CN1269826C - Process for preparing hydrosulphonyl alkoxy silicane - Google Patents
Process for preparing hydrosulphonyl alkoxy silicane Download PDFInfo
- Publication number
- CN1269826C CN1269826C CN 200310112707 CN200310112707A CN1269826C CN 1269826 C CN1269826 C CN 1269826C CN 200310112707 CN200310112707 CN 200310112707 CN 200310112707 A CN200310112707 A CN 200310112707A CN 1269826 C CN1269826 C CN 1269826C
- Authority
- CN
- China
- Prior art keywords
- preparation
- reaction
- raw materials
- transfer catalyst
- alkoxy silanes
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- 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.)
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- -1 hydrosulphonyl Chemical group 0.000 title claims abstract description 20
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title abstract 5
- 125000003545 alkoxy group Chemical group 0.000 title abstract 5
- 238000004519 manufacturing process Methods 0.000 title 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 14
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- 230000006837 decompression Effects 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical group [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract description 4
- 229910000077 silane Inorganic materials 0.000 abstract 4
- 238000004821 distillation Methods 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 8
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The present invention discloses a preparation method for hydrosulphonyl alkoxy silane. Chlorocarbon radical alkoxy silane and sulphide are used as raw materials, phase transfer catalysts are adopted, and a reaction of the raw materials is carried out in the temperature range of 100 to 140 DEG C.; after the raw materials thoroughly react, ammonia gas is introduced, and finally, the hydrosulphonyl alkoxy silane is generated; the reactants are filtered, filtered solution is obtained and then is processed by pressure reduction and rectification, distillation fractions are collected, and the hydrosulphonyl alkoxy silane is obtained. The present invention has the advantages that the new phase transfer catalysts are adopted, the ammonia gas-introducing time and the flow quantity of the ammonia gas are controlled, the selectivity of the reaction can be greatly increased to more than 95%, the purity of products is more than 98%, the yield is more than 85%, and simultaneously, the reaction time is greatly shortened to 8 to 10 hours, the reaction temperature is moderate and is from 100 to 120 DEG C.
Description
Technical field
The present invention relates to a kind of preparation method of mercapto hydrocarbyl alkoxy silanes.
Background technology
The mercapto hydrocarbyl alkoxy silanes mainly is to be applied to polymer modification---as radial, light-cured resin, dyeing and finishing auxiliaries etc.To in the research of mercapto hydrocarbyl alkoxy silanes synthetic, mainly be to adopt chlorocarbon base organoalkoxysilane and thiocarbamide, in the presence of alcoholic solvent, the employing sodium iodide is a catalyzer, under the logical ammonia, reacts 20～40 hours in the past; Be catalyzer perhaps, under the logical ammonia, reacted 20～40 hours, generate the mercapto hydrocarbyl alkoxy silanes at the solvent-free DMF of employing down; Adopt chlorocarbon base organoalkoxysilane and sulphur hydrogenation to receive in addition, in the presence of alcoholic solvent, reaction generated the mercapto hydrocarbyl alkoxy silanes more than 40 hours.The method of more than synthetic mercapto hydrocarbyl alkoxy silanes exists all that long reaction time, yield low (less than 80%), product purity difficulty reach 98% or more, selectivity less than 95%, shortcomings such as while by product many (greater than 10%), waste residue processing cost height.
Summary of the invention
At above problem, the present invention proposes a kind of new process that is suitable for producing the mercapto hydrocarbyl alkoxy silanes, can shorten the reaction times, improve product purity and yield.
Method of the present invention is a reaction raw materials with chlorocarbon base organoalkoxysilane and thiocarbamide or thiosemicarbazide mainly, adopts phase-transfer catalyst, reacts in 100～140 ℃ temperature range; After reaction raw materials fully reacts, feed ammonia, finally just can generate the mercapto hydrocarbyl alkoxy silanes; Again above-mentioned reactant is filtered, obtain filtrate decompression rectifying and collect fraction, just can obtain the mercapto hydrocarbyl alkoxy silanes.The main contents of its specific embodiment are: part chlorocarbon base organoalkoxysilane, thiocarbamide and phase-transfer catalyst are put in the reactor in advance, stirred and heat up.Under 100～120 degree, begin to drip remaining chlorocarbon base organoalkoxysilane.Dropwise, continue insulation 6～8 hours, feed ammonia, after 2～3 hours, cooling is filtered, and obtains filtrate decompression rectifying.
