CN105541897B - A kind of preparation method of 3 NCO propyl trimethoxy silicane - Google Patents
A kind of preparation method of 3 NCO propyl trimethoxy silicane Download PDFInfo
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- CN105541897B CN105541897B CN201610140697.1A CN201610140697A CN105541897B CN 105541897 B CN105541897 B CN 105541897B CN 201610140697 A CN201610140697 A CN 201610140697A CN 105541897 B CN105541897 B CN 105541897B
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- trimethoxy silicane
- propyl trimethoxy
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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 Table
- 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
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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 Table
- 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
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Abstract
The present invention relates to a kind of preparation method of 3 NCO propyl trimethoxy silicane, belongs to technical field of organic chemistry.The present invention adds a small amount of trimethyl orthoacetate mixing, is reacted under agitating and heating vacuum condition, form the mixture of urea propyl silane silane using 3 aminopropyl trimethoxysilanes, urea raw material, dimethyl sulfoxide as solvent；Then, catalyst is added, is continued to react deamination generation isocyanates and sulfate with dilute sulphuric acid；Refilter, the isolated 3 isocyanates propyl trimethoxy silicane product of rectifying.The preparation method of the present invention, raw materials for production are simple and easy to get, production process potential safety hazard is small, reaction condition temperature, production equipment are simple；Compare suitable industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of 3- NCOs propyl trimethoxy silicane, category technique of organic chemistry neck
Domain.
Background technology
3- NCO propyl trimethoxy silicanes are a kind of silane couplers containing NCO active group,
It is to promote the adhesive property between inorganic material and organic material that it, which is acted on,.It is widely used in high-grade polyurethane sealant and is modified poly-
Urethane resin, the tackifier for also being used as room temperature vulcanized silicone rubber, the composition etc. of varnish gum, it is at present, domestic common
The synthetic method of isocyanato silanes has following several：
Patent CN104203910 describes prepares isocyanate compound using phosgene and amine reaction in atent solvent,
This method has the drawback that the hypertoxic gas that phosgene is colorless and odorless, in production process phosgene leakage easily lead to great
Security incident；Patent CN101492468 describe using triphosgene (i.e. solid phosgene) in organic solvent, low temperature (- 5~10
DEG C) under the conditions of with trialkoxy silane base amine reaction prepare trialkoxysilanes isocyanic ester, this method is relative to phosgenation
(gaseous phosgene) security is greatly improved, but solid phosgene is heated or chance moisture content easily decomposes and produces hypertoxic gaseous state light
Gas, potential safety hazard are also larger.Patent CN101307067 describe using carbamate groups alkoxy silane with SiCl4 or
In the environment of SnCl4 regulations are 4-5 to PH, NCO alkoxyl silicone is produced by high temperature (300~500 DEG C) cracking process
Alkane, this method are greatly improved with respect to phosgenation security, but the higher energy for causing production of the temperature in course of reaction
Consume it is larger, under high temperature NCO self-polymerization formed ring body polymer and influence the yield of product, production process is not allowed
It is easy to control.
The content of the invention
It is an object of the invention to：There is provided a kind of technique is simple, reaction condition gently production required for equipment requirement compared with
It is low, it is adapted to the preparation method of the 3- NCO propyl trimethoxy silicanes of industrialized production.
The technical scheme is that：
A kind of preparation method of 3- NCOs propyl trimethoxy silicane, it comprises the following steps：
1）, by 3- aminopropyl trimethoxysilanes, the urea of drying, dimethyl sulfoxide, a small amount of trimethyl orthoacetate put into
Into reactor；
2）, under conditions of stirring be heated to system to 65~95 DEG C, in vacuum -0.08~-0.09MPa reaction deaminations
Gas, react 6~10 hours, stop vacuumizing when reaction system is emerged without obvious bubble, obtain；Urea propyl silane and solvent
Deng the mixture of material；
3）, to reaction system add a small amount of catalyst, the concentrated sulfuric acid of 98% content is pressed 1 using dimethyl sulfoxide (DMSO)：0.5
~0.8 quality obtains mixed diluting liquid, the mixed diluting liquid is slowly added drop-wise into stirring reaction in system than mixed diluting,
At 75~95 DEG C, time for adding is controlled in 4~6h for reaction temperature control；
4）, when system pH value drops to 6~7 stop be added dropwise mixed diluting liquid；Then less than 50 DEG C are cooled to, was sealed
Filter out the ammonium salt of generation and other solid materials；；Filtrate, filtrate decompression rectifying is separated, obtained；3- NCO propyl group
Trimethoxy silane product.
