CN108383868A - A kind of preparation method of high-quality γ-methacryloxypropyl trimethoxy silane - Google Patents
A kind of preparation method of high-quality γ-methacryloxypropyl trimethoxy silane Download PDFInfo
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- CN108383868A CN108383868A CN201810224096.8A CN201810224096A CN108383868A CN 108383868 A CN108383868 A CN 108383868A CN 201810224096 A CN201810224096 A CN 201810224096A CN 108383868 A CN108383868 A CN 108383868A
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- pressure
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- allyl methacrylate
- 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 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
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
Abstract
The present invention relates to a kind of preparation methods of high-quality γ methacryloxypropyl trimethoxy silanes, belong to technical field of organic chemistry, present invention improves over the synthetic methods that allyl methacrylate and trimethoxy hydrogen silane carry out Si―H addition reaction, such as using pressurization, trimethoxy hydrogen silane and anti-feed way is excessively used, a series of improvement is carried out by the preparation method to γ methacryloxypropyl trimethoxy silanes, a kind of synthetic route of high-quality is finally obtained, after above-mentioned improvement, with former technics comparing, the yield of γ methacryloxypropyl trimethoxy silanes is improved significantly, substantially it is held at 93% or more, and the height boiling of rectifying remaining significantly reduces.
Description
Technical field
The present invention relates to a kind of preparation methods of high-quality γ-methacryloxypropyl trimethoxy silane, belong to
Technical field of organic chemistry,
Background technology
γ-methacryloxypropyl trimethoxy silane is a kind of organo functional silanes' coupling agent, mainly to
Improve organic material and inorganic material surface adhesive property, as in fiberglass glass fibre and plastics, rubber, paint, painting
The processing of the materials such as the siliceous filler in material is additionally operable to increase adhesive property in bonding agent, and the resin that it is adapted to includes ring
Oxygen, phenolic aldehyde, melamine, polysulfide polyurethane, polystyrene etc..In unsaturated polyester composite, it can improve multiple
Condensation material mechanical performance, electric property, light transmission can especially increase substantially the green property of composite material.With the idol
Join agent infiltration processing glass, the mechanical strength and electric property of glass fibre reinforced composite material hygrometric state can be improved.In electric wire row
Industry fills the EPDM systems of peroxide crosslinking with the coupling agent treatment clay, improves the consumption factor and than inductance capacitive reactance.This
Product are copolymerized with vinyl acetate and acrylic or methacrylic acid monomer, these polymer are widely used in coating, adhesive and sealing
In agent, excellent bonding force and durability are provided.
It mainly with γ-r-chloropropyl trimethoxyl silane carries out that γ-is obtained by the reaction using Sodium methacrylate both at home and abroad at present
The synthetic route (condensation method) of methacryloxypropyl trimethoxy silane：
Referring to US2007/32673 A1 2007
Condensation method process is simple, but there is also Railway Projects：
1, yield is relatively low, reacts and is not thorough, and generally 80% or so.
2, a large amount of DMF need to be used as solvent, have quite a few loss in reaction, filtering, distillation process, make into
Originally increase, be largely discharged with tail gas of vacuum gas pump when especially rectification under vacuum detaches, keep COD high, seriously pollute environment, together
Shi Huishou DMF expend a large amount of energy consumption and time.
3, a small amount of DMF is remained in finished product, causes prodigious influence to the weatherability of product so that deterioration in quality.
4, the catalyst (tetrabutylammonium bromide or triphenyl ethyl phosphonium bromide phosphine) used in reaction is in normal reaction temperature
Degree is lower to be easy to decompose, and decomposition product is difficult to detach, and influences product purity.
To solve the above-mentioned problems, the conjunction of Si―H addition reaction is carried out using allyl methacrylate and trimethoxy hydrogen silane
At route (hydrosilation method)：
Referring to DE443420 (1996), US5646325 (1997),《γ-methacryloxypropyl trimethoxy silane
Study on the synthesis》Wuhan University Journals Edition 2,003 49 (2) 190-192 such as red legend happiness.
The technique of hydrosilation method is：
AMA and Speier catalyst are added with polymerization inhibitor phenthazine in reaction vessel, equimolar is added dropwise at 90 DEG C or so
The TMS of ratio carries out hydrosilylation, after completion of the reaction, carries out rectification under vacuum and obtains γ-methacryloxypropyl front three
Oxysilane, yield≤80%, purity >=98%.
