CN104045833A - Method for synthesizing dihydroxypropyl-terminated polysiloxane by virtue of microwave radiation - Google Patents
Method for synthesizing dihydroxypropyl-terminated polysiloxane by virtue of microwave radiation Download PDFInfo
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Abstract
The invention discloses a method for synthesizing dihydroxypropyl-terminated polysiloxane by virtue of a microwave radiation. The method comprises four steps, namely (1) the synthesis (hydroxyl protection) of 2-allyl trimethyl silane, (2) the synthesis (hydrosilylation) of 1,3-bis(3-trimethsiloxy) tetramethyldisiloxane, (3) the synthesis (ring opening polymerization) of bis(3-trimethsiloxy) polysiloxane, and (3) the synthesis (hydrolysis reaction) of the dihydroxypropyl-terminated polysiloxane. Heating in each synthesis step is realized by virtue of microwave radiation; the target compound, namely the dihydroxypropyl-terminated polysiloxane, can be obtained highly selectively; the purity of the dihydroxypropyl-terminated polysiloxane is 99.9%.
Description
Technical field
The present invention relates to the method for the synthetic bis-hydroxypropyl terminated polysiloxane of a kind of microwave radiation.
Background technology
Bis-hydroxypropyl terminated polysiloxane can react with isocyanic ester, carboxylic acid etc. multipolymers such as generating polyurethane-polysiloxane, polyester polysiloxane, polycarbonate polysiloxane; Therefore, the research of hydroxyalkyl terminated polysiloxane receives much concern.
Microwave technology is applied more and more extensive in chemical every field in recent years.Utilize the feature of microwave heating, microwave radiation is introduced to Polymer Synthesizing, be expected to accelerate the speed of polyreaction, and can obtain good uniformity, the narrow product of molar mass distribution, thereby improve performance and the quality of product, expand the range of application of product.But microwave radiation is reacted rare report for hydroxyl alkyl-polysiloxane.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art and the method for the synthetic bis-hydroxypropyl terminated polyethers polysiloxane of a kind of microwave radiation is provided, for bis-hydroxypropyl terminated polysiloxane synthetic provides new reactive mode, equipment requirements is low, reduce energy consumption, reduce costs, increase benefit, pollution-free.
Reaction formula of the present invention is as follows:
Synthesizing of the first step, 2-allyl group trimethicone:
Second step, 1, two (the 3-tri-silyloxy propyl group) tetramethyl disiloxanes of 3-synthetic:
Synthesizing of the 3rd step, two (3-tri-silyloxy propyl group) polysiloxane
Wherein, n represents 20～50 integer.
Synthesizing of the 4th step, both-end hydroxypropyl polysiloxane
Concrete steps of the present invention are as follows:
The first step, the preparation (hydroxyl protection) of 2-allyl group trimethicone:
Is furnished with anhydrous CaC1 being furnished with thermometer, agitator and upper end
2in the flask of the reflux exchanger of drying tube, add hmds, under room temperature, drip vinyl carbinol, after 1h dropwises, be warming up to 70～80 ℃, set microwave power 550～650W, reaction times 60～90min, reaction solution is distilled under normal pressure, collect 99～103 ℃ of cuts, obtain 2-allyl group trimethicone.Each material molar ratio of hydroxyl protection reaction process is vinyl carbinol: hmds=1.4:1～2:1.
