CN101805366A - Method for preparing tri(3-trimethoxysilylpropyl) isocyanurate - Google Patents
Method for preparing tri(3-trimethoxysilylpropyl) isocyanurate Download PDFInfo
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- CN101805366A CN101805366A CN 201010150732 CN201010150732A CN101805366A CN 101805366 A CN101805366 A CN 101805366A CN 201010150732 CN201010150732 CN 201010150732 CN 201010150732 A CN201010150732 A CN 201010150732A CN 101805366 A CN101805366 A CN 101805366A
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Abstract
The invention discloses a method for preparing tri(3-trimethoxysilylpropyl) isocyanurate, which comprises the following steps: performing polycondensation reaction on 3-isocyanate group propyl trimethoxy silane serving as a monomer in the presence of a catalyst and a solvent, and concentrating the filtrate obtained by filtering the reaction product to obtain a crude product of 1,3,5-tri[3-(trimethoxysilicyl)propyl]-1,3,5-triazine-2,4,6-triketone. The method has the advantages of low cost, high conversion rate, high purity of the product, good selectivity of the product, simple operation and suitability for industrial production.
Description
Technical field
The present invention relates to the field of chemical synthesis, be specifically related to the preparation method of a kind of three (the silica-based propyl group of 3-trimethoxy) isocyanuric acid ester.
Background technology
1,3,5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazines-2,4,6-triketone (Tris (3-trimethoxysilylpropyl) isocyanurate) has another name called three (the silica-based propyl group of 3-trimethoxy) isocyanuric acid ester, and molecular formula is: C
21H
45N
3O
12Si
3, CAS:26115-70-8,543.9 ℃ of boiling points (760mmHg), normal temperature are stable down, are dissolved in acetonitrile, acetone, N, and dinethylformamides (DMF) etc. are met the water hydrolysis and are gone out methyl alcohol, and its structural formula is as follows:.
Wherein, Me is a methyl.
1,3,5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazine-2,4, the 6-triketone is a kind of good adhesion promoter and linking agent, can effectively improve the cohesive force of polyvinyl chloride materials such as (PVC) to base material, is widely used in various chemical building materials and tackiness agent.It synthesizes the domestic bibliographical information of not seeing as yet.U.S. Pat 5,218,133, US4,654,428 and US3,821, also only be mentioned to the synthetic of relevant intermediate or compound in 218, mainly be to be that raw material separates or the synthetic purpose product 1,3 of purification one kettle way 5-three [3-(trimethoxysilyl) propyl group]-1 without any with 1-r-chloropropyl trimethoxyl silane and potassium cyanate or triphosgene, 3,5-triazine-2,4, the 6-triketone.Because this type of technological reaction system relative complex, so side reaction is many, speed of response is slow, and all patents there is no detailed description to its follow-up sepn process, can not guarantee that the quality of product can meet the demand in market.
Since 1,3,5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazine-2,4, the 6-triketone has characteristics such as boiling point height, viscosity are big, so the unusual difficulty of this product separation and method of purification, can provide in the market 1,3,5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazine-2,4,6-triketone purity mostly is greatly about 95%, can't satisfy the demand of high-end market.
Summary of the invention
The invention provides the preparation method of a kind of transformation efficiency height, product purity height, simple to operate, three (the silica-based propyl group of 3-trimethoxy) isocyanuric acid ester of being suitable for suitability for industrialized production.
The preparation method of a kind of three (the silica-based propyl group of 3-trimethoxy) isocyanuric acid ester comprises step:
With 3-isocyanate group propyl trimethoxy silicane is monomer, carries out polycondensation under catalyzer and solvent existence condition, the reaction product filtrate filtered is concentrated obtain 1,3,5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazine-2,4,6-triketone crude product, obtain 1,3 through aftertreatment again, 5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazine-2,4, the 6-triketone.
Described catalyzer is selected from a kind of in Potassium ethanoate, yellow soda ash, sodium methylate, triphenylphosphine, tri-n-butyl phosphine, the Sodium Benzoate etc., particular methanol sodium.Above-mentioned catalyzer can also be separated from reaction system easily except having improved speed of response, having saved the reaction times, and just can use by recovery set through simple process.
Described solvent is selected from N, dinethylformamide, N, one or more in N--diethylformamide, the dimethyl sulfoxide (DMSO) etc., preferred N, dinethylformamide.Above-mentioned dissolution with solvents performance is good, does not participate in the reaction of system, and the boiling point height, is convenient to control reaction temperature.
Preferred 80 ℃-250 ℃ of described polycondensation temperature, the reaction times is 1 hour-20 hours, further preferred 100 ℃-150 ℃, the reaction times is 3 hours-6 hours.In this temperature and time scope, the selection performance of reaction reaches more than 98%, guarantees the purification of subsequent product.