Hydrosilation method does not use organic solvent, while used Speier catalyst (chloroplatinic acid/aqueous isopropanol)
It there are no decomposition product under well-defined reaction temp, therefore avoid above-mentioned problem.
But hydrosilation method, major problem is that yield is relatively low (≤80%), part AMA unreacteds are thorough, and in rectifying
When the high temperature in stage, side reaction occurs and forms height boiling impurity, therefore the heavy constituent of rectifying remaining is more, cost of material is higher.
Invention content
The present invention for hydrosilation method existing yield it is low, impurity is more the problems such as be improved, by multiple batches of reality
It tests, obtains following improved method：
Specifically, the preparation of high-quality γ-methacryloxypropyl trimethoxy silane provided by the present invention
Method, using allyl methacrylate and trimethoxy hydrogen silane as raw material, the reaction mechanism mechanism of reaction is as follows：
Allyl methacrylate is added into the reaction raw materials system containing trimethoxy hydrogen silane, it is anti-through Si―H addition reaction
It should be made.
Methacrylic acid alkene is added in the initiative selection of the present invention in the reaction raw materials system containing trimethoxy hydrogen silane
Propyl ester has been surprisingly found that it has facilitation outstanding for the abundant conversion of AMA using anti-add mode.
Preferably, the method includes：Into the autoclave pressure equipped with plunger type metering pump entrance, TMS, phenthazine is added
And Speier catalyst, closed reactor open stirring, after being replaced with nitrogen, heat, pressurization, by allyl methacrylate
It is slowly injected into autoclave pressure via plunger type metering pump, after injection, stirring carries out the hydrosilylation, is cooled to room
Temperature pours out reaction solution after pressure release..
Method of the present invention further includes that reaction solution is carried out vacuum fractionation, obtains γ-methacryloxypropyl
The step of trimethoxy silane, specific vacuum fractionation are grasped by those skilled in the art, and the present invention does not limit this especially
It is fixed.
Preferably, the present invention substitutes synthesis under normal pressure using pressuring method, by controlling suitable pressure limit, can promote
AMA conversions are thorough, and ideal reaction pressure is in the preferred 0.2MPa~0.4Mpa of 0.1MPa~0.6Mpa..
Preferably, the reaction temperature of the hydrosilylation of the present invention is 85 ± 5 DEG C.
Preferably, TMS is excessively used in the present invention；The more preferable allyl methacrylate and trimethoxy hydrogen silane
Molar ratio is 1/1.2~1.5, particularly preferably preferably 1/1.3~1.4, and in above-mentioned molar ratio range, AMA reactions can be achieved to the greatest extent
Thoroughly, while unreacted AMA may be avoided to be returned in stage of rectification formation height boiling impurity, excessive TMS later stages rectifying
Receipts are applied mechanically.Preferably, the Speier catalyst is：Chloroplatinic acid/aqueous isopropanol, specially those skilled in the art institute
Solution, the present invention are not particularly limited this.Preferably, condition when raw material is added in the present invention is also controlled, that is, uses nitrogen
Gas displacement after, heating reaction kettle to 85 ± 5 DEG C, control kettle pressure be 0.15 ± 0.05MPa, then by allyl methacrylate via
Plunger type metering pump is slowly injected into autoclave pressure, within the scope of above-mentioned condition, is peomoted the generation of reaction, is improved raw material
Utilization rate (conversion ratio).
The present invention carries out a series of change by the preparation method to γ-methacryloxypropyl trimethoxy silane
Into a kind of synthetic route of high-quality having been finally obtained, using method of the present invention, γ-methacryloxypropyl
The yield of trimethoxy silane is improved significantly, and is held at 93% or more substantially, and the height boiling of rectifying remaining obviously subtracts
It is few.
Embodiment one
Into the 2L autoclave pressures equipped with plunger type metering pump entrance, 476.6g (3.90mol) TMS, 5.8g pheno thiophene is added
Piperazine and 2.2mlSpeier catalyst, closed reactor open stirring, after being replaced with nitrogen, are heated to 85 DEG C, kettle pressure is
365.8g (2.90mol) AMA is slowly injected into via plunger type metering pump in autoclave pressure by 0.15MPa, injection rate is controlled, with kettle
Pressure is no more than subject to 0.3MPa, injection length about 2 hours, after injection, maintains 85 ± 5 DEG C and is stirred to react 2 hours, be cooled to
Room temperature pours out faint yellow reaction solution after pressure release.
