CN1467212A - 聚二有机硅氧烷的制备 - Google Patents
聚二有机硅氧烷的制备 Download PDFInfo
- Publication number
- CN1467212A CN1467212A CNA031372813A CN03137281A CN1467212A CN 1467212 A CN1467212 A CN 1467212A CN A031372813 A CNA031372813 A CN A031372813A CN 03137281 A CN03137281 A CN 03137281A CN 1467212 A CN1467212 A CN 1467212A
- Authority
- CN
- China
- Prior art keywords
- cyclotrisiloxane
- organic
- catalyst system
- system therefor
- alcohol
- 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
Links
- 238000002360 preparation method Methods 0.000 title description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 claims description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 235000015320 potassium carbonate Nutrition 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 2
- 229930195733 hydrocarbon Natural products 0.000 abstract 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 150000005323 carbonate salts Chemical class 0.000 abstract 1
- -1 chloro- Chemical class 0.000 description 47
- 239000000203 mixture Substances 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000012230 colorless oil Substances 0.000 description 4
- 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 4
- 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 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000001254 matrix assisted laser desorption--ionisation time-of-flight mass spectrum Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000002769 thiazolinyl group Chemical group 0.000 description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 125000006043 5-hexenyl group Chemical group 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 125000005041 acyloxyalkyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000002521 alkyl halide group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 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 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
