CN1405169A - 有机硅化合物、及其制造方法和应用 - Google Patents
有机硅化合物、及其制造方法和应用 Download PDFInfo
- Publication number
- CN1405169A CN1405169A CN02127650A CN02127650A CN1405169A CN 1405169 A CN1405169 A CN 1405169A CN 02127650 A CN02127650 A CN 02127650A CN 02127650 A CN02127650 A CN 02127650A CN 1405169 A CN1405169 A CN 1405169A
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- Prior art keywords
- rubber
- silicoorganic compound
- compound
- chain
- general formula
- Prior art date
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- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims description 45
- 238000002360 preparation method Methods 0.000 title claims description 4
- 229920001296 polysiloxane Polymers 0.000 title 1
- 229920001971 elastomer Polymers 0.000 claims abstract description 57
- 239000005060 rubber Substances 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000011541 reaction mixture Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 71
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 24
- 229910000077 silane Inorganic materials 0.000 claims description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910000765 intermetallic Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 4
- 101000923234 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) L-asparaginase 1 Proteins 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- SIWVGXQOXWGJCI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;2-ethenylbenzenesulfonic acid Chemical compound C=CC1=CC=CC=C1C=C.OS(=O)(=O)C1=CC=CC=C1C=C SIWVGXQOXWGJCI-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 230000002265 prevention Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 230000035939 shock Effects 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 abstract description 12
- 150000003961 organosilicon compounds Chemical class 0.000 abstract 3
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- 150000004756 silanes Chemical class 0.000 abstract 1
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 40
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 30
- 229910052717 sulfur Inorganic materials 0.000 description 27
- -1 methacryloxy Chemical group 0.000 description 23
- 239000010936 titanium Substances 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
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- 239000007788 liquid Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 15
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- 239000003795 chemical substances by application Substances 0.000 description 12
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 11
- 238000004513 sizing Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 150000004703 alkoxides Chemical class 0.000 description 9
- 229940059260 amidate Drugs 0.000 description 8
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N methyl alcohol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 150000007944 thiolates Chemical class 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
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- 239000003054 catalyst Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 230000009466 transformation Effects 0.000 description 4
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 101100243399 Caenorhabditis elegans pept-2 gene Proteins 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
