CN110709405A - 含苯并噻唑的硅烷及其制备方法和用途 - Google Patents
含苯并噻唑的硅烷及其制备方法和用途 Download PDFInfo
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- CN110709405A CN110709405A CN201880028776.0A CN201880028776A CN110709405A CN 110709405 A CN110709405 A CN 110709405A CN 201880028776 A CN201880028776 A CN 201880028776A CN 110709405 A CN110709405 A CN 110709405A
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- CN
- China
- Prior art keywords
- eto
- benzothiazole
- rubber
- formula
- silane
- Prior art date
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Links
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 49
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title description 7
- 239000000203 mixture Substances 0.000 claims abstract description 67
- 229920001971 elastomer Polymers 0.000 claims abstract description 58
- 239000005060 rubber Substances 0.000 claims abstract description 55
- 150000004756 silanes Chemical class 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- -1 aralkyl radical Chemical class 0.000 description 40
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 150000001408 amides Chemical class 0.000 description 10
- 150000004703 alkoxides Chemical class 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 150000004820 halides Chemical class 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- 150000007944 thiolates Chemical class 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 150000003949 imides Chemical class 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 7
- 150000003568 thioethers Chemical class 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 235000019241 carbon black Nutrition 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 150000003623 transition metal compounds Chemical class 0.000 description 5
- 150000003624 transition metals Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000002318 adhesion promoter Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical group [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 101100243399 Caenorhabditis elegans pept-2 gene Proteins 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- ZMZSYUSDGRJZNT-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)acetonitrile Chemical compound C1=CC=C2SC(CC#N)=NC2=C1 ZMZSYUSDGRJZNT-UHFFFAOYSA-N 0.000 description 1
- JUIQOABNSLTJSW-UHFFFAOYSA-N 2-Methyl-4,5-dihydro-1,3-thiazole Chemical compound CC1=NCCS1 JUIQOABNSLTJSW-UHFFFAOYSA-N 0.000 description 1
- RCZYGYAQDFYEIX-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yldisulfanyl)propyl-triethoxysilane Chemical compound C1=CC=C2SC(SSCCC[Si](OCC)(OCC)OCC)=NC2=C1 RCZYGYAQDFYEIX-UHFFFAOYSA-N 0.000 description 1
- DIGKGWWSMMWBIZ-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]-n,n-bis(trimethylsilyl)propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN([Si](C)(C)C)[Si](C)(C)C DIGKGWWSMMWBIZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000012988 Dithioester Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- CJYKJCNQDDSJER-UHFFFAOYSA-N [SiH4].S1(C=NC2=C1C=CC=C2)=S Chemical class [SiH4].S1(C=NC2=C1C=CC=C2)=S CJYKJCNQDDSJER-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000012965 benzophenone Chemical class 0.000 description 1
- 150000008366 benzophenones Chemical class 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002540 isothiocyanates Chemical class 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
- 239000006233 lamp black Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 125000005358 mercaptoalkyl group Chemical group 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- DRXHEPWCWBIQFJ-UHFFFAOYSA-N methyl(triphenoxy)silane Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(C)OC1=CC=CC=C1 DRXHEPWCWBIQFJ-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- CUPOOAWTRIURFT-UHFFFAOYSA-N thiophene-2-carbonitrile Chemical compound N#CC1=CC=CS1 CUPOOAWTRIURFT-UHFFFAOYSA-N 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical class NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- QHAHOIWVGZZELU-UHFFFAOYSA-N trichloro(trichlorosilyloxy)silane Chemical compound Cl[Si](Cl)(Cl)O[Si](Cl)(Cl)Cl QHAHOIWVGZZELU-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
- 229910052721 tungsten Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
本发明涉及式I的含苯并噻唑的硅烷，
其通过以下方法制备：使式II的含苯并噻唑的硅烷
与式III的化合物R2‑H(III)反应。式I的含苯并噻唑的硅烷可用于橡胶混合物中。
Description
本发明涉及含苯并噻唑的硅烷，及其制备方法和用途。
已知的是硅烷可用作粘合促进剂。例如，氨基烷基三烷氧基硅烷，甲基丙烯酰氧基烷基三烷氧基硅烷，聚硫烷基三烷氧基硅烷和巯基烷基三烷氧基硅烷用作无机材料和有机聚合物之间的粘合促进剂，还用作交联剂和表面改性剂(E.P.Plueddemann,“SilaneCoupling Agents”,2nd Ed.Plenum Press 1982,p.153-181)。
这些粘合促进剂或偶联剂或粘合剂与填料和弹性体形成粘合，从而在填料表面和弹性体之间产生良好的相互作用。
WO2003097734、US6465581和Macromolecules 2002,35,10026-10037公开了式(RO)a(R'O)3-aSi-Z-Sx-Bt的硅烷，其中Bt是苯并噻唑基，该基团导致橡胶混合物具有高的强度。
CN 104045664A、CN 102344462A和103923115A公开了单硫代苯并噻唑硅烷。
O.Klockmann,J.Hahn,H.Scherer,"The Chemistry of Mercapto Silanes",International Rubber Conference 2009,Nuremberg、A.Wehmeier,O.Klockmann,"Solutions for processing challenges with an advanced silica-silane system",180th Technical Meeting of the rubber Division,American Chemical Society 2011,Cleveland,(p.3)、和C.Roeben,"Application of the high performance silane Si363TM in green tire tread compounds",tire technology conference 2015,Cologne(p.5-6)公开了在生产橡胶混合物的过程中形成的具有与二氧化硅偶联的苯并噻唑基的硅烷。
已知的含苯并噻唑的硅烷的缺点是所得生胶混合物的高混合物粘度，这会导致这些混合物的加工特性差。
本发明的一个目的是提供一种含有苯并噻唑的硅烷，与现有技术中已知的具有相同橡胶值曲线的硅烷相比，其具有改进的加工特性。
本发明提供了一种式I的含苯并噻唑的硅烷，
其中R1相同或不同且为R4O-基团，R4为H、甲基、乙基、丙基、C9-C30支化或非支化的一价烷基、烯基、芳基或芳烷基，
其中R2是烷基聚醚基团-O-(R5-O)m-R6，其中R5相同或不同并且是支化或非支化，饱和或不饱和的脂族二价C1-C30烃基，优选CH2-CH2、CH2-CH(CH3)、-CH(CH3)-CH2-、CH2-CH2-CH2或其混合物，m为1至30，优选2至20，更优选2至15，甚至更优选3至10，特别优选4至7，R6是支化或非支化的C1-C30烷基，优选C11-C30烷基，更优选C12-C20烷基，甚至更优选C12至C15烷基，
R3是支化或非支化，饱和或不饱和的脂族、芳族或混合的脂族/芳族二价C1-C30烃基，
x＝2-10，优选2-4，更优选2，和
n＝0、1或2，优选2。
含苯并噻唑的硅烷可以是式I的含苯并噻唑的硅烷的混合物。
该方法产物可以包括通过式I的含苯并噻唑的硅烷的烷氧基硅烷官能团的水解和缩合反应形成的低聚物。
式I的含苯并噻唑的硅烷可以应用于载体，例如蜡，聚合物或炭黑。