Described 3- aminopropyl trimethoxysilanes, urea, dimethyl sulfoxide mass ratio are 1：0.30~0.35：1.0~
1.5 the input amount of trimethyl orthoacetate is the 3~6% of 3- aminopropyl trimethoxysilane weight.
Described catalyst is one kind in cupric oxide, copper chloride, stannous chloride, copper sulphate, wherein preferably copper sulphate.
The dosage of described catalyst is the 0.5~1.5% of 3- aminopropyl trimethoxysilane weight.
The present invention reaction equation be：
It is an advantage of the invention that：
1st, the primary raw material that the present invention prepares isocynate silane is industrial urea and 3- aminopropyl front three oxosilanes, raw material
It is easy to get, it is cheap.
2nd, production technology of the present invention produces isocyanide using the method production isocyanate products of catalysis deamination compared to phosgenation
Its production security of acid ester product is higher.
3rd, isocynate silane technique is prepared compared to carbamate base silane high-temperature cracking method, the reaction condition temperature
With, energy consumption is low, side reaction is few, product yield is higher.
4th, the equipment requirement that this method technique is simple, reaction condition is gently required for production is relatively low, is adapted to industrialized production.
Embodiment
Embodiment 1：
Mechanical agitation, temperature are loaded onto in 2L reaction flask and takes out negative pressure device, by 537.9g (3.0mol) 3- ammonia
Propyl trimethoxy silicane, 181.2g (3.0mol) urea, 550g dimethyl sulfoxide, 15g trimethyl orthoacetate are put into
In flask, stirring and vacuum plant are opened, is warming up to 90~95 DEG C, vacuum degree control is reacted 9h under -0.085MPa and stopped very
It is empty；Then 3.2g cupric oxide is added into flask as catalyst, the concentrated sulfuric acid 175g (1.75mol) that concentration is 98% is used
It is transferred in constant pressure funnel after 95g dimethyl sulfoxide (DMSO) dilution, is slowly added drop-wise in flask, stirred when being added dropwise, is added dropwise anti-
Answering temperature control, time for adding control has been entered in 6h, and the pH value for being now is 6~7, and temperature of reaction system declines at 80~85 DEG C
To 20~30 DEG C；The material of reaction is led into dry nitrogen pressure filtration with positive press filtration device, filter cake is dried up with nitrogen, collected
To filtrate；This filtrate is used into the isolated 3- NCOs propyl trimethoxy silicane product 595.8g of rectification under vacuum, produced
Product yield 96.5%, it is 98.2% by gas chromatographic detection product content.
Embodiment 2：
Mechanical agitation, temperature are loaded onto in 2L reaction flask and takes out negative pressure device, by 537.9g (3.0mol) 3- ammonia
Propyl trimethoxy silicane, 181.2g (3.0mol) urea, 650g dimethyl sulfoxide, 20g trimethyl orthoacetate are put into
In flask, stirring and vacuum plant are opened, is warming up to 90~95 DEG C, vacuum degree control is reacted 9h under -0.085MPa and stopped very
It is empty；Then 3.2g anhydrous cupric sulfate is added into flask as catalyst, by the concentrated sulfuric acid 164g that concentration is 98%
(1.64mol) is slowly added drop-wise in flask, when being added dropwise with being transferred to after 95g dimethyl sulfoxide (DMSO) dilution in constant pressure funnel
Stirring, at 75~80 DEG C, time for adding control has been entered in 4.5h for drip reacting temperature control, and the pH value for being now is 6.5, reaction
System temperature drops to 20~30 DEG C；The material of reaction is led into dry nitrogen pressure filtration, filter cake nitrogen with positive press filtration device
Air-blowing is done, and collection obtains filtrate；This filtrate is used into the isolated 3- NCOs propyl trimethoxy silicane of rectification under vacuum
Product 601.0g, product yield 97.6%, it is 98.4% by gas chromatographic detection product content.
Embodiment 3：
Mechanical agitation, temperature are loaded onto in 2L reaction flask and takes out negative pressure device, by 537.9g (3.0mol) 3- ammonia
Propyl trimethoxy silicane, 181.2g (3.0mol) urea, 650g dimethyl sulfoxide, 20g trimethyl orthoacetate are put into
In flask, stirring and vacuum plant are opened, is warming up to 90~95 DEG C, vacuum degree control is reacted 9h under -0.085MPa and stopped very
It is empty；Then 4.5g anhydrous cupric sulfate is added into flask as catalyst, by the concentrated sulfuric acid 157g that concentration is 98%
(1.57mol) is slowly added drop-wise in flask, when being added dropwise with being transferred to after 90g dimethyl sulfoxide (DMSO) dilution in constant pressure funnel
Stirring, at 75~80 DEG C, time for adding control has been entered in 4.5h for drip reacting temperature control, and the pH value for being now is 6.5, reaction
System temperature drops to 20~30 DEG C；The material of reaction is led into dry nitrogen pressure filtration, filter cake nitrogen with positive press filtration device
Air-blowing is done, and collection obtains filtrate；This filtrate is used into the isolated 3- NCOs propyl trimethoxy silicane of rectification under vacuum
Product 604.7g, product yield 98.2%, it is 98.9% by gas chromatographic detection product content.
