CN1887888A - Prepn of isocyanate-containing alkyl silane or alkyl siloxane - Google Patents
Prepn of isocyanate-containing alkyl silane or alkyl siloxane Download PDFInfo
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- CN1887888A CN1887888A CN 200610019723 CN200610019723A CN1887888A CN 1887888 A CN1887888 A CN 1887888A CN 200610019723 CN200610019723 CN 200610019723 CN 200610019723 A CN200610019723 A CN 200610019723A CN 1887888 A CN1887888 A CN 1887888A
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Abstract
The process of preparing isocyanate containing alkyl silane or alkyl siloxane includes the following steps: 1. dissolving bis(trichloromethyl) carbonate in inert organic solvent through stirring and adding the solution into dropping pot I; 2. mixing primary amine alkyl silane or amino alkoxy silane, tertiary amine compound and inert organic solvent in the mass ratio of 1 to 1.5-6 to 2-5, and adding the mixture into dropping pot II; cooling the main reaction kettle to -30 deg.c to 30 deg.c, dropping the solution and the mixture into the main reaction kettle and further stirring for reaction; 4. heating the reacted solution in one other reactor, heating to 50-100 for further reaction of 2-4 hr until no primary amine may be detected; 5, high speed centrifugally filtering the reacted mixture; and 6. distilling in a distiller to eliminate solvent and decompression rectifying.
Description
Technical field
The present invention relates to contain the preparation method of alkyl silane isocyanate or isocyanic ester organoalkoxysilane, particularly use two (trichloromethyl) carbonic ether method to produce the method that contains alkyl silane isocyanate or isocyanic ester organoalkoxysilane.Contain alkyl silane isocyanate or isocyanic ester organoalkoxysilane and be mainly used in inorganic, the organic and metal material surface of processing, give them the good bonding between foreign material.
Background technology
Alkyl silane isocyanate or isocyanic ester organoalkoxysilane are mainly used in handles inorganic, organic and metal material surface, gives them to the good bonding between foreign material, to improve the over-all properties of material or goods; With it can with reactions such as amine, azoimide and phosphoric acid ester, obtain corresponding urea groups, azido-and the phosphate-based silane coupling agent of containing; As the room temperature vulcanized silicone rubber tackifier, improve the bonding strength of sizing material to glass, aluminium etc.; As organic polymer properties-correcting agent, realize chemical modification, can be used as the linking agent and the tackifier of tackiness agent, coating, seal gum etc. simultaneously; In addition, it also can be used as glass, polyester, polyurethane-modified dose, and especially modified polyurethane is a kind of very effective means, has opened up new approach for developing high performance silicon modified polyurethane.
At present, domestic and international preparation research to isocyanate-containing alkyl or isocyanic ester organoalkoxysilane mainly contains following four kinds of methods: amino-alkyl silicane and gaseous state phosgene reaction; Amino-alkyl silicane and formyl chloride reaction; Amino-alkyl silicane and dialkyl carbonate reaction; Haloalkyl silane and the reaction of isocyanic ester an alkali metal salt.In the above several method, what phosgenation adopted is gaseous phosgene and the reaction of liquid ammonia hydrocarbyl si lanes, although reaction can realize that with gas-liquid reaction technological operation complexity, security is low; In the method that formyl chloride method and carbonic ether method are adopted, reaction needed at high temperature (100～260 ℃) is that catalyzer carries out cracking and prepares the isocyanate-containing alkyl organoalkoxysilane by alkaline metal organic salt, therefore, and severe reaction conditions; Raw material sodium isocyanate or sylvite toxicity that isocyanic acid an alkali metal salt method is adopted are very big, make troubles for production and research, simultaneously contaminate environment.
Summary of the invention
The objective of the invention is at above-mentioned four kinds of existing defectives of method, adopt brand-new raw material two (trichloromethyl) carbonic ether, catalytic promoter and the solvent system that is complementary with it, design the preparation method who contains alkyl silane isocyanate or isocyanic ester organoalkoxysilane, safe and reliable.
