CN1865264A - Carboxylic silicone grease compounds preparation method - Google Patents
Carboxylic silicone grease compounds preparation method Download PDFInfo
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- CN1865264A CN1865264A CN 200610028009 CN200610028009A CN1865264A CN 1865264 A CN1865264 A CN 1865264A CN 200610028009 CN200610028009 CN 200610028009 CN 200610028009 A CN200610028009 A CN 200610028009A CN 1865264 A CN1865264 A CN 1865264A
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- acid
- carboxylic
- silane
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Abstract
The invention discloses a carboxylic silicon ester compound making method in the organic compound technological domain, which comprises the following steps: adding CuCl(Ph3P)3 in the organic solvent of carboxyl acid and trialkyl silane compound; filling nitrogen in the reactor; heating to 40-190 deg.c through stirring; reacting the carboxyl acid and trialkyl silane to produce carboxylic silicon ester compound hydrogen under the catalyst of CuCl(Ph3P)3; adopting unsaturated carboxylic silicon ester compound as important monomer raw material to make carboxylic silicon ester compound. The invention can be applied in the metabolic medical material as Helen paint, which forms rather smooth film to reduce shipping oil consumption.
Description
Technical field
The invention belongs to organic compound and make the field, be specifically related to a kind of preparation method of carboxylic silicon ester compound.
Background of invention
The carboxylic silicone grease polymkeric substance is widely used in the metabolizability medical material, and seagoing vessel is with coating etc.As seagoing vessel coating, owing to form quite slick film, prevent that the sea cowry class is adsorbed onto on the wheel hull, reduce the shipping oil consumption, reduce cost.Up to now, mainly use the organic tin compound to be coated onto the seagoing vessel hull surface, poison the sea cowry class marine organisms that are adsorbed onto on the wheel hull with poison.Because the organic tin compound is poisonous, seriously polluted ocean and marine organisms, simultaneously by food chain, humanly also take in a large amount of poisonous and harmful organic tin compounds, serious harm human beings'health.World ocean pact in 2009 provides against uses poisonous and harmful organic tin compound to shoot out the seagoing vessel hull surface.Therefore, the nontoxic seagoing vessel coating of exploitation is to go.The synthetic method of carboxylic silicon ester compound is generally carboxylic acid and chlorinated silane reaction, uses for example triethylamine of alkali, the hydrogenchloride that generates in the absorption reaction processes such as liquefied ammonia.Perhaps use Pd, Rh, precious metals such as Pt are as catalyzer, and carboxylic acid and silane reaction generate carboxylic silicone grease.But, since Pd, Rh, and precious metals such as Pt simultaneously can shortening as catalyzer.Therefore, when synthesizing the unsaturated carboxylic acid estersil, being easy to generate a certain amount of saturated carboxylic acid estersil is by product.And the unsaturated carboxylic acid estersil is similar to the rerum natura of by product saturated carboxylic acid estersil, boiling point much at one, separation difficulty.Therefore, product purity is lower, can not satisfy the demand of synthetic next step carboxylic silicone grease polymkeric substance.So far, main synthetic method is:
(1) people such as S.Saito (Japan Kokai Tokkyo Koho, 1992, JP 04154790) has reported Pd/C, and Pt is a catalyzer, saturated carboxylic acid and and silane reaction.
(2) people such as M.Zenbayashi (Japan Kokai Tokkyo Koho, 1992, JP 04154789) has reported that Pd/C is a catalyzer, saturated carboxylic acid and and silane reaction.
(3) people such as S.Masuoka (Japan Kokai Tokkyo Koho, 1993, JP 05025187) has reported that Pt is a catalyzer, saturated carboxylic acid and and silane reaction.
(4) people such as J.Fujino (Japan Kokai Tokkyo Koho, 1998, JP 70212293) has reported that Pd/C is a catalyzer, saturated carboxylic acid and and silane reaction.
(5) people such as M.Matsumoto (Japan Kokai Tokkyo Koho, 2001, JP 20011228839) has reported that Pd/C is a catalyzer, saturated carboxylic acid and and silane reaction.