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 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 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 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 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 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 2
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 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
- 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 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- FMCGSUUBYTWNDP-ONGXEEELSA-N (1R,2S)-2-(dimethylamino)-1-phenyl-1-propanol Chemical compound CN(C)[C@@H](C)[C@H](O)C1=CC=CC=C1 FMCGSUUBYTWNDP-ONGXEEELSA-N 0.000 description 1
- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KMPBCFZCRNKXSA-UHFFFAOYSA-N 2,2,4,4,6,6-hexaethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound CC[Si]1(CC)O[Si](CC)(CC)O[Si](CC)(CC)O1 KMPBCFZCRNKXSA-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 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
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- JOXCDOKKASTCHR-UHFFFAOYSA-N [Si](O)(O)(O)O.[P] Chemical compound [Si](O)(O)(O)O.[P] JOXCDOKKASTCHR-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical class OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 125000005353 silylalkyl group Chemical group 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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Abstract
一种用于制备以下通式(I)的聚二有机硅氧烷的方法,R1-(OSiR2)nOH(I)。该方法是在有碳酸盐作为催化剂存在的情况下,使以下通式(II)的六有机环三硅氧烷,(R2SiO)3(II)与以下通式(III)的醇反应,R1-OH(III)。其中R是相同或不同的且是单价的、任选取代的烃基,R1是单价的、任选取代的烃基,以及n是至少为3的整数。
Description
技术领域
本发明涉及一种用于制备聚二有机硅氧烷的方法,其中每个聚二有机硅氧烷在一个分子链端具有与硅成键的羟基并在另一分子链端具有与硅成键、任选取代的烷氧基。
背景技术
DE-C 4234959(Th.Goldschmidt AG)描述了用烷氧化锂实施六甲基环三硅氧烷的开环聚合及利用氯-、溴-或酰氧基硅烷以终止反应。就安全而言,问题在于由适当醇与金属锂制备烷氧化锂及利用容易生成过氧化物的醚类作为溶剂,即可形成非挥发性过氧化物。再者,烷氧化锂因极易水解而使成本高且不便。
US-A 3,445,426(Dow Corning Corporation)公开了在五配位硅催化剂、或碱金属硅酸盐、硅酸铵或硅酸磷以催化剂量存在的情况下六有机环三硅氧烷的聚合。然而,这些催化剂的缺点是制造昂贵且不方便以及对湿度极敏感。开环聚合作用所用的特定引发剂是醇结合水,总是导致生成聚合物混合物,即OH末端聚合物及单烷氧基末端聚合物。
发明内容
本发明的目的是提供一种用于制备聚二有机硅氧烷的方法,其避免上述缺点且容许使用不敏感的、容易获得的催化剂及极少量几乎不会引发安全问题的溶剂。本发明可达成此目的。
