷与
(B)具有至少两个烷氧基及含有至少一个通过二价C1-C12烃基连接到硅原子上的仲或叔氨基的基团的烷氧基硅烷,在有
(C)布朗斯台德酸或路易斯酸存在的情况下进行反应。
2、根据权利要求1的方法,其中具有端羟基的有机聚硅氧烷(A)优选为具有通式(I)的线型α,ω-二羟基聚(二有机)硅氧烷
HO-[R2SiO]m-H (I)
其中,R为一个选择性地由氟、氯、溴、C1-C4烷氧基烷基或氰基取代的单价C1-C8羟基,及
m的值对应于使具有端羟基的有机聚硅氧烷(A)的粘度为0.05至1000Pa.s。
3、根据权利要求1或2的方法,其中具有通式(II)的烷氧基硅烷优选用作烷氧基硅烷(B),
(R1O)nSiR2 (3-n)R3 (II)
其中,R1和R2分别表示选择性地由氟、氯、溴、C1-C4烷氧基烷基或氰基取代的单价C1-C10烷基,n为2或3,
R3表示具有通式(III)的单价基团,
HpR4 (2-p)N[-R5-NR6]q(CH2)-R5- (III)
R4表示选择性地由氟、氯、溴、C1-C4烷氧基烷基或氰基取代的单价C1-C10烷基,
R5表示选择性地由氟、氯、溴、C1-C4烷氧基烷基或氰基取代的二价C1-C12亚烷基,
R6表示氢基或选择性地由氟、氯、溴、C1-C4烷氧基烷基或氰基取代的单价C1-C10烷基,
P为0或1的值,和
q为0,1,2或3。
4、根据权利要求1-3的方法,其中所述的布朗斯台德或路易斯酸(C)为无机酸、羧酸和磺酸,和能够起路易斯酸作用的金属化合物、金属盐和金属络合盐。
5、根据权利要求1-4的方法,其中将通式(IV)的酸式磷酸酯用作所述酸(C)
(HO)aOP(-O-R7)(3-a) (IV)
其中,R7表示C3-C50的单价烃基,该单价烃基可选择性由羟基、氟、氯、溴、C1-C10烷氧基烷基或氰基取代并能被一种基团中断、该基团能够从两边键接到碳原子上并选自由-O-,-COO-,-OOC-,-CONR2-,-NR2CO-和-CO-组成的组,
a表示1或2的值。
6、根据权利要求5的方法,其中所述烃基R7具有通式(V)
[(CR8 2)b-O]c[(CR9 2)d]o-L-M (V)
其中,R8及R9为一氢基、甲基或羟基,
b及d为2或3,
c为1至15的整数,
o为0或1,
L是一个选自由-O-、-COO-、-OOC-、-CONR2-及-CO-组成的组的基团,且
M是一个选择性地由羟基、氟、氯、溴、C1-C10烷氧基烷基或氰基取代的单价C1-C20烃基,但在任一碳原子上仅有一个R8和R9基可以是一羟基。
7、一种含有由权利要求1-6之一方法制备的反应产物的烷氧基室温硫化-1组合物,其包含有作为主要成分的带有有机基氧基端基的有机聚硅氧烷。
8、根据权利要求7的烷氧基室温硫化-1组合物,其包含有使用权利要求5所述的具有通式(IV)的酸式磷酸酯制得的反应产物。
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DE19733168.8 | 1997-07-31 | ||
DE19733168A DE19733168A1 (de) | 1997-07-31 | 1997-07-31 | Unter Abspaltung von Alkoholen zu Elastomeren vernetzbare Organopolysiloxanmassen |
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US (1) | US6284860B1 (zh) |
EP (1) | EP1000121B1 (zh) |
CN (1) | CN1128847C (zh) |
AU (1) | AU8731398A (zh) |
CA (1) | CA2298655C (zh) |
DE (2) | DE19733168A1 (zh) |
ES (1) | ES2159960T3 (zh) |
WO (1) | WO1999006486A1 (zh) |
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CN104220490A (zh) * | 2012-04-27 | 2014-12-17 | 瓦克化学股份公司 | 制备含氨基基团的有机硅化合物的方法 |
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DE19832686A1 (de) * | 1998-07-21 | 2000-02-03 | Heidelberger Bauchemie Gmbh | Kondensationsvernetzendes Silikon mit hoher Festigkeit |
TW538096B (en) | 1999-06-25 | 2003-06-21 | Shinetsu Chemical Co | Nitrogen atom-containing polysiloxanes, their preparation, and fiber and fabric finishing agent compositions |
JP2001220509A (ja) * | 2000-02-07 | 2001-08-14 | Shin Etsu Chem Co Ltd | 硬化性組成物 |
DE10121514A1 (de) * | 2001-05-03 | 2002-11-14 | Wacker Chemie Gmbh | Unter Abspaltung von Alkoholen aus Alkoxysilylendgruppen zu Elastomeren vernetzbare Massen |
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US20040225079A1 (en) * | 2003-05-05 | 2004-11-11 | Analytical Services And Materials Inc. | Erosion-resistant silicone coatings |