The dimer that comprises 3-isocyanate group propyl trimethoxy silicon in the polycondensation product can be separated it by concentrating, and the dimer that is separated can be used as the reaction raw materials recycle, to reduce cost, economizes on resources.It is that negative pressure concentrates under the condition of 150 ℃-200 ℃ of temperature, vacuum tightness 15Pa-25Pa that described filtrate concentrates condition optimization.
Described aftertreatment can be adopted this area method for purifying and separating commonly used, preferably adopts molecular distillation (being short-path distillation).
The condition optimization of described molecular distillation is: 200 ℃-280 ℃ of temperature, vacuum tightness 0Pa-10Pa.
The flow velocity of material when further optimizing molecular distillation according to the size of the used container of molecular distillation can further improve the quality of product, as color and luster, purity etc., generally with respect to 0.2m
2Molecular still, the flow velocity of material is preferably 80-150g/min during molecular distillation, if energy consumption height then too slowly then easily produces too soon and carries phenomenon secretly, influences the color and luster and the purity of product.
Adopt the inventive method preparation 1,3,5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazines-2,4, the chemical equation of 6-triketone is as follows:
In the present invention's reaction the consumption between starting monomer, catalyzer and the solvent do not had strict restriction.The mol ratio of starting monomer and catalyzer is preferably 10: 0.05-3, more preferably 10: 0.1-0.5; The mass ratio of starting monomer and solvent is preferably 1: 0.5-10, more preferably 1: 1-3.
Compare with general method, technology of the present invention is very novel, has following characteristic:
1) adopt compound such as sodium methylate as catalysts, improved speed of response, saved the reaction times, reaction yield has reached more than 74%, and product selectivity has reached 98% simultaneously.
2) adopt molecular distillation technique, obtain purity greater than 97% 1,3,5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazines-2,4, the 6-triketone has substantially exceeded the technical indicator of external product.
3) adopt molecular distillation technique, saved the energy consumption in the production process, material consumption greatly, and improved production efficiency.
4) the inventive method transformation efficiency height,, product purity height, product selectivity be good, and simple to operate, cost is low, is suitable for suitability for industrialized production.
Embodiment
Embodiment 1
In reactor, drop into dimethyl sulfoxide (DMSO) 2050ml, 3-isocyanate group propyl trimethoxy silicane (GC content 99.0%) 2052.8g (10mol) and sodium methylate 10.8g (0.2mol), the feeding nitrogen replacement goes out the air in the reactor, be warming up to 100 ℃, insulation reaction 6 hours, be cooled to 20 ℃, remove by filter insolubles wherein, obtain filtrate.150 ℃ of temperature, negative pressure is concentrated into till the no overhead product under the condition of vacuum 15Pa with filtrate, obtains reddish-brown viscous liquid 1847g (being crude product, content 85%), and product selectivity 98.5% feeds 0.2m with its speed with 100g/min
2Molecular still in, control molecular still temperature be 200 ℃, vacuum tightness 5Pa, led in 20 minutes, the light constituent that obtains is 1,3,5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazine-2,4, the 6-triketone, weight 1535g, yield 74.78%, content (being purity) 97.64%.
Embodiment 2
In reactor, drop into dimethyl sulfoxide (DMSO) 3075ml, 3-isocyanate group propyl trimethoxy silicane (GC content 99.0%) 2052.8g (10mol), sodium methylate 16.2g (0.3mol), the feeding nitrogen replacement goes out the air in the reactor, be warming up to 130 ℃, insulation reaction 4 hours, be cooled to 20 ℃, remove by filter insolubles wherein.180 ℃ of temperature, negative pressure is concentrated into till the no overhead product under the condition of vacuum 15Pa with filtrate, obtains reddish-brown viscous liquid 1865g (being crude product, content 83.4%), and product selectivity 97.6% feeds 0.2m with its speed with 100g/min
2Molecular still in, control molecular still temperature be 200 ℃, vacuum tightness 2Pa, led in 20 minutes, the light constituent that obtains is 1,3,5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazine-2,4, the 6-triketone, weight 1570g, yield 76.48%, content (being purity) 97.35%.
