CN110256481A - 一种封端巯基硅烷偶联剂及其水相合成方法 - Google Patents
一种封端巯基硅烷偶联剂及其水相合成方法 Download PDFInfo
- Publication number
- CN110256481A CN110256481A CN201910484800.8A CN201910484800A CN110256481A CN 110256481 A CN110256481 A CN 110256481A CN 201910484800 A CN201910484800 A CN 201910484800A CN 110256481 A CN110256481 A CN 110256481A
- Authority
- CN
- China
- Prior art keywords
- coupling agents
- blocked mercaptosilane
- mercaptosilane coupling
- sodium
- silane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007822 coupling agent Substances 0.000 title claims abstract description 28
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910000077 silane Inorganic materials 0.000 claims abstract description 31
- -1 haloalkyl silane Chemical compound 0.000 claims abstract description 30
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000872 buffer Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 12
- 239000012991 xanthate Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 3
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 9
- 150000002357 guanidines Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 230000031709 bromination Effects 0.000 claims description 6
- 238000005893 bromination reaction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 125000005936 piperidyl group Chemical group 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- GIDDQKKGAYONOU-UHFFFAOYSA-N octylazanium;bromide Chemical compound Br.CCCCCCCCN GIDDQKKGAYONOU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 2
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 125000002521 alkyl halide group Chemical group 0.000 claims 1
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- ZLSVALLKHLKICA-UHFFFAOYSA-N hexan-1-amine;hydrobromide Chemical compound [Br-].CCCCCC[NH3+] ZLSVALLKHLKICA-UHFFFAOYSA-N 0.000 claims 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims 1