R3可以优选为-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH(CH3)-、-CH2CH(CH3)-、-CH(CH3)CH2-、-C(CH3)2-、-CH(C2H5)-、-CH2CH2CH(CH3)-、-CH(CH3)CH2CH2-、-CH2CH(CH3)CH2-、-CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-
R1可以优选为甲氧基或乙氧基。
R2可以优选为-O-(C2H4-O)5-C11H23、-O-(C2H4-O)5-C12H25、-O-(C2H4-O)5-C13H27、-O-(C2H4-O)5-C14H29、-O-(C2H4-O)5-C15H31、-O-(C2H4-O)3-C13H27、-O-(C2H4-O)4-C13H27、-O-(C2H4-O)6-C13H27、-O-(C2H4-O)7-C13H27、-O-(CH2CH2-O)5-(CH2)10CH3、-O-(CH2CH2-O)5-(CH2)11CH3、-O-(CH2CH2-O)5-(CH2)12CH3、-O-(CH2CH2-O)5-(CH2)13CH3、-O-(CH2CH2-O)5-(CH2)14CH3、-O-(CH2CH2-O)3-(CH2)12CH3、-O-(CH2CH2-O)4-(CH2)12CH3、-O-(CH2CH2-O)6-(CH2)12CH3、-O-(CH2CH2-O)7-(CH2)12CH3、
或
式I的含苯并噻唑的硅烷可以是：
[C11H23O-(CH2-CH2O)2](EtO)2Si(CH2)3S2Bt、[C11H23O-(CH2-CH2O)3](EtO)2Si(CH2)3S2Bt、[C11H23O-(CH2-CH2O)4](EtO)2Si(CH2)3S2Bt、[C11H23O-(CH2-CH2O)5](EtO)2Si(CH2)3S2Bt、[C11H23O-(CH2-CH2O)6](EtO)2Si(CH2)3S2Bt、[C12H25O-(CH2-CH2O)2](EtO)2Si(CH2)3S2Bt、[C12H25O-(CH2-CH2O)3](EtO)2Si(CH2)3 S2Bt、[C12H25O-(CH2-CH2O)4](EtO)2Si(CH2)3S2Bt、[C12H25O-(CH2-CH2O)5](EtO)2Si(CH2)3 S2Bt、[C12H25O-(CH2-CH2O)6](EtO)2Si(CH2)3S2Bt、[C13H27O-(CH2-CH2O)2](EtO)2Si(CH2)3 S2Bt、[C13H27O-(CH2-CH2O)3](EtO)2Si(CH2)3S2Bt、[C13H27O-(CH2-CH2O)4](EtO)2Si(CH2)3 S2Bt、[C13H27O-(CH2-CH2O)5](EtO)2Si(CH2)3S2Bt、[C13H27O-(CH2-CH2O)6](EtO)2Si(CH2)3 S2Bt、[C14H29O-(CH2-CH2O)2](EtO)2Si(CH2)3S2Bt、[C14H29O-(CH2-CH2O)3](EtO)2Si(CH2)3 S2Bt、[C14H29O-(CH2-CH2O)4](EtO)2Si(CH2)3S2Bt、[C14H29O-(CH2-CH2O)5](EtO)2Si(CH2)3 S2Bt、[C14H29O-(CH2-CH2O)6](EtO)2Si(CH2)3S2Bt、[C15H31O-(CH2-CH2O)2](EtO)2Si(CH2)3 S2Bt、[C15H31O-(CH2-CH2O)3](EtO)2Si(CH2)3S2Bt、[C15H31O-(CH2-CH2O)4](EtO)2Si(CH2)3 S2Bt、[C15H31O-(CH2-CH2O)5](EtO)2Si(CH2)3S2Bt、[C15H31O-(CH2-CH2O)6](EtO)2Si(CH2)3 S2Bt、[C16H33O-(CH2-CH2O)2](EtO)2Si(CH2)3S2Bt、[C16H33O-(CH2-CH2O)3](EtO)2Si(CH2)3 S2Bt、[C16H33O-(CH2-CH2O)4](EtO)2Si(CH2)3S2Bt、[C16H33O-(CH2-CH2O)5](EtO)2Si(CH2)3 S2Bt、[C16H33O-(CH2-CH2O)6](EtO)2Si(CH2)3S2Bt、[C17H35O-(CH2-CH2O)2](EtO)2Si(CH2)3 S2Bt、[C17H35O-(CH2-CH2O)3](EtO)2Si(CH2)3S2Bt、[C17H35O-(CH2-CH2O)4](EtO)2Si(CH2)3 S2Bt、[C17H35O-(CH2-CH2O)5](EtO)2Si(CH2)3S2Bt、[C17H35O-(CH2-CH2O)6](EtO)2Si(CH2)3 S2Bt、[C11H23O-(CH2-CH2O)2]2(EtO)Si(CH2)3S2Bt、[C11H23O-(CH2-CH2O)3]2(EtO)Si(CH2)3 S2Bt、[C11H23O-(CH2-CH2O)4]2(EtO)Si(CH2)3S2Bt、[C11H23O-(CH2-CH2O)5]2(EtO)Si(CH2)3 S2Bt、[C11H23O-(CH2-CH2O)6]2(EtO)Si(CH2)3S2Bt、[C12H25O-(CH2-CH2O)2]2(EtO)Si(CH2)3 S2Bt、[C12H25O-(CH2-CH2O)3]2(EtO)Si(CH2)3S2Bt、[C12H25O-(CH2-CH2O)4]2(EtO)Si(CH2)3 S2Bt、[C12H25O-(CH2-CH2O)5]2(EtO)Si(CH2)3S2Bt、[C12H25O-(CH2-CH2O)6]2(EtO)Si(CH2)3 S2Bt、[C13H27O-(CH2-CH2O)2]2(EtO)Si(CH2)3S2Bt、[C13H27O-(CH2-CH2O)3]2(EtO)Si(CH2)3 S2Bt、[C13H27O-(CH2-CH2O)4]2(EtO)Si(CH2)3S2Bt、[C13H27O-(CH2-CH2O)5]2(EtO)Si(CH2)3 S2Bt、[C13H27O-(CH2-CH2O)6]2(EtO)Si(CH2)3S2Bt、[C14H29O-(CH2-CH2O)2]2(EtO)Si(CH2)3 S2Bt、[C14H29O-(CH2-CH2O)3]2(EtO)Si(CH2)3S2Bt、[C14H29O-(CH2-CH2O)4]2(EtO)Si(CH2)3 S2Bt、[C14H29O-(CH2-CH2O)5]2(EtO)Si(CH2)3S2Bt、[C14H29O-(CH2-CH2O)6]2(EtO)Si(CH2)3 S2Bt、[C15H31O-(CH2-CH2O)2]2(EtO)Si(CH2)3S2Bt、[C15H31O-(CH2-CH2O)3]2(EtO)Si(CH2)3 S2Bt、[C15H31O-(CH2-CH2O)4]2(EtO)Si(CH2)3S2Bt、[C15H31O-(CH2-CH2O)5]2(EtO)Si(CH2)3 S2Bt、[C15H31O-(CH2-CH2O)6]2(EtO)Si(CH2)3S2Bt、[C16H33O-(CH2-CH2O)2]2(EtO)Si(CH2)3 S2Bt、[C16H33O-(CH2-CH2O)3]2(EtO)Si(CH2)3S2Bt、[C16H33O-(CH2-CH2O)4]2(EtO)Si(CH2)3 S2Bt、[C16H33O-(CH2-CH2O)5]2(EtO)Si(CH2)3S2Bt、[C16H33O-(CH2-CH2O)6]2(EtO)Si(CH2)3 S2Bt、[C17H35O-(CH2-CH2O)2]2(EtO)Si(CH2)3S2Bt、[C17H35O-(CH2-CH2O)3]2(EtO)Si(CH2)3 S2Bt、[C17H35O-(CH2-CH2O)4]2(EtO)Si(CH2)3S2Bt、[C17H35O-(CH2-CH2O)5]2(EtO)Si(CH2)3 S2Bt、[C17H35O-(CH2-CH2O)6]2(EtO)Si(CH2)3S2Bt、[C11H23O-(CH2-CH2O)2]3Si(CH2)3 S2Bt、[C11H23O-(CH2-CH2O)3]3Si(CH2)3S2Bt、[C11H23O-(CH2-CH2O)4]3Si(CH2)3 S2Bt、[C11H23O-(CH2-CH2O)5]3Si(CH2)3S2Bt、[C11H23O-(CH2-CH2O)6]3Si(CH2)3 S2Bt、[C12H25O-(CH2-CH2O)2]3Si(CH2)3S2Bt、[C12H25O-(CH2-CH2O)3]3Si(CH2)3 S2Bt、[C12H25O-(CH2-CH2O)4]3Si(CH2)3S2Bt、[C12H25O-(CH2-CH2O)5]3Si(CH2)3 S2Bt、[C12H25O-(CH2-CH2O)6]3Si(CH2)3S2Bt、[C13H27O-(CH2-CH2O)2]3Si(CH2)3 S2Bt、[C13H27O-(CH2-CH2O)3]3Si(CH2)3S2Bt、[C13H27O-(CH2-CH2O)4]3Si(CH2)3 S2Bt、[C13H27O-(CH2-CH2O)5]3Si(CH2)3S2Bt、[C13H27O-(CH2-CH2O)6]3Si(CH2)3 S2Bt、[C14H29O-(CH2-CH2O)2]3Si(CH2)3S2Bt、[C14H29O-(CH2-CH2O)3]3Si(CH2)3 S2Bt、[C14H29O-(CH2-CH2O)4]3Si(CH2)3S2Bt、[C14H29O-(CH2-CH2O)5]3Si(CH2)3 S2Bt、[C14H29O-(CH2-CH2O)6]3Si(CH2)3S2Bt、[C15H31O-(CH2-CH2O)2]3Si(CH2)3 S2Bt、[C15H31O-(CH2-CH2O)3]3Si(CH2)3S2Bt、[C15H31O-(CH2-CH2O)4]3Si(CH2)3 S2Bt、[C15H31O-(CH2-CH2O)5]3Si(CH2)3S2Bt、[C15H31O-(CH2-CH2O)6]3Si(CH2)3 S2Bt、[C16H33O-(CH2-CH2O)2]3Si(CH2)3S2Bt、[C16H33O-(CH2-CH2O)3]3Si(CH2)3 S2Bt、[C16H33O-(CH2-CH2O)4]3Si(CH2)3S2Bt、[C16H33O-(CH2-CH2O)5]3Si(CH2)3 S2Bt、[C16H33O-(CH2-CH2O)6]3Si(CH2)3S2Bt、[C17H35O-(CH2-CH2O)2]3Si(CH2)3 S2Bt、[C17H35O-(CH2-CH2O)3]3Si(CH2)3S2Bt、[C17H35O-(CH2-CH2O)4]3Si(CH2)3 S2Bt、[C17H35O-(CH2-CH2O)5]3Si(CH2)3S2Bt、[C17H35O-(CH2-CH2O)6]3Si(CH2)3 S2Bt、[C11H23O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C12H25O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C12H25O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2S2Bt、[C12H25O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C12H25O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C12H25O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C13H27O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C13H27O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C13H27O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C13H27O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C13H27O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C14H29O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C14H29O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C14H29O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C14H29O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2S2Bt、[C14H29O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C15H31O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C15H31O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C15H31O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C15H31O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