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- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000003365 glass fiber Substances 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
- 150000002736 metal compounds Chemical class 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
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- 239000005061 synthetic rubber Substances 0.000 description 2
- UCEOYIRETCABER-UHFFFAOYSA-N tetradecan-5-ol Chemical compound CCCCCCCCCC(O)CCCC UCEOYIRETCABER-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
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- 239000001993 wax Substances 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-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
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 1
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- 239000012190 activator Substances 0.000 description 1
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- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
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- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
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- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
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- 238000006073 displacement reaction Methods 0.000 description 1
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- YLGZRMLFAGSRHM-UHFFFAOYSA-N dodecanoic acid;tin Chemical compound [Sn].CCCCCCCCCCCC(O)=O YLGZRMLFAGSRHM-UHFFFAOYSA-N 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
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- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
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- 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
- 229910052746 lanthanum Inorganic materials 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
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
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- FGFWCOVNCKWNLU-UHFFFAOYSA-N oxalic acid;tin Chemical compound [Sn].OC(=O)C(O)=O FGFWCOVNCKWNLU-UHFFFAOYSA-N 0.000 description 1
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- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CIZOCKPOEXXEHB-UHFFFAOYSA-N tetradecan-3-ol Chemical compound CCCCCCCCCCCC(O)CC CIZOCKPOEXXEHB-UHFFFAOYSA-N 0.000 description 1
- HRDGAIGDKJXHIU-UHFFFAOYSA-N tetradecan-4-ol Chemical compound CCCCCCCCCCC(O)CCC HRDGAIGDKJXHIU-UHFFFAOYSA-N 0.000 description 1
- KATMMOGJSFLTOP-UHFFFAOYSA-N tetradecan-6-ol Chemical compound CCCCCCCCC(O)CCCCC KATMMOGJSFLTOP-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- PIZNQHDTOZMVBH-UHFFFAOYSA-N thionylimide Chemical class N=S=O PIZNQHDTOZMVBH-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及通式I和/或II有机硅化合物、及其制造方法和应用I、Ⅱ,该化合物是如下制备的：通式III的硅烷与通式R′－OH的醇反应，消除R－OH，然后连续地通过蒸馏由反应混合物中分离R－OH,该有机硅化合物可用于混炼胶中。
Description
技术领域
本发明涉及有机硅化合物、及其制造方法和应用。
背景技术
使用硅烷作为粘结促进剂是已知的。氨基烷基三烷氧基硅烷如3-氨基-丙基三甲氧基硅烷和3-氨基丙基三乙氧基硅烷，甲基丙烯酰氧基烷基三烷氧基硅烷如3-甲基丙烯酰氧基丙基三甲氧基硅烷，多硫烷烷基三烷氧基硅烷如二[3-乙氧基-甲硅烷基丙基]多硫烷和二[3-乙氧基甲硅烷基丙基]-二硫烷，以及巯基烷基三烷氧基硅烷如3-巯基丙基三甲氧基硅烷和3-巯基丙基三乙氧基硅烷，被用作无机材料如玻璃纤维、金属或者氧化物填料与有机材料如热固性树脂、热塑性树脂和弹性体之间的粘结促进剂，或者作为交联剂和表面改性剂。
这些粘结促进剂或者偶联剂或者粘合剂与填料和弹性体都可形成键合，因此可确保填料表面和弹性体之间的良好相互作用。它们降低了混合物的粘度并易于填料的分散。