Technical scheme of the present invention: the concrete steps that the present invention's preparation contains alkyl silane isocyanate or isocyanic ester organoalkoxysilane are as follows:
A, two (trichloromethyl) carbonic ether is dissolved in the inert organic solvents, the ratio of dissolving in is 1: 4～8, fully stirs, and adds to drip among the still I;
B, primary amine class alkyl silane or aminoalkoxy silane, tertiary amine compounds, inert organic solvents mixed to add than 1: 1.5～6: 2～5 by amount of substance drip among the still II;
C, main reaction still III is cooled in-30～30 ℃ of scopes, slowly will drip still I then and the material dropping that drips among the still II is become owner of reactor III, dropwise, continue stirring reaction;
D, change above-mentioned reaction solution over to heatable reactor IV, be warming up to 50～100 ℃ of reaction 2～4h and finish, sampling detects no primary amine class material with gas chromatograph and is as the criterion;
E, the mixture of above-mentioned D item reaction filtered with supercentrifuge after, obtain containing the colourless transparent liquid of alkyl silane isocyanate or isocyanic ester organoalkoxysilane;
F, deviate from solvent at last in still kettle, rectification under vacuum obtains water white alkyl silane isocyanate or isocyanic ester organoalkoxysilane then.
The preparation method of described alkyl silane isocyanate or isocyanic ester organoalkoxysilane, temperature of reaction is-5～5 ℃ in C step main reaction still III.
The preparation method of described alkyl silane isocyanate or isocyanic ester organoalkoxysilane, the temperature of reaction that goes on foot reactor IV at D is 55～75 ℃.
Described primary amine class alkyl silane or aminoalkoxy silane available structural formula are expressed as follows:
In the following formula, R
1With R be the alkyl of saturated straight or branched, carbon chain lengths is C
1～C
8Also can be the aromatic hydrocarbons homologue, R
2Be meant that carbon chain lengths is C
1～C
6Alkyl, aryl, trialkyl silyl, methoxy alcoxyl base class, the positive integer of a=0～3.
Described alkyl silane isocyanate or isocyanic ester organoalkoxysilane available structural formula are expressed as follows:
In the following formula, R
1With R be the alkyl of saturated straight or branched, carbon chain lengths is C
1～C
8Also can be the aromatic hydrocarbons homologue, R
2Be meant that carbon chain lengths is C
1～C
6Alkyl, aryl, trialkyl silyl, methoxy alcoxyl base class, the positive integer of a=0～3.
The structural formula of described two (trichloromethyl) carbonic ether is:
Or two molecule phosgene, its structural formula is:
Described inert organic solvents mainly refers to not and any organic inert solvent of starting material reaction, is specially hydrocarbon fluid-like state organic solvent, chlorinated hydrocarbon liquid organic solvent, ester fluid-like state organic solvent.
Described tertiary amine compounds is compound, fragrant same clan tertiary amine compound or the heterocycle tertiary amine compound that plays the aliphatic tertiary amines of stopper effect in reaction.
Advantage of the present invention: the present invention adopts two (trichloromethyl) carbonic ether method can synthesize the alkyl silane isocyanate or the isocyanic ester organoalkoxysilane of high yield smoothly by control reaction temperature and its decomposition rate.Operational path is simple, raw material is cheap and easy to get, single step reaction just can obtain target product, safe, generate the recyclable utilization of salt simultaneously, environment is not produced any pollution effect, the purity of isocyanate-containing alkyl or isocyanic ester organoalkoxysilane can reach more than 98%, productive rate can reach about 75%, and reaction is control easily, and reaction preference is up to more than 99%.
Embodiment
One, chemical structural formula and relevant explanation:
The structural formula of isocyanate-containing alkyl or isocyanic ester organoalkoxysilane:
R
1With R be that (carbon chain lengths is C for the alkyl of saturated straight or branched
1～C
8); It also can be the homologue class aryl of aromatic hydrocarbons.R
2(carbon chain lengths is C mainly to refer to alkyl
1～C
6), aryl, trialkyl silyl and methoxy alcoxyl base class; The integer of a=0～3.