C15H31O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C17H35O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2S2Bt、[C17H35O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C17H35O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C17H35O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C17H35O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C12H25O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C12H25O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C12H25O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2S2Bt、[C12H25O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C12H25O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S2Bt[C13H27O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C13H27O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C13H27O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C13H27O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C13H27O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C14H29O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C14H29O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C14H29O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C14H29O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C14H29O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2S2Bt、[C15H31O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C15H31O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C15H31O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C15H31O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C15H31O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C17H35O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C17H35O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2S2Bt、[C17H35O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C17H35O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C17H35O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2 S2Bt、[C12H25O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2 S2Bt、[C12H25O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2 S2Bt、[C12H25O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2 S2Bt、[C12H25O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2 S2Bt、[C12H25O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2 S2Bt、[C13H27O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2 S2Bt、[C13H27O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2 S2Bt、[C13H27O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2 S2Bt、[C13H27O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2 S2Bt、[C13H27O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2 S2Bt、[C14H29O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2 S2Bt、[C14H29O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2 S2Bt、[C14H29O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2 S2Bt、[C14H29O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2 S2Bt、[C14H29O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2 S2Bt、[C15H31O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2 S2Bt、[C15H31O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2 S2Bt、[C15H31O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2 S2Bt、[C15H31O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2 S2Bt、[C15H31O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2 S2Bt、[C16H33O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2 S2Bt、[C17H35O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2 S2Bt、[C17H35O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2 S2Bt、[C17H35O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2 S2Bt、[C17H35O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2 S2Bt、[C17H35O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2 S2Bt、[C11H23O-(CH2-CH2O)2](EtO)2Si(CH2)3 S3Bt、[C11H23O-(CH2-CH2O)3](EtO)2Si(CH2)3 S3Bt、[C11H23O-(CH2-CH2O)4](EtO)2Si(CH2)3 S3Bt、[C11H23O-(CH2-CH2O)5](EtO)2Si(CH2)3 S3Bt、[C11H23O-(CH2-CH2O)6](EtO)2Si(CH2)3 S3Bt、[C12H25O-(CH2-CH2O)2](EtO)2Si(CH2)3 S3Bt、[C12H25O-(CH2-CH2O)3](EtO)2Si(CH2)3 S3Bt、[C12H25O-(CH2-CH2O)4](EtO)2Si(CH2)3 S3Bt、[C12H25O-(CH2-CH2O)5](EtO)2Si(CH2)3 S3Bt、[C12H25O-(CH2-CH2O)6](EtO)2Si(CH2)3 S3Bt、[C13H27O-(CH2-CH2O)2](EtO)2Si(CH2)3 S3Bt、[C13H27O-(CH2-CH2O)3](EtO)2Si(CH2)3 S3Bt、[C13H27O-(CH2-CH2O)4](EtO)2Si(CH2)3 S3Bt、[C13H27O-(CH2-CH2O)5](EtO)2Si(CH2)3 S3Bt、[C13H27O-(CH2-CH2O)6](EtO)2Si(CH2)3 S3Bt、[C14H29O-(CH2-CH2O)2](EtO)2Si(CH2)3 S3Bt、[C14H29O-(CH2-CH2O)3](EtO)2Si(CH2)3 S3Bt、[C14H29O-(CH2-CH2O)4](EtO)2Si(CH2)3 S3Bt、[C14H29O-(CH2-CH2O)5](EtO)2Si(CH2)3 S3Bt、[C14H29O-(CH2-CH2O)6](EtO)2Si(CH2)3 S3Bt、[C15H31O-(CH2-CH2O)2](EtO)2Si(CH2)3 S3Bt、[C15H31O-(CH2-CH2O)3](EtO)2Si(CH2)3 S3Bt、[C15H31O-(CH2-CH2O)4](EtO)2Si(CH2)3 S3Bt、[C15H31O-(CH2-CH2O)5](EtO)2Si(CH2)3 S3Bt、[C15H31O-(CH2-CH2O)6](EtO)2Si(CH2)3 S3Bt、[C16H33O-(CH2-CH2O)2](EtO)2Si(CH2)3 S3Bt、[C16H33O-(CH2-CH2O)3](EtO)2Si(CH2)3 S3Bt、[C16H33O-(CH2-CH2O)4](EtO)2Si(CH2)3 S3Bt、[C16H33O-(CH2-CH2O)5](EtO)2Si(CH2)3 S3Bt、[C16H33O-(CH2-CH2O)6](EtO)2Si(CH2)3 S3Bt、[C17H35O-(CH2-CH2O)2](EtO)2Si(CH2)3 S3Bt、[C17H35O-(CH2-CH2O)3](EtO)2Si(CH2)3 S3Bt、[C17H35O-(CH2-CH2O)4](EtO)2Si(CH2)3 S3Bt、[C17H35O-(CH2-CH2O)5](EtO)2Si(CH2)3 S3Bt、[C17H35O-(CH2-CH2O)6](EtO)2Si(CH2)3 S3Bt、[C11H23O-(CH2-CH2O)2]2(EtO)Si(CH2)3 S3Bt、[C11H23O-(CH2-CH2O)3]2(EtO)Si(CH2)3 S3Bt、[C11H23O-(CH2-CH2O)4]2(EtO)Si(CH2)3 S3Bt、[C11H23O-(CH2-CH2O)5]2(EtO)Si(CH2)3 S3Bt、[C11H23O-(CH2-CH2O)6]2(EtO)Si(CH2)3 S3Bt、[C12H25O-(CH2-CH2O)2]2(EtO)Si(CH2)3 S3Bt、[C12H25O-(CH2-CH2O)3]2(EtO)Si(CH2)3 S3Bt、[C12H25O-(CH2-CH2O)4]2(EtO)Si(CH2)3 S3Bt、[C12H25O-(CH2-CH2O)5]2(EtO)Si(CH2)3 S3Bt、[C12H25O-(CH2-CH2O)6]2(EtO)Si(CH2)3 S3Bt、[C13H27O-(CH2-CH2O)2]2(EtO)Si(CH2)3 S3Bt、[C13H27O-(CH2-CH2O)3]2(EtO)Si(CH2)3 S3Bt、[C13H27O-(CH2-CH2O)4]2(EtO)Si(CH2)3 S3Bt、[C13H27O-(CH2-CH2O)5]2(EtO)Si(CH2)3 S3Bt、[C13H27O-(CH2-CH2O)6]2(EtO)Si(CH2)3 S3Bt、[C14H29O-(CH2-CH2O)2]2(EtO)Si(CH2)3 S3Bt、[C14H29O-(CH2-CH2O)3]2(EtO)Si(CH2)3 S3Bt、[C14H29O-(CH2-CH2O)4]2(EtO)Si(CH2)3 S3Bt、[C14H29O-(CH2-CH2O)5]2(EtO)Si(CH2)3 