本发明提供一种制备以下通式(I)的聚二有机硅氧烷的方法:
R1-(OSiR2)nOH (I)
其是在有碳酸盐作为催化剂存在的情况下,通过以下反应实现的。即,使通式(II)的六有机环三硅氧烷与通式(III)的醇反应:
(R2SiO)3 (II)
R1-OH (III)
其中每个R是相同或不同的且是单价的、任选取代的烃基,
R1是单价、任选取代的烃基及
n是至少为3的整数。
每个R基优选为每个基具有1至18个碳原子的单价的、任选取代的烃基。
每个R1基优选为具有1至18个碳原子的单价的、任选取代的烃基。
n优选为3至999的整数,更优选6至200,特别优选9至100。
具体实施方式
烃基R的实例包含烷基如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基及叔戊基、己基如正己基、庚基如正庚基、辛基如正辛基及异辛基、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;烯基如乙烯基、烯丙基、5-己烯基及10-十一碳烯基;环烷基如环戊基、环己基、环庚基及甲基环己基;芳烃基如苯基及萘基;烷芳基如邻、间、对甲苯基、二甲苯基及乙苯基;芳烷基如苄基、以及α-及β-苯乙基。
R基可以是每个基具有1至18个碳原子的单价的取代的烃基。取代的烃基R优选为卤化烃基或含有一个或多个分离氧原子的烃基。这些氧原子优选经由亚烃基桥相连。
取代的烃基R的实例包含卤烷基如3-氯丙基、3,3,3-三氟正丙基、2,2,2,2′,2′,2′-六氟异丙基、七氟异丙基;卤芳基如邻、间、对氯苯基;以及酰氧烷基如乙酰氧乙基及(甲基)丙烯酰氧丙基。
烃基R1的实例包含烷基如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基及叔戊基、己基如正己基、庚基如正庚基、辛基如正辛基及异辛基如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;烯基如烯丙基、5-己烯基及10-十一碳烯基;环烷基如环戊基、环己基、环庚基及甲基环己基;以及芳烃基如苄基、及α-及β-苯乙基。
R1基可是每个基具有1至18个碳原子的单价的取代的烃基。取代的烃基R1优选是含有一个或多个选自以下组中的分离的杂原子的单价烃基:氧、硫、氮、磷及硅,并优选归于以下化合物类:羧酸衍生物、磷酸衍生物、硫醇衍生物、氨基衍生物、腈衍生物、甲硅烷氧基衍生物及(聚)醚衍生物。
取代的烃基R1的实例包括卤烷基如3,3,3-三氟正丙基、2,2,2,2′,2′,2′-六氟异丙基、七氟异丙基;甲硅烷基烷基如三甲基甲硅烷基甲基;酰氧基烷基如2-丙烯酰氧乙基、3-甲基丙烯酰氧丙基或2-(2-丙烯酰氧乙氧基)乙基以及以亚乙氧基数目不同加以区别的低聚物;烷氧基烷基如2-甲氧基乙基、2-(2-甲氧基乙氧基)乙基以及以亚乙氧基数目不同加以区别的低聚物:乙烯基氧烷基如4-乙烯基氧-1-丁基(H2C=CH-O-(CH2)4-)、4-(乙烯基氧甲基)环己基-1-甲基(H2C=CH-O-CH2-(1,4)-C6H10-CH2-)、2-(2-乙烯基氧乙氧基)-1-乙基(H2C=CH-O-CH2CH2-O-CH2CH2-);由巯基-SH取代的烃基如2-巯基-1-乙基(HS-CH2CH2-)、1-巯基-2-丙基(HS-CH2(H3C)CH-);由氰基-CN取代的烃基如2-氰基-1-乙基(NC-(CH2)3-);由-C(=O)基取代的烃基如2-氧代-1-丙基(H3C-C(=O)CH2-);由式-NR2 3(其中R2是氢原子或C1至C10烃基)的氨基取代的烃基如2-N,N-二甲氨基-1-乙基((H3C)2N-(CH2)、3-N,N-二甲氨基-1-丙基((H3C)2N-(CH2)3-)及3-N,N-二甲氨基-2-丙基((H3C)2NCH2(CH3)CH-);以及具有光引发剂功能的基团如-CH2CH2-O-p-C6H4-C(=O)-C(CH3)2-OH(“Irgacure 2959”);或具有杂环的基团如3,4-二氢-2H-吡喃基-2-甲基-1-基、(2-呋喃基)-1-甲基、2-吗啉代-1-乙基、2-哌啶子基-1-乙基、2-吡咯烷基(Pyrrolidino)-1-乙基;手性有机基如(1R,2S)-(-)-2-二甲氨基-1-苯基-1-丙基(源自(-)-N-甲基麻黄碱)、((R)-(+)-2-呋喃基)-2-乙基;手性或外消旋羟基羧酸酯衍生物,例如,乳酸衍生物,如:
L-(-)H3C-(CH2)3-OOC-(H3C)HC-、
L-(-)H3C-CH2-OOC-(H3C)HC-、
D-(+)(H3C)3C-OOC-(H3C)HC-;
具有以下通式的聚醚基:
H2C=CR2-CmH2m-[(OC2H4)x(OC3H6)y(OC4H8)]-(无规或嵌段分布),其中,R2是氢原子或烷基,m、x、y及z各自是0或整数(其中x+y+z>0),条件是本发明方法所用式(III)的对应醇在40℃温度仍是液体,且x、y及z优选各自是0或1至20的整数,R优选是氢原子或甲基且m优选是0或1至9的整数;
H2C=CR2-CO-[(OC2H4)x(OC3H6)y]-(无规或嵌段分布)其中,R2是氢原子或烷基,x及y各自是0或整数(其中x+y>0),条件是本发明方法所用式(III)的对应醇在40℃温度仍是液体,且x及y优选各自为0或1至20的整数;
R3-[(OC2H4)x(OC3H6)y(OC4H8)z]-(无规或嵌段分布)其中R3是烷基或酰基,优选C1-C4烷基或乙酰基,x、y及z各自是0或整数(其中x+y+z>0),条件是本发明方法所用式(III)的对应醇在40℃温度仍是液体,且优选x、y及z各自是0或1至20的整数。
R优选为烷基,更优选为甲基。
R1优选为烷基、烯基或取代的烃基,更优选为乙基、正丙基、异丙基、正丁基或异丁基。
本发明的有机(聚)硅氧烷的实例是下式的有机(聚)硅氧烷:
(H3C)2CH-CH2-(OSiMe2)n-OH
H3C-(CH2)2-(OSiMe2)n-OH
(H3C)2CH-(OSiMe2)n-OH
H3C-CH2-(OSiMe2)n-OH
H3C-(OSiMe2)n-OH
H2C=CH-CH2-(OSiMe2)n-OH
H2C=CH-(CH2)9-(OSiMe2)n-OH
H2C=CH-C(O)O-CH2-CH2-(OSiMe2)n-OH
H2C=CH-C(O)-(OC2H4)2-(OSiMe2)n-OH
(H3C)3Si-CH2-(OSiMe2)n-OH
L-(-)H3C-CH2-OOC-(H3C)HC-(OSiMe2)n-OH
H2C=CH-O-(CH2)4-(OSiMe2)n-OH
H2C-C(=O)CH2-(OSiMe2)n-OH
(H3C)2N-(CH2)2-(OSiMe2)n-OH
CH2=CHCH2-[(OC2H4)20(OC3H6)20]-[OSi(CH3)2]n-OH
HS-CH2CH2-(OSiMe2)n-OH
其中Me是甲基且n限定如上。
本发明有机(聚)硅氧烷优选在25℃的粘度为4毫帕斯卡·秒至9×105毫帕斯卡·秒。
本发明方法所用六有机环三硅氧烷(II)的实例是六甲基环三硅氧烷、六乙基环三硅氧烷、1,3,5-三甲基-1,3,5-三乙基环-2,4,6-三硅氧烷及1,3,5-三甲基-1,3,5-三(3,3,3-三氟丙基)环-2,4,6-三硅氧烷。
本发明方法所用六有机环三硅氧烷(II)优选为六甲基环三硅氧烷(以下简称“D3”)。
本发明方法所用催化剂优选为结合于载体材料上的碳酸盐。
本发明方法所用催化剂优选为碱金属碳酸盐、或结合于载体材料上的碱金属碳酸盐。
本发明方法所用催化剂可以为单一型或由至少两种不同类型该等催化剂所形成的混合物。
碱金属碳酸盐的实例包含碳酸钾及碳酸铯,并且优选碳酸钾。
载体材料的实例包括氧化铝、二氧化钛、氧化锆、沸石、硅胶、硅藻土及离子交换树脂,并且优选氧化铝。
本发明方法特别优选使用碳酸钾,尤其优选结合至氧化铝上的碳酸钾。
例如,通过烘干磨碎在一起的氧化铝与碳酸钾的混合物以蒸发氧化铝与碳酸钾在水中的混合物,或在碳酸钾存在的情况下水解三异丙氧化铝、四异丙氧化锆或四异丙氧化钛来制备结合至载体材料上的碳酸钾。
本发明方法的优点是所用催化剂容易获得且在空气中的处理工作简单。依照本发明方法、用本发明催化剂、即在多相催化的情况下制备有机(聚)硅氧烷还具有所用固体催化剂可例如通过简单过滤容易地自反应混合物中除去的优点。
在本发明方法中,以所用六有机环三硅氧烷的总重量为基准,催化剂的使用量优选为0.01至1重量%,更优选为0.1至0.5重量%。
在本发明方法中,所制备的有机(聚)硅氧烷分子链端处的烷氧基是经由所用醇(III)引入。优选使用乙醇、正丙醇、异丙醇、正丁醇或异丁醇。
本发明方法所用六有机环三硅氧烷(II)对醇(III)的比值可决定产物的平均链长。由于动力学效应,为达成某一平均链长,所用六有机环三硅氧烷对醇的比值可需要与理论上化学计量值有所差异而使用超量的六有机环三硅氧烷或醇。最佳比值可由预先实验加以测定。以1摩尔醇(III)为基准,六有机环三硅氧烷(II)的使用量优选为0.1至333摩尔,更优选0.1至10摩尔。
为增加该反应的选择性,本发明方法可在极性的非质子有机溶剂、任选与非极性溶剂形成混合物存在下实施。极性的非质子有机溶剂的实例包括丙酮、甲基异丁基酮(MIBK)、甲基乙基酮(MEK)、二甲基甲酰胺、二甲亚砜、乙腈、四氢呋喃、乙醚、二丁醚、甲基叔丁基醚、二乙二醇二甲醚、聚乙二醇二甲醚、乙酸正丁酯及乙酸乙酯。非极性溶剂的实例包括甲苯、二甲苯、环己烷、甲基环己烷、庚烷及硅氧烷如八甲基环四硅氧烷、十甲基环五硅氧烷、六甲基二硅氧烷或八甲基三硅氧烷。
