CN103275322A - Polysiloxane and catalytic synthesis method thereof - Google Patents
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Abstract
The invention relates to the technical field of synthesis of fine chemical industry and in particular relates to a polysiloxane and a catalytic synthesis method thereof. The synthetic method is as follows: first, adding a reactant Gamma-(2, 3-epoxypropoxy) propyltrimethoxysilicane and a reactant dimethyldiethoxylsilane in a reaction device, second, stirring the above mixture for 1-60 min at the room temperature, rising the temperature to 40-80 DEG C in water-bath or oil-bath, using organic dilute acids as catalysts, adding dropwise organic solvents, the organic dilute acids and deionized water one by one, and keeping a constant-temperature reaction for 2-12 h, third, removing the organic solvents by reduced pressure distillation, adding a methylbenzene solvent firstly, and then adding alkaline solid powder to neutralize the reaction solution until the reaction solution is neutral, fourth, removing undissolved substances by filtration under reduced pressure, removing the methylbenzene by reduced pressure distillation, so as to obtain the product polysiloxane K-D. The polysiloxane and the catalytic synthesis method thereof are advantaged by high processing efficiency, high yield rate of finished products, simple and mature process, low production cost, high economic benefits, and are suitable for mass production and sales.
Description
Technical field
The present invention relates to technical field of fine chemical synthesis, particularly a kind of polysiloxane and process for catalytic synthesis thereof.
Background technology
Polysiloxane has characteristics such as the good transparency, resistant of high or low temperature, weathering resistance, thermostability, is widely used in the modification and aviation field of novel cosmetic prescription, high temperature material, LED packaged material Resins, epoxy.The main organotin that uses is as catalyzer in the synthetic method of traditional polysiloxane, but organotin is a kind of toxic substance, contacts with human body, local hormesis to skin, respiratory tract, cornea, can cause the whole body poisoning by skin or cerebral edema, in addition dead.Therefore, European Union's successively issue regulations such as 89/677/EEC, 1999/51/EC and 2002/61/EC, the use of restriction organo-tin compound.
Chinese patent application number is 200610035149.9 patent of invention, a kind of synthetic method of polyoxy silane is disclosed, in reactor, add reaction monomers, catalyzer and water, after stirring at normal temperatures, reactor is placed microwave reaction field internal reaction, add the termination thing and namely get the polymerisate polysiloxane, it stops thing is carbonic acid gas, sulfuric acid or hydrochloric acid, and its catalyzer is potassium hydroxide or sodium hydroxide etc.This documents utilizes the method for microwave exposure to substitute traditional process for thermosynthesizing that adds, and reaction process does not need additionally to add water and carries out DeR.But there is following shortcoming in this documents: 1, must utilize microwave exposure, increase synthetic cost; 2, this synthetic method must be used the termination thing, has increased the difficulty of reactants separate; 3, adopt alkaline matter as catalyzer, be difficult to control the condensation reaction of silane coupling agent, be unfavorable for scale operation.
Chinese patent application number is 201210594059.9 patent of invention, a kind of chloromethyl poly(oxygen-silicon) alkane and synthetic method thereof of containing disclosed, its selected reactant is octamethylcyclotetrasiloxane, chloromethyl ring body, end-capping reagent and catalyzer, wherein, catalyzer is the vitriol oil, hydrochloric acid etc., end-capping reagent is hexamethyldisiloxane, 1,3-divinyl tetramethyl disiloxane etc.; Above-mentioned two reaction monomers dehydration back adding end-capping reagent and catalyzer are carried out polyreaction, heat up then, remove the small molecules low-boiling-point substance in the material under vacuum state, cooling makes chloride methyl polysiloxane.But this documents must be used end-capping reagent, increases the separating difficulty of reactant; Adopt the vitriol oil or hydrochloric acid as catalyzer, catalysis excessive velocities, uncontrollable reaction process, the product quality of chloride methyl polysiloxane are difficult to guarantee that product yield is lower.
Summary of the invention
The objective of the invention is provides a kind of process for catalytic synthesis of polyoxy silane at above-mentioned deficiency of the prior art, has the working (machining) efficiency height, finished product yield height, technology are simply ripe, and production cost is low, the economic benefit advantages of higher is suitable for scale operation and the sale of polysiloxane.