Reaction solution is subjected to vacuum fractionation by filler still (Φ 2.5*100cm, glass spring filler), recycling is excessive
108gTMS collects 120-125 DEG C/670-780Pa fraction 673g, yield 93.45%, purity 99.41% (GC), high-boiling components
29.7g。
Embodiment two
Into the 2L autoclave pressures equipped with plunger type metering pump entrance, 461g (3.77mol) TMS, 6.3g phenthazine is added
And 2.7mlSpeier catalyst, closed reactor open stirring, after being replaced with nitrogen, are heated to 85 DEG C, kettle pressure is
365.8g (2.9mol) AMA is slowly injected into via plunger type metering pump in autoclave pressure by 0.15MPa, controls injection rate, kettle pressure
0.2-0.4MPa, injection length about 2 hours after injection, maintain 85 ± 5 DEG C and are stirred to react 2 hours, be cooled to room temperature, let out
Faint yellow reaction solution is poured out after pressure.
Reaction solution is subjected to vacuum fractionation by filler still (Φ 2.5*100cm, glass spring filler), recycling is excessive
110gTMS collects 120-125 DEG C/670-780Pa fraction 678g, yield 94.16%, purity 99.70% (GC), high-boiling components
28.5g。
Embodiment three
Into the 2L autoclave pressures equipped with plunger type metering pump entrance, 496g (4.06mol) TMS, 5.8g phenthazine is added
And 2.7mlSpeier catalyst, closed reactor open stirring, after being replaced with nitrogen, are heated to 85 DEG C, kettle pressure is
365.8g (2.9mol) AMA is slowly injected into via plunger type metering pump in autoclave pressure by 0.15MPa, controls injection rate, kettle pressure
0.2-0.4MPa, injection length about 2 hours after injection, maintain 85 ± 5 DEG C and are stirred to react 2 hours, be cooled to room temperature, let out
Faint yellow reaction solution is poured out after pressure.
Reaction solution is subjected to vacuum fractionation by filler still (Φ 2.5*100cm, glass spring filler), recycling is excessive
107gTMS collects 120-125 DEG C/670-780Pa fraction 675g, yield 93.74%, purity 99.64% (GC), high-boiling components
29.4g。
Example IV
Into the 2L autoclave pressures equipped with plunger type metering pump entrance, 476.6g (3.90mol) TMS, 5.8g pheno thiophene is added
Piperazine and 2.9mlSpeier catalyst, closed reactor open stirring, after being replaced with nitrogen, are heated to 85 DEG C, kettle pressure is
365.8g (2.90mol) AMA is slowly injected into via plunger type metering pump in autoclave pressure by 0.15MPa, controls injection rate, kettle pressure
0.2-0.4MPa is injection length about 2 hours, after injection, maintains 85 ± 5 DEG C and is stirred to react 2 hours, be cooled to room temperature,
Faint yellow reaction solution is poured out after pressure release.
Reaction solution is subjected to vacuum fractionation by filler still (Φ 2.5*100cm, glass spring filler), recycling is excessive
110gTMS collects 120-125 DEG C/670-780Pa fraction 679g, yield 94.30%, purity 99.78% (GC), high-boiling components
30.1g。
Embodiment five
Into the 2L autoclave pressures equipped with plunger type metering pump entrance, 496.1g (4.06mol) TMS, 5.8g pheno thiophene is added
Piperazine and 2.9mlSpeier catalyst, closed reactor open stirring, after being replaced with nitrogen, are heated to 85 DEG C, kettle pressure is
365.8g (2.90mol) AMA is slowly injected into via plunger type metering pump in autoclave pressure by 0.15MPa, controls injection rate, 0.2-
0.4MPa, injection length about 2 hours after injection, maintain 85 ± 5 DEG C and are stirred to react 2 hours, room temperature is cooled to, after pressure release
Pour out faint yellow reaction solution.
Reaction solution is subjected to vacuum fractionation by filler still (Φ 2.5*100cm, glass spring filler), recycling is excessive
106gTMS collects 120-125 DEG C/670-780Pa fraction 677g, yield 94.02%, purity 99.69% (GC), high-boiling components
29.5g。
Claims (10)
1. a kind of preparation method of high-quality γ-methacryloxypropyl trimethoxy silane, with methacrylic acid allyl
Ester is raw material with trimethoxy hydrogen silane, it is characterised in that：
Allyl methacrylate is added into the reaction raw materials system containing trimethoxy hydrogen silane, through hydrosilylation system
.