视所用包括碳酸根的催化剂类型而定,以醇与六有机环三硅氧烷的总重量为基准,极性、非质子有机溶剂的使用量优选为0-50重量%,更优选5至30重量%,特别优选5至20重量%。
为达成反应混合物的较佳均匀化,总是以醇与六有机环三硅氧烷的总重量为基准,非极性有机溶剂的使用量可以为0-80重量%,优选50-70重量%。
为增加该反应的选择性和/或速率,本发明方法中可使用不同溶剂的混合物。
反应终止之后,通常是通过蒸馏除去溶剂。然而,如果本发明的聚硅氧烷需要在溶液内进一步加工,可省略将溶剂除去。视用途而定,在此情况下也可使用不能再用蒸馏方式除去的高沸点液体如聚二甲基硅氧烷作溶剂。
为增加反应的选择性和/或速率,在本发明的方法内也可使用以下组中的相转移催化剂:季铵盐如苄基三乙基氯化铵,冠醚如18-冠-6、1,4,7,10,13-六氧环十八烷或聚乙二醇二甲醚,或叔胺如4-二甲氨基吡啶、N,N-二甲基环己胺或1,4-二氮二环[2,2,2]辛烷。
为清除微量水分,本发明方法内也可有利地使用干燥剂如沸石、无水硫酸钠或无水硫酸镁。
当使用溶剂时,虽然本发明方法也可在较低温度下实施,但优选在所用反应物熔点以上的温度实施为佳,更优选60℃至80℃的温度。
虽然也可能使用较高或较低的压力,本发明方法的实施最好在环境压力下,即在的1020百帕斯卡(绝对)的压力下。
视所用反应温度、反应物及溶剂的类型及数量而定,本发明方法内的反应时间优选0.25至48小时。通过冷却至室温和/或过滤可在未完全转化时将反应终止。通过添加酸如乙酸、甲酸、2-乙基己酸或磷酸也可终止该反应。催化剂的制备
将10.1克(0.1摩尔)氧化铝(由Merck得到)与6.9克(0.1摩尔)无水碳酸钾(由Merck得到)混合、研磨并在200℃温度下加热24小时。将该粉末储存在密封的玻璃容器内。
实施例1
将222克(1摩尔)六甲基环三硅氧烷、96.2克(1.6摩尔)2-丙醇p.a.(由Merck得到)及20克的0.4纳米分子筛(由Merck得到)所形成的混合物加热至60℃并与1克催化剂(其制备方法如以上所述)在46.4%克(0.8摩尔)丙酮p.a.(由Merck得到)中的悬浮液加以混合。在60℃温度下将该混合物搅拌4小时并通过硅胶60(由Merck得到)过滤,在40℃及5毫巴的旋转蒸发器内将该滤液浓缩。制得241.6克透明的、无色油状物,依照29Si NMR谱及MALDI-TOF质谱所得结果,该油状物对应于下式的聚硅氧烷:
(CH3)2CH-[OSi(CH3)2]44-OH实施例2
将222克(1摩尔)六甲基环三硅氧烷、36.8克(0.8摩尔)乙醇(由Merck得到)及20克的0.4纳米分子筛(由Merck得到)的混合物加热至50℃并与1克催化剂(其制备方法如以上所述)及0.3克(0.0013摩尔)苄基三乙基氯化铵(由Merck得到)在56.4克(0.6摩尔)二甲亚砜(由Merck得到)内的悬浮液加以混合。在50℃温度下将该混合物搅拌4小时并通过硅胶60(由Merck得到)过滤,在50℃及5毫巴的旋转蒸发器内,将该滤液浓缩,利用分液漏斗将分离的二甲亚砜除去。制得234克透明的、无色油状物,依照29Si-NMR谱及MALDI-TOF质谱所得结果,该油状物对应于下式的聚硅氧烷:
C2H5-[OSi(CH3)2]15-OH实施例3
将111克(0.5摩尔)六甲基环三硅氧烷及26克(0.2摩尔)甲基丙烯酸2-羟乙酯(由Merck得到)的混合物加热至50℃并与0.5克催化剂(其制备方法如以上所述)在23.2克(0.4摩尔)丙酮(由Merck得到)内的悬浮液加以混合。在50℃将该混合物搅拌120分钟,并通过硅胶60(由Merck得到)过滤,在100℃及5毫巴的旋转蒸发器内将该滤液浓缩。制得121克透明的、无色油状物,依照29Si-NMR谱,该油状物对应于下式的聚硅氧烷:
CH2=C(CH3)-C(O)O-C2H4-[OSi(CH3)2]12-OH实施例4
将111克(0.5摩尔)六甲基环三硅氧烷、23.2克(0.4摩尔)烯丙醇(由Merck得到)及88.8克(0.3摩尔)八甲基环四硅氧烷的混合物加热至80℃并与0.5克催化剂(其制备方法如以上所述)在23.2克(0.4摩尔)丙酮(由Merck得到)中的悬浮液加以混合。在80℃将该混合物搅拌5小时,并通过硅胶60(由Merck得到)过滤,并在60℃及5毫巴的旋转蒸发器内将该滤液浓缩。制得118克油状物,依照29Si-NMR谱及MALDI-TOF质谱所得结果,该油状物对应于下式的聚硅氧烷:
CH2=CHCH2-[OSi(CH3)2]14-OH实施例5