S3Bt、[C14H29O-(CH2-CH2O)6]2(EtO)Si(CH2)3 S3Bt、[C15H31O-(CH2-CH2O)2]2(EtO)Si(CH2)3 S3Bt、[C15H31O-(CH2-CH2O)3]2(EtO)Si(CH2)3 S3Bt、[C15H31O-(CH2-CH2O)4]2(EtO)Si(CH2)3 S3Bt、[C15H31O-(CH2-CH2O)5]2(EtO)Si(CH2)3 S3Bt、[C15H31O-(CH2-CH2O)6]2(EtO)Si(CH2)3 S3Bt、[C16H33O-(CH2-CH2O)2]2(EtO)Si(CH2)3 S3Bt、[C16H33O-(CH2-CH2O)3]2(EtO)Si(CH2)3 S3Bt、[C16H33O-(CH2-CH2O)4]2(EtO)Si(CH2)3 S3Bt、[C16H33O-(CH2-CH2O)5]2(EtO)Si(CH2)3 S3Bt、[C16H33O-(CH2-CH2O)6]2(EtO)Si(CH2)3 S3Bt、[C17H35O-(CH2-CH2O)2]2(EtO)Si(CH2)3 S3Bt、[C17H35O-(CH2-CH2O)3]2(EtO)Si(CH2)3 S3Bt、[C17H35O-(CH2-CH2O)4]2(EtO)Si(CH2)3 S3Bt、[C17H35O-(CH2-CH2O)5]2(EtO)Si(CH2)3 S3Bt、[C17H35O-(CH2-CH2O)6]2(EtO)Si(CH2)3 S3Bt、[C11H23O-(CH2-CH2O)2]3Si(CH2)3 S3Bt、[C11H23O-(CH2-CH2O)3]3Si(CH2)3S3Bt、[C11H23O-(CH2-CH2O)4]3Si(CH2)3 S3Bt、[C11H23O-(CH2-CH2O)5]3Si(CH2)3S3Bt、[C11H23O-(CH2-CH2O)6]3Si(CH2)3 S3Bt、[C12H25O-(CH2-CH2O)2]3Si(CH2)3S3Bt、[C12H25O-(CH2-CH2O)3]3Si(CH2)3 S3Bt、[C12H25O-(CH2-CH2O)4]3Si(CH2)3S3Bt、[C12H25O-(CH2-CH2O)5]3Si(CH2)3 S3Bt、[C12H25O-(CH2-CH2O)6]3Si(CH2)3S3Bt、[C13H27O-(CH2-CH2O)2]3Si(CH2)3 S3Bt、[C13H27O-(CH2-CH2O)3]3Si(CH2)3S3Bt、[C13H27O-(CH2-CH2O)4]3Si(CH2)3 S3Bt、[C13H27O-(CH2-CH2O)5]3Si(CH2)3S3Bt、[C13H27O-(CH2-CH2O)6]3Si(CH2)3 S3Bt、[C14H29O-(CH2-CH2O)2]3Si(CH2)3S3Bt、[C14H29O-(CH2-CH2O)3]3Si(CH2)3 S3Bt、[C14H29O-(CH2-CH2O)4]3Si(CH2)3S3Bt、[C14H29O-(CH2-CH2O)5]3Si(CH2)3 S3Bt、[C14H29O-(CH2-CH2O)6]3Si(CH2)3S3Bt、[C15H31O-(CH2-CH2O)2]3Si(CH2)3 S3Bt、[C15H31O-(CH2-CH2O)3]3Si(CH2)3S3Bt、[C15H31O-(CH2-CH2O)4]3Si(CH2)3 S3Bt、[C15H31O-(CH2-CH2O)5]3Si(CH2)3S3Bt、[C15H31O-(CH2-CH2O)6]3Si(CH2)3 S3Bt、[C16H33O-(CH2-CH2O)2]3Si(CH2)3S3Bt、[C16H33O-(CH2-CH2O)3]3Si(CH2)3 S3Bt、[C16H33O-(CH2-CH2O)4]3Si(CH2)3S3Bt、[C16H33O-(CH2-CH2O)5]3Si(CH2)3 S2Bt、[C16H33O-(CH2-CH2O)6]3Si(CH2)3S3Bt、[C17H35O-(CH2-CH2O)2]3Si(CH2)3 S3Bt、[C17H35O-(CH2-CH2O)3]3Si(CH2)3S3Bt、[C17H35O-(CH2-CH2O)4]3Si(CH2)3 S3Bt、[C17H35O-(CH2-CH2O)5]3Si(CH2)3S3Bt、[C17H35O-(CH2-CH2O)6]3Si(CH2)3 S3Bt、[C11H23O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C11H23O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C11H23O-(CH2-CH2O)4]EtO)2Si(CH2)2C(CH3)2 S3Bt、[C11H23O-(CH2-CH2O)5]EtO)2Si(CH2)2C(CH3)2 S3Bt、[C11H23O-(CH2-CH2O)6]EtO)2Si(CH2)2C(CH3)2 S3Bt、[C12H25O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C12H25O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C12H25O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C12H25O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C12H25O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2S3Bt、[C13H27O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C13H27O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C13H27O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C13H27O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C13H27O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C14H29O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C14H29O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C14H29O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C14H29O-(CH2-CH2O)5](EtO)2Si CH2)2C(CH3)2 S3Bt、[C14H29O-(CH2-CH2O)6](EtO)2Si CH2)2C(CH3)2 S3Bt、[C15H31O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C15H31O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2S3Bt、[C15H31O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C15H31O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C15H31O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C16H33O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C16H33O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C16H33O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C16H33O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C16H33O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C17H35O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C17H35O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C17H35O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C17H35O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2S3Bt、[C17H35O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S3Bt、[C11H23O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C11H23O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C11H23O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C11H23O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C11H23O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C12H25O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C12H25O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C12H25O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C12H25O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C12H25O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C13H27O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2S3Bt、[C13H27O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C13H27O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C13H27O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C13H27O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C14H29O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C14H29O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C14H29O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C14H29O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C14H29O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C15H31O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C15H31O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C15H31O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2S3Bt、[C15H31O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C15H31O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C16H33O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C16H33O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C16H33O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C16H33O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C16H33O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C17H35O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C17H35O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C17H35O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C17H35O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S3Bt、[C17H35O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2S3Bt、[C11H23O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2 