- 235000019796 monopotassium phosphate Nutrition 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 235000015424 sodium Nutrition 0.000 claims 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000009938 salting Methods 0.000 abstract 1
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract 1
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 29
- 239000000047 product Substances 0.000 description 14
- 239000000460 chlorine Substances 0.000 description 11
- 239000006229 carbon black Substances 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- 235000001508 sulfur Nutrition 0.000 description 5
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MCEBKLYUUDGVMD-UHFFFAOYSA-N [SiH3]S(=O)=O Chemical compound [SiH3]S(=O)=O MCEBKLYUUDGVMD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- LRCPOJGBEQAERD-UHFFFAOYSA-M [P].[Br-].C(CCC)[P+](CCCC)(CCCC)CCCC Chemical compound [P].[Br-].C(CCC)[P+](CCCC)(CCCC)CCCC LRCPOJGBEQAERD-UHFFFAOYSA-M 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical group [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229940075933 dithionate Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 2
- WLTVMXLKVVOCGZ-UHFFFAOYSA-N CCCCCCCC[K] Chemical compound CCCCCCCC[K] WLTVMXLKVVOCGZ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 description 1
- VQNVZLDDLJBKNS-UHFFFAOYSA-N carbamimidoylazanium;bromide Chemical compound Br.NC(N)=N VQNVZLDDLJBKNS-UHFFFAOYSA-N 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005358 mercaptoalkyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- JCBJVAJGLKENNC-UHFFFAOYSA-M potassium ethyl xanthate Chemical compound [K+].CCOC([S-])=S JCBJVAJGLKENNC-UHFFFAOYSA-M 0.000 description 1
- OMKVZYFAGQKILB-UHFFFAOYSA-M potassium;butoxymethanedithioate Chemical compound [K+].CCCCOC([S-])=S OMKVZYFAGQKILB-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical group CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- FZGRPBJBMUNMQH-UHFFFAOYSA-N trimethyl-$l^{3}-chlorane Chemical compound CCl(C)C FZGRPBJBMUNMQH-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