Second step, synthetic (addition of silicon hydrogen) of two (the 3-tri-silyloxy propyl group) tetramethyl disiloxanes of 1,3-:
Being housed, agitator, thermometer, nitrogen conduit and upper end be furnished with anhydrous CaC1
2in the flask of the reflux condensing tube of drying tube, add 2-allyl group trimethicone and the agent of Tetrachloroplatinum/Isopropanol catalysis; under nitrogen protection, open microwave reactor, set 90～120 ℃ of temperature of reaction; microwave power 600～850W; to temperature of reaction, start slowly to drip 1,1,3; 3-tetramethyl disiloxane; after 1h adds, insulation reaction 4～8h, stopped reaction.Low-boiling point material is removed in underpressure distillation, collect the cut of 144～146 ℃, obtain colourless transparent liquid and be 1, two (the 3-tri-silyloxy propyl group) tetramethyl disiloxanes of 3-, each material molar ratio of addition reaction of silicon with hydrogen is: 2-allyl group trimethicone: 1,1,3,3-tetramethyl disiloxane: Tetrachloroplatinum=2.3:1:7.5 * 10
-4～3.5:1:7.5 * 10
-4.
The 3rd step, synthetic two (the 3-tri-silyloxy propyl group) polysiloxane (ring-opening polymerization) of microwave radiation:
Take Tetramethylammonium hydroxide as catalyzer, under nitrogen protection, by 1, two (the 3-tri-silyloxy propyl group) tetramethyl disiloxanes of 3-and octamethylcyclotetrasiloxane carry out polyreaction, 80～90 ℃ of temperature of reaction, reaction times 10～12h, microwave power 500～550W, reaction finishes rear underpressure distillation and removes unreacted octamethylcyclotetrasiloxane and low-boiling-point substance, obtain light yellow transparent liquid and be two (3-tri-silyloxy propyl group) polysiloxane, this polyreaction material molar ratio is: 1, two (3-tri-silyloxy propyl group) tetramethyl disiloxanes of 3-: octamethylcyclotetrasiloxane: Tetramethylammonium hydroxide=1:20～50:0.2～0.4,
The 4th step, microwave radiation is synthesized bis-hydroxypropyl terminated polysiloxane (hydrolysis reaction):
Take p-methyl benzenesulfonic acid as catalyzer, two (3-tri-silyloxy propyl group) polysiloxane are hydrolyzed, 90～110 ℃ of hydrolysis temperatures, reaction times 2～2.5h, microwave power 600～850W, underpressure distillation vacuum tightness is 0.996, collects 78～80 ℃ of cuts; This hydrolysis reaction mol ratio is: two (3-tri-silyloxy propyl group) polysiloxane of 1,3-: water: p-methyl benzenesulfonic acid=1:1～1.3:0.06～0.08.
The comprehensive forefathers of the present invention work to both-end hydroxypropyl terminated polysiloxane study on the synthesis, from improving product yield, the easy industrializing implementation that is easy to is considered, adopt temperature controllable non-pulse type micro-wave reactor, under microwave radiation condition, first adopt hmds to react with the hydroxyl on vinyl carbinol, with trimethylsilyl, hydroxyl is protected, obtain 2-allyl group trimethicone (ATMS), then by synthetic ATMS and 1, 1, 3, 3-tetramethyl disiloxane (HMM) carries out addition reaction of silicon with hydrogen under microwave radiation condition, obtain 1, two (the 3-tri-silyloxy propyl group) tetramethyl disiloxanes (DTMS) of 3-, it is catalyzer that reaction adopts Tetrachloroplatinum, and the addition of traditional silicon hydrogen generally all adopts the aqueous isopropanol of Platinic chloride to carry out, the present invention adopts and is more easy to get, platinum content higher not containing the Tetrachloroplatinum of crystal water as catalyzer, make this product there is higher cost performance.Next synthetic DTMS is at octamethylcyclotetrasiloxane (D
h 4) and a small amount of Tetramethylammonium hydroxide catalysis under carry out ring-opening polymerization, make two (3-tri-silyloxy propyl group) polysiloxane of a series of different molar masss, last two (3-tri-silyloxy propyl group) polysiloxane is hydrolyzed under a small amount of Catalyzed by p-Toluenesulfonic Acid, and generally such reaction is and carries out alcoholysis under acid catalysis condition, this both avoided organic solvent residual, improved the purity of product, simultaneously also without the consumption of a large amount of organic solvents.