The mole proportioning of above-mentioned reaction raw materials is: chlorocarbon base organoalkoxysilane: sulfide is 1: 5～5: 1.
Above-mentioned mercapto hydrocarbyl alkoxy silanes can be represented with following expression:
HS(CH
2)
aSiR
3-b(OR)
b
In the following formula: R is a saturated alkyl, and its carbon chain lengths is C
1～C
12
A is 〉=1 integer;
B is 0～3 integer.
Described phase-transfer catalyst can be represented with following expression:
R
1R
2R
3R
4N
+·X
-
In the following formula: R
1～4Group is the saturated alkyl group, and its carbon chain lengths is C
1～C
16
The X group is a halogen, refers to chlorine, bromine especially.Described phase-transfer catalyst is best with the tri-n-octyl methyl ammonium chloride.And the consumption of phase-transfer catalyst is 0.1%～10% of a reaction raw materials gross weight.
The speed of described feeding ammonia is benchmark with the amount of every mol chlorocarbon base organoalkoxysilane, and its speed is 0～10ml/smol chlorocarbon base organoalkoxysilane, but is not 0.
Described chlorocarbon base organoalkoxysilane can be represented with following structural formula:
Cl(CH
2)
aSiR
3-b(OR)
b
In the following formula: R is a saturated alkyl, and its carbon chain lengths is C
1～C
12
A is 〉=1 integer;
B is 0～3 integer.
Advantage of the present invention is: by using new phase-transfer catalyst and to leading to the control of ammonia time and flow, making reaction preference improve greatly---greater than 95%.The purity of product mercapto hydrocarbyl alkoxy silanes is greater than 98%, and yield is more than 85%.Simultaneously having shortened the reaction times greatly, is 8～10 hours, and temperature of reaction is comparatively gentle, between 100～120 ℃.
Embodiment
The present invention is further described by the following embodiment.
Example one:
In reaction flask, add 198g 3-r-chloropropyl trimethoxyl silane (95%, GC) and thiocarbamide 90g, under the logical ammonia condition (2ml/s), in the reaction 8～10 hours down of 100～120 degree, sampling, stratographic analysis show that 20% above r-chloropropyl trimethoxyl silane has participated in reaction.
Example two:
In reaction flask, add 198g 3-r-chloropropyl trimethoxyl silicon (95%, GC) and thiocarbamide 90g, DMF (N, dinethylformamide) 20g, under the logical ammonia condition (2ml/s), reacted 8～10 hours down in 110～120 degree, the sampling stratographic analysis shows that 98% above r-chloropropyl trimethoxyl silane has participated in reaction, but has 30～40% height to boil.Cooling is filtered, and 90～110 ℃/1.3kPa～13kPa cut is collected in filtrate decompression rectifying, and stratographic analysis purity is more than 98%, and yield is about 65%.
Example three:
In reaction flask, add 198g 3-r-chloropropyl trimethoxyl silane (95%, GC) and thiocarbamide 90g, four butyl bromation amine 20g, under the logical ammonia condition (2ml/s), reacted 8～10 hours down in 100～120 degree, sampling, stratographic analysis show that 60% above r-chloropropyl trimethoxyl silane has participated in reaction, and high boiling material content is less than 5%.Cooling is filtered, and obtains filtrate decompression and collects 90～110 ℃/1.3kPa～13kPa, purity assay about 90%.
Example four:
In reaction flask, add 198g 3-r-chloropropyl trimethoxyl silane (95%, GC) and thiocarbamide 90g, trioctylphosphine methyl ammonia chloride 20g, reacted 8～10 hours down in 110～120 degree, (2ml/s) continues reaction 2～3 hours under the logical ammonia condition, the sampling stratographic analysis shows that 98% above r-chloropropyl trimethoxyl silane has participated in reaction, and height boils about 5%.Cooling is filtered, and 90～110 ℃/1.3kPa～13kPa cut is collected in filtrate decompression rectifying, and stratographic analysis purity is more than 98%, and yield is about 85%.
Example five:
In reaction flask, add 221g 3-chloropropyl triethoxysilane (95%, GC) and thiocarbamide 90g, trioctylphosphine methyl ammonia chloride 20g,, in the reaction 8～10 hours down of 110～120 degree, (2ml/s) continues reaction 2～3 hours under the logical ammonia condition.The sampling stratographic analysis shows that 98% above r-chloropropyl trimethoxyl silane has participated in reaction, and height boils about 2～3%.Cooling is filtered, and 130～140 ℃/1.3kPa～13kPa cut is collected in filtrate decompression rectifying, and stratographic analysis purity is more than 98%, and yield is about 90%.