Two, Fan Ying principle:
Three, the concrete main chemical raw material that adopts and the explanation of product:
1, the alkylalkoxy silane of primary amine class:
Its constitutional features requires: R
1With R be that (carbon chain lengths is C for the alkyl of saturated straight or branched
1～C
8); It also can be the homologue of aromatic hydrocarbons.
R
1With main alkyl group such as the methyl of R, ethyl, propyl group, butyl, hexyl, phenyl, octyl group; R
2Main group such as methyl, ethyl, propyl group, butyl, hexyl, phenyl, trimethyl silicon based and beta-methoxy-oxyethyl group etc.
2, two (trichloromethyl) carbonic ether: what this acyl chloride reaction material used is three molecule phosgene, concrete physical and chemical index is: two (trichloromethyl) carbonic ether (being called for short BTC), because of it is a kind of extremely stable white crystals body, fusing point is 78～82 ℃, boiling point is 202～203 ℃, the smell that similar phosgene is arranged, its molecular formula are CO (OCCl
3)
2, solid proportion is 1.78g/cm
3, proportion is 1.629g/cm under the molten state
3, dissolve in organic solvents such as benzene, ethanol, ether, chloroform, tetrahydrofuran (THF), meet hot water and sodium hydroxide and then decompose.Its reactive behavior of BTC and phosgene are similar, can react with multiple compound such as alcohol, aldehyde, amine, acid amides, carboxylic acid, phenol, azanol, but also cyclocondensation prepare heterogeneous ring compound.
3, tertiary amine compounds: such material plays inhibitor action in reaction.Mainly be the compound (as Trimethylamine, tripropylamine, Tributylamine) of aliphatic tertiary amines, necessary condition can be selected aromatic series class tertiary amine compound (as xylidine and Diethyl Aniline) or heterocycle tertiary amine compound (as pyridine, picoline etc.) for use.
4, solvent: mainly refer to not and any organic inert solvent of starting material reaction, be specially hydrocarbon class (toluene, hexane, sherwood oil, hexanaphthene), chlorinated hydrocarbon (chlorobenzene, methylene dichloride) and ester class (ethyl acetate and tetrahydrofuran (THF)).
Four, concrete reactions steps:
A, two (trichloromethyl) carbonic ether is dissolved in the inert organic solvents, the ratio of dissolving in is 1: 4～8, fully stirs, and adds to drip among the still I;
B, primary amine class alkyl silane or aminoalkoxy silane, tertiary amine compounds, inert organic solvents mixed to add than 1: 1.5～6: 2～5 by amount of substance drip among the still II;
C, main reaction still III is cooled in-30～30 ℃ of scopes, slowly will drip still I then and the material dropping that drips among the still II is become owner of reactor III, dropwise, continue reaction 1～2h;
D, change above-mentioned reaction solution over to heatable reactor IV, be warming up to 50～100 ℃ of reaction 2～4h and finish, sampling detects no primary amine class material with gas chromatograph and is as the criterion;
E, the mixture of above-mentioned D item reaction filtered with supercentrifuge after, obtain containing the colourless transparent liquid of alkyl silane isocyanate or isocyanic ester organoalkoxysilane;
F, deviate from solvent at last in still kettle, rectification under vacuum obtains water white alkyl silane isocyanate or isocyanic ester organoalkoxysilane then.
Optimal reaction temperature is-5～5 ℃ in C step main reaction still III.
Optimal reaction temperature at D step reactor IV is 55～75 ℃.
Five, embodiment:
Synthesizing of example one, isocyanic ester propyl-triethoxysilicane:
1,20 gram two (trichloromethyl) carbonic ethers is dissolved in the tetrahydrofuran solution with 150ML and add among the constant pressure funnel A;
2 mixed solutions with 44 gram aminopropyl triethoxysilanes and 70 gram pyridines adding 60ML tetrahydrofuran (THF)s add among the constant pressure funnel B;
3, under 0 ℃～5 ℃, respectively A, B mixed solution are slowly splashed in the 500ml four-hole boiling flask, dropwised in 2 hours, continue 0 ℃ of reaction 2 hours;
4, be warming up to 65 ℃ of reactions 1 hour;
5, reduce to room temperature, filter and remove tetrahydrofuran (THF);
6, last, 130 ℃/20mmHg of bp, underpressure distillation obtains isocyanic ester propyl-triethoxysilicane product, and 36.6g, productive rate are 70%, and product content is 98.15%.