The advantage that this invention compared with prior art had is: the present invention adopts microwave radiation synthetic bis-hydroxypropyl terminated polysiloxane under normal pressure, lesser temps, for bis-hydroxypropyl terminated polysiloxane synthetic provides new reactive mode, equipment requirements is low, reduce energy consumption, reduce costs, increase benefit, pollution-free, meet the concept of Green Chemistry.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The preparation process of both-end hydroxypropyl polysiloxane of the present invention is carried out in four steps:
The first step is furnished with thermometer, agitator and upper end and is furnished with anhydrous CaC1
2in the flask of the reflux exchanger of drying tube, add hmds 96.8g, set microwave power 600W, stir and be warming up to 75 ℃, drip 58.08g vinyl carbinol, 1h dropwises rear intensification and sets 120 ℃ of temperature of reaction, stopped reaction after reaction 4h.Reaction solution is distilled under normal pressure, collect 99～103 ℃ of cuts, obtain 2-allyl group trimethicone, yield 80%.
Second step is furnished with anhydrous CaC1 agitator, thermometer, nitrogen conduit and upper end are housed
2the 2-allyl group trimethicone and the agent of 0.039g Tetrachloroplatinum/Isopropanol catalysis that in the flask of the reflux condensing tube of drying tube, add 30g to prepare, nitrogen tube stretches into logical nitrogen deoxygenation 20min in flask, high-speed stirring 10min, after repeatedly emptying, open microwave reactor, set microwave power 700W, to 90 ℃ of temperature of reaction, start slowly to drip 13.4g1,1,3,3-tetramethyl disiloxane, after 1h adds, reaction 90min, stopped reaction.Low-boiling point material is removed in underpressure distillation, collects the cut of 144～146 ℃, obtains colourless transparent liquid and is two (the 3-tri-silyloxy propyl group) tetramethyl disiloxanes of 1,3-, yield 77.6%.
The 3rd step in agitator, thermometer, nitrogen conduit and upper end are housed are furnished with the flask of anhydrous CaC12 drying tube reflux condensing tube, add prepared by 3.85g 1, two (the 3-tri-silyloxy propyl group) tetramethyl disiloxanes of 3-, 65.7g octamethylcyclotetrasiloxane and 0.028g catalyzer Tetramethylammonium hydroxide, open microwave reactor, set microwave power 500W, 80 ℃ of temperature of reaction, insulation reaction 10h, reaction finishes post-heating to 140～145 ℃, insulation 1h, catalyzer is decomposed completely, stopped reaction.Reaction solution is carried out to underpressure distillation, and decompression steams after unreacted octamethylcyclotetrasiloxane and low-boiling-point substance, obtains light yellow transparent liquid and is product, yield 86%.
Two (3-tri-silyloxy propyl group) polysiloxane, 0.396 water and the agent of 0.02g Catalyzed by P-Toluenesulfonic Acid that the 4th step adds 138g to prepare in the there-necked flask that agitator, thermometer, reflux condensing tube are housed, set microwave power 600W, 90 ℃ of reaction 2h of temperature of reaction, stopped reaction.Reaction solution is carried out to underpressure distillation, and the decompression of water circulation vacuum pump steams by product hexamethyldisiloxane, obtains both-end hydroxypropyl polysiloxane product, yield 88.2%.