本发明描述了一种封端巯基硅烷偶联剂及其水相合成的方法，它涉及一种含硫硅烷偶联剂的制备方法，其中硫醇官能团的氢原子已被取代，其相应通式可表示为(R1O)3Si‑R2‑S‑C(＝S)‑OR3。本发明解决了现有封端巯基硅烷偶联剂品种单一、合成封端巯基硅烷成本高、污染大、周期长、工艺复杂的技术问题。其方法如下：一、将一定量的黄原酸盐溶于水中，配成一定质量分数的盐溶液；二、向黄原酸盐溶液中加入相转移催化剂和缓冲剂，然后再滴加相应的卤烷基硅烷(R1O)3Si‑R2‑X，在一定温度下搅拌反应一段时间，经分液、过滤、蒸馏后制得目标产物。采用本发明方法的封端巯基硅烷偶联剂的生产成本较低、简单高效、臭味小、安全环保，易于规模化生产。
Description
技术领域
本发明涉及含硫硅烷偶联剂及其制备方法，具体涉及一种封端巯基硅烷偶联剂及其水相合成的方法。
背景技术
在橡胶行业中，白炭黑和炭黑已被广泛用作补强填充剂。白炭黑在橡胶领域中的用量和补强效果仅次于炭黑。早在上世纪90年代，随着人们对轮胎性能要求的提高，“绿色轮胎”技术逐渐兴起，轿车轮胎胎面胶中开始使用白炭黑-含硫硅烷的搭配体系。含硫硅烷偶联剂是主要用作橡胶填料的表面改性剂，可以提高轮胎、橡胶制品的耐磨性和耐老化性能。其中，具有划时代意义的含硫硅烷偶联剂是双(三乙氧基硅丙基)四硫化物(TESPT/Si-69)。
尽管Si-69已经使用了40多年，但是它在合成与使用过程中也存在诸多缺点：如：(1)合成工艺复杂，后处理繁琐，产品质量较难控制，品质不稳定。(2)合成过程耗能大，废水排放量大。(3)Si-69在橡胶混炼过程中需要较长的时间和较高温度才能与白炭黑充分反应。当混炼温度超过160℃时多硫键可能断裂，容易引起胶料焦烧、门尼粘度增大，不利于白炭黑粒子的分散，需要多次混炼(需用3～6段)。(4)Si-69在使用时产生的乙醇，在高温混炼时因其快速气化导致橡胶制品的气孔率增大，同时也不利于环保。
针对多硫硅烷偶联剂的这些问题，美国康普顿公司开发了封端巯基硅烷偶联剂3-辛酰基硫代-1-丙基三甲氧基硅烷(NXT)并于2002年投放市场。NXT用于白炭黑填充的胎面胶具有降低胶料粘度，减少混炼段数，改善胶料加工性能，促进白炭黑分散，延长胶料焦烧时间与储存期，减少成品中挥发物含量，提高胎面胶耐老化性能等一系列优点。
传统的封端巯基硅烷偶联剂的合成路线有很多种，主要包括以下几种方法：1、以巯基硅烷为起点，其与酰卤发生反应，金属钠为卤素吸收剂，合成封端巯基硅烷偶联剂。2、以巯基硅烷为起点，其与酰卤发生反应，有机碱作为酸吸收剂，合成封端巯基硅烷偶联剂。3、以Si-69或Si-75为起点，通过金属钠的断链作用，使单硫键再与酰卤发生反应，有机碱作为酸吸收剂，合成封端巯基硅烷偶联剂。传统方法的缺点主要有以下几个方面：1、方法1、2是在甲苯、己烷、石油醚等溶剂中进行的，增加了制造成本和安全风险。2、方法3用的反应原料为金属钠作为反应物，由于金属钠价格昂贵，而且不便于储存，存在较大的安全隐患，不利于大规模生产。3、方法1、2使用的巯基硅烷偶联剂为原料，该原料价格昂贵，产品收率低且有较重的刺激性气味，使用十分不便。
目前关于封端型巯基硅烷偶联剂研究最多的就是硫代羧酸酯硅烷。CN103193816A公开了一种水相合成硫代羧酸酯硅烷偶联剂的制备方法，该方法将硫化物或硫氢化物与酰卤或酸酐混合，加入相转移催化剂、pH控制剂、氢氧化物和H2S催化氧化催化剂，通入氧气并控制压力和温度条件下搅拌反应得硫代羧酸盐复合液；然后向硫代羧酸盐复合液中加入相转移催化剂，然后再滴加氯丙基三乙氧基硅烷，加入硅羟基保护剂回流反应得到硫代羧酸酯硅烷偶联剂。尽管该方法可以取得较好的转化率，但是该方法需要加入pH控制剂、氢氧化物、H2S催化氧化催化剂以及硅羟基保护剂等，会造成生产成本的增加而且不利于产品的纯化，并且通入氧气严格控制压力等操作也对要求更加苛刻，不利于大规模工业化生产。US20050277781A1公开了一种制备硫代羧酸酯硅烷的方法，该方法通过卤代烷基硅烷与硫代羧酸盐水溶液的反应制备硫代羧酸酯硅烷，同时还公开了由硫化物和/或氢硫化物和酰基氯和/或酸酐制备硫代羧酸盐水溶液的方法。但是，该方法存在产品收率较低、反应时间长、生产效率较低等问题，并且该方法提供的硫代羧酸盐水溶液的制备方法也存在生产效率不高、反应时间过长的问题。CN1834099A公开了一种含硫双硅烷偶联剂及其制备方法，其特征是在有机催化剂作用下，将脂肪二酰氯与巯烃基硅烷在有机溶剂中、在氮气保护下进行低温反应。