In the foregoing description, do not add catalyzer in the example one, added non-phase-transfer catalyst in the example two, added phase-transfer catalyst in example three, example four, the example five.
Claims (9)
1, the preparation method of mercapto hydrocarbyl alkoxy silanes is characterized in that: with chlorocarbon base organoalkoxysilane and thiocarbamide or thiosemicarbazide is reaction raw materials, adopts phase-transfer catalyst, reacts in 100～140 ℃ temperature range; After reaction raw materials fully reacts, feed ammonia, finally just can generate the mercapto hydrocarbyl alkoxy silanes; Again above-mentioned reactant is filtered, obtain filtrate decompression rectifying and collect fraction, just can obtain the mercapto hydrocarbyl alkoxy silanes.
2, preparation method as claimed in claim 1 is characterized in that: the mole proportioning of described reaction raw materials is: chlorocarbon base organoalkoxysilane: sulfide is 1: 5～5: 1.
3, preparation method as claimed in claim 1 is characterized in that: described mercapto hydrocarbyl alkoxy silanes can be represented with following expression:
HS(CH
2)
aSiR
3-b(OR)
b
In the following formula: R is a saturated alkyl, and its carbon chain lengths is C
1～C
12
A is 〉=1 integer;
B is 0～3 integer.
4, preparation method as claimed in claim 1 is characterized in that: described phase-transfer catalyst can be represented with following expression:
R
1R
2R
3R
4N
+·X
-
In the following formula: R
1～4Group is the saturated alkyl group, and its carbon chain lengths is C
1～C
16
The X group is a halogen.
5, as claim 1 or 4 described preparation methods, it is characterized in that: described phase-transfer catalyst is a tri-n-octyl methyl ammonium chloride.
As claim 1 or 4 described preparation methods, it is characterized in that 6, the consumption of described phase-transfer catalyst is 0.1%～10% of a reaction raw materials gross weight.
7, preparation method as claimed in claim 1 is characterized in that: described temperature of reaction is 100 ℃～120 ℃.
8, preparation method as claimed in claim 1 is characterized in that: the speed of feeding ammonia is benchmark with the amount of every mol chlorocarbon base organoalkoxysilane, and its speed is 0～10ml/s, but is not 0.
9, preparation method as claimed in claim 1 is characterized in that: described chlorocarbon base organoalkoxysilane can be represented with following structural formula:
Cl(CH
2)
aSiR
3-b(OR)
b
In the following formula: R is a saturated alkyl, and its carbon chain lengths is C
1～C
12
A is 〉=1 integer;
B is 0～3 integer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310112707 CN1269826C (en) | 2003-12-22 | 2003-12-22 | Process for preparing hydrosulphonyl alkoxy silicane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310112707 CN1269826C (en) | 2003-12-22 | 2003-12-22 | Process for preparing hydrosulphonyl alkoxy silicane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1631891A CN1631891A (en) | 2005-06-29 |
| CN1269826C true CN1269826C (en) | 2006-08-16 |
Family
ID=34843319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310112707 Expired - Lifetime CN1269826C (en) | 2003-12-22 | 2003-12-22 | Process for preparing hydrosulphonyl alkoxy silicane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1269826C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423528B (en) * | 2007-11-02 | 2012-07-25 | 张家港市国泰华荣化工新材料有限公司 | Method for preparing mercaptoalkyl alkoxy silane |
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2003
- 2003-12-22 CN CN 200310112707 patent/CN1269826C/en not_active Expired - Lifetime
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|---|---|
| CN1631891A (en) | 2005-06-29 |
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|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder |
Address after: 215600 No.35 Nanhai Road, Jiangsu Yangzijiang International Chemical Industrial Park, Zhangjiagang, Suzhou, Jiangsu Province Patentee after: Zhangjiagang Guotai-Huarong New Chemical Materials Co.,Ltd. Address before: 215631 Jiangsu city of Zhangjiagang province Xincheng Xincheng Road No. 112 Patentee before: Zhangjiagang Guotai-Huarong New Chemical Materials Co.,Ltd. |
|
| CP02 | Change in the address of a patent holder | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060816 |
|
| CX01 | Expiry of patent term |