S3Bt、[C11H23O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2S3Bt、[C11H23O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2 S3Bt、[C11H23O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2S3Bt、[C11H23O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2 S3Bt、[C12H25O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2S3Bt、[C12H25O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2 S3Bt、[C12H25O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2S3Bt、[C12H25O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2 S3Bt、[C12H25O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2S3Bt、[C13H27O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2 S3Bt、[C13H27O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2S3Bt、[C13H27O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2 S3Bt、[C13H27O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2S3Bt、[C13H27O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2 S3Bt、[C14H29O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2S3Bt、[C14H29O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2 S3Bt、[C14H29O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2S3Bt、[C14H29O-(CH2-CH2O)5]3Si CH2)2C(CH3)2 S3Bt、[C14H29O-(CH2-CH2O)6]3Si CH2)2C(CH3)2S3Bt、[C15H31O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2 S3Bt、[C15H31O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2S3Bt、[C15H31O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2 S3Bt、[C15H31O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2S3Bt、[C15H31O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2 S3Bt、[C16H33O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2S3Bt、[C16H33O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2 S3Bt、[C16H33O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2S3Bt、[C16H33O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2 S3Bt、[C16H33O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2S3Bt、[C17H35O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2 S3Bt、[C17H35O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2S3Bt、[C17H35O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2 S3Bt、[C17H35O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2S3Bt、[C17H35O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2 S3Bt、[C11H23O-(CH2-CH2O)2](EtO)2Si(CH2)3S4Bt、[C11H23O-(CH2-CH2O)3](EtO)2Si(CH2)3 S4Bt、[C11H23O-(CH2-CH2O)4](EtO)2Si(CH2)3S4Bt、[C11H23O-(CH2-CH2O)5](EtO)2Si(CH2)3 S4Bt、[C11H23O-(CH2-CH2O)6](EtO)2Si(CH2)3S4Bt、[C12H25O-(CH2-CH2O)2](EtO)2Si(CH2)3 S4Bt、[C12H25O-(CH2-CH2O)3](EtO)2Si(CH2)3S4Bt、[C12H25O-(CH2-CH2O)4](EtO)2Si(CH2)3 S4Bt、[C12H25O-(CH2-CH2O)5](EtO)2Si(CH2)3S4Bt、[C12H25O-(CH2-CH2O)6](EtO)2Si(CH2)3 S4Bt、[C13H27O-(CH2-CH2O)2](EtO)2Si(CH2)3S4Bt、[C13H27O-(CH2-CH2O)3](EtO)2Si(CH2)3 S4Bt、[C13H27O-(CH2-CH2O)4](EtO)2Si(CH2)3S4Bt、[C13H27O-(CH2-CH2O)5](EtO)2Si(CH2)3 S4Bt、[C13H27O-(CH2-CH2O)6](EtO)2Si(CH2)3S4Bt、[C14H29O-(CH2-CH2O)2](EtO)2Si(CH2)3 S4Bt、[C14H29O-(CH2-CH2O)3](EtO)2Si(CH2)3S4Bt、[C14H29O-(CH2-CH2O)4](EtO)2Si(CH2)3 S4Bt、[C14H29O-(CH2-CH2O)5](EtO)2Si(CH2)3S4Bt、[C14H29O-(CH2-CH2O)6](EtO)2Si(CH2)3 S4Bt、[C15H31O-(CH2-CH2O)2](EtO)2Si(CH2)3S4Bt、[C15H31O-(CH2-CH2O)3](EtO)2Si(CH2)3 S4Bt、[C15H31O-(CH2-CH2O)4](EtO)2Si(CH2)3S4Bt、[C15H31O-(CH2-CH2O)5](EtO)2Si(CH2)3 S4Bt、[C15H31O-(CH2-CH2O)6](EtO)2Si(CH2)3S4Bt、[C16H33O-(CH2-CH2O)2](EtO)2Si(CH2)3 S4Bt、[C16H33O-(CH2-CH2O)3](EtO)2Si(CH2)3S4Bt、[C16H33O-(CH2-CH2O)4](EtO)2Si(CH2)3 S4Bt、[C16H33O-(CH2-CH2O)5](EtO)2Si(CH2)3S4Bt、[C16H33O-(CH2-CH2O)6](EtO)2Si(CH2)3 S4Bt、[C17H35O-(CH2-CH2O)2](EtO)2Si(CH2)3S4Bt、[C17H35O-(CH2-CH2O)3](EtO)2Si(CH2)3 S4Bt、[C17H35O-(CH2-CH2O)4](EtO)2Si(CH2)3S4Bt、[C17H35O-(CH2-CH2O)5](EtO)2Si(CH2)3 S4Bt、[C17H35O-(CH2-CH2O)6](EtO)2Si(CH2)3S4Bt、[C11H23O-(CH2-CH2O)2]2(EtO)Si(CH2)3 S4Bt、[C11H23O-(CH2-CH2O)3]2(EtO)Si(CH2)3S4Bt、[C11H23O-(CH2-CH2O)4]2(EtO)Si(CH2)3 S4Bt、[C11H23O-(CH2-CH2O)5]2(EtO)Si(CH2)3S4Bt、[C11H23O-(CH2-CH2O)6]2(EtO)Si(CH2)3 S4Bt、[C12H25O-(CH2-CH2O)2]2(EtO)Si(CH2)3S4Bt、[C12H25O-(CH2-CH2O)3]2(EtO)Si(CH2)3 S4Bt、[C12H25O-(CH2-CH2O)4]2(EtO)Si(CH2)3S4Bt、[C12H25O-(CH2-CH2O)5]2(EtO)Si(CH2)3 S4Bt、[C12H25O-(CH2-CH2O)6]2(EtO)Si(CH2)3S4Bt、[C13H27O-(CH2-CH2O)2]2(EtO)Si(CH2)3 S4Bt、[C13H27O-(CH2-CH2O)3]2(EtO)Si(CH2)3S4Bt、[C13H27O-(CH2-CH2O)4]2(EtO)Si(CH2)3 S4Bt、[C13H27O-(CH2-CH2O)5]2(EtO)Si(CH2)3S4Bt、[C13H27O-(CH2-CH2O)6]2(EtO)Si(CH2)3 S4Bt、[C14H29O-(CH2-CH2O)2]2(EtO)Si(CH2)3S4Bt、[C14H29O-(CH2-CH2O)3]2(EtO)Si(CH2)3 S4Bt、[C14H29O-(CH2-CH2O)4]2(EtO)Si(CH2)3S4Bt、[C14H29O-(CH2-CH2O)5]2(EtO)Si(CH2)3 S4Bt、[C14H29O-(CH2-CH2O)6]2(EtO)Si(CH2)3S4Bt、[C15H31O-(CH2-CH2O)2]2(EtO)Si(CH2)3 S4Bt、[C15H31O-(CH2-CH2O)3]2(EtO)Si(CH2)3S4Bt、[C15H31O-(CH2-CH2O)4]2(EtO)Si(CH2)3 S4Bt、[C15H31O-(CH2-CH2O)5]2(EtO)Si(CH2)3S4Bt、[C15H31O-(CH2-CH2O)6]2(EtO)Si(CH2)3 S4Bt、[C16H33O-(CH2-CH2O)2]2(EtO)Si(CH2)3S4Bt、[C16H33O-(CH2-CH2O)3]2(EtO)Si(CH2)3 S4Bt、[C16H33O-(CH2-CH2O)4]2(EtO)Si(CH2)3S4Bt、[C16H33O-(CH2-CH2O)5]2(EtO)Si(CH2)3 S4Bt、[C16H33O-(CH2-CH2O)6]2(EtO)Si(CH2)3S4Bt、[C17H35O-(CH2-CH2O)2]2(EtO)Si(CH2)3 S4Bt、[C17H35O-(CH2-CH2O)3]2(EtO)Si(CH2)3S4Bt、[C17H35O-(CH2-CH2O)4]2(EtO)Si(CH2)3 S4Bt、[C17H35O-(CH2-CH2O)5]2(EtO)Si(CH2)3S4Bt、[C17H35O-(CH2-CH2O)6]2(EtO)Si(CH2)3 S4Bt、[C11H23O-(CH2-CH2O)2]3Si(CH2)3 S4Bt、[C11H23O-(CH2-CH2O)3]3Si(CH2)3S4Bt、[C11H23O-(CH2-CH2O)4]3Si(CH2)3 S4Bt、[C11H23O-(CH2-CH2O)5]3Si(CH2)3S4Bt、[C11H23O-(CH2-CH2O)6]3Si(CH2)3 S4Bt、[C12H25O-(CH2-CH2O)2]3Si(CH2)3S4Bt、[C12H25O-(CH2-CH2O)3]3Si(CH2)3 S4Bt、[C12H25O-(CH2-CH2O)4]3Si(CH2)3S4Bt、[C12H25O-(CH2-CH2O)5]3Si(CH2)3 S4Bt、[C12H25O-(CH2-CH2O)6]3Si(CH2)3S4Bt、[C13H27O-(CH2-CH2O)2]3Si(CH2)3 S4Bt、[C13H27O-(CH2-CH2O)3]3Si(CH2)3S4Bt、[C13H27O-(CH2-CH2O)4]3Si(CH2)3 S4Bt、[C13H27O-(CH2-CH2O)5]3Si(CH2)3S4Bt、[C13H27O-(CH2-CH2O)6]3Si(CH2)3 S4Bt、[C14H29O-(CH2-CH2O)2]3Si(CH2)3S4Bt、[C14H29O-(CH2-CH2O)3]3Si(CH2)3 