还已知的是，使用在硅原子上有三个烷氧基取代基的常规市售硅烷粘结促进剂(DE 22 55 577)，会在与填料粘合期间以及之后导致释放大量的醇。因为所用的硅烷通常是三甲氧基和三乙氧基取代的，所以释放大量的相应醇-甲醇和乙醇。
还已知的是，甲氧基和乙氧基取代的硅烷比相应的长链烷氧基取代的硅烷具有更高的反应活性，并由此能够更为快速地使它们本身与填料键合在一起，所以从经济方面考虑，甲氧基和乙氧基取代的硅烷的使用是不可或缺的。
已知有机硅化合物的一个缺点是在硅烷与填料键合期间以及之后会向环境中释放挥发性的醇如甲醇和乙醇
本发明的目的是生产在与填料键合期间释放更少量的挥发性醇并同时具有更高的反应活性的有机硅化合物。
发明内容
本发明提供以下通式I和/或II的有机硅化合物：(I)
(II)式中R是甲基或乙基；
R′可相同或不同，代表C9-C30支链或直链单价烷基或者烯基、芳基、芳烷基、支链或直链C2-C30烷基醚基、支链或直链C2-C30烷基聚醚基、或者R3Si，其中R是C1-C30支链或直链烷基或烯基、芳烷基、或芳基，
R″代表支链或直链的、饱和或不饱和的、脂族的、芳香的或者脂族/芳香混合的二价C1-C30烃基，
X是NH(3-n)，其中n＝1、2、3而m＝1；O(C＝O)-R，其中n＝1而m＝1；SH，其中n＝1而m＝1；S，其中n＝2而m＝1-10，以及它们的混合物；S(C＝O)-R，其中n＝1而m＝1；或者H，其中n＝1而m＝1。
R″可代表CH2、CH2CH2、CH2CH2CH2、CH2CH2CH2CH2、CH(CH3)、CH2CH(CH3)、C(CH3)2、CH(C2H5)、CH2CH2CH(CH3)、CH2CH(CH3)CH2或者
根据本发明的通式I或II的有机硅化合物可以是：
本发明还提供一种根据本发明的有机硅化合物的制造方法，其特征在于通式III的硅烷
(III)其中R、R″、X、m和n与以上定义相同，与通式R′-OH的醇反应，其中R′与以上定义相同，消除R-OH，然后连续地通过蒸馏由反应混合物中分离R-OH。
在根据本发明的方法中，可得到混合物，其中一个、二个、三个RO基团或者没有RO基团被R′O基团置换。RO基团与R′O基团的比例可通过通式III硅烷与通式R′-OH醇的摩尔比来确定。例如，当n＝1时，具有根据通式I之平均组成的有机硅化合物可通过使2摩尔当量的通式R′-OH醇与1摩尔当量的通式III硅烷反应来制备。例如，当n＝2时，具有根据通式I之平均组成的有机硅化合物可通过使4摩尔当量的通式R′-OH醇与1摩尔当量的通式III硅烷反应来制备。
该混合物可以原样使用或者分离成单个的化合物。
当R′＝R3Si时，通式III的硅烷可与R3Si-OH或者与R3Si-O-SiR3反应。化合物R3Si-O-SiR3可水解形成R3Si-OH，然后与通式III的硅烷反应。
该反应可用中性、酸性或者碱性催化剂来加速，如盐酸、硫酸、磷酸、甲酸、乙酸、对甲苯磺酸、氢氧化钠溶液、氢氧化钾溶液、甲醇钠、乙醇钠、Deloxan ASP I/9、Amberlyst 15离子交换树脂或者金属化合物。
金属化合物也可以是过渡金属化合物。
可用作催化剂的金属化合物是金属氯化物、金属氧化物、金属氯氧化物、金属醇盐、金属羟醇盐(oxyalkoxide)、金属酰胺化物、金属酰亚胺化物、或者带有多个结合配体的过渡金属化合物。例如，金属化合物可以是：
第3主族金属的卤化物、酰胺化物或者醇盐(M3+＝B、Al、Ga、In、Tl：M3+(OMe)3、M3+(OEt)3、M3+(OC3H7)3、M3+(OC4H9)3)，
镧系元素(稀土元素，元素周期表中原子数为58-71的元素)的卤化物、氧化物、酰亚胺化物、醇盐、酰胺化物、硫醇盐以及化合物上上述类别的取代基与多个结合配体的组合，
第3副族金属的卤化物、氧化物、酰亚胺化物、醇盐、酰胺化物、硫醇盐以及化合物上上述类别的取代基与多个结合配体的组合(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主族元素的卤化物、酰胺化物、硫醇盐或者醇盐(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)，
第4副族元素的卤化物、氧化物、酰亚胺化物、醇盐、酰胺化物、硫醇盐以及化合物上上述类别的取代基与多个结合配体的组合(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)，
第5副族元素的卤化物、氧化物、酰亚胺化物、醇盐、酰胺化物、硫醇盐以及化合物上上述类别的取代基与多个结合配体的组合(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)，
第6副族元素的卤化物、氧化物、酰亚胺化物、醇盐、酰胺化物、硫醇盐以及化合物上上述类别的取代基与多个结合配体的组合(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)，或者
第7副族元素的卤化物、氧化物、酰亚胺化物、醇盐、酰胺化物、硫醇盐以及化合物上上述类别的取代基与多个结合配体的组合(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))。
上述金属化合物可在金属上具有游离的配位部位。
通过添加水产生可水解的金属化合物而形成的金属化合物也可用作催化剂。
在一个具体的实施方案中，可使用钛酸酯作为催化剂，例如原钛酸四正丁基酯或者原钛酸四异丙基酯。
金属化合物可以是无水的，其结果是可向反应混合物中引入更少量的水，并得到更少的寡聚硅烷化合物。
反应在20-200℃之间的温度进行。为避免缩合反应，在无水气氛、优选惰性气体氛围下进行反应是有利的。
根据本发明的有机硅化合物可用作无机材料(如比例纤维、金属、氧化物填料、二氧化硅)与有机聚合物(如热固性树脂、热塑性树脂、弹性体)之间的粘结促进剂，或者作为交联剂和表面改性剂。根据本发明的有机硅化合物可在填充有二氧化硅和/或淀粉的轮胎中用作粘结促进剂。
本发明还提供混炼胶，其特征在于含有橡胶、填料例如沉淀二氧化硅、任选的其他橡胶助剂、以及至少一种根据本发明的有机硅化合物。
相对于所用橡胶重量，根据本发明的有机硅化合物的用量可以是0.1～20重量％。
根据本发明的有机硅化合物以及填料的添加优选在100～200℃的主温度(Massetemperatur)下进行。但是也可以在低温(40～100℃)下接着与其他橡胶助剂一起添加。
有机硅化合物可以纯物质形式或者施加到有机或无机惰性载体上的形式添加到混炼过程中。优选的载体材料是二氧化硅、蜡、热塑性树脂、天然或者合成的硅酸盐、氧化铝或者炭黑。
作为填料，下列物质可以用于本发明的混炼胶中：
—炭黑：这里使用的炭黑可以是由灯黑、炉黑或气黑方法制备，BET比表面为20～200m2/g，例如SAF、ISAF、HSAF、HAF、FEF或GPF炭黑。这些炭黑也可以任选含有如Si的杂原子。
—高分散性二氧化硅，例如由硅酸盐溶液沉淀或卤化硅燃烧水解制备，比表面为5～1000m2/g、优选为20～400m2/g(BET比表面)，主要颗粒尺寸为10～400nm。这些二氧化硅还可以是任选地与诸如Al、Mg、Ca、Ba、Zn和钛等其它金属氧化物的混合氧化物。
—合成硅酸盐例如硅酸铝、碱土金属硅酸盐如硅酸镁或硅酸钙，其BET比表面为20～400m2/g，主要颗粒直径为10～400nm。
—合成或者天然的氧化铝和氢氧化铝。
—天然硅酸盐，例如高岭土和其它自然存在的二氧化硅。
—玻璃纤维和玻璃纤维制品(毡片、纱条)或玻璃微珠。
优选使用BET比表面为20～400m2/g且通过硅酸盐溶液沉淀制得的高分散性硅酸。其添加量优选是每100份橡胶5～150份。
