CN101012237B - Synthesis method of vinyl alkoxy silane - Google Patents
Synthesis method of vinyl alkoxy silane Download PDFInfo
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- CN101012237B CN101012237B CN2007100514274A CN200710051427A CN101012237B CN 101012237 B CN101012237 B CN 101012237B CN 2007100514274 A CN2007100514274 A CN 2007100514274A CN 200710051427 A CN200710051427 A CN 200710051427A CN 101012237 B CN101012237 B CN 101012237B
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- alkoxy silane
- acetylene
- reaction
- silane
- vinyl alkoxy
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Abstract
The invention discloses a synthesizing method of vinyl alkoxy silane, which comprises the following steps: adopting acetylene and alkoxy silane as raw maerial; using silicon hydrogenating method; making platiunum compound or complex as catalyst and polymethyl vinyl alkoxy silane or triphenylphosphine as catalyst promoter under 30-120 deg.c; adopting inert solvent as reacting solvent; controlling the flow speed of acetylene at 40-200mL/min; reacting to produce the product.
Description
Technical field
The present invention relates to a kind of synthetic method of organo silane coupling agent, i.e. the synthetic method of vinyl alkoxy silane.
Background technology
Vinyl alkoxy silane is the silane coupling agent of a class excellent property, can be used as the surface treatment of glass fibre, the Inorganic Fillers Filled plastics, the linking agent of crosslinked polyethylene, the adhesive accelerant of difficult sticking material etc., at present both at home and abroad generally by acetylene and the addition of hydrogen silicon alcoholysis synthesis of vinyl organoalkoxysilane again, also can be synthetic by acetylene and the addition of organoalkoxysilane silicon hydrogen.The former technology is complicated, severe reaction conditions, and product yield is not high yet; And that the latter has a Material Cost is low, and no hydrogenchloride generates in the production process, and to not corrosion of equipment, yield advantages of higher.
USP2,637,738 (1952) point out to make catalyzer with the 8th family's metal, under 130 ℃, 2.4MPa pressure, acetylene are fed in the triethoxyl silane reaction 2 hours, just can make vinyl three ethoxy silane.But, the product yield of this technology not high (about 50%), and need High Temperature High Pressure, dangerous big in the reaction process, industrial production is had any problem.
USP5,041,595 (1991) discloses a kind of method of synthesis of high purity vinyl alkoxy silane, has suppressed the generation of by product tetraalkyl silane preferably by the content of chlorion and alkylamine in the control reaction raw materials.Reaction is solvent with the dichlorobenzene, the 50ppm chloroplatinic acid catalyst, and the 200ppm thiodiphenylamine is made promotor, and the acetylene flow velocity is 0.36mol/h, and the triethoxyl silane flow velocity is 0.22mol/h, reacts 2h down at 100 ℃, and yield is 92.2%.This method acetylene is excessive big, and raw materials cost increases.
Okamoto M.Chem.Commun., 2002:1634 have reported that (active ingredient is Pt (NH to an immobilized liquid-phase catalyst SLPC
3)
4Cl
2H
2O, high boiling solvent are polyoxyethylene glycol, and carrier adopts silica gel or aluminum oxide) be used for the gas-phase silicon addition reaction of hydrogen of catalyzing acetylene (44KPa) and Trimethoxy silane (11KPa), temperature of reaction is 150 ℃, the yield of product vinyltrimethoxy silane only is 67%.
Hamao W.Jorunal of Organometallic Chemistry Volume195Page363 (1980) has reported a kind of with platinum complex PtCl
2(PPh
3)
2Make the method for catalyzer synthesis of vinyl organoalkoxysilane, be reflected in the inert solvent, temperature is to carry out product yield under 80 ℃ can reach 97%, but the reaction times is 10h than length.
Magormedov G K,
O V, Izmailov B A, et al.Vinylsilane, the catalyst system that SU810704.1981 adopts eight cobalt-carbonyls, tetrahydrofuran (THF), potassiumiodide or ether or their mixture to form, triethoxy hydrogen silicon can carry out the normal pressure addition reaction with acetylene, temperature is 15～20 ℃, and the yield of product vinyltriethoxysilane is more than 90%.But catalyst levels is bigger.
Zhao Ming is the chemical engineer, it is raw material that 1996:52 has introduced with triethoxyl silane and acetylene, closes under the effect of platinum at dichloro bi triphenyl phosphine, and temperature is that reaction 2-4h can a step addition make vinyltriethoxysilane under 90-130 ℃, product yield is not high, is 75%.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of vinyl alkoxy silane, it is to utilize silicon hydrogen additive process synthesis of vinyl organoalkoxysilane, product yield height.