S4Bt、[C14H29O-(CH2-CH2O)4]3Si(CH2)3S4Bt、[C14H29O-(CH2-CH2O)5]3Si(CH2)3 S4Bt、[C14H29O-(CH2-CH2O)6]3Si(CH2)3S4Bt、[C15H31O-(CH2-CH2O)2]3Si(CH2)3 S4Bt、[C15H31O-(CH2-CH2O)3]3Si(CH2)3S4Bt、[C15H31O-(CH2-CH2O)4]3Si(CH2)3 S4Bt、[C15H31O-(CH2-CH2O)5]3Si(CH2)3S4Bt、[C15H31O-(CH2-CH2O)6]3Si(CH2)3 S4Bt、[C16H33O-(CH2-CH2O)2]3Si(CH2)3S4Bt、[C16H33O-(CH2-CH2O)3]3Si(CH2)3 S4Bt、[C16H33O-(CH2-CH2O)4]3Si(CH2)3S4Bt、[C16H33O-(CH2-CH2O)5]3Si(CH2)3 S4Bt、[C16H33O-(CH2-CH2O)6]3Si(CH2)3S4Bt、[C17H35O-(CH2-CH2O)2]3Si(CH2)3 S4Bt、[C17H35O-(CH2-CH2O)3]3Si(CH2)3S4Bt、[C17H35O-(CH2-CH2O)4]3Si(CH2)3 S4Bt、[C17H35O-(CH2-CH2O)5]3Si(CH2)3S4Bt、[C17H35O-(CH2-CH2O)6]3Si(CH2)3 S4Bt、[C11H23O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C11H23O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C11H23O-(CH2-CH2O)4]EtO)2Si(CH2)2C(CH3)2 S4Bt、[C11H23O-(CH2-CH2O)5]EtO)2Si(CH2)2C(CH3)2 S4Bt、[C11H23O-(CH2-CH2O)6]EtO)2Si(CH2)2C(CH3)2 S4Bt、[C12H25O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2S4Bt、[C12H25O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C12H25O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C12H25O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C12H25O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C13H27O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C13H27O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C13H27O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C13H27O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C13H27O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C14H29O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C14H29O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C14H29O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2S4Bt、[C14H29O-(CH2-CH2O)5](EtO)2Si CH2)2C(CH3)2 S4Bt、[C14H29O-(CH2-CH2O)6](EtO)2SiCH2)2C(CH3)2 S4Bt、[C15H31O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C15H31O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C15H31O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C15H31O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C15H31O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C16H33O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C16H33O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C16H33O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C16H33O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C16H33O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2S4Bt、[C17H35O-(CH2-CH2O)2](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C17H35O-(CH2-CH2O)3](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C17H35O-(CH2-CH2O)4](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C17H35O-(CH2-CH2O)5](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C17H35O-(CH2-CH2O)6](EtO)2Si(CH2)2C(CH3)2 S4Bt、[C11H23O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C11H23O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C11H23O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C11H23O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C11H23O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C12H25O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C12H25O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2S4Bt、[C12H25O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C12H25O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C12H25O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C13H27O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C13H27O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C13H27O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C13H27O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C13H27O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C14H29O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C14H29O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C14H29O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C14H29O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2S4Bt、[C14H29O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C15H31O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C15H31O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C15H31O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C15H31O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C15H31O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C16H33O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C16H33O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C16H33O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C16H33O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C16H33O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C17H35O-(CH2-CH2O)2]2(EtO)Si(CH2)2C(CH3)2S4Bt、[C17H35O-(CH2-CH2O)3]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C17H35O-(CH2-CH2O)4]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C17H35O-(CH2-CH2O)5]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C17H35O-(CH2-CH2O)6]2(EtO)Si(CH2)2C(CH3)2 S4Bt、[C11H23O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2 S4Bt、[C11H23O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2 S4Bt、[C11H23O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2 S4Bt、[C11H23O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2 S4Bt、[C11H23O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2 S4Bt、[C12H25O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2 