CN100415754C - Carboxylic silicone grease compounds preparation method - Google Patents
Carboxylic silicone grease compounds preparation method Download PDFInfo
- Publication number
- CN100415754C CN100415754C CNB2006100280135A CN200610028013A CN100415754C CN 100415754 C CN100415754 C CN 100415754C CN B2006100280135 A CNB2006100280135 A CN B2006100280135A CN 200610028013 A CN200610028013 A CN 200610028013A CN 100415754 C CN100415754 C CN 100415754C
- Authority
- CN
- China
- Prior art keywords
- acid
- phosphine
- carboxylic
- compound
- carboxylic acid
- 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.)
- Expired - Fee Related
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relate to a preparation method of a carboxylic silicone grease compound, which belongs to the technical field of organic compounds. The method comprises: organic phosphor compounds are added into an organic solvent of carboxyl acid and trialkyl silane compounds. Nitrogen is filled in a reaction container and heated to 60 to 130 DEG C while stirring. With the catalysis of metal zinc and compounds thereof, the carboxylic acid reacts with the trialkyl silane to produce the carboxylic silicon ester compound and hydrogen. An unsaturated carboxylic silicon ester compound is an important monomer raw material for preparing a carboxylic silicon ester polymer. The carboxylic acid silicone grease polymer is widely used as a metabolizability medical material and a coating for seagoing vessels. As the coating for seagoing vessels, the carboxylic acid silicone grease polymer can form a very smooth film; thus, seashells are prevented from being absorbed on seagoing vessel bodies, the oil consumption of shipping is reduced, and cost is reduced The method has the advantages of simple process and convenient operation and is easy for large-scale commercial production.
Description
Technical field
The invention belongs to the organic compound preparing technical field, be specially the 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, and therefore, developing nontoxic seagoing vessel coating is to go.Present method technology is simple, and is easy to operate, is easy to large-scale industrial production, and very important economic worth is arranged.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 10212293) 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.
Because aforesaid method needs Pd/C mostly, 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.Its step is as follows: organic phosphine compound is added in the organic solvent of carboxylic acid, trialkyl silica alkyl compound.Be full of nitrogen in the reaction vessel, stir then down, be heated to 60-130 ℃.Under the catalysis of organic phosphine and compound thereof, carboxylic acid and the reaction of trialkyl silane generate carboxylic silicon ester compound hydrogen.The organic phosphine compound usage quantity is 0.1-1.0 a times of carboxylic acid compound weight, and control reaction temperature is 60 ℃ ~ 130 ℃; After dripping end, continue to stir 24-48 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, phenylformic acid, toluylic acid, phenylpropionic acid, furancarboxylic acid, thiophene phenol formic acid, styracin, vinylformic acid, 2-methacrylic acid, butenoic acid, toxilic acid or fumaric acid.
Among the present invention, organic phosphine compound is alkylphosphines such as triethyl phosphine, tripropyl phosphine, tributylphosphine, tri-butyl phosphine, three amyl group phosphines; Cycloalkyl phosphines such as three cyclopentyl phosphines, tricyclohexyl phosphine; Aromatic base phosphines such as triphenylphosphine, three (p-methylphenyl) phosphine, three (p-methoxyphenyl) phosphine; Aromatic base phosphine oxides such as triphenylphosphine oxide, three (p-methylphenyl) phosphine oxide, three (p-methoxyphenyl) phosphine oxide; Both one or more mixtures of organic phosphine compound.
Among the present invention, the 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, employed 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, the hexamethylphosphoramide etc.
Among the present invention, stirring reaction is cooled to room temperature after finishing, and steams solvent, and underpressure distillation obtains product.