将111克(0.5摩尔)六甲基环三硅氧烷及29.6克(0.4摩尔)2-甲基-1-丙醇(由Merck得到)的混合物加热至60℃并与0.5克无水碳酸钾(由Merck得到)在23.2克(0.4摩尔)丙酮p.a.(由Merck得到)所形成的悬浮液加以混合。在60℃将该混合物搅拌120分钟并通过硅胶60(由Merck得到)过滤,在40℃及5毫巴的旋转蒸发器内将该滤液浓缩。制得124克透明的、无色油状物,依照29Si-NMR谱及MALDI-TOF质谱所得结果,该油状物对应于下式的聚硅氧烷:
(CH3)2CHCH2-[OSi(CH3)2]22-OH
Claims (13)
1.一种用于制备以下通式(I)的聚二有机硅氧烷的方法,
R1-(OSiR2)nOH (I)
该方法是在有碳酸盐作为催化剂存在的情况下,使以下通式(II)的六有机环三硅氧烷,
(R2SiO)3 (II)
与以下通式(III)的醇反应,
R1-OH (III)
其中R是相同或不同的且是单价的、任选取代的烃基,
R1是单价的、任选取代的烃基,以及
n是至少为3的整数。
2.如权利要求1的方法,其中所述反应在极性的、非质子有机溶剂存在下实施。
3.如权利要求1或2的方法,其中所用催化剂为结合至载体材料上的碳酸盐。
4.如权利要求1或2的方法,其中所用催化剂为碱金属碳酸盐。
5.如权利要求1或2的方法,其中所用催化剂为结合至载体材料上的碱金属碳酸盐。
6.如权利要求1或2的方法,其中所用催化剂为碳酸钾。
7.如权利要求1或2的方法,其中所用催化剂为结合至载体材料上的碳酸钾。
8.如权利要求1或2的方法,其中所用催化剂为结合至氧化铝上的碳酸钾。
9.如权利要求1-8之一的方法,其中也使用非极性有机溶剂。
10.如权利要求1-9之一的方法,其中所述六有机环三硅氧烷(II)的使用量为每摩尔醇(III)0.1至333摩尔。
11.如权利要求1-10之一的方法,其中以所用六有机环三硅氧烷(II)的总重量为基准,所述催化剂的使用量为0.01至1重量%。
12.如权利要求1-11之一的方法,其中所用六有机环三硅氧烷(II)为六甲基环三硅氧烷。
13.如权利要求1-12之一的方法,其中所用醇(III)为乙醇、正丙醇、异丙醇、正丁醇或异丁醇。
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EP (1) | EP1369449B1 (zh) |
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US20040256242A1 (en) * | 2003-06-17 | 2004-12-23 | Melody Brian John | Method of anodizing valve metal derived anode bodies and electrolyte therefore |
DE102005022856A1 (de) * | 2005-05-18 | 2006-11-23 | Wacker Chemie Ag | Verfahren zur Herstellung von Diorganopolysiloxanen |
US8329761B2 (en) * | 2006-02-13 | 2012-12-11 | Eastman Kodak Company | Oil-in-oil emulsions |
DE102007046736A1 (de) | 2007-09-28 | 2009-04-02 | Evonik Goldschmidt Gmbh | Verwendung linearer Siloxane und Verfahren zu deren Herstellung |
ES2909196T3 (es) * | 2018-07-27 | 2022-05-05 | Henkel Ag & Co Kgaa | Proceso para la preparación de poliorganosiloxanos |
US11931673B2 (en) | 2018-11-28 | 2024-03-19 | Wacker Chemie Ag | Defoaming formulations containing organopolysiloxanes |
EP3887016B1 (de) | 2018-11-28 | 2022-06-15 | Wacker Chemie AG | Entschäumerformulierungen enthaltend organopolysiloxane |