US7033673B2 (en) | 2003-07-25 | 2006-04-25 | Analytical Services & Materials, Inc. | Erosion-resistant silicone coatings for protection of fluid-handling parts |
DE10351804A1 (de) | 2003-11-06 | 2005-06-09 | Wacker-Chemie Gmbh | Verfahren zur Erhöhung der Elastizität von feuchtigkeitsgehärteten Elastomeren |
FR2916970B1 (fr) * | 2007-06-05 | 2010-03-12 | Oreal | Kit comprenant des composes x et y fonctionnalises alpha-alcoxysilane. |
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DE102015207673A1 (de) | 2015-04-27 | 2016-10-27 | Wacker Chemie Ag | Verfahren zur Herstellung von Aminogruppen aufweisenden Organosiliciumverbindungen |
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US4536540A (en) * | 1983-08-02 | 1985-08-20 | General Electric Company | Scavengers for ammonia in RTV compositions |
JPH0639567B2 (ja) * | 1986-05-22 | 1994-05-25 | 東レ・ダウコ−ニング・シリコ−ン株式会社 | 硬化性オルガノポリシロキサン組成物 |
DE3801389A1 (de) | 1988-01-19 | 1989-07-27 | Wacker Chemie Gmbh | Unter abspaltung von alkoholen zu elastomeren vernetzbare organopolysiloxanmassen |
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DE19507416C1 (de) | 1995-03-03 | 1996-09-19 | Bayer Ag | Kondensationsvernetzende Polysiloxanmassen, ein Verfahren zu deren Herstellung sowie deren Verwendung |
-
1997
- 1997-07-31 DE DE19733168A patent/DE19733168A1/de not_active Withdrawn
-
1998
- 1998-07-02 WO PCT/EP1998/004099 patent/WO1999006486A1/de active IP Right Grant
- 1998-07-02 AU AU87313/98A patent/AU8731398A/en not_active Abandoned
- 1998-07-02 ES ES98938683T patent/ES2159960T3/es not_active Expired - Lifetime
- 1998-07-02 CA CA002298655A patent/CA2298655C/en not_active Expired - Fee Related
- 1998-07-02 US US09/463,206 patent/US6284860B1/en not_active Expired - Fee Related
- 1998-07-02 DE DE59800861T patent/DE59800861D1/de not_active Expired - Fee Related
- 1998-07-02 EP EP98938683A patent/EP1000121B1/de not_active Revoked
- 1998-07-02 CN CN98807401A patent/CN1128847C/zh not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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CA2298655C (en) | 2004-11-02 |
WO1999006486A1 (de) | 1999-02-11 |
DE59800861D1 (de) | 2001-07-19 |
EP1000121B1 (de) | 2001-06-13 |
AU8731398A (en) | 1999-02-22 |
ES2159960T3 (es) | 2001-10-16 |
US6284860B1 (en) | 2001-09-04 |
CN1128847C (zh) | 2003-11-26 |
CA2298655A1 (en) | 1999-02-11 |
DE19733168A1 (de) | 1999-02-04 |
EP1000121A1 (de) | 2000-05-17 |
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