尽管该方法工艺流程简单，产率高，但是缺点在于所用的原料巯烃基价格昂贵，成本高，同时酰氯腐蚀性较高，对于生产设备的要求较高，难以普及。CN104829645A公开了一种制备硫代羧酸酯硅烷偶联剂的方法，该方法包括两个步骤，首先是将硫氢化钠溶解于水中得到硫氢化钠水溶液，然后向其中加入相转移催化剂并控制温度，将酰卤滴加到硫氢化钠水溶液中得到硫代羧酸钠的水溶液，第二步是加入另外一种相转移催化剂并滴加氯丙基三乙氧基硅烷，控制温度反应得到硫代羧酸酯硅烷偶联剂。其缺点在于原料用到了酰卤，对设备的腐蚀性较大，同时反应分两步进行，时间较长，降低了生产效率。CN1931862A公开了一种含硫硅烷偶联剂及其合成方法。其方法为以甲醇为溶剂，氯丙基三甲氧基硅烷和乙基黄原酸钾为原料，通过高纯氮气保护，生成黄原酸酯丙基三甲氧基硅烷。其缺点是采用有机溶剂作溶剂，增加了成本，同时反应周期太长，效率低。
本发明的目的是开发一种新型的封端巯基硅烷偶联剂，并采用水相合成方法生产，大幅度降低生产成本的同时还有利于环保。
发明内容
本发明描述了一种封端巯基硅烷偶联剂及其水相合成的方法，它涉及一种含硫硅烷偶联剂的制备方法，其相应通式可表示为(R1O)3Si-R2-S-C(＝S)-OR3。本发明解决了现有封端巯基硅烷偶联剂种类单一以及生产成本高、污染大、周期长的技术问题。其合成步骤如下：一、将黄盐酸盐溶于水中制成质量分数为10-45％黄盐酸盐溶液；二、向黄盐酸盐溶液中加入相转移催化剂和缓冲剂，其中相转移催化剂和缓冲剂加入的总量为卤烷基硅烷质量的0.5～10％，制成的催化剂溶液的质量分数为1～20％，缓冲剂溶液的浓度为0.005～0.5mol/L；三、向步骤二的混合溶液中逐渐滴加纯度在98％以上的卤烷基硅烷，卤烷基硅烷和黄原酸盐的摩尔比为1.02～1.2：1，反应温度为50～90℃，滴加卤烷基硅烷的时间为1～30min，优选5～20min，搅拌速度为300～900r/min，加热并搅拌，每隔一段时间取试样并用气相色谱分析试样，当卤烷基硅烷的含量在反应物中恒定时即可停止加热；四、将步骤三得到的混合产物在5～-10℃低温环境中冷却10min～30min，过滤，分液，取上层油相液，再用吸水树脂或者无水硫酸钠干燥；五、对步骤四中干燥后的产物进行减压蒸馏，减压蒸馏的真空度≥0.09MPa，温度80～150℃，蒸馏得到封端巯基硅烷偶联剂。
其中，
R1彼此独立地表示H或者(C1-C8)烷基，优选甲基或者乙基，
R2表示直链或者支链、饱和或者不饱和的(C1-C8)二价烃基，优选CH2，CH2CH2，CH2CH2CH2，CH2CH2CH2CH2，CH(CH)3，CH2CH(CH3)，C(CH3)，CH(C2H5)，CH2CH2CH(CH3)，CH2CH(CH3)CH2。
R3表示直链或支链、饱和或者不饱和的(C1-C17)烷基，优选CH3，C2H5，C3H7，C4H9，C5H11，C6H13，C7H15，C8H16。
步骤一中的黄原酸盐可以为钠盐、钾盐或者铵盐，黄原酸盐溶液的质量分数优选10～40％。
步骤二中相转移催化剂和缓冲剂加入的总量优选为为卤烷基硅烷质量的0.5～8％，制成的催化剂溶液的质量分数优选为5～15％。
步骤二中相转移催化剂为苯甲基三乙基氯化铵、三辛基甲基氯化铵、三乙基己基溴化铵、三乙基辛基溴化铵、四甲基溴化铵、四丁基溴化磷、四丁基碘化铵、四丁基氯化铵、四丁基溴化铵、苄基三乙基氯化铵、苄基三乙基溴化铵、十二烷基三甲基氯化铵、十二烷基三甲基溴化铵、18-冠-6、15-冠-5、聚乙二醇二烷基醚、六丁基氯化胍、六丁基溴化胍、六乙基溴化胍、三哌啶基氯化胍或三哌啶基溴化胍中的一种或几种的混合物。
步骤二中缓冲剂为磷酸钠、磷酸钾、磷酸氢钠、磷酸氢钾、磷酸二氢钠、磷酸二氢钾、硼酸钠、硼酸钾、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、亚硫酸钠或者它们的混合物。
步骤二中缓冲剂溶液的浓度优选为0.008～0.48mol/L。
步骤三中卤烷基硅烷和黄原酸盐的摩尔比优选1.05～1.1：1，反应温度优选60～80℃，滴加卤烷基硅烷的时间优选5～20min，搅拌速度优选300～800r/min。
步骤三中卤烷基硅烷(R1O)3Si-R2-X优选为(CH3O)3Si-CH2-Cl，(CH3O)3Si-CH2-CH2-Cl，(CH3O)3Si-CH2-CH2-CH2-Cl，(CH3O)3Si-CH2-CH2-CH2-CH2-Cl，(CH3O)3Si-CH2-CH2-CH2-CH2-CH2-Cl，(C2H5O)3Si-CH2-Cl，(C2H5O)3Si-CH2-CH2-Cl，(C2H5O)3Si-CH2-CH2-CH2-Cl，(C2H5O)3Si-CH2-CH2-CH2-CH2-Cl，(C2H5O)3Si-CH2-CH2-CH2-CH2-CH2-Cl。
