CN101054389B - Process for preparing allyltriethoxysilicane - Google Patents
Process for preparing allyltriethoxysilicane Download PDFInfo
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- CN101054389B CN101054389B CN200710072285A CN200710072285A CN101054389B CN 101054389 B CN101054389 B CN 101054389B CN 200710072285 A CN200710072285 A CN 200710072285A CN 200710072285 A CN200710072285 A CN 200710072285A CN 101054389 B CN101054389 B CN 101054389B
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- reaction
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- tetrahydrofuran
- magnesium
- propenyl chloride
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Abstract
The present invention provides a preparation method of allyl triethoxysilane. The material comprise : tetrahydrofuran accounting for effective dimension 20-40% of reaction container, 0.7-1mol magnesium, 0.9-1.3mol chloropropene and 0.7-1mol triethoxyhydrosilicon. adding 8-10% mixture of tetrahydrofuran, magnesium, chloropropene and triethoxyhydrosilicon in reaction container, adding the other chloropropene and triethoxyhydrosilicon mixture in dripping funnel, stirring, heating for inspiring reaction, controlling reaction temperature at 60-70 degree, opening dripping funnel when reaction being stable, dropping chloropropene and triethoxyhydrosilicon mixture in reaction kettle, then heating the reaction kettle to keep it at microboiling state 3-4 hours, reducing the temperature, removing solid salt from the solution, Distilling filtrate, and collecting distillate of 160-165 degree i.e. allyl triethoxysilane. The synthesis reaction can accomplish in one step and yield can amount to 50%.
Description
(1) technical field
That the present invention relates to is a kind of preparation method of organic compound, specifically a kind of preparation method of allyl triethoxysilane.
(2) background technology
Allyltriethoxysilane is a kind of in numerous organo silane coupling agents, and it is of many uses, is applicable to unsaturated polyester, acrylic resin, also can be used for vulcanized rubber properties-correcting agent, finishing agent for glass fibre, high density polyethylene(HDPE) linking agent etc.Allyl group three TMOSs self have a particular performances, can be used for the bonding of other mechanically resistant materials such as viton, trifluoropropyl siloxane and metal, allyltriethoxysilane is that other material is irreplaceable in the property of handling on viton, the trifluoropropyl siloxane, has solved very good viton, the trifluoropropyl siloxane of performance and has been difficult to a bonding application difficult problem.
But at present domestic still do not have the study on the synthesis of this kind silane coupling agent and use report.Learn from document, USSR (Union of Soviet Socialist Republics) scientist adopts the Grignard reagent method at laboratory study, reaction is a two-step approach, at first in specific solvent, synthesize Grignard reagent by propenyl chloride and MAGNESIUM METAL, Grignard reagent after separating is carrying out the molecular radical exchange with tetraethoxy, obtain allyltriethoxysilane, product yield 30%; U.S. scientist adopts pyrocondensation legal, pyrocondensation legal raw materials used be propenyl chloride, trichlorosilane, ethanol, reaction principle is that propenyl chloride and trichlorosilane react the generation allyltrichlorosilane under high temperature (more than 600 ℃) condition, allyltrichlorosilane carries out esterification with ethanol again, generate allyltriethoxysilane, because two-step reaction all has hydrogen chloride gas to generate, can pollute environment, moreover the thermal condensation temperature of reaction is higher, the synthesis material propenyl chloride at high temperature two keys of C=C very easily ruptures, therefore the synthesis yield of this method is very low, product yield only 10～20%.And a large amount of hydrogen chloride gas of thermal condensation reaction generation, can pollute environment, production unit there is corrosion.
(3) summary of the invention
The object of the present invention is to provide a kind of synthesis yield height, the simple preparation method of allyl triethoxysilane that realizes easily of technology.