Embodiment 3
In reactor, drop into N, dinethylformamide 2052ml, 3-isocyanate group propyl trimethoxy silicane (GC content 99.0%) 2052.8g (10mol), sodium methylate 21.6g (0.4mol), the feeding nitrogen replacement goes out the air in the reactor, be warming up to 150 ℃, insulation reaction 3 hours, be cooled to 20 ℃, remove by filter insolubles wherein.150 ℃ of temperature, negative pressure is concentrated into till the no overhead product under the condition of vacuum 15Pa with filtrate, obtains reddish-brown viscous liquid 1901g (being crude product, content 86.1%), and product selectivity 99.1% feeds 0.2m with its speed with 150g/min
2Molecular still in, control molecular still temperature be 230 ℃, vacuum tightness 10Pa, led in 15 minutes, the light constituent that obtains is 1,3,5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazine-2,4, the 6-triketone, weight 1601g, yield 77.99%, content (being purity) 98.05%.
Embodiment 4
In reactor, drop into N, dinethylformamide 3000ml, 3-isocyanate group propyl trimethoxy silicane (GC content 99.0%) 2052.8g, tributylphosphine 20.2g (0.1mol), the feeding nitrogen replacement goes out the air in the reactor, be warming up to 150 ℃, insulation reaction 4 hours, be cooled to 20 ℃, remove by filter insolubles wherein.150 ℃ of temperature, negative pressure is concentrated into till the no overhead product under the condition of vacuum 20Pa with filtrate, obtains reddish-brown viscous liquid 1935g (being crude product, content 82.7%), and product selectivity 98.3% feeds 0.2m with its speed with 100g/min
2Molecular still in, control molecular still temperature be 250 ℃, vacuum tightness 10Pa, led in 20 minutes, the light constituent that obtains is 1,3,5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazine-2,4, the 6-triketone, weight 1533g, yield 74.68%, content (being purity) 98.23%.
Embodiment 5
In reactor, drop into N, N-diethylformamide 3000ml, 3-isocyanate group propyl trimethoxy silicane (GC content 99.0%) 2052.8g (10mol), Potassium ethanoate 49g (0.5mol), the feeding nitrogen replacement goes out the air in the reactor, slowly be warming up to 150 ℃, insulation reaction 4 hours, be cooled to 20 ℃, by the sand core filter press filtration to concentration kettle.200 ℃ of temperature, negative pressure is concentrated into till the no overhead product under the condition of vacuum 15Pa with filtrate, obtains reddish-brown viscous liquid 2001g (being crude product, content 85.7%), and product selectivity 98.7% feeds 0.2m with its speed with 130g/min
2Molecular still in, control molecular still temperature be 220 ℃, vacuum tightness 5Pa led to about 20 minutes, obtained 1,3,5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazines-2,4,6-triketone 1705g, yield 83.06%, content (being purity) 97.66%.
Claims (10)
1. the preparation method of one kind three (the silica-based propyl group of 3-trimethoxy) isocyanuric acid ester comprises step:
With 3-isocyanate group propyl trimethoxy silicane is monomer, carries out polycondensation under catalyzer and solvent existence condition, the reaction product filtrate filtered is concentrated obtain 1,3,5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazine-2,4,6-triketone crude product, obtain 1,3 through aftertreatment again, 5-three [3-(trimethoxysilyl) propyl group]-1,3,5-triazine-2,4, the 6-triketone.
2. preparation method according to claim 1 is characterized in that, described catalyzer is selected from a kind of in Potassium ethanoate, yellow soda ash, sodium methylate, triphenylphosphine, tri-n-butyl phosphine, the Sodium Benzoate.
3. preparation method according to claim 2 is characterized in that described catalyzer is selected from sodium methylate.
4. preparation method according to claim 1 is characterized in that described solvent is selected from N, dinethylformamide, N, one or more in N-diethylformamide, the dimethyl sulfoxide (DMSO).
5. preparation method according to claim 4 is characterized in that described solvent is selected from N, dinethylformamide.
6. preparation method according to claim 1 is characterized in that, described polycondensation temperature is 80 ℃-250 ℃, and the reaction times is 1 hour-20 hours.
7. preparation method according to claim 6 is characterized in that, described polycondensation temperature is 100 ℃-150 ℃, and the reaction times is 3 hours-6 hours.
8. preparation method according to claim 1 is characterized in that, it is that negative pressure concentrates under the condition of 150 ℃-200 ℃ of temperature, vacuum tightness 15Pa-25Pa that described filtrate concentrates condition.
9. preparation method according to claim 1 is characterized in that, molecular distillation is adopted in described aftertreatment;
The condition of described molecular distillation is: 200 ℃-280 ℃ of temperature, vacuum tightness 0Pa-10Pa.