步骤四中冷却的低温环境优选0～-10℃，冷却时间优选10min～20min。
步骤五中减压蒸馏的真空度≥0.09MPa，优选温度90～130℃时蒸馏得到封端巯基硅烷偶联剂。
根据本发明通式(R1O)3Si-R2-S-C(＝S)-OR3以及水相合成方法优选的新型封端巯基硅烷为(CH3O)3Si-CH2-S-C(＝S)-OCH3，(CH3O)3Si-CH2-S-C(＝S)-OC2H5，(CH3O)3Si-CH2-S-C(＝S)-OC3H7，(CH3O)3Si-CH2-S-C(＝S)-OC4H9，(CH3O)3Si-CH2-S-C(＝S)-OC5H11，(CH3O)3Si-CH2-S-C(＝S)-OC6H13，(CH3O)3Si-CH2-S-C(＝S)-OC7H15，(CH3O)3Si-CH2-S-C(＝S)-OC8H17，(CH3O)3Si-CH2-CH2-S-C(＝S)-OCH3，(CH3O)3Si-CH2-CH2-S-C(＝S)-OC2H5，(CH3O)3Si-CH2-CH2-S-C(＝S)-OC3H7，(CH3O)3Si-CH2-CH2-S-C(＝S)-OC4H9，(CH3O)3Si-CH2-CH2-S-C(＝S)-OC5H11，(CH3O)3Si-CH2-CH2-S-C(＝S)-OC6H13，(CH3O)3Si-CH2-CH2-S-C(＝S)-OC7H15，(CH3O)3Si-CH2-CH2-S-C(＝S)-OC8H17，(CH3O)3Si-CH2-CH2-CH2-S-C(＝S)-OCH3，(CH3O)3Si-CH2-CH2-CH2-S-C(＝S)-OC2H5，(CH3O)3Si-CH2-CH2-CH2-S-C(＝S)-OC3H7，(CH3O)3Si-CH2-CH2-CH2-S-C(＝S)-OC4H9，(CH3O)3Si-CH2-CH2-CH2-S-C(＝S)-OC5H11，(CH3O)3Si-CH2-CH2-CH2-S-C(＝S)-OC6H13，(CH3O)3Si-CH2-CH2-CH2-S-C(＝S)-OC7H15，(CH3O)3Si-CH2-CH2-CH2-S-C(＝S)-OC8H17，(C2H5O)3Si-CH2-S-C(＝S)-OCH3，(C2H5O)3Si-CH2-S-C(＝S)-OC2H5，(C2H5O)3Si-CH2-S-C(＝S)-OC3H7，(C2H5O)3Si-CH2-S-C(＝S)-OC4H9，(C2H5O)3Si-CH2-S-C(＝S)-OC5H11，(C2H5O)3Si-CH2-S-C(＝S)-OC6H13，(C2H5O)3Si-CH2-S-C(＝S)-OC7H15，(C2H5O)3Si-CH2-S-C(＝S)-OC8H17，(C2H5O)3Si-CH2-CH2-S-C(＝S)-OC2H5，(C2H5O)3Si-CH2-CH2-S-C(＝S)-OCH3，(C2H5O)3Si-CH2-CH2-S-C(＝S)-OC3H7，(C2H5O)3Si-CH2-CH2-S-C(＝S)-OC4H9，(C2H5O)3Si-CH2-CH2-S-C(＝S)-OC5H11，(C2H5O)3Si-CH2-CH2-S-C(＝S)-OC6H13，(C2H5O)3Si-CH2-CH2-S-C(＝S)-OC7H15，(C2H5O)3Si-CH2-CH2-S-C(＝S)-OC8H17，(C2H5O)3Si-CH2-CH2-CH2-S-C(＝S)-OCH3，(C2H5O)3Si-CH2-CH2-CH2-S-C(＝S)-OC2H5，(C2H5O)3Si-CH2-CH2-CH2-S-C(＝S)-OC3H7，(C2H5O)3Si-CH2-CH2-CH2-S-C(＝S)-OC4H9，(C2H5O)3Si-CH2-CH2-CH2-S-C(＝S)-OC5H11，(C2H5O)3Si-CH2-CH2-CH2-S-C(＝S)-OC6H13，(C2H5O)3Si-CH2-CH2-CH2-S-C(＝S)-OC7H15，(C2H5O)3Si-CH2-CH2-CH2-S-C(＝S)-OC8H17。
本发明与现有技术相比，具有以下积极效果：
本发明提供了一种新型的封端巯基硅烷偶联剂的设计思路，并且通过水相法合成。首先原料上避免使用了味道刺鼻并且价格较高的巯基硅烷，生产成本降低；以水作溶剂，经济环保；通过加入合适配比的相转移催化剂来提高反应速率；使用缓冲剂来控制溶液相的pH值，防止原料卤烷基硅烷的水解凝胶；反应时间短，效率高。