上述填料可以单独使用或以混合物使用。在该方法特别优选的实施方案中，生产胶料时，相对于每100重量份橡胶可以使用10～150重量份的淡颜色填料，任选与0～100重量份的炭黑以及0.3～10重量份根据本发明的有机硅化合物一起使用。
除天然橡胶外，合成橡胶也适于生产根据本发明的混炼胶。优选的合成橡胶是例如W.Hofmann在《橡胶工艺学》(Genter Verlag，斯图加特，1980)一书中介绍过的。这样的橡胶特别包括：
-聚丁二烯(BR)；
-聚异戊二烯(IR)；
-苯乙烯/丁二烯共聚物(SBR)，其中苯乙烯含量1～60重量％，优选2～50重量％；
-异丁烯/异戊二烯共聚物(IIR)；
-丁二烯/丙烯腈共聚物(NBR)，其中丙烯腈含量5～60重量％，优选10～50重量％；
-部分氢化或全部氢化的NBR橡胶(HNBR)；
-乙烯/丙烯/二烯烃共聚物(EPDM)；以及这些橡胶的混合物。玻璃转化温度为-50℃以上的阴离子聚合S-SBR(溶液SBR)及其与二烯烃橡胶的混炼胶特别适于生产汽车轮胎。
根据本发明的硫化橡胶可以含有其他橡胶助剂，例如反应促进剂、防老剂、热稳定剂、光稳定剂、抗臭氧剂、操作助剂、增塑剂、增粘剂、发泡剂、染料、颜料、石蜡、增量剂、有机酸、阻聚剂、金属氧化物以及活化剂，如三乙醇胺、聚乙二醇、己三醇，这些助剂都是橡胶工业中熟知的。
这些橡胶助剂可以按照预定用途控制加量。一般用量例如是橡胶用量的0.1～50重量％。硫或者能提供硫的物质可用作硫化剂。本发明混炼胶还可以含硫化促进剂。适宜的硫化促进剂例如有：巯基苯并噻唑类、亚磺酰胺类、胍类、秋兰姆类、二硫代氨基甲酸盐类、硫脲类和硫代碳酸盐类。硫化促进剂和硫的用量是橡胶用量的0.1～10重量％，优选0.1～5重量％。
本发明混炼胶的硫化可以在温度100～200℃、优选130～180℃，任选压力10～200巴下进行。橡胶与填料、任选橡胶助剂以及根据本发明的有机硅化合物的混炼，可以在已知混炼设备如开炼机、密炼机和螺杆混炼机中进行。
本发明混炼胶适于生产模制品，例如生产充气轮胎、胎面、电缆护套、软管、传动带、输送带、辊筒罩面、轮胎、鞋底、密封环和防震元件。
根据本发明的有机硅化合物的优点是与已知的硅烷相比在恒定的反应活性下释放更少量的甲醇或者乙醇。由于是非活性的，非挥发性醇不会由硅烷中分离，或者由于它们是非挥发性的，仍保留在聚合物基质中。在各种情况下，它们都不释放在环境中。
具体实施方式
实施例1
首先在室温下将200.0g的二(3-三乙氧基甲硅烷基丙基)多硫烷(式III，其中R＝乙基，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)和70.0g的1-十二烷醇(R′＝C12H25)添加至装配有蒸馏装置的1L四口烧瓶中，然后与1.0g的Amberlyst 15混合。将黄色溶液加热至100-130℃，蒸馏除去所得的乙醇，然后在1.5小时内滴加210g的1-十二烷醇。通过蒸馏连续除去所形成的乙醇。在反应将要结束时，将温度短暂地升高至150℃。在80℃、50mbar的真空下，在旋转蒸发器中蒸馏混合物。得到408.5g(99.4％)的式I(其中R＝乙基，R′＝C12H25，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)黄色液体。
实施例2
首先在室温下将200.0g的二(3-三乙氧基甲硅烷基丙基)多硫烷(式III，其中R＝乙基，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)和70.0g的1-十二烷醇(R′＝C12H25)添加至装配有蒸馏装置的1L四口烧瓶中，然后与0.7g的对甲苯磺酸-水合物混合。将黄色溶液加热至100-105℃，蒸馏除去所得的乙醇，然后在1.5小时内滴加210g的1-十二烷醇。通过蒸馏连续除去所形成的乙醇。在反应将要结束时，将温度短暂地升高至130℃。在80℃、50mbar的真空下，在旋转蒸发器中蒸馏混合物。得到389.1g(94.7％)的式I(其中R＝乙基，R′＝C12H25，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)黄色液体。
实施例3
首先在室温下将200.0g的二(3-三乙氧基甲硅烷基丙基)多硫烷(式III，其中R＝乙基，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)和60.6g的二乙二醇单丁基醚(R′＝(CH2)2-O-(CH2)2-O-C4H9)添加至装配有蒸馏装置的1L四口烧瓶中，然后与1.0g的Amberlyst 15混合。将黄色溶液加热至115-130℃，蒸馏除去所得的乙醇，然后在1.5小时内滴加183.2g的二乙二醇单丁基醚。通过蒸馏连续除去所形成的乙醇。在80℃、25mbar的真空下，在旋转蒸发器中蒸馏混合物。得到367.2g(98.2％)的式I(其中R＝乙基，R′＝(CH2)2-O-(CH2)2-O-C4H9，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)黄色液体。
实施例4
首先在室温下将200.0g的二(3-三乙氧基甲硅烷基丙基)多硫烷(式III，其中R＝乙基，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)和60.9g的二乙二醇单丁基醚(R′＝(CH2)2-O-(CH2)2-O-C4H9)添加至装配有蒸馏装置的1L四口烧瓶中，然后与0.7g的对甲苯磺酸-水合物混合。将黄色溶液加热至120-130℃，蒸馏除去所得的乙醇，然后在1.5小时内滴加182.8g的二乙二醇单丁基醚。通过蒸馏连续除去所形成的乙醇。在80℃、20mbar的真空下，在旋转蒸发器中蒸馏混合物。得到358.5g(95.1％)的式I(其中R＝乙基，R′＝(CH2)2-O-(CH2)2-O-C4H9，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)黄色液体。
实施例5
首先在室温下将200.0g的二(3-三乙氧基甲硅烷基丙基)多硫烷(式III，其中R＝乙基，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)、和80.5g的1-十四烷醇(R′＝-C14H29)添加至装配有蒸馏装置的1L四口烧瓶中，然后与0.7g的对甲苯磺酸-水合物混合。将黄色溶液加热至120-130℃，蒸馏除去所得的乙醇，然后在2小时内滴加241.7g的1-十四烷醇。通过蒸馏连续除去所形成的乙醇。在80℃、20mbar的真空下，在旋转蒸发器中蒸馏混合物。得到432.1g(95.4％)的式I(其中R＝乙基，R′＝C14H29，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)黄色液体。
实施例6
首先在室温下将200.0g的二(3-三乙氧基甲硅烷基丙基)多硫烷(式III，其中R＝乙基，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)和80.5g的1-十四烷醇(R′＝-C14H29)添加至装配有蒸馏装置的1L四口烧瓶中，然后与1.0g得自于Degussa的Deloxan ASP I/9混合。将黄色溶液加热至120-130℃，蒸馏除去所得的乙醇，然后在2小时内滴加241.7g的1-十四烷醇。通过蒸馏连续除去所形成的乙醇。在80℃、20mbar的真空下，在旋转蒸发器中蒸馏混合物。得到448.3g(99.0％)的式I(其中R＝乙基，R′＝-C14H29，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)黄色液体。
实施例7
