CN109438502B - Alpha isocyanate methyl silane and preparation method thereof - Google Patents
Alpha isocyanate methyl silane and preparation method thereof Download PDFInfo
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- CN109438502B CN109438502B CN201811186576.6A CN201811186576A CN109438502B CN 109438502 B CN109438502 B CN 109438502B CN 201811186576 A CN201811186576 A CN 201811186576A CN 109438502 B CN109438502 B CN 109438502B
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- isocyanate
- cyanate
- methylsilane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
Abstract
The invention discloses alpha isocyanate methyl silane and a preparation method thereof. Compared with the traditional method, the method has simpler route, avoids the process from halosilane to aminosilane, and is a preferred way for preparing the alpha isocyanate methylsilane.
Description
Technical Field
The invention relates to the field of silane coupling agents, in particular to alpha isocyanate methylsilane and a preparation method thereof.
Background
The isocyanate silane contains isocyanate groups which can participate in the reaction and siloxane groups which can undergo moisture curing. Therefore, the adhesive is increasingly applied to the polymer field to improve the bonding capability of products such as coatings, adhesives and the like on interfaces of walls, automobiles and the like.
The isocyanate group in the alpha isocyanate methylsilane has stronger activity due to the influence of adjacent silicon atoms, so that the reactivity of the isocyanate and hydroxyl in a high molecular system is higher. In articles exposed to public by the european union in 2010, the amount of organotin catalyst should be less than 0.1%. Therefore, the polyether resin and the polyurethane resin terminated by the alpha isocyanate methyl silane can be environment-friendly resin without adding an organic tin catalyst in the synthesis and glue preparation processes.
Currently, the research direction of isocyanate silane mainly aims at the trend of research on the synthesis of gamma-isocyanate propyl silane and the related technology of alpha-isocyanate methyl silane, and isocyanate silane is mainly synthesized by a phosgene method and a carbonic acid derivative pyrolysis method, wherein the former method has high phosgene toxicity, the latter method needs pyrolysis, and the requirements on production devices and production processes are harsh.
The invention mainly utilizes halogenated silane coupling agent and cyanate to react under the action of catalyst to prepare the alpha isocyanate silane. Compared with the traditional method, the method has simple preparation process, avoids the process from the halogenated silane to the aminosilane, and has low requirements on production devices and production processes compared with the traditional method; the environment is protected, the safety is realized, and the pollution is small; high yield and purity.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides alpha isocyanate methylsilane and a preparation method thereof.
The preparation method of the alpha isocyanate methylsilane comprises the following steps: adding an alpha halogenated silane coupling agent, cyanate and a catalyst into a solvent, uniformly stirring, completely dissolving the alpha halogenated silane coupling agent, cyanate and the catalyst, heating to 100-140 ℃, reacting for 1-3 hours, filtering the solution, and then carrying out reduced pressure distillation to obtain alpha isocyanate methylsilane; wherein, the alpha halogenated silane coupling agent, the cyanate and the catalyst are mixed according to the mass ratio of 1: (1.5-2): (0.001-0.005).
Wherein the chemical general formula of the alpha halogenated silane coupling agent is as follows:
wherein R1, R2 and R3 are each CnH2n+1And OCmH2m+1N is more than or equal to 1, m is more than or equal to 1; x is a halogen element.
In addition, the X is chlorine or bromine.
In addition, the cyanate is one of sodium cyanate, potassium cyanate and ammonium cyanate.
In addition, the catalyst is a nickel complex, and the nickel complex contains one or two elements of Cl and N.
In addition, the solvent is one of p-dimethylaminopyridine, 4-pyrrolylpyridine, quinoline, N-dimethylaniline, N-dimethylformamide and pyrrolidone.
The invention also comprises the alpha isocyanate methylsilane prepared by the preparation method of the alpha isocyanate methylsilane.
The invention provides a preparation method of alpha isocyanate methylsilane. Provides a simpler method for preparing isocyanate silane with high activity, improves the safety and reduces the cost in the preparation process of the silane.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
180.7g (1mol) of alpha-chloro-trimethoxysilane, 130g (2mol) of sodium cyanate and 0.292g (0.001mol) of a nickel complex were converted into (DME) NiCl2Adding the mixture into pyrrolidone, stirring uniformly, heating to 140 ℃, reacting for 1h, filtering the solution, and distilling under reduced pressure to obtain alpha isocyanate methyltrimethoxysilane fraction.
Example 2
267.7g (1mol) of alpha-bromo-triethoxysilane, 162g (2mol) of potassium cyanate and 1.56g (0.005mol) of nickel complex C20H20ClN3Adding Ni into quinoline, stirring uniformly, heating to 100 ℃, reacting for 2h, filtering the solution, and distilling under reduced pressure to obtain alpha isocyanate methyl triethoxysilane fraction.
Example 3
164.7g (1mol) (. alpha. -chloro-methyl) methyldimethoxysilane (Cl-CH)2-Si(CH3)(OCH3)2) 97.5g (1.5mol) of sodium cyanate and 0.292g of nickel complex (DME) NiCl2Adding the mixture into N, N-dimethylformamide, uniformly stirring, heating to 140 ℃, reacting for 1h, filtering the solution, and distilling under reduced pressure to obtain (alpha isocyanate methyl) methyldimethoxysilane fraction.