附图说明
图1示意了乙基黄原酸酯硅烷的红外光谱。
图2示意了乙基黄原酸酯基硅烷偶联剂的核磁共振氢谱。
图3示意了丁基黄原酸酯基硅烷产品外观。
具体实施方式
下面结合具体实施例进一步说明本发明的技术方案，但这些实施例不能理解为对技术方案的限制。
实施例1
一种封端巯基硅烷偶联剂及其水相合成方法，包括如下步骤：称取乙基黄原酸钠6g，加入14g蒸馏水，在50℃下以450r/min的速度搅拌10min，再加入0.4g十二烷基三甲基氯化铵、0.1g四丁基溴化铵以及0.25g Na2CO3，搅拌10min，再逐滴加入γ-氯丙基三乙氧基硅烷20g，同时升温至70℃，待滴加完毕后继续反应60min后停止，自然冷却30min，分液，取上层有机相，向其中加入少量活性炭并在50℃下搅拌30min后过滤，对滤液进行减压蒸馏，真空度为0.095MPa，温度为110℃，得到黄色目标产物。其红外光谱图和核磁共振氢谱分别如图1和图2所示。
实施例2
称取丁基黄原酸钾7.52g，加入蒸馏水17.54g，在55℃下以500r/min的速度搅拌10min，再加入0.6g四丁基氯化铵和0.37g苄基三乙基溴化铵以及0.36g NaHCO3，搅拌10min，再逐滴加入γ-氯丙基三乙氧基硅烷19.24g，同时升温至75℃，待滴加完毕后继续反应40min后停止反应，放入-5℃的环境中冷却10min，分液，取上层有机层，向其中加入少量活性炭并在50℃下搅拌25min后过滤，对得到的溶液减压蒸馏，条件为真空度为0.09MPa，温度为120℃，得到淡黄色目标产物。其产品如图3所示。
实施例3
称取4.6g辛基黄原酸钾，加入去离子水10.7g，在50℃下以650r/min搅拌12min，再加入四丁基溴化磷0.48g，再加入0.13g Na2CO3和0.1g K2CO3，继续在50℃下搅拌10min，再逐滴滴加γ-氯丙基三乙氧基硅烷9.62g，同时升温至78℃，待滴加完毕后继续反应20min后停止，放入0℃的环境中冷却10min，静置分液，取上层有机层，加入少量活性炭并在50℃下搅拌30min后过滤，对得到的溶液减压蒸馏，条件为真空度为0.096MPa，温度为122℃，最终得到目标产物。
以上所述并非是对本发明的限制，应当指出：对于本技术领域的普通技术人员来说，在不脱离本发明实质范围的前提下，还可以做出若干变化、改型、添加或替换，这些改进和润饰也应视为本发明的保护范围。
Claims (12)
1.一种封端巯基硅烷偶联剂及其水相合成方法，其特征在于它们的通式可表示为(Ι)
(R1O)3Si-R2-S-C(＝S)-OR3 (Ι)
其中，R1彼此独立地表示H或(C1-C8)烷基，R2表示直链或支链、饱和或不饱和的(C1-C8)二价烃基，R3表示直链或支链、饱和或者不饱和的(C1-C17)烷基。
2.根据权利要求1所述的一种封端巯基硅烷偶联剂的结构，其特征在于可由通式为(R1O)3Si-R2-X的卤烷基硅烷与黄原酸盐反应制得。
3.根据权利要求1和2所述的一种封端巯基硅烷偶联剂的结构，其特征在于黄原酸盐可以为钠盐、钾盐或者铵盐；通式为(R1O)3Si-R2-X的卤烷基硅烷可以是：
(CH3O)3Si-CH2-Cl，(CH3O)3Si-CH2-CH2-Cl，(CH3O)3Si-CH2-CH2-CH2-Cl，(CH3O)3Si-CH2-CH2-CH2-CH2-Cl，(CH3O)3Si-CH2-CH2-CH2-CH2-CH2-Cl，(C2H5O)3Si-CH2-Cl，(C2H5O)3Si-CH2-CH2-Cl，(C2H5O)3Si-CH2-CH2-CH2-Cl，(C2H5O)3Si-CH2-CH2-CH2-CH2-Cl，(C2H5O)3Si-CH2-CH2-CH2-CH2-CH2-Cl等。
4.根据权利要求1、2、3所述的一种封端巯基硅烷偶联剂及其水相合成方法，其特征在于制备方法包括如下步骤：一、将黄盐酸盐溶于水中制成黄盐酸盐溶液；二、向黄盐酸盐溶液中加入相转移催化剂和缓冲剂，搅拌至溶解；三、向步骤二的混合溶液中逐渐滴加纯度在98％以上的卤烷基硅烷，加热并搅拌，每隔一段时间取试样并用气相色谱分析试样，当卤烷基硅烷的含量在反应物中恒定时即可停止加热；四、将步骤三得到的混合产物在低温环境中冷却一定时间，过滤，分液，取上层油相液，再用吸水树脂或者无水硫酸钠干燥；五、对步骤四中干燥后的产物进行减压蒸馏，得到纯度较高的封端巯基硅烷偶联剂。
5.根据权利要求1-4所述的方法，其特征在于步骤一制得的黄原酸盐溶液的质量分数为10-45％，优选10～40％。