S4Bt、[C12H25O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2S4Bt、[C12H25O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2S4Bt、[C12H25O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2S4Bt、[C12H25O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2S4Bt[C13H27O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2S4Bt、[C13H27O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2S4Bt、[C13H27O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2S4Bt、[C13H27O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2S4Bt、[C13H27O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2S4Bt、[C14H29O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2S4Bt、[C14H29O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2S4Bt、[C14H29O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2S4Bt、[C14H29O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2S4Bt、[C14H29O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2S4Bt、[C15H31O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2S4Bt、[C15H31O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2S4Bt、[C15H31O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2S4Bt、[C15H31O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2S4Bt、[C15H31O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2S4Bt、[C16H33O-(CH2-CH2O)2]3Si CH2)2C(CH3)2S4Bt、[C16H33O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2S4Bt、[C16H33O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2S4Bt、[C16H33O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2S4Bt、[C16H33O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2S4Bt、[C17H35O-(CH2-CH2O)2]3Si(CH2)2C(CH3)2S4Bt、[C17H35O-(CH2-CH2O)3]3Si(CH2)2C(CH3)2S4Bt、[C17H35O-(CH2-CH2O)4]3Si(CH2)2C(CH3)2S4Bt、[C17H35O-(CH2-CH2O)5]3Si(CH2)2C(CH3)2S4Bt、[C17H35O-(CH2-CH2O)6]3Si(CH2)2C(CH3)2S4Bt、
其中Bt为苯并噻唑基团。
式I的含苯并噻唑的硅烷可以优选为：
具有R1＝-O-C2H5,R2＝-O-(CH2CH2O)5-C13H27和R3＝-(CH2)3-的式I的硅烷，和
具有R1＝-O-C2H5,R2＝-O-(CH2CH2O)5-C13H27和R3＝-(CH2)2C(CH3)2-的式I的硅烷。
特别优选的化合物为[C13H27O-(CH2-CH2O)5](EtO)2Si(CH2)3S2Bt。
本发明还提供了一种制备本发明的式I的含苯并噻唑的硅烷的方法，
其中，R1，R2，R3，x和n分别如上定义，其特征在于式II的含苯并噻唑的硅烷，
与式III的化合物反应
R2-H(III)。
式II的含苯并噻唑的硅烷可以优选为：
(EtO)3Si(CH2)3S2Bt、(EtO)3Si(CH2)2C(CH3)2S2Bt、(EtO)3Si(CH2)3S3Bt、(EtO)3Si(CH2)2C(CH3)2S3Bt或(EtO)3Si(CH2)3S4Bt、(EtO)3Si(CH2)2C(CH3)2S4Bt，
其中Bt为苯并噻唑基团。
式III的化合物可以优选为：[C11H23O-(CH2-CH2O)2]OH、[C11H23O-(CH2-CH2O)3]OH、[C11H23O-(CH2-CH2O)4]OH、[C11H23O-(CH2-CH2O)5]OH、[C11H23O-(CH2-CH2O)6]OH、[C12H25O-(CH2-CH2O)2]OH、[C12H25O-(CH2-CH2O)3]OH、[C12H25O-(CH2-CH2O)4]OH、[C12H25O-(CH2-CH2O)5]OH、[C12H25O-(CH2-CH2O)6]OH、[C13H27O-(CH2-CH2O)2]OH、[C13H27O-(CH2-CH2O)3]OH、[C13H27O-(CH2-CH2O)4]OH、[C13H27O-(CH2-CH2O)5]OH、[C13H27O-(CH2-CH2O)6]OH、[C14H29O-(CH2-CH2O)2]OH、[C14H29O-(CH2-CH2O)3]OH、[C14H29O-(CH2-CH2O)4]OH、[C14H29O-(CH2-CH2O)5]OH、[C14H29O-(CH2-CH2O)6]OH、[C15H31O-(CH2-CH2O)2]OH、[C15H31O-(CH2-CH2O)3]OH、[C15H31O-(CH2-CH2O)4]OH、[C15H31O-(CH2-CH2O)5]OH、[C15H31O-(CH2-CH2O)6]OH、[C16H33O-(CH2-CH2O)2]OH、[C16H33O-(CH2-CH2O)3]OH、[C16H33O-(CH2-CH2O)4]OH、[C16H33O-(CH2-CH2O)5]OH、[C16H33O-(CH2-CH2O)6]OH、[C17H35O-(CH2-CH2O)2]OH、[C17H35O-(CH2-CH2O)3]OH、[C17H35O-(CH2-CH2O)4]OH、[C17H35O-(CH2-CH2O)5]OH或[C17H35O-(CH2-CH2O)6]OH。
可以使用1H，13C和29Si NMR的方法分析本发明的含苯并噻唑的硅烷。
在根据本发明的方法中，可以将式II的含苯并噻唑的硅烷计量到式III的化合物中。
在根据本发明的方法中，优选将式III的化合物计量到式II的含苯并噻唑的硅烷中。
在根据本发明的方法中，相对于式III化合物，可以以1:1至1:3，优选1:1至1:2的摩尔比，更优选以1:1至1.1:1的比例，使用式II的含苯并噻唑的硅烷。
根据本发明的方法可以在催化剂存在消除R1-H下进行。
用作反应催化剂的化合物可以是含金属的或不含金属的。
所使用的不含金属的化合物可以是有机酸，例如三氟乙酸，三氟甲磺酸或对甲苯磺酸，三烷基铵化合物E3NH+Z-或碱，例如三烷基胺NE3，其中E＝烷基且Z-＝平衡离子。
用作反应催化剂的金属化合物可以为过渡金属化合物。
用于催化剂的金属化合物可以为金属氯化物、金属氧化物、金属氯氧化物、金属硫化物、金属硫氯化物、金属醇盐、金属硫醇盐、金属氧基醇盐、金属酰胺、金属酰亚胺或包含多个结合配体的过渡金属化合物。
例如，所用的金属化合物可以是第3主族的卤化物、酰胺或醇盐(M3+＝B，Al，Ga，In，Tl：M3+(OMe)3，M3+(OEt)3，M3+(OC3H7)3，M3+(OC4H9)3)，
涉及的镧系元素(元素周期表中的原子数58至71的稀土元素)化合物上多个结合配体的取代基类别的卤化物，氧化物，硫化物，酰亚胺，醇盐，酰胺，硫醇盐以及组合，
涉及的第3过渡金属族化合物上多个结合配体的取代基类别的卤化物、氧化物、硫化物、酰亚胺、醇盐、酰胺、硫醇盐以及组合(M3+＝Sc，Y，La：M3+(OMe)3、M3+(OEt)3、M3+(OC3H7)3、M3+(OC4H9)3、cpM3+(Cl)2、cp cpM3+(OMe)2、cpM3+(OEt)2、cpM3+(NMe2)2，其中cp＝环戊二烯基)，
第4主族的卤化物、硫化物、酰胺、硫醇盐或醇盐(M4+＝Si、Ge、Sn，Pb:M4+(OMe)4、M4+(OEt)4、M4+(OC3H7)4、M4+(OC4H9)4；M2+＝Sn，Pb:M2+(OMe)2、M2+(OEt)2、M2+(OC3H7)2、M2+(OC4H9)2)、二月桂酸锡，二乙酸锡、Sn(OBu)2
涉及的第4过渡金属族化合物上多个结合配体的取代基类别的卤化物、氧化物、硫化物、酰亚胺、醇盐、酰胺、硫醇盐以及组合(M4+＝Ti、Zr、Hf:(M4+(F)4、M4+(Cl)4、M4+(Br)4、M4+(I)4；M4+(OMe)4、M4+(OEt)4、M4+(OC3H7)4、M4+(OC4H9)4、cp2Ti(Cl)2、cp2Zr(Cl)2、cp2Hf(Cl)2、cp2Ti(OMe)2、cp2Zr(OMe)2、cp2Hf(OMe)2、cpTi(Cl)3、cpZr(Cl)3、cpHf(Cl)3；cpTi(OMe)3、cpZr(OMe)3、cpHf(OMe)3、M4+(NMe2)4、M4+(NEt2)4、M4+(NHC4H9)4)，
涉及的第5过渡金属族化合物上多个结合配体的取代基类别的卤化物、氧化物、硫化物、酰亚胺、醇盐、酰胺、硫醇盐以及组合(M5+,M4+或M3+＝V、Nb、Ta:M5+(OMe)5、M5+(OEt)5、M5+(OC3H7)5、M5+(OC4H9)5、M3+O(OMe)3、M3+O(OEt)3、M3+O(OC3H7)3、M3+O(OC4H9)3、cpV(OMe)4、cpNb(OMe)3、cpTa(OMe)3；cpV(OMe)2、cpNb(OMe)3、cpTa(OMe)3)，
涉及的第6过渡金属族化合物上多个结合配体的取代基类别的卤化物、氧化物、硫化物、酰亚胺、醇盐、酰胺、硫醇盐以及组合(M6+、M5+或M4+＝Cr、Mo、W:M6+(OMe)6、M6+(OEt)6、M6+(OC3H7)6、M6+(OC4H9)6、M6+O(OMe)4、M6+O(OEt)4、M6+O(OC3H7)4、M6+O(OC4H9)4、M6+O2(OMe)2、M6+O2(OEt)2、M6+O2(OC3H7)2、M6+O2(OC4H9)2、M6+O2(OSiMe3)2)或
涉及的第7过渡金属族化合物上多个结合配体的取代基类别的卤化物、氧化物、硫化物、酰亚胺、醇盐、酰胺、硫醇盐以及组合(M7+、M6+、M5+或M4+＝Mn、Re:M7+O(OMe)5、M7+O(OEt)5、M7+O(OC3H7)5、M7+O(OC4H9)5、M7+O2(OMe)3、M7+O2(OEt)3、M7+O2(OC3H7)3、M7+O2(OC4H9)3、M7+O2(OSiMe3)3、M7+O3(OSiMe3)、M7+O3(CH3))。
金属和过渡金属化合物可以在金属上具有自由配位点。
所用催化剂也可以为金属或过渡金属化合物，其通过加水得到可水解的金属或过渡金属化合物来形成。
在特定的实施方案中，可以使用钛酸酯(例如原钛酸四正丁酯或原钛酸四异丙酯)作为催化剂。
该反应可以在隔绝空气的条件下进行。
该反应可以在保护性气体气氛下(例如在氩气或氮气下，优选在氮气下)进行。
本发明的方法可以在大气压，加压或减压下进行。优选地，根据本发明的方法可以在减压下进行。
加压可以为1.1巴至100巴，优选地1.5巴至50巴，更优选地2巴至20巴，非常优选地2至10巴的压力。
减压可以是1毫巴至1000毫巴，优选1毫巴至500毫巴，更优选1毫巴至250毫巴，非常优选5毫巴至100毫巴的压力。
该反应可以在20-200℃，优选50-170℃，更优选80-150℃的温度下进行。为了避免缩合反应，有利的是在无水环境中，理想地在惰性气体环境中进行反应。
在反应之后或反应过程中，可以除去醇R1-H，优选将其蒸馏掉。
随后可以将反应产物干燥。
式I的含苯并噻唑的硅烷可用作无机材料(例如玻璃珠，玻璃薄片，玻璃表面，玻璃纤维)或氧化性填料(优选二氧化硅，例如沉淀和热解法二氧化硅)
和有机聚合物(例如热固性塑料，热塑性塑料或弹性体)之间的粘合促进剂，或作为交联剂和用于氧化表面的表面改性剂。
式I的含苯并噻唑的硅烷可用作填充橡胶混合物中的偶联剂，例如轮胎胎面，工业橡胶制品或鞋底。
本发明还提供了一种橡胶混合物，其包含：
(A)一种橡胶或多种橡胶的混合物，
(B)填料和
(C)至少一种通式I的含苯并噻唑的硅烷。
橡胶(A)可以优选为二烯橡胶，优选天然橡胶，聚异戊二烯，聚丁二烯，苯乙烯-丁二烯共聚物，异丁烯/异戊二烯共聚物，丁二烯/丙烯腈共聚物，乙烯/丙烯/二烯共聚物(EPDM)，部分氢化或完全氢化的NBR橡胶。
所用橡胶可以为天然橡胶和/或合成橡胶。例如，优选的合成橡胶描述在W.Hofmann,Kautschuktechnologie[Rubber Technology],Genter Verlag,Stuttgart1980中。这些合成橡胶可以包括：
聚丁二烯(BR)，
聚异戊二烯(IR)，
苯乙烯/丁二烯共聚物(例如乳液SBR(E-SBR)或溶液SBR(S-SBR)，其苯乙烯含量优选为1-60重量％，更优选为5-50重量％(SBR))，
氯丁二烯(CR)
异丁烯/异戊二烯共聚物(IIR)，
丁腈/丙烯腈共聚物，其丙烯腈含量为5-60重量％，优选10-50重量％(NBR)，
部分氢化或完全氢化的NBR橡胶(HNBR)，
乙烯/丙烯/二烯共聚物(EPDM)
也具有官能团例如羧基、硅烷醇或环氧基的上述橡胶，例如环氧化NR，羧基官能化的NBR或胺(NR2)，硅烷醇(-SiOH)-或硅氧基(-Si-OR)官能化SBR，
和这些橡胶的混合物。上述橡胶可以另外为硅或锡偶联的。
在优选的实施方案中，橡胶可以是硫磺可硫化的。为了生产汽车轮胎胎面，特别可以使用玻璃化转变温度高于-50℃的阴离子聚合的S-SBR橡胶(溶液SBR)，以及其与二烯橡胶的混合物。特别优选地可以使用丁二烯部分具有大于20重量％的乙烯基分数的S-SBR橡胶。非常特别优选地可以使用其丁二烯部分具有大于50重量％的乙烯基分数的S-SBR橡胶。
优选可以使用具有大于50重量％，优选大于60重量％的S-SBR含量的上述橡胶的混合物。