首先在室温下将200.0g的二(3-三乙氧基甲硅烷基丙基)多硫烷(式III，其中R＝乙基，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)和50.4g的二乙二醇单乙基醚(R′＝(CH2)2-O-(CH2)2-O-C2H5)添加至装配有蒸馏装置的1L四口烧瓶中，然后与0.7g的对甲苯磺酸-水合物混合。将黄色溶液加热至125-130℃，蒸馏除去所得的乙醇，然后在1.5小时内滴加151.2g的二乙二醇单乙基醚。通过蒸馏连续除去所形成的乙醇。在80℃、25mbar的真空下，在旋转蒸发器中蒸馏混合物。得到321.0g(96.6％)的式I(其中R＝乙基，R′＝(CH2)2-O-(CH2)2-O-C2H5，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)黄色液体。
实施例8
首先在室温下将200.0g的二(3-三乙氧基甲硅烷基丙基)多硫烷(式III，其中R＝乙基，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)和50.4g的二乙二醇单乙基醚(R′＝(CH2)2-O-(CH2)2-O-C2H5)添加至装配有蒸馏装置的1L四口烧瓶中，然后与1.0g的Amberlyst 15混合。将黄色溶液加热至125℃，蒸馏除去所得的乙醇，然后在1.5小时内滴加151.2g的二乙二醇单乙基醚。通过蒸馏连续除去所形成的乙醇。在80℃、25mbar的真空下，在旋转蒸发器中蒸馏混合物。得到321.9g(96.9％)的式I(其中R＝乙基，R′＝(CH2)2-O-(CH2)2-O-C2H5，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)黄色液体。
实施例9
首先在室温下将200.0g的二(3-三乙氧基甲硅烷基丙基)多硫烷(式III，其中R＝乙基，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)和71.8g的二乙二醇单己基醚(R′＝(CH2)2-O-(CH2)2-O-C6H13)添加至装配有蒸馏装置的1L四口烧瓶中，然后与0.7g的对甲苯磺酸-水合物混合。将黄色溶液加热至125℃，蒸馏除去所得的乙醇，然后在1.5小时内 滴加214.2g的二乙二醇单己基醚。通过蒸馏连续除去所形成的乙醇。在80℃、25mbar的真空下，在旋转蒸发器中蒸馏混合物。得到414.4g(99.4％)的式I(其中R＝乙基，R′＝(CH2)2-O-(CH2)2-O-C6H13，R″＝CH2CH2CH2，X＝S，n＝2，而m＝3.8)黄色液体。
实施例10
首先在室温下将125.2g的3-巯基丙基三乙氧基硅烷(式III，其中R＝-CH2CH3，R″＝-CH2CH2CH2-，X＝-SH，n＝1，而m＝1)和22.5g的1-十四烷醇(R′＝-C14H29)添加至装配有蒸馏装置的1L四口烧瓶中，然后与1.0g的对甲苯磺酸-水合物混合。将黄色溶液加热至120℃，然后在开始蒸馏出乙醇时，立即在1.5小时内添加202.6g的1-十四烷醇。通过蒸馏连续除去所形成的乙醇。在80℃、20mbar的真空下，在旋转蒸发器中蒸馏混合物。得到298.8g(98.9％)的式I(其中R＝-CH2CH3，R′＝-C14H29，R″＝-CH2CH2CH2-，X＝-SH，n＝1，m＝1)无色液体。
实施例11在实际的橡胶应用中测试有机硅化合物
混炼胶所用的配方在下表1中给出。这里的单位“phr”表示相对于100份所用生胶的重量份。生产混炼胶及其硫化胶的一般工艺在W.Hofmann的《橡胶工艺手册》(Hanser Verlag，1994)一书中介绍过。
表1
| 混炼胶1参比物 | 混炼胶2 | 混炼胶3 | 混炼胶4 | 混炼胶5 | 混炼胶6 | 混炼胶7 | 混炼胶8 | 混炼胶9 | |
| 第一段 | |||||||||
| Buna VSL5025-1 | 96 | 96 | 96 | 96 | 96 | 96 | 96 | 96 | 96 |
| BunaCB 24 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| Ultrasil 7000GR | 80 | 80 | 80 | 80 | 80 | 80 | 80 | 80 | 80 |
| Si69 | 6.4 | - | - | - | - | - | - | - | - |
| 实施例1 | - | 13.01 | - | - | - | - | - | - | - |
| 实施例2 | - | - | 13.35 | - | - | - | - | - | - |
| 实施例3 | - | - | - | - | - | - | - | - | - |
| 实施例4 | - | - | - | 11.82 | - | - | - | - | - |
| 实施例5 | - | - | - | - | 14.5 | - | - | - | - |
| 实施例6 | - | - | - | - | - | 13.61 | - | - | - |
| 实施例7 | - | - | - | - | - | - | 10.30 | - | - |
| 实施例8 | - | - | - | - | - | - | - | 10.30 | - |
| 实施例9 | - | - | - | - | - | - | - | - | 13.27 |
| ZnO | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| 硬脂酸 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Naftolen | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Vulkanox 4020 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Protektor G35P | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| 第二段 | |||||||||
| 配料段1 | |||||||||
| 第三段 | |||||||||
| 配料段2 | |||||||||
| Vulkacit D | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Vulkacit CZ | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| 硫磺 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
聚合物VSL 5025-1是从拜耳公司获得的一种苯乙烯含量25重量％、丁二烯含量为75重量％的溶液聚合的SBR共聚物。该共聚物含有37.5phr油，其Mooney粘度(ML 1+4/100℃)大约为50。
聚合物Buna CB 24是从拜耳公司获得的顺式-1，4聚丁二烯(钕型)，其顺式-1，4含量至少为97％、Mooney粘度为44±5。
Naftolen ZD是购自Chemetall的芳烃油。Vulkanox 4020是购自拜耳公司的6PPD，Protektor G35P是购自HB-Fuller GmbH的抗臭氧剂蜡。Vulkacit D(DPG)和Vulkacit CZ(CBS)是拜耳公司的市售产品。
Ultrasil 7000 GR是从Degussa AG获得的易于分散的沉淀二氧化硅，其BET比表面为175m2/g。Si 69是二-(3-[三乙氧甲硅烷基]-丙基)四硫烷，是Degussa AG的商品。