Another object of the present invention is at above-mentioned deficiency of the prior art, and a kind of polyoxy silane is provided, and has Heat stability is good, weathering resistance, the characteristics that high and low temperature resistance is good.
Purpose of the present invention is achieved through the following technical solutions.
A kind of process for catalytic synthesis of polysiloxane may further comprise the steps.
(1) in reaction unit, adds organic solvent, reactant γ-(2, the 3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane, the mol ratio of reactant γ-(2,3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane is 1:12～5:3.
The organic solvent effect is to make the dissolving of reactant γ-(2,3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane, for next step catalyzed reaction creates conditions.Wherein, reactant γ-(2,3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane are that common commercially available product all can.
(2) with above-mentioned reactant γ-(2, the 3-glycidoxy) mixture of propyl trimethoxy silicane and reactant dimethyldiethoxysilane composition at room temperature stirred 1～60 minute, water-bath or oil bath are warming up to 40～80 ℃, with organic diluted acid as catalyzer, drip organic solvent, organic diluted acid and deionized water one by one, total mol ratio of organic solvent and mixture is 1:1～1:3, total mol ratio of organic diluted acid and mixture is 0.01:1～1:1, total mol ratio of deionized water and mixture is 1:1～2:1, dropwises back isothermal reaction 2～12 hours.
As catalyzer, provide protonic acid to reactant with organic diluted acid, impel chemical reaction takes place between the reactant, accelerate speed of reaction, enhance productivity.The effect of deionized water is to promote the alkoxyl group hydrolysis but can generate water in the reaction process simultaneously, so should control the consumption of deionized water, making total mol ratio of deionized water and mixture is 1:1～2:1, avoids the carrying out of excessive water inhibited reaction.
(3) organic solvent is removed in underpressure distillation, adds solvent toluene to product and dissolves again, adds alkali solid powder neutralization reaction liquid then to neutral.
The purpose of this step is the acid in the neutralization reaction, and organic diluted acid salt of formation is insoluble to toluene, can remove, and toluene can dissolve organism such as K-D, can't dissolve inorganics, is convenient to both and separates; Select for use in addition toluene can make unreacted completely reactant further reacted in this step, total mol ratio of product and toluene is: 1:1～1:3.
(4) decompress filter is removed insolubles, carries out underpressure distillation again and removes toluene, can obtain reaction product polysiloxane K-D.
Is the chemical name of reaction product polysiloxane K-D? are its characteristic or advantage?
Wherein, in the described step (1), the mol ratio of reactant γ-(2,3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane is 1:4～3:2.
Wherein, in the described step (2), described organic solvent is at least a in tetrahydrofuran (THF), ethanol or the methyl alcohol.
Preferably, described organic solvent is tetrahydrofuran (THF), and tetrahydrofuran (THF) can form hydrogen bond with intermediate product in reaction process, inhibited reaction speed, and the product viscosity that is unlikely to generate is excessive.Wherein, intermediate product is exactly the product that reacts with reactant DEDMS of a siloxane bond fracture among the reactant KH-560, perhaps the product that reacts with reactant DEDMS of two siloxane bonds fractures of a siloxane bond fracture among the reactant KH-560.
Tetrahydrofuran (THF) is the heterocycle organic compound, and it is one of the strongest polarity ethers, is used as a kind of solvent of middle polarity when chemical reaction and extraction.It is colourless transparent liquid, and ethereal odor is arranged, relative density 0.89, molecular weight 72.11, fusing point-108.5 ℃, 66 ℃ of boiling points, flash-point-17.2 ℃, 321.1 ℃ of spontaneous ignition temperatures, refractive index 1.407.The organic liquid that tetrahydrofuran (THF) (THF) is colourless, can have less viscosity miscible with water, at normal temperatures and pressures, the chemical formula of this heterogeneous ring compound can be write (CH
2)
4O is because it is that a kind of liquid scope is very long, so be a kind of middle polarity non-protonic solvent commonly used.Its main application is to make the precursor of high molecular polymer.Tetrahydrofuran (THF) is a kind of important organic synthesis raw material and is the solvent of excellent property that be specially adapted to dissolve PVC, polyvinylidene chloride and butylaniline are widely used as topcoating, protective system, printing
Printing ink, tape and film coating solvent, and as reaction solvent.