Aforesaid method needs Pd/C mostly, and Pt makes catalyzer, and therefore, when synthesizing the unsaturated carboxylic acid estersil, being easy to generate a certain amount of saturated carboxylic acid estersil is by product.And the unsaturated carboxylic acid estersil is similar to the rerum natura of by product saturated carboxylic acid estersil, and boiling point is difficult to separate much at one, and product purity is lower, can not satisfy the demand of synthesis of carboxylic acid estersil polymkeric substance.
Summary of the invention
It is simple to the objective of the invention is to propose a kind of technology, is easy to form the preparation method of the carboxylic silicon ester compound of mass-producing.
The preparation method of the carboxylic silicon ester compound that the present invention proposes, concrete steps are as follows: with Catalysts Cu Cl (Ph
3P)
3Add in the organic solvent of carboxylic-acid, trialkyl silica alkyl compound, be full of nitrogen in the reaction vessel; Be heated to 40-190 ℃ under stirring; At CuCl (Ph
3P)
3Catalysis under, the reaction of carboxylic acid and trialkyl silane generates carboxylic silicon ester compound hydrogen.CuCl (Ph
3P)
3Usage quantity is 0.01-1.0 a times of carboxylic acid compound weight, and control reaction temperature is 40 ℃ ~ 190 ℃; Stirred 4-22 hour.
Among the present invention, described carboxylic-acid is acetate, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, certain herbaceous plants with big flowers acid is full or lipid acid etc.; Phenylformic acid, toluylic acid, phenylpropionic acid, furancarboxylic acid, thiophene phenol formic acid or styracin, or contain other substituting group fragrance same clan organic carboxyl acid compounds; Vinylformic acid, 2-methacrylic acid, butenoic acid, toxilic acid or fumaric acid unsaturated fatty acids etc.
Among the present invention, described trialkyl silica alkyl compound is triethyl silicane, tripropyl silane, tri isopropyl silane, three normal-butyl silane, uncle's normal-butyl dimethylsilane or tri-phenyl-silane etc.
Among the present invention, described organic solvent is benzene, toluene, ethylbenzene, isopropyl benzene, second cyanogen, phenethyl cyanogen, ethyl acetate, tetrahydrofuran (THF), dioxane, N, one or more mixed solvents in dinethylformamide, N,N-dimethylacetamide or the hexamethylphosphoramide equal solvent.
Stirring reaction is cooled to room temperature after finishing, and steams solvent, and underpressure distillation obtains product.
Among the present invention, at CuCl (Ph
3P)
3Catalysis under, the reaction of carboxylic acid and trialkyl silane generates carboxylic silicon ester compound hydrogen.Characteristics of the present invention are: utilize CuCl (Ph
3P)
3As catalyzer, realized the dehydrogenation estersil reaction of carboxylic acid and trialkyl silane.The advantage of present method is that (1) uses low price CuCl (Ph
3P)
3Avoid the hydrogenation side reaction of unsaturated carboxylic acid estersil for catalyzer (2), do not needed to be further purified product, reduced production cost, and had practicality and Yi Hangxing, be easy to form industrially scalable, had higher industrial application value.
The inventive method technology is simple, is easy to form large-scale production, is with a wide range of applications.
Embodiment
In the three-necked bottle of embodiment 1:100 milliliter, thermometer is installed, agitator adds phenylformic acid (0.1 mole, 12.2 grams), CuCl (Ph
3P)
3(0.12g), (0.1mol, 11.6g), benzene first cyanogen (40 milliliters) begins to be heated with stirring to 190 ℃ to triethyl silicane then.Restir is 22 hours under this temperature.Be cooled to room temperature then, steam solvent, underpressure distillation obtains products benzene formic acid triethyl estersil, and productive rate is 89%.
In the three-necked bottle of embodiment 2:100 milliliter, thermometer is installed, agitator adds phenylformic acid (0.1 mole, 12.2 grams), CuCl (Ph
3P)
3(0.6g), (0.1mol, 11.6g), second cyanogen (45 milliliters) begins to be heated with stirring to 40 ℃ to triethyl silicane then.Restir is 18 hours under this temperature.Be cooled to room temperature then, steam solvent, underpressure distillation obtains products benzene formic acid triethyl estersil, and productive rate is 85%.