Embodiment 2
The first step and second step are with embodiment 1;
The 3rd step is furnished with anhydrous CaC1 agitator, thermometer, nitrogen conduit and upper end are housed
2in the flask of drying tube reflux condensing tube, add prepared by 3.85g 1, two (the 3-tri-silyloxy propyl group) tetramethyl disiloxanes of 3-, 78.8g octamethylcyclotetrasiloxane and 0.034g catalyzer Tetramethylammonium hydroxide, open microwave reactor, set 85 ℃ of microwave power 550W temperature of reaction, insulation reaction 11h, reaction finishes post-heating to 140～145 ℃, insulation 1h, decomposes catalyzer, stopped reaction completely.Reaction solution is carried out to underpressure distillation, and decompression steams after unreacted octamethylcyclotetrasiloxane and low-boiling-point substance, obtains light yellow transparent liquid and is product, yield 89.4%;
Two (3-tri-silyloxy propyl group) polysiloxane, 0.396 water and the agent of 0.02g Catalyzed by P-Toluenesulfonic Acid that the 4th step adds 164g to prepare in the there-necked flask that agitator, thermometer, reflux condensing tube are housed, set 100 ℃ of microwave power 650W, temperature of reaction, reaction 2h, stopped reaction.Reaction solution is carried out to underpressure distillation, and the decompression of water circulation vacuum pump steams by product hexamethyldisiloxane, obtains both-end hydroxypropyl polysiloxane product, yield 90.1%.
Embodiment 3
The first step and second step are with example 1;
The 3rd step is furnished with anhydrous CaC1 agitator, thermometer, nitrogen conduit and upper end are housed
2in the flask of drying tube reflux condensing tube, add prepared by 3.85g 1, two (the 3-tri-silyloxy propyl group) tetramethyl disiloxanes of 3-, 98.6g octamethylcyclotetrasiloxane and 0.034g catalyzer Tetramethylammonium hydroxide, open microwave reactor, set 90 ℃ of microwave power 550W temperature of reaction, reaction 12h, reaction finishes post-heating to 140～145 ℃, insulation 1h, decomposes catalyzer, stopped reaction completely.Reaction solution is carried out to underpressure distillation, and decompression steams after unreacted octamethylcyclotetrasiloxane and low-boiling-point substance, obtains light yellow transparent liquid and is product, yield 90.6%;
Two (3-tri-silyloxy propyl group) polysiloxane, 0.396 water and the agent of 0.02g Catalyzed by P-Toluenesulfonic Acid that the 4th step adds 258g to prepare in the there-necked flask that agitator, thermometer, reflux condensing tube are housed, set 110 ℃ of microwave power 800W, temperature of reaction, reaction 2h, stopped reaction.Reaction solution is carried out to underpressure distillation, and the decompression of water circulation vacuum pump steams by product hexamethyldisiloxane, obtains both-end hydroxypropyl polysiloxane product, yield 91.2%.
It should be noted that: the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record previous embodiment is modified, or part technical characterictic is wherein replaced on an equal basis.
Within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (5)
1. the method for the synthetic bis-hydroxypropyl terminated polysiloxane of a microwave radiation; it is characterized by: with hmds, vinyl carbinol, 1; 1; 3; 3-tetramethyl disiloxane and octamethylcyclotetrasiloxane are starting raw material; under microwave radiation condition, through hydroxyl protection, the addition of silicon hydrogen, ring-opening polymerization and hydrolysis reaction, obtain target compound bis-hydroxypropyl terminated polysiloxane.
2. the method for the synthetic bis-hydroxypropyl terminated polysiloxane of a kind of microwave radiation as claimed in claim 1, is characterized in that: described hydroxyl protection reaction is under normal temperature, is furnished with anhydrous CaC1 being furnished with thermometer, agitator, constant pressure funnel and upper end
2in the flask of the reflux exchanger of drying tube; add vinyl carbinol; rear dropping hmds; after dropwising, 1h is warming up to 70～80 ℃; set microwave power 550～650W, reaction times 60～90min, collects the cut of 99～103 ℃ under normal pressure; obtain 2-allyl group trimethicone, in described hydroxyl protection process, molar ratio is: vinyl carbinol: hmds=1.4:1～2:1.