6.根据权利要求1-5所述的方法，其特征在于步骤二中相转移催化剂和缓冲剂加入的总量为卤烷基硅烷质量的0.5～10％，优选0.5～8％，制成的催化剂溶液的质量分数为1～20％，优选5～15％。
7.根据权利要求1-6所述的方法，其特征在于步骤二中相转移催化剂为苯甲基三乙基氯化铵、三辛基甲基氯化铵、三乙基己基溴化铵、三乙基辛基溴化铵、四甲基溴化铵、四丁基溴化磷、四丁基碘化铵、四丁基氯化铵、四丁基溴化铵、苄基三乙基氯化铵、苄基三乙基溴化铵、十二烷基三甲基氯化铵、十二烷基三甲基溴化铵、18-冠-6、15-冠-5、聚乙二醇二烷基醚、六丁基氯化胍、六丁基溴化胍、六乙基溴化胍、三哌啶基氯化胍或三哌啶基溴化胍中的一种或几种的混合物。
8.根据权利要求1-6所述的方法，其特征在于步骤二中缓冲剂为磷酸钠、磷酸钾、磷酸氢钠、磷酸氢钾、磷酸二氢钠、磷酸二氢钾、硼酸钠、硼酸钾、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、亚硫酸钠或者它们的混合物。
9.根据权利要求1-6所述的方法，其特征在于步骤二中缓冲剂溶液的浓度为0.005～0.5mol/L，优选为0.008～0.48mol/L。
10.根据权利要求1-9所述的方法，其特征在于步骤三中卤烷基硅烷和黄原酸盐的摩尔比为1.02～1.2：1，优选1.05～1.1：1，反应温度为50～90℃，优选60～80℃，滴加卤烷基硅烷的时间为1～30min，优选5～20min，搅拌速度为300～900r/min，优选300～800r/min。
11.根据权利要求1-10所述的方法，其特征在于步骤四中冷却的低温环境为5～-10℃，优选0～-10℃，冷却时间为5min～30min，优选10min～20min。
12.根据权利要求1-11所述的方法，其特征在于步骤五中减压蒸馏的真空度≥0.09MPa，温度80～150℃，优选温度90～130℃时蒸馏得到封端巯基硅烷偶联剂。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910484800.8A CN110256481A (zh) | 2019-06-05 | 2019-06-05 | 一种封端巯基硅烷偶联剂及其水相合成方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910484800.8A CN110256481A (zh) | 2019-06-05 | 2019-06-05 | 一种封端巯基硅烷偶联剂及其水相合成方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110256481A true CN110256481A (zh) | 2019-09-20 |
Family
ID=67916817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910484800.8A Pending CN110256481A (zh) | 2019-06-05 | 2019-06-05 | 一种封端巯基硅烷偶联剂及其水相合成方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110256481A (zh) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1931862A (zh) * | 2006-08-11 | 2007-03-21 | 浙江大学 | 一种含硫硅烷偶联剂及其合成方法 |
| JP2012057105A (ja) * | 2010-09-10 | 2012-03-22 | Bridgestone Corp | ゴム組成物、加硫ゴム及びタイヤ |
| CN103534305A (zh) * | 2011-03-02 | 2014-01-22 | 莫门蒂夫性能材料股份有限公司 | 包含封端的巯基硅烷的橡胶组合物以及由其制备的制品 |
-
2019
- 2019-06-05 CN CN201910484800.8A patent/CN110256481A/zh active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1931862A (zh) * | 2006-08-11 | 2007-03-21 | 浙江大学 | 一种含硫硅烷偶联剂及其合成方法 |
| JP2012057105A (ja) * | 2010-09-10 | 2012-03-22 | Bridgestone Corp | ゴム組成物、加硫ゴム及びタイヤ |