2. according to the method described in claim 1, it is characterized in that：Including：To the pressure equipped with plunger type metering pump entrance
In kettle, TMS, phenthazine and Speier catalyst is added, closed reactor opens stirring, after being replaced with nitrogen, heats, pressurization,
Allyl methacrylate is slowly injected into via plunger type metering pump in autoclave pressure, after injection, stirring carries out the silicon
Addition reaction of hydrogen is cooled to room temperature, reaction solution is poured out after pressure release.
3. method according to claim 1 or 2, it is characterised in that：The reaction pressure of the hydrosilylation exists
0.1MPa~0.6Mpa.
4. according to the method described in claim 3, it is characterized in that：The reaction pressure of the hydrosilylation 0.2MPa~
0.4Mpa。
5. according to claim 1-4 any one of them methods, it is characterised in that：The reaction temperature of the hydrosilylation is
85±5℃。
6. according to claim 1-5 any one of them methods, it is characterised in that：TMS is excessively used.
7. according to the method described in claim 6, it is characterized in that：The allyl methacrylate and trimethoxy hydrogen silane
Molar ratio be 1/1.2~1.5.
8. according to the method described in claim 7, it is characterized in that：The allyl methacrylate and trimethoxy hydrogen silane
Molar ratio be 1/1.3~1.4.
9. according to claim 1-8 any one of them methods, it is characterised in that：The Speier catalyst is：Chloroplatinic acid/
Aqueous isopropanol.
10. according to claim 2-9 any one of them methods, it is characterised in that：After being replaced with nitrogen, heating reaction kettle to 85
± 5 DEG C, control kettle pressure is 0.15 ± 0.05MPa, then allyl methacrylate is slowly injected into pressure via plunger type metering pump
In power kettle.
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| CN201810224096.8A CN108383868A (en) | 2018-03-19 | 2018-03-19 | A kind of preparation method of high-quality γ-methacryloxypropyl trimethoxy silane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280046A (en) * | 2020-11-13 | 2021-01-29 | 杭州崇耀科技发展有限公司 | Preparation method of alkyne bond-containing polyether modified organic silicon |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04128294A (en) * | 1990-09-19 | 1992-04-28 | Tonen Corp | Production of gamma-methacryloxypropylsilane compound |
| US5646325A (en) * | 1994-09-24 | 1997-07-08 | Huels Aktiengesellschaft | Process for the preparation of 3-acryloyloxypropylalkoxysilanes |
| JPH11100387A (en) * | 1997-09-29 | 1999-04-13 | Nissei Kagaku Kogyo Kk | Production of gamma-methacryloyloxypropylsilanes |
| CN101121724A (en) * | 2007-09-27 | 2008-02-13 | 湖北武大有机硅新材料股份有限公司 | Method for preparing 3-(methacryloxy)propyltrimethoxysilane |
| CN101362775A (en) * | 2006-08-10 | 2009-02-11 | 德古萨有限责任公司 | System and process for continuous industrial preparation of organosilanes |
-
2018
- 2018-03-19 CN CN201810224096.8A patent/CN108383868A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04128294A (en) * | 1990-09-19 | 1992-04-28 | Tonen Corp | Production of gamma-methacryloxypropylsilane compound |
| US5646325A (en) * | 1994-09-24 | 1997-07-08 | Huels Aktiengesellschaft | Process for the preparation of 3-acryloyloxypropylalkoxysilanes |
| JPH11100387A (en) * | 1997-09-29 | 1999-04-13 | Nissei Kagaku Kogyo Kk | Production of gamma-methacryloyloxypropylsilanes |
| CN101362775A (en) * | 2006-08-10 | 2009-02-11 | 德古萨有限责任公司 | System and process for continuous industrial preparation of organosilanes |
| CN101121724A (en) * | 2007-09-27 | 2008-02-13 | 湖北武大有机硅新材料股份有限公司 | Method for preparing 3-(methacryloxy)propyltrimethoxysilane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280046A (en) * | 2020-11-13 | 2021-01-29 | 杭州崇耀科技发展有限公司 | Preparation method of alkyne bond-containing polyether modified organic silicon |
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