The object of the present invention is achieved like this:
Raw material consists of the tetrahydrofuran (THF) that accounts for reaction vessel useful volume 20%～40%, 0.7～1mol magnesium, 0.9～1.3mol propenyl chloride and 0.7～1mol triethoxy hydrogen silicon, with tetrahydrofuran (THF), magnesium, the 8-10% of the mixture of propenyl chloride and triethoxy hydrogen silicon joins in the reaction vessel, the mixture of remaining propenyl chloride and triethoxy hydrogen silicon adds in the dropping funnel, under agitation, slowly add thermal booster reaction, 60～70 ℃ of control reaction temperature, after question response is steady, open dropping funnel, the mixture of drip chloro propylene and triethoxy hydrogen silicon in reactor, dropwise, heat to reactor, make it keep slight boiling condition 3～4 hours, reaction finishes the back cooling, and Generation Liquid is removed solid salt, with the filtrate distillation, collect 160～165 ℃ of cuts and be allyltriethoxysilane.
For prove effect of the present invention we according to Soviet Union's document (k.ardrianov.and.M.kamenskayaJ.Gen.Chem (U.S.S.R) 8,969-71 (1938)) processing condition and the data that provide in the report, carried out revision test, the result is disappointing, the product that synthesizes is tested with iodination, unparalleled key composition exists in the molecule, detect through infrared spectrometer again, find the two key peaks of no C=C in the spectrogram, contrast with the standard spectrogram, do not conform to yet, illustrate that the final product that synthesizes is not an allyltriethoxysilane.
The present invention has proposed new synthetic route according to organic chemical reactions mechanism and through molecular designing, adopts propenyl chloride and MAGNESIUM METAL to prepare Grignard reagent, and Grignard reagent and triethoxy hydrogen pasc reaction obtain the purpose product then.Reaction equation is:
Mg+CH
2＝CHCH
2Cl→CH
2＝CHCH
2MgCl
CH
2＝CHCH
2MgCl+HSi(OC
2H
5)
3→CH
2＝CHCH
2Si(OC
2H
5)
3+MgHCl↓
Because very easily oxidation of Grignard reagent, in separation, washing and exsiccant process, though carry out under nitrogen protection, it is oxidized also to keep away unavoidable part Grignard reagent, causes the inefficiency of Grignard reagent, thereby has reduced the yield of purpose product; In Dui Geshi reagent wash and exsiccant process, adopt a large amount of organic solvents, can cause the loss of solvent, cause environmental pollution simultaneously.Our stepwise reaction no longer in test, employing adds reaction system simultaneously with the mixture of propenyl chloride and triethoxyl silane, the oxidation of Grignard reagent and the generation of side reaction have been avoided, one step of reaction is finished, reduce synthetic difficulty, simplified synthesis step, shortened reaction time, reduce the loss of solvent, improved product yield.The present invention is a raw material by magnesium, propenyl chloride, triethoxy hydrogen silicon, and tetrahydrofuran (THF) is that solvent prepares the purpose product, and one step of building-up reactions finishes, and product yield can reach 50%, surpasses the data from abroad report.
(4) embodiment
For example the present invention is done in more detail below and describes:
Embodiment 1, to having snake type condenser, electric mixer, dropping funnel, thermometer, in the 500mL reactor of well heater, the tetrahydrofuran (THF) that adds 100mL, 5g magnesium, the propenyl chloride of 4g and the mixture of triethoxyl silane, the mixture 39g of remaining propenyl chloride and triethoxyl silane adds in the dropping funnel, under agitation, slowly add thermal booster reaction, reaction is in case initiation stops heating immediately, if reaction is violent, to the reactor cooling, after question response is steady, open dropping funnel rapidly, the mixture of drip chloro propylene and triethoxy hydrogen silicon in reactor, dropwise,, remain temperature of reaction at 60～70 ℃ to the reactor heating, make it keep slight boiling condition, reacted 3～4 hours, reaction finishes the back cooling, and Generation Liquid is removed solid salt, filtrate is distilled, collect 160～165 ℃ of cuts, thick product 120g, thick product through distill 98% allyltriethoxysilane 20g, theoretical must measuring is 42g, product yield 47.6%.