Among the present invention, under the catalysis of organic phosphine compound, carboxylic acid and the reaction of trialkyl silane generate carboxylic silicon ester compound hydrogen.Characteristics of the present invention are: utilize organic phosphine compound as catalyzer, realized the dehydrogenation estersil reaction of carboxylic acid and trialkyl silane.The advantage of present method is that (1) uses low-cost organic phosphine compound to avoid the hydrogenation side reaction of unsaturated carboxylic acid estersil as catalyzer (2), do not need to be further purified product, reduced production cost, and have practicality and Yi Hangxing, be easy to form industrially scalable, have 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 (0.1 mole in phenylformic acid, 12.2 gram), and triethyl silicane (0.1mol, 11.6g), tributylphosphine (0.001mol, 0.118g), N, dinethylformamide (40 milliliters) begins to be heated with stirring to 100 ℃ then.Restir is 48 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 2:100 milliliter, thermometer is installed, agitator adds (0.1 mole in phenylformic acid, 12.2 gram), and tributylphosphine (0.002mol, 0.236g), triethyl silicane (0.1mol, 11.6g), N, dinethylformamide (45 milliliters) begins to be heated with stirring to 120 ℃ then.Restir is 24 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 92%.
In the three-necked bottle of embodiment 3:100 milliliter, thermometer is installed, agitator adds (0.1 mole of toluylic acid, 13.6 gram), and tri-butyl phosphine (0.001mol, 0.118g), tripropyl silane (0.1mol, 15.8g), N,N-dimethylacetamide (50 milliliters) begins to be heated with stirring to 110 ℃ then.Restir is 29 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 95%.
In the three-necked bottle of embodiment 4:100 milliliter, thermometer is installed, and agitator adds (0.1 mole of toluylic acid, 13.6 gram), thricyclohexyl base phosphine (0.001mol, 0.280g), tripropyl silane (0.1mol, 15.8g), N,N-dimethylacetamide (55 milliliters) begins to be heated with stirring to 130 ℃ then.Restir is 22 hours under this temperature.Be cooled to room temperature then, steam solvent, underpressure distillation obtains products benzene acetate triethyl estersil, and productive rate is 88%.
Claims (4)
1. the preparation method of a carboxylic silicon ester compound is characterized by: in the organic solvent of organic phosphine compound adding carboxylic acid and trialkyl silica alkyl compound; Be full of nitrogen in the reaction vessel, stir down, be heated to 60-130 ℃; The organic phosphine compound usage quantity is 0.1-1.0 a times of carboxylic acid compound weight, and control reaction temperature is 60 ℃-130 ℃; After dripping end, continue to stir 24-48 hour; Wherein, described organic phosphine compound class is triethyl phosphine, tripropyl phosphine, tributylphosphine, tri-butyl phosphine, three amyl group phosphines, three cyclopentyl phosphines, tricyclohexyl phosphine, triphenylphosphine, three (p-methylphenyl) phosphine, three (p-methoxyphenyl) phosphine; One or more mixtures in triphenylphosphine oxide, three (p-methylphenyl) phosphine oxide, three (p-methoxyphenyl) phosphine oxide.
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, certain herbaceous plants with big flowers acid, phenylformic acid, toluylic acid, phenylpropionic acid, furancarboxylic acid, thiophene phenol formic acid, styracin, vinylformic acid, 2-methacrylic acid, butenoic acid, toxilic acid or fumaric acid.