Product is through the gas chromatograph analysis: product purity 98.15%; The FT-IR infrared spectrometer and
1The H-NMR mass spectroscopy characterizes: at 2272cm-1 be-charateristic avsorption band of NCO;
1The H-NMR mass spectroscopy: (3.31, t ,-NCH
2-), (1.67, m ,-CH
2-), (0.58, t, ,-CH
2Si-), (3.83, q, ,-OCH
2-), (1.23, t ,-CH
3) be respectively the chemical shift of 5 different chemical environment hydrogen.
Synthesizing of embodiment two, isocyanic ester propyl group methyldiethoxysilane:
1,20 gram two (trichloromethyl) carbonic ethers is dissolved in the tetrahydrofuran solution with 150ML and add among the constant pressure funnel A;
2,38.2 donaxine propyl group methyldiethoxysilane, 70 gram pyridines and 80ML tetrahydrofuran (THF) mixed solution are added among the constant pressure funnel B;
3, under-5 ℃～0 ℃, respectively A, B mixed solution are slowly splashed in the 500ml four-hole boiling flask, dropwised in 2 hours, continue-5 ℃～0 ℃ reaction 2 hours;
4 are warming up to 60 ℃ of reactions 1 hour
5, reduce to room temperature, filter and remove tetrahydrofuran (THF);
6, last, bp91～93 ℃/9mmHg underpressure distillation obtains isocyanic ester propyl group methyldiethoxysilane product, and 29.50g, productive rate are 68%, and content is 97.60%.
Product is through the gas chromatograph analysis: product purity 97.60%; The FT-IR infrared spectrometer and
1The H-NMR mass spectroscopy characterizes: at 2272cm-1 be-charateristic avsorption band of NCO;
1The H-NMR mass spectroscopy: (3.31, t ,-NCH
2-), (1.4, m ,-CH
2-), (1.3, t ,-CH
2Si-), (3.83, q ,-OCH
2-), (1.23, t, ,-CH
3), (0.14, s ,-SiCH
3) be respectively the chemical shift of 6 different chemical environment hydrogen.
Synthesizing of embodiment three, isocyanic ester propyl-triethoxysilicane:
1,20 gram two (trichloromethyl) carbonic ethers are dissolved in the toluene solution of 150ML adds among the constant pressure funnel A;
2,44 gram aminopropyl triethoxysilanes and 50 gram xylidines are added among the mixed solution adding constant pressure funnel B of 60ML toluene;
3, under 0 ℃～5 ℃, respectively A, B mixed solution are slowly splashed in the 500ml four-hole boiling flask, dropwised in 2 hours, continue 0 ℃ of reaction 2 hours;
4, be warming up to 65 ℃ of reactions 1 hour;
5, reduce to room temperature, filter and remove toluene;
6, last, 130 ℃/20mmHg of bp underpressure distillation obtains isocyanic ester propyl-triethoxysilicane product, and 31.47g, productive rate are 64%, and product content is 97.92%.