The present invention is achieved like this, it is to be raw material with acetylene and organoalkoxysilane, adopt silicon hydrogen additive process, at normal pressure, under temperature 30-120 ℃ the condition, make catalyzer with platinum compound or complex compound, poly-ethylene methacrylic radical siloxane or triphenylphosphine are made promotor, inert solvent is made reaction solvent, and control acetylene flow velocity is 40-200mL/min, makes the product vinyl alkoxy silane;
Described organoalkoxysilane is: triethoxyl silane, Trimethoxy silane, methyl dimethoxysilane, methyldiethoxysilane, three (2-methoxy ethoxy) silane;
Described platinum compound catalyzer is: chloroplatinic acid catalyst, the mol ratio of catalyzer and organoalkoxysilane are 1-100 * 10
-5: 1;
Described inert solvent is: inert solvents such as toluene, sherwood oil, chlorobenzene, dimethylbenzene, hexanaphthene, normal hexane, benzene, and preferred solvent is a toluene, sherwood oil, chlorobenzene;
The add-on of poly-ethylene methacrylic radical siloxane of described promotor or triphenylphosphine is 0.1-10 a times of catalyzer molar weight, and preferred version is 0.5-5 times;
Described temperature of reaction preferred version is 70-100 ℃;
Described acetylene flow velocity preferred version is 40-200mL/min;
Advantage of the present invention is: (1) catalyst levels is few, and active good, and stability is high; (2) product vinyl alkoxy silane yield is greater than 97.5%; (3) side reaction is few, and secondary adduct content is low; (4) synthetic method is simple, the reaction conditions gentleness, and equipment requirements is simple.
Embodiment
Embodiment 1
Be reflected in the there-necked flask that 100ml is equipped with thermometer and prolong and carry out, in reaction flask, add 20mL triethoxyl silane, 20mL toluene, 1.2 * 10
-5The mol chloroplatinic acid catalyst, 1.8g gathers the ethylene methacrylic radical siloxane, and acetylene gas purifying and drying feed reactor after overregulate the current stabilizer and the under meter bubbling of flow, 80 ℃ of temperature of reaction, the acetylene flow velocity is 120mL/min, reaction 3h, yield is 97.5%.
Embodiment 2
Be reflected in the there-necked flask that 100ml is equipped with thermometer and prolong and carry out, in reaction flask, add 20ml Trimethoxy silane, 20mL toluene, 2.5 * 10
-5The mol chloroplatinic acid catalyst, 3.7g gathers the ethylene methacrylic radical siloxane, and acetylene gas purifying and drying feed reactor after overregulate the current stabilizer and the under meter bubbling of flow, 70 ℃ of temperature of reaction, the acetylene flow velocity is 100mL/min, reaction 3h.Yield is 92%.
Embodiment 3
Be reflected in the there-necked flask that 1000ml is equipped with thermometer and prolong and carry out, in reaction flask, add 250mL triethoxyl silane, 200mL sherwood oil, 2.5 * 10
-4The mol chloroplatinic acid catalyst, 36g gathers the ethylene methacrylic radical siloxane, and acetylene gas purifying and drying feed reactor after overregulate the current stabilizer and the under meter bubbling of flow, 80 ℃ of temperature of reaction, the acetylene flow velocity is 120mL/min, reaction 4h.Yield is 95%.
Embodiment 4
Be reflected in the there-necked flask that 1000ml is equipped with thermometer and prolong and carry out, in reaction flask, add 200ml triethoxyl silane, 200mL chlorobenzene, 2.5 * 10
-4The mol chloroplatinic acid catalyst, the 0.1g triphenylphosphine, acetylene gas purifying and drying feed reactor after overregulate the current stabilizer and the under meter bubbling of flow, 100 ℃ of temperature of reaction, the acetylene flow velocity is 100mL/min, reaction 4h.Yield is 84%.
Embodiment 5
Be reflected in the there-necked flask that 1000ml is equipped with thermometer and prolong and carry out, in reaction flask, add 200ml Trimethoxy silane, 200mL toluene, 1.5 * 10
-4The mol chloroplatinic acid catalyst, the 0.06g triphenylphosphine, acetylene gas purifying and drying feed reactor after overregulate the current stabilizer and the under meter bubbling of flow, 100 ℃ of temperature of reaction, the acetylene flow velocity is 120mL/min, reaction 4h, yield is 82%.
Embodiment 6
Be reflected in the there-necked flask that 100ml is equipped with thermometer and prolong and carry out, in reaction flask, add 20mL methyl dimethoxysilane, 20mL sherwood oil, 1.5 * 10
-5The mol chloroplatinic acid catalyst, 2.0g gathers the ethylene methacrylic radical siloxane, and acetylene gas purifying and drying feed reactor after overregulate the current stabilizer and the under meter bubbling of flow, 80 ℃ of temperature of reaction, the acetylene flow velocity is 120mL/min, reaction 3h, yield is 92.5%.