In the three-necked bottle of embodiment 3:100 milliliter, thermometer is installed, agitator adds toluylic acid (0.1 mole, 13.6 grams), CuCl (Ph
3P)
3(1.36g), (0.1mol, 15.8g), second cyanogen (50 milliliters) begins to be heated with stirring to 80 ℃ to tripropyl silane then.Restir is 10 hours under this temperature.Be cooled to room temperature then, steam solvent, underpressure distillation obtains products benzene formic acid triethyl estersil, and productive rate is 90%.
In the three-necked bottle of embodiment 4:100 milliliter, thermometer is installed, agitator adds toluylic acid (0.1 mole, 13.6 grams), CuCl (Ph
3P)
3(1.2g), (0.1mol, 15.8g), dioxane (55 milliliters) begins to be heated with stirring to 80 ℃ to tripropyl silane then.Restir is 11 hours under this temperature.Be cooled to room temperature then, steam solvent, underpressure distillation obtains products benzene acetate triethyl estersil, and productive rate is 93%.
Claims (4)
1, a kind of preparation method of carboxylic silicon ester compound is characterized in that the (Ph with Catalysts Cu Cl
3P)
3Add in the organic solvent of carboxylic acid, trialkyl silica alkyl compound; Be full of nitrogen in the reaction vessel; Be heated to 40-190 ℃ under stirring; CuCl (Ph
3P)
3Usage quantity be carboxylic acid compound weight 0.01-1.0 doubly, control reaction temperature is 40 ℃ ~ 190 ℃; Stirred 4-22 hour.
2, preparation method according to claim 1 is characterized in that described carboxylic-acid is acetate, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, the full or lipid acid of certain herbaceous plants with big flowers acid; Phenylformic acid, toluylic acid, phenylpropionic acid, furancarboxylic acid, thiophene phenol formic acid or styracin, or contain other substituting group fragrance same clan organic carboxyl acid compounds; Vinylformic acid, 2-methacrylic acid, butenoic acid, toxilic acid or fumaric acid unsaturated fatty acids.
3, preparation method according to claim 1 is characterized in that described trialkyl silica alkyl compound is triethyl silicane, tripropyl silane, tri isopropyl silane, three normal-butyl silane, uncle's normal-butyl dimethylsilane or tri-phenyl-silane.
4, preparation method according to claim 1, it is characterized in that described organic solvent is benzene, toluene, ethylbenzene, isopropyl benzene, second cyanogen, phenethyl cyanogen, ethyl acetate, tetrahydrofuran (THF), dioxane, N, one or more mixed solvents in dinethylformamide, N,N-dimethylacetamide or the hexamethylphosphoramide solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610028009 CN1865264A (en) | 2006-06-22 | 2006-06-22 | Carboxylic silicone grease compounds preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610028009 CN1865264A (en) | 2006-06-22 | 2006-06-22 | Carboxylic silicone grease compounds preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1865264A true CN1865264A (en) | 2006-11-22 |
Family
ID=37424428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610028009 Pending CN1865264A (en) | 2006-06-22 | 2006-06-22 | Carboxylic silicone grease compounds preparation method |
Country Status (1)
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|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432080C (en) * | 2006-09-27 | 2008-11-12 | 宁夏大学 | Liquid-phase method for synthesizing organo-silicon ester |
| CN110862751A (en) * | 2019-11-18 | 2020-03-06 | 中国船舶重工集团公司第七二五研究所 | Organic silicon ester marine antifouling material and preparation method thereof |
-
2006
- 2006-06-22 CN CN 200610028009 patent/CN1865264A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432080C (en) * | 2006-09-27 | 2008-11-12 | 宁夏大学 | Liquid-phase method for synthesizing organo-silicon ester |
| CN110862751A (en) * | 2019-11-18 | 2020-03-06 | 中国船舶重工集团公司第七二五研究所 | Organic silicon ester marine antifouling material and preparation method thereof |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
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