Example 4
166g (1mol) (. alpha. -fluoro-methyl) methyldiethoxysilane (F-CH)2-Si(CH3)(OC2H5)2) 102g (1.7mol) of ammonium cyanate and 0.292g of nickel complex (DME) NiCl2Adding the mixture into N, N-dimethylaniline, stirring uniformly, heating to 130 ℃, reacting for 1h, filtering the solution, and distilling under reduced pressure to obtain (alpha isocyanate methyl) methyldiethoxysilane fraction.
Example 5
329.2g (1mol) (alpha astatine-methyl) methyldimethoxysilane (At-CH)2-Si(CH3)(OCH3)2) 105g (1.6mol) of sodium cyanate and 0.28g of nickel complex (DME) NiCl2Adding the mixture into 4-pyrrolylpyridine, stirring uniformly, heating to 130 ℃, reacting for 1h, filtering the solution, and distilling under reduced pressure to obtain (alpha isocyanate methyl) methyldimethoxysilane fraction.
Example 6
262g (1mol) of alpha-iodo-methyltrimethoxysilane (I-CH)2-Si(OCH3)3) 97.5g (1.5mol) of sodium cyanate and 0.27g of nickel complex (DME) NiCl2Adding the mixture into p-dimethylaminopyridine, uniformly stirring, heating to 140 ℃, reacting for 1h, filtering the solution, and distilling under reduced pressure to obtain alpha isocyanate methyltrimethoxysilane fraction.
The yields and purities of the three isocyanate methylsilanes were as follows:
yield-actual mass of product/theoretical mass of product
Purity: CG-MS, using heptane as solvent, at 120 deg.C
From the results of the yield and purity of the examples, it can be seen that the yield of the alpha isocyanate methylsilane obtained by the preparation method of the invention is as high as 95% and the purity is as high as 97%.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A preparation method of alpha isocyanate methylsilane is characterized by comprising the following steps: adding an alpha halogenated silane coupling agent, cyanate and a catalyst into a solvent, uniformly stirring, completely dissolving the alpha halogenated silane coupling agent, cyanate and the catalyst, heating to 100-140 ℃, reacting for 1-3 hours, filtering the solution, and then carrying out reduced pressure distillation to obtain alpha isocyanate methylsilane; wherein, the alpha halogenated silane coupling agent, the cyanate and the catalyst are mixed according to the mass ratio of 1: 1.5-2: 0.001 to 0.005; the catalyst is a nickel complex, and the nickel complex contains one or two elements of Cl and N.
2. The method of claim 1, wherein the α -halosilane coupling agent has the general chemical formula:
wherein R1, R2 and R3 are each CnH2n+1And OCmH2m+1N is more than or equal to 1, m is more than or equal to 1; x is a halogen element.
3. The method of preparing an alpha isocyanate methylsilane according to claim 2, wherein X is chlorine or bromine.
4. The method of claim 1, wherein the cyanate is one of sodium cyanate, potassium cyanate, and ammonium cyanate.
5. The method for preparing an alpha isocyanate methylsilane according to claim 1, wherein the solvent is one of p-dimethylaminopyridine, 4-pyrroliylpyridine, quinoline, N-dimethylaniline, N-dimethylformamide and pyrrolidone.
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| CN109438502B true CN109438502B (en) | 2021-05-07 |
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Citations (4)
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| CN1538993A (en) * | 2001-08-09 | 2004-10-20 | 电化学工业有限公司（国际） | Alcoxy cross-linking single-component mosture-hardening materials |
| CN1615323A (en) * | 2002-01-17 | 2005-05-11 | 电化学工业有限公司（国际） | Cross-linkable polymer blends containing alkoxysilane-terminated polymers |
| CN106366108A (en) * | 2015-07-23 | 2017-02-01 | 华东师范大学 | Functionalized cyanosilane, synthesis method and applications thereof |
| CN107641494A (en) * | 2017-10-12 | 2018-01-30 | 济南大学 | A kind of coupling agent modified fluid sealant of α isocyanato silanes |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008074804A (en) * | 2006-09-25 | 2008-04-03 | Shin Etsu Chem Co Ltd | Method for producing silane compound having isocyanate group |
| JP2012057148A (en) * | 2010-08-10 | 2012-03-22 | Kaneka Corp | Curable composition |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1538993A (en) * | 2001-08-09 | 2004-10-20 | 电化学工业有限公司（国际） | Alcoxy cross-linking single-component mosture-hardening materials |
| CN1615323A (en) * | 2002-01-17 | 2005-05-11 | 电化学工业有限公司（国际） | Cross-linkable polymer blends containing alkoxysilane-terminated polymers |
| CN106366108A (en) * | 2015-07-23 | 2017-02-01 | 华东师范大学 | Functionalized cyanosilane, synthesis method and applications thereof |
| CN107641494A (en) * | 2017-10-12 | 2018-01-30 | 济南大学 | A kind of coupling agent modified fluid sealant of α isocyanato silanes |
Non-Patent Citations (1)
| Title |
|---|
| Reaction of triethylsilylacetic acid chloride with diazomethane and trimethylsilyl azide;Baukov, Yu. I.et al.,;《Zhurnal Obshchei Khimii》;19741231;第44卷;第955-956页 * |
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