橡胶可以是官能化橡胶，其中官能团可以是胺和/或酰胺和/或尿烷和/或脲和/或氨基硅氧烷和/或硅氧烷和/或甲硅烷基和/或烷基甲硅烷基，例如N,N-双(三甲基甲硅烷基)氨基丙基甲基二乙氧基硅烷或甲基三苯氧基硅烷，和/或卤代甲硅烷基和/或硅烷硫化物和/或硫醇和/或羟基和/或乙氧基和/或环氧基和/或羧基和/或锡，例如四氯化锡或二丁基二氯锡，和/或硅烷醇和/或六氯二硅氧烷和/或硫代羧基和/或腈和/或氮氧化物和/或酰胺基和/或亚氨基和/或氨基甲酸酯和/或尿素和/或二甲基咪唑啉酮和/或2-甲基-2-噻唑啉和/或2-苯并噻唑乙腈和/或2-噻吩甲腈和/或2-(N-甲基-N-3-三甲氧基甲硅烷基丙基)噻唑啉和/或碳二亚胺和/或具有氨基和/或异氰酸酯和/或异硫氰酸酯和/或肼和/或磺酰基和/或亚磺酰基和/或恶唑啉和/或酯基的N-取代的氨基醛和/或N-取代的氨基酮和/或N-取代的氨基硫醛和/或N-取代的氨基硫酮和/或二苯甲酮和/或硫代二苯甲酮。
本发明橡胶混合物所用的填料包括以下填料：
炭黑：此处使用的炭黑是通过灯黑法，炉黑法，气黑法或热法生产的，BET表面积为20-200m2/g。炭黑还可任选地包含杂原子，例如Si。
非晶态二氧化硅，例如通过从硅酸盐溶液中沉淀或卤化硅火焰水解生产的，其比表面积为5-1000m2/g，优选为20-400m2/g(BET表面积)，且初级粒径从10nm到400nm。二氧化硅也可以任选地为与其他金属氧化物(例如Al，Mg，Ca，Ba，Zn和钛)的氧化物的混合氧化物的形式。
BET表面积为20-400m2/g，初级粒径为10-400nm的合成硅酸盐(例如硅酸铝)，碱土金属硅酸盐(例如硅酸镁或硅酸钙)。
合成或天然氧化铝和合成或天然氢氧化铝。
天然硅酸盐，例如高岭土和其他天然存在的二氧化硅。
玻璃纤维和玻璃纤维产品(垫子，线)或玻璃微珠。
在每种情况下，基于100份橡胶，可以优选使用5-150重量份的量的无定形二氧化硅，所述无定形二氧化硅是通过从硅酸盐溶液中沉淀而产生的，BET表面积为20-400m2/g，特别是从100m2/g到250m2/g。
非常特别优选地，可以使用沉淀二氧化硅作为填料。
所述填料可以单独使用或混合使用。
根据本发明的橡胶混合物可包含5-150重量份的填料(B)和0.1-25重量份，优选2-20重量份，更优选5-15重量份的式I的含苯并噻唑的硅烷(C)，其中重量份为基于100重量份的橡胶计。
根据本发明的硅烷与所用的硫化促进剂的重量比可以大于3，优选大于5。
本发明的式I的含苯并噻唑的硅烷的优点在于它们能够生产具有足够加工特性的高度强化的橡胶混合物。根据本发明的硅烷的另一个优点是，即使在仅包含少量硫化促进剂的橡胶混合物中，它们也能实现高强化。
实施例
比较例1：2-[[3-(三乙氧基甲硅烷基)丙基]二硫]苯并噻唑的制备
2-[[3-(三乙氧基甲硅烷基)丙基]二硫代]苯并噻唑如US6465581实施例1中制备，但是使用CH2Cl2作为溶剂。
实施例1：2-[[((3,6,9,12,15-五氧二十八烷氧基)(二乙氧基)甲硅烷基)丙基]二硫]苯并噻唑的制备
向比较例1的2-[[3-(三乙氧基甲硅烷基)丙基]二硫]苯并噻唑(0.150mol)中加入3,6,9,12,15-五氧二十八烷-1-醇(0.150mol)和Ti(OnBu)4(0.05重量％/2-[[3-(三乙氧基甲硅烷基)丙基]二硫]苯并噻唑)。将混合物加热至140℃，蒸馏出形成的乙醇，并在1小时后，达到400-600mbar的压力。1小时后，将压力降至16-200mbar，并将混合物搅拌4小时。随后，使反应混合物冷却至室温，并将反应产物过滤。获得粘稠液体的2-[[((3,6,9,12,15-五氧二十八烷氧基)(二乙氧基)甲硅烷基)丙基]二硫]苯并噻唑(收率：85％，酯交换度31％＝0.93mol聚醚醇/Si)。
通过13C NMR的方法测定纯度。在NMR中，与62.1ppm处的键合变体相比，CH2基团的位移为61.8ppm(与OH基团相邻)是特征性的，可以与58.0ppm处的硅原子上残留的环氧基进行比较。
实施例2：2-[[((双-3,6,9,12,15-五氧二十八烷氧基)(乙氧基)甲硅烷基)丙基]二硫]苯并噻唑的制备
向比较例1的2-[[3-(三乙氧基甲硅烷基)丙基]二硫]苯并噻唑(0.150mol)中加入3,6,9,12,15-五氧二十八烷-1-醇(0.300mol)和Ti(OnBu)4(0.05重量％/2-[[3-(三乙氧基甲硅烷基)丙基]二硫]苯并噻唑)。将混合物加热至140℃，蒸馏出形成的乙醇，并在1小时后，达到400-600mbar的压力。1小时后，将压力降至16-200mbar，并将混合物搅拌4小时。随后，使反应混合物冷却至室温，并将反应产物过滤。获得粘稠液体的2-[[((双-3,6,9,12,15-五氧二十八烷氧基)(乙氧基)甲硅烷基)丙基]二硫]苯并噻唑(收率：98％，酯交换度65％＝1.95mol聚醚醇/Si)。
通过13C NMR的方法测定纯度。在NMR中，与62.1ppm处的键合变体相比，CH2基团的位移为61.8ppm(与OH基团相邻)是特征性的，可以与58.0ppm处的硅原子上残留的环氧基进行比较。
实施例3：2-[[((三-3,6,9,12,15-五氧二十八烷氧基)甲硅烷基)丙基]二硫]苯并噻唑的制备
向比较例1的2-[[3-(三乙氧基甲硅烷基)丙基]二硫]苯并噻唑(0.150mol)中加入3,6,9,12,15-五氧二十八烷-1-醇(0.450mol)和Ti(OnBu)4(0.05重量％/2-[[3-(三乙氧基甲硅烷基)丙基]二硫]苯并噻唑)。将混合物加热至140℃，蒸馏出形成的乙醇，并在1小时后，达到400-600mbar的压力。1小时后，将压力降至16-200mbar，并将混合物搅拌4小时。随后，使反应混合物冷却至室温，并将反应产物过滤。获得粘稠液体的2-[[((三-3,6,9,12,15-五氧二十八烷氧基)甲硅烷基)丙基]二硫]苯并噻唑(收率：94％，酯交换度＞95％＝＞2.85mol聚醚醇/Si)。
通过13C NMR的方法测定纯度。在NMR中，与62.1ppm处的键合变体相比，CH2基团的位移为61.8ppm(与OH基团相邻)是特征性的，可以与58.0ppm处的硅原子上残留的环氧基进行比较。
实施例4：橡胶混合物
在该实施例中，将本发明的硅烷与现有技术中已知的含苯并噻唑的硅烷进行比较。
下表1中列出了用于橡胶混合物的配方。在该表中，单位phr是指基于100份所用的粗橡胶的重量份。
用于实施例混合物I的本发明的硅烷I是在实施例I中制备的本发明的硅烷。其结构对应于通式I，其中R1＝乙氧基，R2＝O(C2H4O)5C13H27，R3＝–CH2CH2CH2-，n＝2。
用于实施例混合物II的本发明的硅烷II是在实施例II中制备的本发明的硅烷II。其结构对应于通式I，其中R1＝乙氧基，R2＝O(C2H4O)5C13H27，R3＝–CH2CH2CH2-，n＝1。
用于实施例混合物III的本发明的硅烷III是在实施例III中制备的本发明的硅烷。其结构对应于通式I，其中R2＝O(C2H4O)5C13H27，R3＝–CH2CH2CH2-，n＝0。
计量入根据本发明的硅烷，从而使硅烷与硫化促进剂Vulkacit CZ的比例超过数值5。
通常，在橡胶混合物中使用1.5phr至2.5phr的硫化促进剂量。在该实施例中，仅使用0.8phr的硫化促进剂Vulkacit CZ，因此在每种情况下所用的硅烷与促进剂的比例均大于5。
用于对照混合物I和II的硅烷
和Si 363TM可购自Evonik Industries AG。用于对照混合物III的硅烷为2-[[3-(三乙氧基甲硅烷基)丙基]二硫]苯并噻唑，其在比较例1中制备。
表1
所用的物质：
a聚合物VSL 4526-2是Lanxess AG的溶液聚合的SBR共聚物，其苯乙烯含量为26重量％，丁二烯含量为74重量％。该共聚物包含26重量％的油，门尼粘度(ML1+4/100℃)为50。
聚合物Buna CB 24为Bayer AG的顺式1,4-聚丁二烯(钕型)，顺式1,4含量至少为96％，门尼粘度为44。
7000GR为Evonik Industries AG的易分散二氧化硅，BET表面积为170m2/g。
所用的工艺油为Hansen&Rosenthal KG的Vivatec 500。Vulkanox 4020(6PPD)、Vulkacit CZ(CBS)和Vulkacit D(DPG)为Lanxess Deutschland GmbH的商业产品，Protektor G3108为Paramelt B.V.的抗臭氧蜡。助活化剂Perkacit Richon TBzTD(四苄基秋兰姆四硫化物)为Weber&Schaer GmbH&Co KG的产品。
Corax N330为Orion Engineered Carbons GmbH的商用炭黑。
根据表2中所述的混合说明，在1.5升内部混合器(E型)中，批料温度为155℃，分三步制备混合物。
表2
生产橡胶混合物及其硫化产物的一般方法描述在“Rubber TechnologyHandbook”,W.Hofmann,Hanser Verlag 1994中。
根据表3中指定的测试方法进行橡胶测试。
表3
所有混合物均通过在165℃的压力下硫化15分钟来生产试样。表4列出了获得的橡胶数据。
表4
所有三个实施例混合物的门尼粘度ML(1+4)[100℃]低于含有现有技术中已知的硅烷的对照混合物II和III。与含有常规硅烷
的对照混合物I的比较表明，在实施例混合物中，对照混合物II和III的有利橡胶值曲线得以保持。与对照混合物I相比，在300％伸长率下的模量和300％/100％模量增强指数仍然高得多。tanδ、60℃值明显降低所表示的迟滞损耗大大降低了。
对于本领域技术人员而言，令人惊讶且出乎意料的是，根据本发明的具有最低用量的硅烷的实施例混合物I具有最平衡的橡胶值曲线。其具有实施例混合物的最高动态模量E*(0℃)。门尼粘度与包含常规硅烷
的对照混合物I的数量级相同。与对照混合物II和III相比，拉伸强度有所提高。同时，它具有较高的断裂伸长率。
实施例5：
在该实施例中，将在包含天然橡胶的橡胶混合物中的本发明的硅烷与含有现有技术中已知的苯并噻唑的硅烷进行比较。
下表5中列出了用于橡胶混合物的配方。单位phr再次是指基于100份所用的粗橡胶的重量份。硅烷的用量要与二氧化硅的用量相匹配。
用于实施例混合物I的本发明的硅烷I是在实施例I中制备的本发明的硅烷。其结构对应于通式I
其中R1＝乙氧基，R2＝O(C2H4O)5C13H27，R3＝–CH2CH2CH2-和n＝2。
用于实施例混合物II的本发明的硅烷II是在实施例II中制备的本发明的硅烷。其结构对应于通式I
其中R1＝乙氧基，R2＝O(C2H4O)5C13H27，R3＝–CH2CH2CH2-，n＝1。
用于实施例混合物III的本发明的硅烷III是在实施例III中制备的本发明的硅烷。其结构对应于通式I
其中R2＝O(C2H4O)5C13H27，R3＝–CH2CH2CH2-，n＝0。
用于对照混合物I和II的硅烷
和Si 363TM可购自Evonik Industries AG。用于对照混合物III的硅烷为2-[[3-(三乙氧基甲硅烷基)丙基]二硫]苯并噻唑，其在比较例1中制备。如实施例4中所述可得到其他化学品。
根据本发明的硅烷以等摩尔剂量使用。
表5
根据表6中所述的混合说明，在1.5升内部混合器(E型)中在批料温度为150℃下分三阶段制备混合物。所有混合物通过在150℃的压力下硫化来生产试样。根据表3中指定的测试方法进行橡胶测试。结果如表7中所示。
表6
表7
对于所有三种实施例混合物，门尼粘度均低于对照混合物III的粘度。所有实施例混合物均比三种对照混合物具有更高的拉伸强度和更高的300％模量。同时，所有这些实施例混合物的断裂伸长率都有所增加。与对照混合物相比，增加的60℃的落球回弹值以及较低的tanδ(60℃)的值是其他的优点。
Claims (10)
1.一种式I的含苯并噻唑的硅烷，
其中R1相同或不同且为R4O-基团，R4为H、甲基、乙基、丙基、C9-C30支化或非支化的一价烷基、烯基、芳基或芳烷基，
R2为烷基聚醚基-O-(R5-O)m-R6，其中R5相同或不同，为支化或非支化、饱和或不饱和的脂肪族二价C1-C30烃基，m为1至30，并且R6是支化或非支化的C1-C30烷基，
R3是支化或非支化、饱和或不饱和的脂族、芳族或混合的脂族/芳族二价C1-C30烃基，
x＝2-10和
n＝0、1或2。
2.根据权利要求1所述的含苯并噻唑的硅烷，其特征在于，R1为甲氧基或乙氧基。
3.根据权利要求1所述的含苯并噻唑的硅烷，其特征在于，R2＝-O-(CH2CH2O)5-C13H27。
4.根据权利要求1所述的含苯并噻唑的硅烷，其特征在于，R1＝-O-C2H5，R2＝-O-(CH2CH2O)5-C13H27，R3＝(CH2)3，x＝2，且n＝2。
5.一种制备根据权利要求1的式I的含苯并噻唑的硅烷的方法，其特征在于，式II的含苯并噻唑的硅烷
与式III的化合物反应
R2-H(III)，
其中R1、R2、R3、x和n具有上述的定义。
6.根据权利要求5的制备所述式I的含苯并噻唑的硅烷的方法，其特征在于，反应在催化剂存在消除R1-H下进行。
7.权利要求1的式I的含苯并噻唑的硅烷在填充的橡胶混合物中作为偶联剂的用途。
8.橡胶混合物，其包括
(A)一种橡胶或多种橡胶的混合物，
(B)填料，和
(C)至少一种权利要求1的通式I的含苯并噻唑的硅烷。
9.根据权利要求8所述的橡胶混合物，其特征在于，所使用的硅烷与所使用的硫化促进剂的比例大于5。
10.根据权利要求8所述的橡胶混合物，其特征在于，
(A)是天然橡胶或橡胶与天然橡胶的混合物。
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