Product is through the gas chromatograph analysis: product purity 97.92%; The FT-IR infrared spectrometer and
1The H-NMR mass spectroscopy characterizes: at 2272cm-1 be-charateristic avsorption band of NCO;
1The H-NMR mass spectroscopy: (3.31, t, J=6.6Hz ,-NCH
2-), (1.67, m ,-CH
2-), (0.58, t, J=8.1Hz ,-CH
2Si-), (3.83, q, J=1.66 ,-OCH
2-), (1.23, t, J=6.6Hz ,-CH
3) be respectively the chemical shift of 5 different chemical environment hydrogen
Synthesizing of embodiment four, isocyanic ester propyl trimethoxy silicane:
1,20 gram two (trichloromethyl) carbonic ethers are dissolved in the dichloroethane solution of 150ML adds among the constant pressure funnel A;
2,39.3 gram aminopropyl trimethoxysilane and 50 gram Tributylamines are added among the mixed solution adding constant pressure funnel B of 60ML ethylene dichloride;
3, under-12 ℃～-8 ℃, respectively A, B mixed solution are slowly splashed in the 500ml four-hole boiling flask, dropwised in 2 hours, continue reaction below-8 ℃ 2 hours;
4, be warming up to 60 ℃ of reactions 1 hour;
5, reduce to room temperature, filter and remove ethylene dichloride;
6, last, 85 ℃/9mHg of bp, underpressure distillation obtains isocyanic ester propyl trimethoxy silicane product, and 25.30g, productive rate are 62%, and product content is 98.20%
Product is through the gas chromatograph analysis: product purity 98.20%; The FT-IR infrared spectrometer and
1The H-NMR mass spectroscopy characterizes: at 2272cm-1 be-charateristic avsorption band of NCO;
1The H-NMR mass spectroscopy: (3.31, t ,-NCH
2-) (1.4, m ,-CH
2-), (0.58, t ,-CH
2Si-), (3.55, t ,-OCH
3) be respectively the chemical shift of 4 different chemical environment hydrogen.
Equally, other isocyanate-containing alkyl or isocyanic ester organoalkoxysilane series products are also made as stated above.
Core of the present invention is to have provided the method that a kind of usefulness two (trichloromethyl) carbonic ether is raw material manufacturing isocyanate-containing alkyl or isocyanic ester organoalkoxysilane series products.Therefore, every with aforesaid method and be equal to replacement, all belong to protection scope of the present invention.
Claims (8)
1. contain the preparation method of alkyl silane isocyanate or isocyanic ester organoalkoxysilane, concrete steps are as follows: you are not
A, two (trichloromethyl) carbonic ether is dissolved in the inert organic solvents, the ratio of dissolving in is 1: 4～8, fully stirs, and adds to drip among the still I;
B, primary amine class alkyl silane or aminoalkoxy silane, tertiary amine compounds, inert organic solvents mixed to add than 1: 1.5～6: 2～5 by amount of substance drip among the still II;
C, main reaction still III is cooled in-30～30 ℃ of scopes, slowly will drip still I then and the material dropping that drips among the still II is become owner of reactor III, dropwise, continue stirring reaction;
D, change above-mentioned reaction solution over to heatable reactor IV, be warming up to 50～100 ℃ of reactions and finish, sampling detects no primary amine class material with gas chromatograph and is as the criterion;
E, the mixture of above-mentioned D item reaction filtered with supercentrifuge after, obtain containing the colourless transparent liquid of alkyl silane isocyanate or isocyanic ester organoalkoxysilane;
F, deviate from solvent at last in still kettle, rectification under vacuum obtains water white alkyl silane isocyanate or isocyanic ester organoalkoxysilane then.
2. the preparation method of alkyl silane isocyanate according to claim 1 or isocyanic ester organoalkoxysilane is characterized in that: temperature of reaction is-5～5 ℃ in C step main reaction still III.
3. the preparation method of alkyl silane isocyanate according to claim 1 and 2 or isocyanic ester organoalkoxysilane is characterized in that: the temperature of reaction at D step reactor IV is 55～75 ℃.
4. preparation method according to claim 1 and 2 is characterized in that: described primary amine class alkyl silane or aminoalkoxy silane available structural formula are expressed as follows:
In the following formula, R
1With R be the alkyl of saturated straight or branched, carbon chain lengths is C
1～C
8Also can be the aromatic hydrocarbons homologue, R
2Be meant that carbon chain lengths is C
1～C
6Alkyl, aryl, trialkyl silyl, methoxy alcoxyl base class, the positive integer of a=0～3.
5. preparation method according to claim 1 and 2 and condition is characterized in that: described alkyl silane isocyanate or isocyanic ester organoalkoxysilane available structural formula are expressed as follows:
In the following formula, R
1With R be the alkyl of saturated straight or branched, carbon chain lengths is C
1～C
8Also can be the aromatic hydrocarbons homologue, R
2Be meant that carbon chain lengths is C
1～C
6Alkyl, aryl, trialkyl silyl, methoxy alcoxyl base class, the positive integer of a=0～3.