Embodiment 2, in the 500mL reactor that has snake type condenser, electric mixer, dropping funnel, thermometer, well heater, the tetrahydrofuran (THF), 8g magnesium, the propenyl chloride of 10g and the mixture of triethoxyl silane that add 200mL, the mixture 89g of remaining propenyl chloride and triethoxyl silane adds in the dropping funnel, the same example of other conditions, after the reaction thick product 280g, thick product through distill 98% allyltriethoxysilane 41g, theoretical must measuring is 78g, product yield 52.6%.
Claims (1)
1. preparation method of allyl triethoxysilane, it is characterized in that: raw material consists of the tetrahydrofuran (THF) that accounts for reactor useful volume 20%～40%, 0.7～1mol magnesium, 0.9～1.3mol propenyl chloride and 0.7～1mol triethoxy hydrogen silicon, with tetrahydrofuran (THF), magnesium, the 8-10% of the mixture of propenyl chloride and triethoxy hydrogen silicon joins in the reaction vessel, the mixture of remaining propenyl chloride and triethoxy hydrogen silicon adds in the dropping funnel, under agitation, slowly add thermal booster reaction, 60～70 ℃ of control reaction temperature, after question response is steady, open dropping funnel, the mixture of drip chloro propylene and triethoxy hydrogen silicon in reactor, dropwise, heat to reactor, make it keep slight boiling condition 3～4 hours, reaction finishes the back cooling, Generation Liquid is removed solid salt, with the filtrate distillation, collects 160～165 ℃ of cuts and is allyltriethoxysilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710072285A CN101054389B (en) | 2007-05-30 | 2007-05-30 | Process for preparing allyltriethoxysilicane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710072285A CN101054389B (en) | 2007-05-30 | 2007-05-30 | Process for preparing allyltriethoxysilicane |
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|---|---|
| CN101054389A CN101054389A (en) | 2007-10-17 |
| CN101054389B true CN101054389B (en) | 2010-05-26 |
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| CN200710072285A Expired - Fee Related CN101054389B (en) | 2007-05-30 | 2007-05-30 | Process for preparing allyltriethoxysilicane |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831851A (en) * | 2017-01-24 | 2017-06-13 | 广东信翼科技有限公司 | A kind of preparation method of allyl silicane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB663770A (en) * | 1947-10-02 | 1951-12-27 | Libbey Owens Ford Glass Co | Preparation of silicon-containing heteropolymers |
| US2595729A (en) * | 1945-03-09 | 1952-05-06 | Westinghouse Electric Corp | Organosilicon compounds and conductors insulated therewith |
| US3403050A (en) * | 1964-12-28 | 1968-09-24 | Stauffer Chemical Co | Water repellent compositions for porous substrates |
-
2007
- 2007-05-30 CN CN200710072285A patent/CN101054389B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2595729A (en) * | 1945-03-09 | 1952-05-06 | Westinghouse Electric Corp | Organosilicon compounds and conductors insulated therewith |
| GB663770A (en) * | 1947-10-02 | 1951-12-27 | Libbey Owens Ford Glass Co | Preparation of silicon-containing heteropolymers |
| US3403050A (en) * | 1964-12-28 | 1968-09-24 | Stauffer Chemical Co | Water repellent compositions for porous substrates |
Non-Patent Citations (2)
| Title |
|---|
| 李瑞琦,郭示欣.特种橡胶助剂烯丙基三乙氧基硅烷合成工艺研究.化学工程师 2.2002,(2),16,21. |
| 李瑞琦,郭示欣.特种橡胶助剂烯丙基三乙氧基硅烷合成工艺研究.化学工程师 2.2002,(2),16,21. * |
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| CN101054389A (en) | 2007-10-17 |
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