Claims (4)
- A kind of 1. preparation method of 3- NCOs propyl trimethoxy silicane, it is characterised in that：It comprises the following steps：1）, 3- aminopropyl trimethoxysilanes, the urea of drying, dimethyl sulfoxide, a small amount of trimethyl orthoacetate put into instead Answer in device；2）, heating systems are to 65~95 DEG C under conditions of stirring, in vacuum -0.08~-0.09MPa reaction deamination gas, reaction 6 ~10 hours, stop vacuumizing when reaction system is emerged without obvious bubble, obtain the material such as urea propyl silane and solvent Mixture；3）, to reaction system add a small amount of catalyst, the concentrated sulfuric acid of 98% content is pressed 1 using dimethyl sulfoxide (DMSO)：0.5~0.8 Quality than mixed diluting, obtain mixed diluting liquid, the mixed diluting liquid be slowly added drop-wise to stirring reaction in system, reaction temperature At 75~95 DEG C, time for adding is controlled in 4~6h for degree control；4）, when system pH value drops to 6~7 stop be added dropwise mixed diluting liquid；Then less than 50 DEG C are cooled to, sealed and filters out Fall the ammonium salt of generation and other solid matters；Filtrate is obtained, filtrate decompression rectifying is separated, obtains 3- NCO propyl group trimethoxies Base silane product.
- 2. a kind of preparation method of 3- NCOs propyl trimethoxy silicane according to claim 1, its feature exist In：Described 3- aminopropyl trimethoxysilanes, urea, dimethyl sulfoxide mass ratio are 1：0.30~0.35：1.0~1.5, former second The input amount of sour trimethyl is the 3~6% of 3- aminopropyl trimethoxysilane weight.
- 3. a kind of preparation method of 3- NCOs propyl trimethoxy silicane according to claim 1, its feature exist In：Described catalyst is one kind in cupric oxide, copper chloride, stannous chloride, copper sulphate.
- 4. a kind of preparation method of 3- NCOs propyl trimethoxy silicane according to claim 1, its feature exist In：The dosage of described catalyst is the 0.5~1.5% of 3- aminopropyl trimethoxysilane weight.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864169A (en) * | 2018-06-09 | 2018-11-23 | 河北晟凯新材料科技有限公司 | A method of improving isocyanate group propyl-triethoxysilicane yield |
| CN109400640B (en) * | 2018-11-21 | 2021-02-23 | 江西晨光新材料股份有限公司 | Preparation method of 3-isocyanic acid propyl trialkoxysilane |
| CN110128465A (en) * | 2019-06-25 | 2019-08-16 | 荆州市江汉精细化工有限公司 | A method of isocyanato silanes are prepared with hydrosilylation |
| CN119528815B (en) * | 2025-01-22 | 2025-03-28 | 东营市天正化工有限公司 | Method for preparing 5-nitrobenzimidazolone through continuous nitration |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4697009A (en) * | 1985-07-06 | 1987-09-29 | Degussa Aktiengesellschaft | N-silylpropyl-N'-acyl-ureas and process for their production |
| CN104262382A (en) * | 2014-09-10 | 2015-01-07 | 成都硅宝科技股份有限公司 | Preparation method of ureido silane coupling agent |
-
2016
- 2016-03-14 CN CN201610140697.1A patent/CN105541897B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4697009A (en) * | 1985-07-06 | 1987-09-29 | Degussa Aktiengesellschaft | N-silylpropyl-N'-acyl-ureas and process for their production |
| CN104262382A (en) * | 2014-09-10 | 2015-01-07 | 成都硅宝科技股份有限公司 | Preparation method of ureido silane coupling agent |
Non-Patent Citations (1)
| Title |
|---|
| 含异氰酸酯基丙基三乙氧基硅烷的合成;张先林等;《浙江化工》;20080526;第39卷(第2期);第11-13页 * |
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Address after: Luochang Town, Shashi District, Jingzhou City, Hubei Province Patentee after: Hubei Jianghan New Material Co.,Ltd. Address before: 434000 No.2 Road, Shashi District Economic and Technological Development Zone, Jingzhou City, Hubei Province Patentee before: JINGZHOU JIANGHAN FINE CHEMICAL Co.,Ltd. |
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