The molecular formula of ethanol is C
2H
5OH is a kind of of alcohols, is the major ingredient of wine, is commonly called as alcohol, and it is a kind of inflammable, volatile colourless transparent liquid under normal temperature, normal pressure, and its aqueous solution has special, pleasant fragrance, and slightly with irritating.Ethanol is a kind of good solvent, can dissolve many
Inorganics, can dissolve many organism again, so ethanol commonly used dissolves plant pigments or medicinal ingredients wherein, also ethanol commonly used all can dissolve organism and the inorganics of participating in reaction as the solvent of reaction, increases contact area, improves speed of reaction.The physical properties of ethanol is main relevant with the character of its low-carbon (LC) straight chain alcohol.Hydroxyl in the molecule can form
Hydrogen bond, so the ethanol viscosity is very big, also not as good as close
Relative molecular mass Organic compoundPolarity is big.Under the room temperature, ethanol is colourless inflammable, and the volatile liquid of peat-reek is arranged.As solvent, ethanol is volatile, and can with water,
Acetic acid,
Acetone, benzene,
Tetracol phenixin, chloroform, ether,
Ethylene glycol, glycerine, nitro
Methane,
PyridineWith
TolueneEqual solvent is miscible.
Methyl alcohol (molecular formula CH
3OH) being a kind of organic compound, is the simplest alcohols.Methyl alcohol is very light, volatility is high, colourless, inflammable and poisonous.Be typically used as solvent, frostproofer, fuel or neutralizing agent.Another name: another name for, another name for.Outward appearance and proterties: achromaticity and clarification liquid has irritating smell.Little have an alcohol like smell, volatile, easily flow, blue flame is smokelessly arranged during burning, can dissolve each other with organic solvents such as water, alcohol, ethers, can with multiple compound formation azeotropic mixture, can be miscible with multiple compound formation solvent, solubility property is better than ethanol, can dissolve the plurality of inorganic salt class, as sodium iodide,
Calcium chloride,
Ammonium nitrate, copper sulfate,
Silver Nitrate, ammonium chloride and sodium-chlor etc.
Wherein, in the described step (2), described organic diluted acid catalyzer is dilute sulphuric acid or dilute hydrochloric acid.
Preferably, the dilute sulphuric acid that described organic diluted acid is 25% massfraction or the dilute sulphuric acid of 17% massfraction for reactant provides protonic acid, are conducive to impel reactant generation chemical reaction, improve speed of reaction, the dilute sulphuric acid volatility than dilute hydrochloric acid a little less than.
Reaction mechanism of the present invention (1) is:
Wherein,
Reaction mechanism of the present invention (2) is:
Wherein,
Wherein, in the described step (2), described churning time is 1～30 minute, and water-bath or oil bath intensification temperature are 50～70 ℃, and the isothermal reaction time is 5～10 hours, guarantees that reactant fully reacts.
Wherein, in the described step (2), total mol ratio of described organic solvent and mixture is 1:1～1:2.5, and total mol ratio of organic diluted acid and mixture is 0.01:1～0.05:1, and total mol ratio of deionized water and mixture is 1:1～1.5:1.
Wherein, in the described step (3), the alkali solid powder is at least a in sodium bicarbonate, yellow soda ash, salt of wormwood, sodium hydroxide, potassium hydroxide or the calcium hydroxide.
The alkali solid powder is used for organic diluted acid of neutralization reaction, and organic diluted acid salt of formation is insoluble to toluene and removes.
The sodium bicarbonate sodium bicarbonate is commonly called as " sodium bicarbonate ", " soda powder ", " bicarb of soda ", white fine crystals, and the solubleness in water is less than yellow soda ash.Sodium bicarbonate disengages carbonic acid gas (CO beginning to work after water is combined
2), present weakly alkaline when water-soluble.Sodium bicarbonate is a kind of white alkaline powder soluble in water, disengages carbonic acid gas CO beginning to work after water is combined
2, in acidic liquid, react faster, and along with envrionment temperature raises, the effect that disengages gas is faster.