| CN103534305A (zh) * | 2011-03-02 | 2014-01-22 | 莫门蒂夫性能材料股份有限公司 | 包含封端的巯基硅烷的橡胶组合物以及由其制备的制品 |
Non-Patent Citations (1)
| Title |
|---|
| REG: "1363385-23-2等", 《STN》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3978103A (en) | Sulfur containing organosilicon compounds | |
| ES486091A1 (es) | Procedimiento para la preparacion de bis-(sililetil)-oligo- sulfuros | |
| US4129585A (en) | Process for the production of sulfur containing organosilicon compounds | |
| JP4025386B2 (ja) | 硫黄含有有機珪素化合物の製造方法 | |
| US8008524B2 (en) | Process for the preparation of thiocarboxylate silane | |
| CN103351401A (zh) | 一种含硫硅烷偶联剂及其制备方法 | |
| EP1700861A1 (de) | Verfahren zur Herstellung von Organosilanen | |
| US4082790A (en) | Method of preparing mercaptans | |
| WO2003002573A2 (en) | Preparation of sulfur-containing organosilicon compounds using a buffered phase transfer catalysis process | |
| TWI243175B (en) | Process for the preparation of sulfur-containing organosilicon compounds | |
| EP1419164A1 (en) | Process for the preparation of sulfur-containing organosilicon compounds | |
| CN105601661B (zh) | 利用通道反应装置制备巯基硅烷偶联剂的方法 | |
| CN110256481A (zh) | 一种封端巯基硅烷偶联剂及其水相合成方法 | |
| Abel | 854. The alkylthiotrimethylsilanes: preparations and some properties | |
| CN103193816A (zh) | 水相合成硫代羧酸酯硅烷偶联剂的制备方法 | |
| KR20010086591A (ko) | 오가노실릴알킬 폴리설판의 제조방법 | |
| CN103804410A (zh) | 杂质低、气味浅的多硫化物硅烷偶联剂的水相制备方法 | |
| CN102491991B (zh) | 含β-二羰基的有机硅偶联剂及其制备方法 | |
| CN104926854B (zh) | 一种常压低温水相制备巯丙基三乙氧基硅烷的方法 | |
| CN107522730A (zh) | 一种γ‑巯丙基三乙氧基硅烷的制备方法 | |
| CN108794537A (zh) | 一种抗硫中毒铂金络合物的制备方法 | |
| CN109134844B (zh) | 双-[3-(乙氧基二(聚乙二醇单甲醚基)硅)丙基]-四硫化物的制备方法 | |
| CN112920216A (zh) | 双-[3-(三乙氧基硅)-丙基]-二硫化物的制备方法 | |
| Smith et al. | Synthesis of allyl silanes using trimethylsilyllithium in the presence of copper (I) iodide | |
| CN106986907A (zh) | 用于制备倍他米松的中间体的制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190920 |