混炼胶是在密炼机中按照表2中的混炼说明生产的。
表2
| 第1段 | |
| 定型 | |
| 混炼装置转数冲压压力空腔容积填充度贯流温度 | Werner&Pfleiderer E-型70min-15.5bar1.58L0.5670℃ |
| 混炼程序 | |
| 0～1分钟1～3分钟3～4分钟4分钟4～5分钟5分钟胶料温度储存 | Buna VSL 5025-1+Buna CB 241/2填料、ZnO、硬脂酸、Naftolen ZD、硅烷1/2填料、抗氧剂清洗混炼，可调整转数排料145～150℃室温下24小时 |
| 第2段 | |
| 定型 | |
| 混炼装置转数填充度 | 如第1段，但有以下不同：80min-10.53 |
| 混炼程序 | |
| 0～2分钟2～5分钟5分钟胶料温度储存 | 第1段胶料的破碎通过转数的变化，保持胶料温度150℃排料150℃室温下4小时 |
| 第3段 | |
| 定型 | |
| 混炼装置转数填充度贯流温度 | 如第1段，但有以下不同：40min-10.5150℃ |
| 混炼程序 | |
| 0～2分钟2分钟胶料温度 | 第2段胶料、促进剂、硫磺排料并在实验室开炼机中压片(直径200mm，长度450mm，贯流温度50℃)均化：切割左侧3x，右侧3x，并折叠薄通，8x采用窄辊距(1mm)，3x采用宽辊距(3.5mm)然后取出薄片85-90℃ |
表3总结了橡胶试验方法。
表3
| 物性试验 | 标准/条件 |
| ML 1+4，100℃，第3段 | DIN 53523/3，ISO 667 |
| 硫化仪试验，165℃Dmax-Dmin(dNm)T10％和t90％(分钟) | DIN 53529/3，ISO 6502 |
| 环上拉伸试验，23℃拉伸强度(MPa)模量(MPa)断裂伸长率(％) | DIN0 53504，ISO 37 |
| 邵尔A硬度，23℃ | DIN53 505 |
| 粘弹性，0℃和60℃，16Hz，50N初始力和25 N力幅度复合模量E*(MPa)损耗因子tanδ() | DIN53 513，ISO 2856 |
| 落珠回弹率，23℃(％) | ASTMD 5308 |
| Goodrich扰度仪0.25英寸，25分钟，23℃ | DIN 53 533，ASTM D 623 A |
| DIN磨耗，10N力(mm3) | DIN 53 516 |
| 分散性() | ISO/DIS 11 345 |
工艺橡胶试验的结果示于表4a和4b中。混炼胶是在165℃下硫化20分钟。
表4a：生炼胶结果
| 特征 | 单位 | 1 | 2 | 3 | 4 | 5 |
| 胶料温度，第1段胶料温度，第2段ML(1+4)，100℃，第3段 | [℃][℃][MU] | 14814762 | 14714646 | 14714547 | 14714852 | 14614445 |
| MDR，165℃，3°Dmax-Dmint10％t20％t90％t80％-t20％ | [dNm][min][min][min][min] | 15.741.693.1211.064.58 | 13.5423.219.019.7 | 13.382.163.5319.619.97 | 15.261.983.378.763.22 | 13.252.113.4519.9210.5 |
表4a：生炼胶结果(续)
| 特征 | 单位 | 6 | 7 | 8 | 9 |
| 胶料温度，第1段胶料温度，第2段ML(1+4)，100℃，第3段 | [℃][℃][MU] | 14814645 | 14514758 | 14514858 | 14614749 |
| MDR，165℃，3°Dmax-Dmint10％t20％t90％t80％-t20％ | [dNm][min][min][min][min] | 13.232.193.519.069.39 | 15.351.833.167.682.8 | 15.621.632.858.23.07 | 14.9523.368.363.08 |
表4b：硫化胶结果
| 特征 | 单位 | 1 | 2 | 3 | 4 |
| 拉伸试验，环拉伸强度模量100％模量300％模量300％/100％断裂伸长率 | [MPa][MPa][MPa][-][％] | 11.51.78.85.2360 | 13.41.47.75.5430 | 12.71.47.65.4420 | 13.91.68.05.0440 |
| 邵尔A硬度 | [SH] | 62 | 58 | 57 | 61 |
| 落球回弹率，60℃ | [％] | 59.4 | 65.2 | 65.0 | 61.3 |
| DIN磨耗 | [mm3] | 56 | 60 | 55 | 65 |
| Goodrich扰度仪接触温度穿刺针温度永久定型 | [℃][℃][％] | 631126.5 | 571043.8 | 591064.2 | 591015.9 |
| E*，0℃E*，60℃损耗因子，tanδ0℃损耗因子，tanδ60℃ | [MPa][MPa][-][-] | 19.87.80.4760.104 | 10.660.3510.089 | 11.76.40.3540.093 | 16.67.30.4520.096 |
| Phillips分散性 | [-] | 8 | 8 | 8 | 8 |
表4b：硫化胶结果(续)
| 特征 | 单位 | 5 | 6 | 7 | 8 | 9 |
| 拉伸试验，环拉伸强度模量100％模量300％模量300％/100％断裂伸长率 | [MPa][MPa][MPa][-][％] | 11.91.47.45.3400 | 12.11.47.75.5400 | 14.71.78.44.9440 | 14.71.68.25.1450 | 13.11.67.74.8430 |
| 邵尔A硬度 | [SH] | 57 | 56 | 62 | 60 | 60 |
| 落球回弹率，60℃ | [％] | 65.3 | 65.3 | 61.4 | 61.4 | 63.3 |
| DIN磨耗 | [mm3] | 55 | 53 | 65 | 63 | 53 |
| Goodrich扰度仪接触温度穿刺针温度永久定型 | [℃][℃][％] | 601083.2 | 571033.6 | 601014.7 | 621065.5 | 54963.8 |
| E*，0℃E*，60℃损耗因子，tanδ0℃损耗因子，tanδ60℃Phillips分散性 | [MPa][MPa][-][-][-] | 19.26.10.4620.0998 | 195.90.4680.0928 | 13.67.20.3910.0888 | 177.70.4470.0998 | 11.76.70.3540.0848 |
由表4a和4b的数据可以看出，包含根据本发明之有机硅化合物的混炼胶的Mooney粘度低于参比混炼胶1的粘度。
包含根据本发明之有机硅化合物(醚)的混炼胶具有更快的硫化速度。对于所有的混炼胶，补强因子都处于高水平，同时拉伸强度和断裂伸长率都可以与Si69参比混炼胶相媲美。DIN磨损对于所有混炼胶都是良好的。静橡胶值证实形成了二氧化硅-硅烷-橡胶键合。
Goodrich扰度仪试验表明包含长链醇的混炼胶产生更低的热聚集，并具有更好的永久性定型。MTS试验清楚地揭示更低的动态刚度值以及更低的tanδ60℃(更低的滚动阻力)。
实施例12