Yellow soda ash is white powder or particle, and odorlessness has alkalescence, is the salt of alkalescence, and water-absorbent is arranged.Begin to lose in the time of 400 ℃
Carbonic acid gas, to meet acid and decompose and effervesce, water-soluble and glycerine is insoluble to
EthanolThe aqueous solution is strong basicity,
PH11.6, relative density 2.53,851 ℃ of fusing points have pungency.
The chemical formula K of salt of wormwood
2CO
3, relative molecular mass: 138.19, proterties: colourless crystallization or white particle.Water absorbability is arranged.Non-hygroscopic after containing abundant moisture, soluble in water, be dissolved in ethanol hardly.The aqueous solution is strong basicity, and pungency is arranged.
Sodium hydroxide, molecular formula is NaOH, has severe corrosive, and its aqueous solution is strong basicity, and pure cerium hydroxide sodium is that white solid can and have water absorbability with particle, and sodium hydroxide is dissolved in ethanol and methyl alcohol, with acid neutralization reaction can take place.
Potassium hydroxide (chemical formula: KOH), caustic potash, white solid, water-soluble, pure, but be insoluble to ether.Very easily moisture absorption and deliquescence in air.Can generate salt of wormwood with carbon dioxide reaction, can the acid-base neutralisation reaction can take place with acid.
Calcium hydroxide chemical formula Ca (OH)
2Be commonly called as white lime, liming, or slaked lime, white solid is slightly soluble in water, and its aqueous solution often is called liming, is alkalescence.Thereby absorbing carbon dioxide and water etc. are rotten in air, claim it to have water-absorbent usually, and calcium hydroxide can be followed acid-respons, generate salt and water.Wherein, in the described step (1), the structural formula of reactant γ-(2,3-glycidoxy) propyl trimethoxy silicane is:
,
The structural formula of reactant dimethyldiethoxysilane is:
Reactant γ-(2,3-glycidoxy) propyl trimethoxy silicane, another name silane coupling agent KH-560, these product are colourless transparent liquid, are soluble in the multiple organic solvent facile hydrolysis, condensation forms polysiloxane, and is overheated, and there are easy polymerization down in illumination, superoxide, 120 ℃ of boiling points, quality standard: the appearance colorless transparent liquid, can make two kinds of material couplings, improve products machinery intensity, improve matrix material electrical property, weather-proof and solidity to corrosion, be applicable to glass reinforced plastic/tackiness agent etc.
Reactant dimethyldiethoxysilane (DEDMS), molecular formula are (CH
3) 2Si (C
2H
5O)
2, colourless transparent liquid.Be mainly used in the constitution controller in the silicon rubber preparation, chainextender and silicone oil synthesis material during organosilicon product is synthetic.Chinese another name: di ethoxy di methyl-monosilane, diethoxy dimethyl silicon alkane, molecular formula: (CH
3) 2Si (C
2H
5O)
2, molecular weight 148.28, proterties: colourless transparent liquid.
Another object of the present invention is achieved through the following technical solutions.
A kind of polysiloxane, its structural formula is as follows:
Wherein,
Wherein, the viscosity of polyoxy silane is 1000～5000cps.Preferably, its viscosity is 1300～4500cps.
Beneficial effect of the present invention:
(1) catalyzer is selected the dilute sulphuric acid of 25% massfraction or the dilute hydrochloric acid of 17% massfraction for use, avoid using the use of toxic substance organotin, and solvent cheap, be simple and easy to, postprocessing working procedures is simple, is suitable for scale operation.
(2) viscosity of the polysiloxane K-D that makes reaches 1000～5000 cps, and productive rate is 45～75%, has Heat stability is good, and weathering resistance, the characteristics that high and low temperature resistance is good are applied in the Electronic Packaging technology effective.
(3) technical maturity of the present invention, simple, stable reaction is conducive to general promotion and application, the economic benefit height.