6. preparation method according to claim 1 and 2 and condition is characterized in that: the structural formula of described two (trichloromethyl) carbonic ether is:
Or two molecule phosgene, its structural formula is:
7. require described preparation method according to right 1, it is characterized in that: described inert organic solvents is meant not and any organic inert solvent of starting material reaction, is specially hydrocarbon fluid-like state organic solvent, chlorinated hydrocarbon liquid organic solvent, ester fluid-like state organic solvent.
8. require described preparation method according to right 1, it is characterized in that: described tertiary amine compounds is compound, fragrant same clan tertiary amine compound or the heterocycle tertiary amine compound that plays the aliphatic tertiary amines of stopper effect in reaction.
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|---|---|---|---|
| CNB2006100197231A CN100465179C (en) | 2006-07-27 | 2006-07-27 | Prepn of isocyanate-containing alkyl silane or alkyl siloxane |
Applications Claiming Priority (1)
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|---|---|---|---|
| CNB2006100197231A CN100465179C (en) | 2006-07-27 | 2006-07-27 | Prepn of isocyanate-containing alkyl silane or alkyl siloxane |
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|---|---|
| CN1887888A true CN1887888A (en) | 2007-01-03 |
| CN100465179C CN100465179C (en) | 2009-03-04 |
Family
ID=37577170
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008144987A1 (en) * | 2007-06-01 | 2008-12-04 | Zhangjiagang Huasheng Chemicals Co., Ltd. | Preparation of isocyanate-containing alkyl silane |
| CN101161657B (en) * | 2007-10-26 | 2010-10-13 | 杭州师范大学 | Method for synthesizing isocynate silane coupling agent |
| CN101492468B (en) * | 2009-03-06 | 2011-08-10 | 常州胜杰化工有限公司 | Method of preparing trialkoxysilanes isocyanic ester |
| CN104262384A (en) * | 2014-08-21 | 2015-01-07 | 爱斯特（成都）生物制药有限公司 | Device and method for rectification purification of 3-isocyanatopropyltriethoxysilane |
| CN105273232A (en) * | 2014-07-12 | 2016-01-27 | 卢桂才 | Isocyanate alkoxy silane waterproof bridging agent for asphalt and cement, and waterproof product and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3584024A (en) * | 1963-09-06 | 1971-06-08 | Union Carbide Corp | Condensable isocyanato substituted siloxanes and phosgenation process for making same |
| FR2574796B1 (en) * | 1984-12-18 | 1990-11-02 | Kaseihin Cy Inc C S | PROCESS FOR THE PREPARATION OF SILICON-CONTAINING ISOCYANATE COMPOUNDS |
-
2006
- 2006-07-27 CN CNB2006100197231A patent/CN100465179C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008144987A1 (en) * | 2007-06-01 | 2008-12-04 | Zhangjiagang Huasheng Chemicals Co., Ltd. | Preparation of isocyanate-containing alkyl silane |
| CN101784555B (en) * | 2007-06-01 | 2013-04-24 | 江苏华盛精化工股份有限公司 | Preparation of isocyanate-containing alkyl silane |
| CN101161657B (en) * | 2007-10-26 | 2010-10-13 | 杭州师范大学 | Method for synthesizing isocynate silane coupling agent |
| CN101492468B (en) * | 2009-03-06 | 2011-08-10 | 常州胜杰化工有限公司 | Method of preparing trialkoxysilanes isocyanic ester |
| CN105273232A (en) * | 2014-07-12 | 2016-01-27 | 卢桂才 | Isocyanate alkoxy silane waterproof bridging agent for asphalt and cement, and waterproof product and application thereof |
| CN104262384A (en) * | 2014-08-21 | 2015-01-07 | 爱斯特（成都）生物制药有限公司 | Device and method for rectification purification of 3-isocyanatopropyltriethoxysilane |
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|---|---|
| CN100465179C (en) | 2009-03-04 |
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