首先在室温下将180.0g的二(3-三乙氧基甲硅烷基丙基)二硫烷(式III，其中R＝乙基，R″＝CH2CH2CH2，X＝S，n＝2，而m＝2.2)和80.5 g的1-十四烷醇(R′＝-C14H29)添加至装配有蒸馏装置的1L四口烧瓶中，然后与0.7g的对甲苯磺酸-水合物混合。将黄色溶液加热至120-130℃，蒸馏除去所得的乙醇，然后在2小时内滴加237.5g的1-十四烷醇。通过蒸馏连续除去所形成的乙醇。在80℃、20mbar的真空下，在旋转蒸发器中蒸馏混合物。得到418.5g(98.0％)的式I(其中R＝乙基，R′＝-C14H29，R″＝CH2CH2CH2，X＝S，n＝2，而m＝2.2)黄色液体。
实施例13
在旋转蒸发器上，使125.2g的3-巯基丙基三乙氧基硅烷(式III，其中R＝-CH2CH3，R″＝-CH2CH2CH2-，X＝-SH，n＝1，m＝1)、225.1g的1-十四烷醇(R′＝-C14H29)和1.0g的对甲苯磺酸-水合物的混合物在1L烧瓶中加热至110℃，然后在4小时内通过40mbar下的真空蒸馏除去所形成的乙醇。得到298.5g(98.8％)的式I(其中R＝-CH2CH3，R′＝-C14H29，R″＝-CH2CH2CH2-，X＝-SH，n＝1，m＝1)无色液体。实施例14
在旋转蒸发器上，使200.0g的二(3-三乙氧基甲硅烷基丙基)多硫烷(式III，其中R＝乙基，R″＝CH2CH2CH2，X＝S，n＝2，m＝3.8)、322.2g的1-十四烷醇(R′＝-C14H29)和1.0g的对甲苯磺酸-水合物的混合物在1L烧瓶中加热至110℃，然后在4小时内通过40mbar下的真空蒸馏除去所形成的乙醇。得到448.1g(99.0％)的式I(其中R＝乙基，R′＝-C14H29，R″＝CH2CH2CH2，X＝S，n＝2，m＝3.8)黄色液体。
实施例15
在旋转蒸发器上，使含有150g的Si69(式III化合物，其中R＝-CH2CH3，R2＝-CH2CH2CH2-，X＝S，n＝2，m＝1-10、平均为3.8)、4倍摩尔量的十四烷醇与所述量的催化剂的混合物在1L烧瓶中加热至所述的温度，然后在120分钟内通过40mbar下的真空蒸馏除去所形成的乙醇(表5)。冷却后，得到式I(其中R＝-CH2CH3，R2＝-CH2CH2CH2-，X＝S，n＝2，m＝1-10)相对高粘度的黄色-橙色液体。
Si69是得自于Degussa AG的二(3-三乙氧基甲硅烷基丙基)多硫烷，其平均硫烷链长为3.8。
Ti(OC2H5)4、Ti(OC3H7)4、和Ti(OC4H9)4是由Aldrich制备的。对甲苯磺酸和对甲苯磺酸钠是由Merck-Schuchardt制备的。
实施例16
在旋转蒸发器上，使含有100g的Si69(式III化合物，其中R＝-CH2CH3，R2＝-CH2CH2CH2-，X＝S，n＝2，m＝1-10、平均为3.8)、4倍摩尔量的相应醇与所述量的催化剂的混合物在500ml的三口烧瓶中加热至130℃，然后在120分钟内通过蒸馏除去所形成的乙醇(表6)。冷却后，得到式I(其中R＝-CH2CH3，R2＝-CH2CH2CH2-，X＝S，n＝2，m＝1-10)相对高粘度的黄色-橙色液体。
表5和6显示了相应的NMR分析结果。
核磁共振分析结果是使用Bruker DRX 500 NMR光谱仪根据本领域技术人员已知的规则和操作程序得到的。所用的质谱频率对于29Si核是99.35MHz，而对于1H核为500MHz。
在各种情况下都使用四甲基硅烷(TMS)作为参比化合物。
转化率定义为1H NMR积分(Si-O-CxHy)除以1H NMR积分(Si-O-Et)与1H NMR积分(Si-O-CxHy)×0.66之和而得到的商。转化率称为1的百分数。100％转化率是指6当量的EtO中有4当量已经被置换，而2当量的EtO仍保留在硅上。
低聚物的量通过29Si NMR来确定，其中比较Si(OEt)3和Si(OEt)2-O-Si(OEt)2信号的积分。
在可比或者甚至更低的催化剂摩尔浓度时，根据本发明使用金属化合物的方法的酯交换转化率在更低的温度下比使用其他催化剂时的高。另外，所形成的低聚物的量也更低。如果使用对甲苯磺酸钠盐作为对甲苯磺酸-水合物的无水等价物，却发现即使使用大量的催化剂，转化率也比使用钛醇盐时的低(表6)。
表5
| 醇 | 催化剂 | 催化剂量(分别等摩尔)g | 温度℃ | 时间min | 酯交换转化率(4OR‘＝100％) | 低聚物的量(对比Si-NMR积分，Si(OR)3＝100％；低聚物＝x％) |
| 十四烷醇 | Ti(OC4H9)4 | 0,3 | 110 | 120 | ＞99 | 5,5 |
| 十四烷醇 | Ti(OC4H9)4 | 0,15 | 110 | 120 | ＞99 | 4,8 |
| 十四烷醇 | Ti(OC4H9)4 | 0,075 | 110 | 120 | 93 | 6,6 |
| 十四烷醇 | 对甲苯磺酸-水合物 | 0,168 | 110 | 120 | 98 | 6,5 |
| 十四烷醇 | 对甲苯磺酸-水合物 | 0,084 | 110 | 120 | 86 | 5,8 |
| 十四烷醇 | 对甲苯磺酸-水合物 | 0,042 | 110 | 120 | 52 | 7,7 |
| 十四烷醇 | Ti(OC4H9)4 | 0,3 | 90 | 120 | ＞99 | 5,4 |
| 十四烷醇 | Ti(OC4H9)4 | 0,15 | 90 | 120 | ＞99 | 4,8 |
| 十四烷醇 | Ti(OC4H9)4 | 0,075 | 90 | 120 | 91 | 4,7 |
| 十四烷醇 | 对甲苯磺酸-水合物 | 0,168 | 90 | 120 | ＞99 | 5,9 |
| 十四烷醇 | 对甲苯磺酸-水合物 | 0,084 | 90 | 120 | 85 | 6,3 |
| 十四烷醇 | 对甲苯磺酸-水合物 | 0,042 | 90 | 120 | 49 | 5,5 |
表6
| 醇 | 催化剂 | 催化剂量(分别等摩尔)lng | 温度(℃) | 时间(min) | 酯交换转化率(4OR‘＝100％) | 低聚物的量(对比Si-NMR积分，R‘Si(OR)3＝100，低聚物＝x) |
| 十二烷醇十四烷醇二乙二醇单丁基醚 | Ti(OC4H9)4Ti(OC4H9)4Ti(OC4H9)4 | 0,50,50,5 | 130130130 | 120120120 | ＞99＞99＞99 | 8,786,9 |
| 十二烷醇十四烷醇二乙二醇单丁基醚 | Ti(OC3H7)4Ti(OC3H7)4Ti(OC3H7)4 | 0,50,50,5 | 130130130 | 120120120 | ＞99＞99＞99 | 10,39,311 |
| 十二烷醇十四烷醇二乙二醇单丁基醚 | Ti(OC2H5)4Ti(OC2H5)4Ti(OC2H5)4 | 0,50,50,5 | 130130130 | 120120120 | ＞99＞99＞99 | 7,78,710,5 |
| 十二烷醇十四烷醇二乙二醇单丁基醚 | 甲苯磺酸钠盐C7H7NaO3S甲苯磺酸钠盐C7H7NaO3S甲苯磺酸钠盐C7H7NaO3S | 0,50,50,5 | 130130130 | 120120120 | 525352 | 4,74,84,8 |
Claims (10)
1、通式I和/或II的有机硅化合物：(I)(II)式中R是甲基或乙基；
R′可相同或不同，代表C9-C30支链或直链单价烷基或者烯基、芳基、芳烷基、支链或直链C2-C30烷基醚基、支链或直链C2-C30烷基聚醚基、或者R3Si，其中R是C1-C30支链或直链烷基或烯基、芳烷基、或芳基，
R″代表支链或直链、饱和或不饱和、脂族、芳香或者脂族/芳香混合的二价C1-C30烃基，
X是NH(3-n)，其中n＝1、2、3而m＝1；O(C＝O)-R，其中n＝1而m＝1；SH，其中n＝1而m＝1；S，其中n＝2而m＝1-10，以及它们的混合物；S(C＝O)-R，其中n＝1而m＝1；或者H，其中n＝1而m＝1。