(4) utilize polysiloxane K-D that method of the present invention makes and epoxy blend to prepare to have the good transparency, the product of resistant of high or low temperature (second-order transition temperature increases with K-D content and descends, as table 1), weathering resistance, thermostability characteristics such as (as table 2).
The second-order transition temperature of table 1 K-D modified bisphenol A type Resins, epoxy 828.
The thermogravimetric parameter of the unmodified bisphenol A type epoxy resin 828 of table 2 and K-D modified bisphenol A type Resins, epoxy 828.
| Numbering | T d5%(℃) | T d50%(℃) | R 750(%) |
| Unmodified epoxy resin 828 | 355 | 412 | 13.5 |
| P-5%K-D | 452 | 495 | 24.3 |
| P-15%K-D | 429 | 493 | 26.5 |
Embodiment
With the following Examples the present invention is further described.
Embodiment 1.
A kind of process for catalytic synthesis of polysiloxane may further comprise the steps:
(1) in the four-hole boiling flask that has reflux condensing tube, thermometer, dropping funnel and stirring rake, adds reactant γ-(2, the 3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane, the mol ratio of reactant γ-(2,3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane is 1:12;
(2) above-mentioned reaction mixture was at room temperature stirred 1 minute, water-bath or oil bath are warming up to 80 ℃, with the dilute sulphuric acid of 25% massfraction as catalyzer, utilize dropping funnel slowly to drip dilute sulphuric acid and the deionized water of organic solvent tetrahydrofuran, 25% massfraction, total mol ratio of described organic solvent and mixture is 1:1.07, total mol ratio of dilute sulphuric acid and mixture is 0.01:1, and total mol ratio of deionized water and mixture is 1:1, dropwises back isothermal reaction 2 hours;
(3) organic solvent is removed in underpressure distillation, adds solvent toluene to product and dissolves again, adds alkali solid powder sodium bicarbonate neutralization reaction liquid then to neutral;
(4) decompress filter is removed insolubles, carries out underpressure distillation again and removes toluene, can obtain reaction product polysiloxane K-D.
The viscosity of the product polysiloxane K-D that the present invention makes is 1085cps, and productive rate is 74.6%.
Embodiment 2.
A kind of process for catalytic synthesis of polysiloxane may further comprise the steps:
(1) in the four-hole boiling flask that has reflux condensing tube, thermometer, dropping funnel and stirring rake, adds reactant γ-(2, the 3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane, the mol ratio of reactant γ-(2,3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane is 5:12;
(2) above-mentioned reaction mixture was at room temperature stirred 15 minutes, water-bath or oil bath are warming up to 70 ℃, with the dilute hydrochloric acid of 17% massfraction as catalyzer, utilize dropping funnel slowly to drip dilute hydrochloric acid and the deionized water of organic solvent ethanol, 17% massfraction, total mol ratio of described organic solvent and mixture is 1:1.53, total mol ratio of dilute hydrochloric acid and mixture is 0.03:1, and total mol ratio of deionized water and mixture is 1.2:1, dropwises back isothermal reaction 5 hours;
(3) organic solvent is removed in underpressure distillation, adds solvent toluene to product and dissolves again, adds alkali solid powder yellow soda ash neutralization reaction liquid then to neutral;
(4) decompress filter is removed insolubles, carries out underpressure distillation again and removes toluene, can obtain reaction product polysiloxane K-D.
The viscosity of the product polysiloxane K-D that the present invention makes is 1365cps, and productive rate is 69.2%.
Embodiment 3.
A kind of process for catalytic synthesis of polysiloxane may further comprise the steps:
(1) reactant γ-(2 in the four-hole boiling flask that has reflux condensing tube, thermometer, dropping funnel and stirring rake, the 3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane, the mol ratio of reactant γ-(2,3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane is 5:6;
(2) above-mentioned reaction mixture was at room temperature stirred 30 minutes, water-bath or oil bath are warming up to 60 ℃, with the dilute sulphuric acid of 25% massfraction as catalyzer, utilize dropping funnel slowly to drip dilute sulphuric acid and the deionized water of organic solvent methyl alcohol, 25% massfraction, total mol ratio of described organic solvent and mixture is 1:1.96, total mol ratio of dilute sulphuric acid and mixture is 0.05:1, and total mol ratio of deionized water and mixture is 1.5:1, dropwises back isothermal reaction 7 hours;
(3) organic solvent is removed in underpressure distillation, adds solvent toluene to product and dissolves again, adds alkali solid powder salt of wormwood neutralization reaction liquid then to neutral;
(4) decompress filter is removed insolubles, carries out underpressure distillation again and removes toluene, can obtain reaction product polysiloxane K-D.