10. preparation method according to claim 1 is characterized in that, the mol ratio of monomer and catalyzer is 10: 0.05-3; The mass ratio of starting monomer and solvent is 1: 0.5-10.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483283A (en) * | 2013-09-13 | 2014-01-01 | 天津利安隆新材料股份有限公司 | Synthesis method for antioxidant 1790 |
| EP3272758A1 (en) | 2016-07-22 | 2018-01-24 | Evonik Degussa GmbH | Methodfor the preparation of tris [3- (alkoxysilyl) propyl] isocyanurates |
| EP3372609A1 (en) | 2017-03-08 | 2018-09-12 | Evonik Degussa GmbH | Process for the preparation of tris[3-(alkoxysilyl)propyl]isocyanurates |
| EP3372608A1 (en) | 2017-03-08 | 2018-09-12 | Evonik Degussa GmbH | Process for the preparation of tris[3-(alkoxysilyl)propyl]isocyanurats |
| US10377776B2 (en) | 2017-03-08 | 2019-08-13 | Evonik Degussa Gmbh | Process for preparing tris[3-(alkoxysilyl)propyl]isocyanurates |
| CN115403609A (en) * | 2022-05-09 | 2022-11-29 | 江苏瑞洋安泰新材料科技有限公司 | Preparation method of tris [3- (trimethoxysilyl) propyl ] isocyanurate |
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| CN101189246A (en) * | 2005-06-03 | 2008-05-28 | 莫门蒂夫功能性材料公司 | Process for the production of isocyanatosilane and silylisocyanurate |
| CN101189247A (en) * | 2005-04-14 | 2008-05-28 | 莫门蒂夫功能性材料公司 | Process for making silylisocyanurate |
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2010
- 2010-04-19 CN CN 201010150732 patent/CN101805366A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101189247A (en) * | 2005-04-14 | 2008-05-28 | 莫门蒂夫功能性材料公司 | Process for making silylisocyanurate |
| CN101189246A (en) * | 2005-06-03 | 2008-05-28 | 莫门蒂夫功能性材料公司 | Process for the production of isocyanatosilane and silylisocyanurate |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483283A (en) * | 2013-09-13 | 2014-01-01 | 天津利安隆新材料股份有限公司 | Synthesis method for antioxidant 1790 |
| EP3272758A1 (en) | 2016-07-22 | 2018-01-24 | Evonik Degussa GmbH | Methodfor the preparation of tris [3- (alkoxysilyl) propyl] isocyanurates |
| EP3372609A1 (en) | 2017-03-08 | 2018-09-12 | Evonik Degussa GmbH | Process for the preparation of tris[3-(alkoxysilyl)propyl]isocyanurates |
| EP3372608A1 (en) | 2017-03-08 | 2018-09-12 | Evonik Degussa GmbH | Process for the preparation of tris[3-(alkoxysilyl)propyl]isocyanurats |
| CN108570069A (en) * | 2017-03-08 | 2018-09-25 | 赢创德固赛有限公司 | The method for being used to prepare three [3- (alkoxysilyl) propyl] isocyanuric acid esters |
| CN108570070A (en) * | 2017-03-08 | 2018-09-25 | 赢创德固赛有限公司 | The method for being used to prepare three [3- (alkoxysilyl) propyl] isocyanuric acid esters |
| US10125156B2 (en) | 2017-03-08 | 2018-11-13 | Evonik Degussa Gmbh | Process for preparing tris[3-(alkoxysilyl)propyl]isocyanurates |
| US10364260B2 (en) | 2017-03-08 | 2019-07-30 | Evonik Degussa Gmbh | Process for preparing tris[3-(alkoxysilyl)propyl] isocyanurates |
| US10377776B2 (en) | 2017-03-08 | 2019-08-13 | Evonik Degussa Gmbh | Process for preparing tris[3-(alkoxysilyl)propyl]isocyanurates |
| US10703769B2 (en) | 2017-03-08 | 2020-07-07 | Evonik Operations Gmbh | Process for preparing tris[3-(dialkylalkoxysilyl)propyl]isocyanurates |
| US10711018B2 (en) | 2017-03-08 | 2020-07-14 | Evonik Operations Gmbh | Process for preparing tris[3-(alkyldialkoxysilyl)propyl]isocyanurates |
| CN108570069B (en) * | 2017-03-08 | 2022-07-05 | 赢创运营有限公司 | Process for preparing tris [3- (alkoxysilyl) propyl ] isocyanurate |
| CN115403609A (en) * | 2022-05-09 | 2022-11-29 | 江苏瑞洋安泰新材料科技有限公司 | Preparation method of tris [3- (trimethoxysilyl) propyl ] isocyanurate |
| CN115403609B (en) * | 2022-05-09 | 2023-11-03 | 江苏瑞洋安泰新材料科技有限公司 | Preparation method of tris [3- (trimethoxysilyl) propyl ] isocyanurate |
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Application publication date: 20100818 |