3. a kind of microwave radiation as claimed in claim 1 is synthesized the method for bis-hydroxypropyl terminated polysiloxane, it is characterized in that: described addition reaction of silicon with hydrogen is to take Tetrachloroplatinum/Virahol as catalyzer, under nitrogen protection, by 1,1,3,3-tetramethyl disiloxane drops in 2-allyl group trimethicone, temperature of reaction is 90～120 ℃, reaction times is 4～8h, and microwave power 600～850W, obtains 1, two (the 3-tri-silyloxy propyl group) tetramethyl disiloxanes of 3-, underpressure distillation vacuum tightness is under 0.099MPa, to collect the cut of 144～146 ℃; The molar ratio of described addition reaction of silicon with hydrogen is: 2-allyl group trimethicone: 1,1,3,3-tetramethyl disiloxane: Tetrachloroplatinum=2.3:1:7.5 * 10
-4～3.5:1:7.5 * 10
-4.
4. a kind of microwave radiation as claimed in claim 1 is synthesized the method for bis-hydroxypropyl terminated polysiloxane; it is characterized in that: described ring-opening polymerization is to take Tetramethylammonium hydroxide as catalyzer; under microwave radiation and nitrogen protection; by two (3-tri-silyloxy propyl group) tetramethyl disiloxane and the octamethylcyclotetrasiloxane (D of 1,3-
h 4) carry out polyreaction, 80～90 ℃ of temperature of reaction, reaction times 10～12h, microwave power 500～550W, reaction finishes rear underpressure distillation and removes unreacted octamethylcyclotetrasiloxane and low-boiling-point substance, obtain light yellow transparent liquid and be two (3-tri-silyloxy propyl group) polysiloxane, described polyreaction mol ratio is: two (3-tri-silyloxy propyl group) tetramethyl disiloxanes of 1,3-: octamethylcyclotetrasiloxane: Tetramethylammonium hydroxide=1:20～50:0.2～0.4.
5. a kind of microwave radiation as claimed in claim 1 is synthesized the method for bis-hydroxypropyl terminated polysiloxane, it is characterized in that: described hydrolysis reaction is to take p-methyl benzenesulfonic acid as catalyzer, two (3-tri-silyloxy propyl group) polysiloxane are hydrolyzed, 90～110 ℃ of hydrolysis temperatures, reaction times 2～2.5h, microwave power 600～850W, underpressure distillation vacuum tightness is 0.996, collects 78～80 ℃ of cuts; Hydrolysis reaction mol ratio is: two (3-tri-silyloxy propyl group) polysiloxane of 1,3-: water: p-methyl benzenesulfonic acid=1:1～1.3:0.06～0.08.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848956A (en) * | 2019-04-30 | 2020-10-30 | 万华化学集团股份有限公司 | Polysiloxane with end group of phenolic group and preparation method thereof |
| CN117757341A (en) * | 2023-12-29 | 2024-03-26 | 深圳市安信达存储技术有限公司 | Anti-radiation processing method for embedded memory chip in space environment satellite |
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2014
- 2014-07-02 CN CN201410312188.3A patent/CN104045833B/en active Active
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| 朱晓丽: "有机硅改性水性聚氨酯的研究", 《中国优秀博硕士学位论文全文数据库（博士）工程科技I辑》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848956A (en) * | 2019-04-30 | 2020-10-30 | 万华化学集团股份有限公司 | Polysiloxane with end group of phenolic group and preparation method thereof |
| CN111848956B (en) * | 2019-04-30 | 2022-03-11 | 万华化学集团股份有限公司 | Polysiloxane with end group of phenolic group and preparation method thereof |
| CN117757341A (en) * | 2023-12-29 | 2024-03-26 | 深圳市安信达存储技术有限公司 | Anti-radiation processing method for embedded memory chip in space environment satellite |
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Address after: No.61 Xiyan Road, Yanta District, Xi'an City, Shaanxi Province, 710054 Patentee after: Shaanxi Chemical Research Institute Co.,Ltd. Address before: No.61 Xiyan Road, Yanta District, Xi'an City, Shaanxi Province, 710054 Patentee before: SHAANXI RESEARCH DESIGN INSTITUTE OF PETROLEUM CHEMICAL INDUSTRY |