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 employed 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, the hexamethylphosphoramide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100280135A CN100415754C (en) | 2006-06-22 | 2006-06-22 | Carboxylic silicone grease compounds preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100280135A CN100415754C (en) | 2006-06-22 | 2006-06-22 | Carboxylic silicone grease compounds preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1865265A CN1865265A (en) | 2006-11-22 |
| CN100415754C true CN100415754C (en) | 2008-09-03 |
Family
ID=37424429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100280135A Expired - Fee Related CN100415754C (en) | 2006-06-22 | 2006-06-22 | Carboxylic silicone grease compounds preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100415754C (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4222953A (en) * | 1979-08-06 | 1980-09-16 | Dow Corning Corporation | Method of preparing organosiloxanes and methylchloride |
| US4778910A (en) * | 1987-12-14 | 1988-10-18 | Lopata Research & Development Corporation | Method of making alkylalkoxysilanes |
| JPH0525187A (en) * | 1991-07-20 | 1993-02-02 | Nippon Oil & Fats Co Ltd | Production of polymerizable monomer |
| JPH0525188A (en) * | 1991-07-20 | 1993-02-02 | Nippon Oil & Fats Co Ltd | Production of polymerizable monomer |
-
2006
- 2006-06-22 CN CNB2006100280135A patent/CN100415754C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4222953A (en) * | 1979-08-06 | 1980-09-16 | Dow Corning Corporation | Method of preparing organosiloxanes and methylchloride |
| US4778910A (en) * | 1987-12-14 | 1988-10-18 | Lopata Research & Development Corporation | Method of making alkylalkoxysilanes |
| JPH0525187A (en) * | 1991-07-20 | 1993-02-02 | Nippon Oil & Fats Co Ltd | Production of polymerizable monomer |
| JPH0525188A (en) * | 1991-07-20 | 1993-02-02 | Nippon Oil & Fats Co Ltd | Production of polymerizable monomer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1865265A (en) | 2006-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6315412B2 (en) | Method for producing bis (aminomethyl) cyclohexane | |
| CN104250236A (en) | Synthetic method of gamma-alkyl oxyacyl methyl-gamma-butyrolactone and delta- alkyl oxyacyl methyl-delta-valerolactone | |
| CN100415754C (en) | Carboxylic silicone grease compounds preparation method | |
| JPH11315083A (en) | Production of 3-glycidyloxypropyltrialkoxysilane | |
| CN107954962B (en) | Preparation method of 4, 4-dihalogenotetrahydropyran | |
| CN1865264A (en) | Carboxylic silicone grease compounds preparation method | |
| Yoshimura et al. | Pinacol couplings of a series of aldehydes and ketones with SmI2/Sm/Me3SiCl in DME | |
| Houllemare et al. | Synthesis of homoallylic (but-3-enylic) alcohols from aldehydes with allylic chlorides, tin (II) chloride and potassium iodide in water | |
| CN102476975A (en) | Method for catalytic oxidation of cycloketone in the presence of magnesium and aluminum modified titanosilicate molecular sieve | |
| CN105732694A (en) | Method for adsorbing and purifying 1, 1, 1, 3, 5, 5, 5-heptamethyltrisiloxane | |
| CN1830984A (en) | Method for preparing carboxylic silicon ester compound | |
| CN102627558B (en) | Preparation method of vinyl carboxylate | |
| CN112625007A (en) | Method for preparing glycidyl methacrylate | |
| WO2016005943A1 (en) | Metal-catalyzed asymmetric 1,4-conjugate addition of vinylboron compounds to 2-substituted-4-oxy- cyclopent-2-en-l-ones yielding prostaglandins and prostaglandin analogs | |
| Wen et al. | Perfectly green organocatalysis: quaternary ammonium base triggered cyanosilylation of aldehydes | |
| JP5438447B2 (en) | Method for producing hydrosilyl compound | |
| US9701601B2 (en) | Optically active axially chiral alpha-allenic alcohol, synthesis method and use thereof | |
| CN103113399B (en) | A kind of method preparing dimethyl vinyl chlorosilane | |
| JP3852550B2 (en) | Method for producing mercapto group-containing alkoxysilane compound | |
| CN107428674A (en) | The isomerization method of 1,3,3 trimethyl 1 (aminomethyl) aminocyclohexanes | |
| CN1189463C (en) | Method for preparing monochlorophthalic anhydride by means of chloration of phthalic anhydride | |
| CN105693455A (en) | Synthetic method for 1,5,9-cyclododecatriene | |
| CN111018899A (en) | Method for preparing 1, 1-boron alkyne compound by metal catalysis of terminal olefin | |
| CN1935813A (en) | Liquid-phase method for synthesizing organo-silicon ester | |
| CN1150141A (en) | Process for synthesizing cyclopropyl carboxylic ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080903 Termination date: 20110622 |