Embodiment 7
Be reflected in the there-necked flask that 2500ml is equipped with thermometer and prolong and carry out, in reaction flask, add 500mL triethoxyl silane, 400mL toluene, 5.0 * 10
-4The mol chloroplatinic acid catalyst, 70g gathers the ethylene methacrylic radical siloxane, and acetylene gas purifying and drying feed reactor after overregulate the current stabilizer and the under meter bubbling of flow, 80 ℃ of temperature of reaction, the acetylene flow velocity is 100mL/min, reaction 4h, yield is 79.5%.
Embodiment 8
Be reflected in the there-necked flask that 100ml is equipped with thermometer and prolong and carry out, in reaction flask, add 20mL methyldiethoxysilane, 20mL chlorobenzene, 2.0 * 10
-5The mol chloroplatinic acid catalyst, 3.2g gathers the ethylene methacrylic radical siloxane, and acetylene gas purifying and drying feed reactor after overregulate the current stabilizer and the under meter bubbling of flow, 80 ℃ of temperature of reaction, the acetylene flow velocity is 120mL/min, reaction 3h, yield is 91%.
Embodiment 9
Be reflected in the there-necked flask that 1000ml is equipped with thermometer and prolong and carry out, in reaction flask, add 200mL three (2-methoxy ethoxy) silane, 200mL toluene, 3.0 * 10
-4The mol chloroplatinic acid catalyst, 40g gathers the ethylene methacrylic radical siloxane, and acetylene gas purifying and drying feed reactor after overregulate the current stabilizer and the under meter bubbling of flow, 70 ℃ of temperature of reaction, the acetylene flow velocity is 100mL/min, reaction 4h, yield is 81%.
Claims (3)
1. the synthetic method of a vinyl alkoxy silane, it is characterized in that it is is raw material with acetylene and organoalkoxysilane, adopt silicon hydrogen additive process, at normal pressure, under temperature 30-120 ℃ the condition, make catalyzer with platinum compound, poly-ethylene methacrylic radical siloxane is made promotor, inert solvent is made reaction solvent, controls certain acetylene flow velocity 40-200ml/min, makes the product vinyl alkoxy silane; Described organoalkoxysilane is: triethoxyl silane, Trimethoxy silane, methyl dimethoxysilane, methyldiethoxysilane; Described platinum compound catalyzer is: chloroplatinic acid catalyst; The mol ratio of catalyzer and organoalkoxysilane is 1-100 * 10
-5: 1.
2. the synthetic method of vinyl alkoxy silane according to claim 1 is characterized in that inert solvent is: toluene, sherwood oil, chlorobenzene, dimethylbenzene, hexanaphthene, normal hexane, benzene.
3. the synthetic method of vinyl alkoxy silane according to claim 1, the add-on that it is characterized in that the poly-ethylene methacrylic radical siloxane of promotor be the catalyzer molar weight 0.1-10 doubly.
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| EP2540683A1 (en) * | 2011-06-28 | 2013-01-02 | 3B-Fibreglass SPRL | Glass fibre sizing composition |
| US10184026B2 (en) * | 2014-12-22 | 2019-01-22 | Dow Global Technologies Llc | Hydrosilylation method |
| CN105622660B (en) * | 2015-12-21 | 2019-06-07 | 安徽硅宝有机硅新材料有限公司 | A kind of secondary aminosilane coupling agent preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1228435A (en) * | 1998-03-07 | 1999-09-15 | 南昌大学 | Synthesis method of vinyl chlorine-containing silane |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1228435A (en) * | 1998-03-07 | 1999-09-15 | 南昌大学 | Synthesis method of vinyl chlorine-containing silane |
Non-Patent Citations (4)
| Title |
|---|
| Hamao Watanabe et al..Convinient laboratory synthesis of vinylic silicon compounds via the reactions of acetylene with hydrosilanes catalyzed by group-VIII metal phosphine complexes.《Journal of organometallic chemistry》.1980,(第195期),363-373. * |
| 盛晓莉.乙炔和三氯硅烷的加成反应探讨.《科技进展》.2002,(第6期),25-28. * |
| 袁光谱 等.聚乙烯基硅氧烷-铂络合物的合成及其对硅氢加成反应的催化作用的研究.《催化学报》.1988,第9卷(第1期),52-56. |
| 袁光谱等.聚乙烯基硅氧烷-铂络合物的合成及其对硅氢加成反应的催化作用的研究.《催化学报》.1988,第9卷(第1期),52-56. * |
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