The viscosity of the product polysiloxane K-D that the present invention makes is 2871cps, and productive rate is 49.6%.
Embodiment 4.
A kind of process for catalytic synthesis of polysiloxane may further comprise the steps:
(1) in the four-hole boiling flask that has reflux condensing tube, thermometer, dropping funnel and stirring rake, adds reactant γ-(2, the 3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane, the mol ratio of reactant γ-(2,3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane is 5:4;
(2) above-mentioned reaction mixture was at room temperature stirred 45 minutes, water-bath or oil bath are warming up to 50 ℃, with the dilute sulphuric acid of 25% massfraction as catalyzer, utilize dropping funnel slowly to drip dilute sulphuric acid and the deionized water of organic solvent tetrahydrofuran, 25% massfraction, total mol ratio of described organic solvent and mixture is 1:2.19, total mol ratio of dilute sulphuric acid and mixture is 0.08:1, and total mol ratio of deionized water and mixture is 1.7:1, dropwises back isothermal reaction 9 hours;
(3) organic solvent is removed in underpressure distillation, adds solvent toluene to product and dissolves again, adds alkali solid powdered sodium hydroxide neutralization reaction liquid then to neutral;
(4) decompress filter is removed insolubles, carries out underpressure distillation again and removes toluene, can obtain reaction product polysiloxane K-D.
The viscosity of the product polysiloxane K-D that the present invention makes is 3450cps, and productive rate is 56.8%.
Embodiment 5.
A kind of process for catalytic synthesis of polysiloxane may further comprise the steps:
(1) in the four-hole boiling flask that has reflux condensing tube, thermometer, dropping funnel and stirring rake, adds reactant γ-(2, the 3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane, the mol ratio of reactant γ-(2,3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane is 5:3;
(2) above-mentioned reaction mixture was at room temperature stirred 60 minutes, water-bath or oil bath are warming up to 40 ℃, with the dilute hydrochloric acid of 17% massfraction as catalyzer, utilize dropping funnel slowly to drip dilute hydrochloric acid and the deionized water of organic solvent tetrahydrofuran, 17% massfraction, total mol ratio of described organic solvent and mixture is 1:2.41, total mol ratio of dilute hydrochloric acid and mixture is 0.09:1, and total mol ratio of deionized water and mixture is 1.95:1, dropwises back isothermal reaction 12 hours;
(3) organic solvent is removed in underpressure distillation, adds solvent toluene to product and dissolves again, adds alkali solid powder potassium hydroxide neutralization reaction liquid then to neutral;
(4) decompress filter is removed insolubles, carries out underpressure distillation again and removes toluene, can obtain reaction product polysiloxane K-D.
The viscosity of the product polysiloxane K-D that the present invention makes is 4480cps, and productive rate is 44.9%.
Should be noted that at last; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although with reference to preferred embodiment the present invention has been done to explain; those of ordinary skill in the art is to be understood that; can make amendment or be equal to replacement technical scheme of the present invention, and not break away from essence and the scope of technical solution of the present invention.
Claims (10)
1. the process for catalytic synthesis of a polysiloxane is characterized in that, may further comprise the steps:
(1) in reaction unit, adds reactant γ-(2, the 3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane, the mol ratio of reactant γ-(2,3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane is 1:12～5:3;
(2) with above-mentioned reactant γ-(2, the 3-glycidoxy) mixture of propyl trimethoxy silicane and reactant dimethyldiethoxysilane composition at room temperature stirred 1～60 minute, water-bath or oil bath are warming up to 40～80 ℃, with organic diluted acid as catalyzer, drip organic solvent, organic diluted acid and deionized water one by one, total mol ratio of organic solvent and mixture is 1:1～1:3, total mol ratio of organic diluted acid and mixture is 0.01:1～1:1, total mol ratio of deionized water and mixture is 1:1～2:1, dropwises back isothermal reaction 2～12 hours;
(3) organic solvent is removed in underpressure distillation, adds solvent toluene to product and dissolves again, adds alkali solid powder neutralization reaction liquid then to neutral;
(4) decompress filter is removed insolubles, carries out underpressure distillation again and removes toluene, can obtain reaction product polysiloxane K-D.