2、如权利要求1所述的有机硅化合物，其特征在于R″代表CH2、CH2CH2、CH2CH2CH2、CH2CH2CH2CH2、CH(CH3)、CH2CH(CH3)、C(CH3)2、CH(C2H5)、CH2CH2CH(CH3)、CH2CH(CH3)CH2或者
3、如权利要求1所述的有机硅化合物的制造方法，其特征在于通式III的硅烷
(III)其中R、R″、X、m和n与以上定义相同，与通式R′-OH的醇反应，其中R′与以上定义相同，消除R-OH，然后连续地通过蒸馏由反应混合物中分离R-OH。
4、如权利要求3所述的方法，其特征在于使用盐酸、硫酸、磷酸、甲酸、乙酸、对甲苯磺酸、氢氧化钠溶液、氢氧化钾溶液、甲醇钠、乙醇钠、Deloxan ASP I/9、Amberlyst 15离子交换树脂作为催化剂。
5、如权利要求3所述的方法，其特征在于使用金属化合物作为催化剂。
6、如权利要求3所述的方法，其特征在于反应在20-200℃之间的温度进行。
7、如权利要求3所述的方法，其特征在于反应在无水的惰性气体氛围下进行。
8、混炼胶，其含有橡胶、填料、任选的其他橡胶助剂以及至少一种如权利要求1所述的有机硅化合物。
9、如权利要求1所述的有机硅化合物在制备模制品中的应用。
10、如权利要求1所述的有机硅化合物在充气轮胎、胎面、电缆护套、软管、传动带、输送带、辊筒罩面、轮胎、鞋底、密封环和防震元件中的应用。
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- 2002-07-09 DE DE50205120T patent/DE50205120D1/de not_active Expired - Fee Related
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- 2002-07-09 ES ES03023188T patent/ES2252606T3/es not_active Expired - Lifetime
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|---|---|---|---|---|
| CN1858053B (zh) * | 2005-05-03 | 2012-05-02 | 赢创德固赛有限公司 | 制造巯基有机基(烷氧基硅烷)的方法 |
| CN101426800B (zh) * | 2006-02-21 | 2013-04-03 | 莫门蒂夫性能材料股份有限公司 | 含有有机官能硅烷的橡胶组合物 |
| CN101024711B (zh) * | 2006-02-24 | 2010-08-11 | 赢创德固赛有限公司 | 橡胶混合物 |
| CN101516895B (zh) * | 2006-07-17 | 2013-05-15 | 赢创德固赛有限责任公司 | 含硅偶联剂的混合物 |
| CN102344462A (zh) * | 2011-07-20 | 2012-02-08 | 江苏麒祥高新材料有限公司 | 一种低挥发性苯并噻唑巯基硅烷及其制备方法 |
| CN103923115A (zh) * | 2011-07-20 | 2014-07-16 | 江苏麒祥高新材料有限公司 | 2－硫醇基苯并噻唑和氯乙基乙基二乙氧基硅烷制备的苯并噻唑巯基硅烷及制备方法 |
| CN104045664A (zh) * | 2011-07-20 | 2014-09-17 | 江苏麒祥高新材料有限公司 | 2－硫醇基苯并噻唑和氯丙基三乙氧基硅烷制备的苯并噻唑巯基硅烷 |
| CN103923115B (zh) * | 2011-07-20 | 2016-03-30 | 江苏麒祥高新材料有限公司 | 2－硫醇基苯并噻唑和氯乙基乙基二乙氧基硅烷制备的苯并噻唑巯基硅烷及制备方法 |
| CN104045664B (zh) * | 2011-07-20 | 2016-07-06 | 江苏麒祥高新材料有限公司 | 2－硫醇基苯并噻唑和氯丙基三乙氧基硅烷制备的苯并噻唑巯基硅烷 |
| CN106674593A (zh) * | 2016-12-03 | 2017-05-17 | 北京化工大学 | 含乙烯基醚链段的硅烷偶联剂及其制备方法和应用 |
| CN112566971A (zh) * | 2018-08-16 | 2021-03-26 | 赢创运营有限公司 | 橡胶混合物 |
| CN113512196A (zh) * | 2021-07-19 | 2021-10-19 | 中交上海三航科学研究院有限公司 | 一种烃基硅醇的醇溶液及制备方法 |
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| PL355358A1 (en) | 2003-02-10 |
| HUP0202572A2 (hu) | 2004-12-28 |
| ES2217229T3 (es) | 2004-11-01 |
| HU230367B1 (hu) | 2016-03-29 |
| KR20030014115A (ko) | 2003-02-15 |
| DE50205120D1 (de) | 2006-01-05 |
| BR0203045A (pt) | 2003-05-27 |
| DE50205449D1 (de) | 2006-02-02 |
| JP4414638B2 (ja) | 2010-02-10 |
| BR0203045B1 (pt) | 2014-04-29 |
| CZ304653B6 (cs) | 2014-08-20 |
| US6849754B2 (en) | 2005-02-01 |
| PL207554B1 (pl) | 2010-12-31 |
| MY127353A (en) | 2006-11-30 |
| EP1285926B1 (de) | 2004-05-12 |
| CZ20022650A3 (cs) | 2003-09-17 |
| ATE311396T1 (de) | 2005-12-15 |
| ATE266669T1 (de) | 2004-05-15 |
| CN1323083C (zh) | 2007-06-27 |
| EP1285926A1 (de) | 2003-02-26 |
| MXPA02007540A (es) | 2005-02-17 |
| IL151066A (en) | 2006-09-05 |
| US20050004386A1 (en) | 2005-01-06 |
| TWI225064B (en) | 2004-12-11 |
| ES2254847T3 (es) | 2006-06-16 |
| IL151066A0 (en) | 2003-04-10 |
| UA77155C2 (en) | 2006-11-15 |
| US20030130535A1 (en) | 2003-07-10 |
| HU0202572D0 (zh) | 2002-10-28 |
| US7323582B2 (en) | 2008-01-29 |
| ATE314381T1 (de) | 2006-01-15 |
| KR100964805B1 (ko) | 2010-06-23 |
| ES2252606T3 (es) | 2006-05-16 |
| JP2005035889A (ja) | 2005-02-10 |
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