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US2634252A (en) * | 1949-05-25 | 1953-04-07 | Dow Corning | Method of polymerizing organosiloxanes with alkoxides and alcohol-hydroxide complexes |
US2744923A (en) * | 1951-06-22 | 1956-05-08 | Union Carbide & Carbon Corp | Preparation of organopolysiloxanes |
US3146251A (en) * | 1961-07-31 | 1964-08-25 | Dow Corning | Preparation of linear siloxanes |
US3445426A (en) * | 1966-08-22 | 1969-05-20 | Dow Corning | Pentavalent silane and tetravalent boron catecholates as polymerization catalysts |
GB1217335A (en) * | 1967-04-10 | 1970-12-31 | Midland Silicones Ltd | Polymerisation of siloxanes |
US3799967A (en) * | 1971-10-08 | 1974-03-26 | Lilly Co Eli | Synthetic prostaglandins |
BE793513A (fr) * | 1971-12-30 | 1973-06-29 | Stauffer Chemical Co | Alcoxysiloxanols |
US4113690A (en) * | 1971-12-30 | 1978-09-12 | Sws Silicones Corporation | Silicone elastomers containing alkoxysiloxanols |
JP2842443B2 (ja) * | 1988-09-30 | 1999-01-06 | 東レ・ダウコーニング・シリコーン株式会社 | 片方の末端に重合性官能基を有するオルガノポリシロキサンの製造方法 |
US5329034A (en) * | 1990-08-09 | 1994-07-12 | Sagami Chemical Research Center | Silanol compounds, polymerizable monomers and polymers having mesogenic groups |
GB9105372D0 (en) | 1991-03-14 | 1991-05-01 | Dow Corning Sa | Method of making siloxane compositions |
DE4234959C1 (de) * | 1992-10-16 | 1994-04-07 | Goldschmidt Ag Th | Organopolysiloxane mit einer endständigen Alkoxygruppe und einer am anderen Kettenende befindlichen weiteren funktionellen Gruppe sowie Verfahren zu ihrer Herstellung |
JP3414446B2 (ja) * | 1993-07-23 | 2003-06-09 | 財団法人相模中央化学研究所 | ヒドロキシシリル基を末端に有するポリオキシエチレン化合物、四級塩を末端に有するブロック共重合体、および経皮吸収促進剤 |
GB9703552D0 (en) * | 1997-02-20 | 1997-04-09 | Dow Corning | Polymerisation of cyclosiloxanes in the presence of fillers |
US6037486A (en) * | 1997-12-08 | 2000-03-14 | General Electric Company | Cracking of fluorosilicones to produce 1,3, 5-tris (3,3,3-trifluoropropyl)-1,3,5-trimethylcyclotrisiloxane |
JP4949550B2 (ja) * | 2000-12-11 | 2012-06-13 | 信越化学工業株式会社 | 化粧料 |
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