2. the process for catalytic synthesis of a kind of polysiloxane according to claim 1, it is characterized in that: in the described step (1), the mol ratio of reactant γ-(2,3-glycidoxy) propyl trimethoxy silicane and reactant dimethyldiethoxysilane is 1:4～3:2.
3. the process for catalytic synthesis of a kind of polysiloxane according to claim 1 is characterized in that: in the described step (2), described organic solvent is at least a in tetrahydrofuran (THF), ethanol or the methyl alcohol.
4. the process for catalytic synthesis of a kind of polysiloxane according to claim 1, it is characterized in that: in the described step (2), described organic diluted acid catalyzer is dilute sulphuric acid or dilute hydrochloric acid.
5. the process for catalytic synthesis of a kind of polysiloxane according to claim 1, it is characterized in that: in the described step (2), described churning time is 1～30 minute, and water-bath or oil bath intensification temperature are 50～70 ℃, and the isothermal reaction time is 5～10 hours.
6. the process for catalytic synthesis of a kind of polysiloxane according to claim 1, it is characterized in that: in the described step (2), total mol ratio of described organic solvent and mixture is 1:1～1:2.5, total mol ratio of organic diluted acid and mixture is 0.01:1～0.05:1, and total mol ratio of deionized water and mixture is 1:1～1.5:1.
7. the process for catalytic synthesis of a kind of polysiloxane according to claim 1 is characterized in that: in the described step (3), the alkali solid powder is at least a in sodium bicarbonate, yellow soda ash, salt of wormwood, sodium hydroxide, potassium hydroxide or the calcium hydroxide.
8. the process for catalytic synthesis of a kind of polysiloxane according to claim 1, it is characterized in that: in the described step (1), the structural formula of reactant γ-(2,3-glycidoxy) propyl trimethoxy silicane is:
,
The structural formula of reactant dimethyldiethoxysilane is:
9. the polysiloxane that the process for catalytic synthesis of any described a kind of polysiloxane makes in the claim 1～8, it is characterized in that: its structural formula is as follows:
Wherein,
10. a kind of polysiloxane according to claim 9, it is characterized in that: its viscosity is 1000～5000cps.
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| CN104387589A (en) * | 2014-11-14 | 2015-03-04 | 东莞兆舜有机硅新材料科技有限公司 | High-refractivity LED (light-emitting diode) packaging adhesive tackifier, and preparation method and application thereof |
| CN105038233A (en) * | 2014-04-17 | 2015-11-11 | 松下知识产权经营株式会社 | Resin composition and method for manufacturing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712760A (en) * | 2009-11-06 | 2010-05-26 | 株洲时代电气绝缘有限责任公司 | Organic silicone resin containing epoxy groups and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712760A (en) * | 2009-11-06 | 2010-05-26 | 株洲时代电气绝缘有限责任公司 | Organic silicone resin containing epoxy groups and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038233A (en) * | 2014-04-17 | 2015-11-11 | 松下知识产权经营株式会社 | Resin composition and method for manufacturing the same |
| CN105038233B (en) * | 2014-04-17 | 2020-06-23 | 松下知识产权经营株式会社 | Resin composition and method for producing same |
| CN104387589A (en) * | 2014-11-14 | 2015-03-04 | 东莞兆舜有机硅新材料科技有限公司 | High-refractivity LED (light-emitting diode) packaging adhesive tackifier, and preparation method and application thereof |
| CN104387589B (en) * | 2014-11-14 | 2017-02-22 | 东莞兆舜有机硅科技股份有限公司 | High-refractivity LED (light-emitting diode) packaging adhesive tackifier, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
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| CN103275322B (en) | 2015-07-15 |
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