CN103275322B - Polysiloxane and catalytic synthesis method thereof - Google Patents
Polysiloxane and catalytic synthesis method thereof Download PDFInfo
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- -1 Polysiloxane Polymers 0.000 title claims abstract description 42
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000376 reactant Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003960 organic solvent Substances 0.000 claims abstract description 32
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 14
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- 239000000047 product Substances 0.000 claims description 24
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 21
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- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 4
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 125000003545 alkoxy group Chemical group 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
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- MVGLBXWFOSHCCP-UHFFFAOYSA-N chloroform;tetrachloromethane Chemical compound ClC(Cl)Cl.ClC(Cl)(Cl)Cl MVGLBXWFOSHCCP-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
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- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical group C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
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- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
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- Silicon Polymers (AREA)
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 invention relates to the technical field of fine chemical synthesis, and particularly relates to polysiloxane and a catalytic synthesis method thereof.
Background
Polysiloxane has the characteristics of good transparency, high and low temperature resistance, weather resistance, thermal stability and the like, and is widely applied to the fields of novel cosmetic formulations, high temperature resistant materials, modification of epoxy resin of LED packaging materials and aviation. In the traditional synthesis method of polysiloxane, organotin is mainly used as a catalyst, but organotin is a toxic substance, has the irritation effect on skin, respiratory tract and cornea when contacting with a human body, and can cause general poisoning and even death through skin or brain edema. Thus, the European Union has issued the 89/677/EEC, 1999/51/EC, and 2002/61/EC regulations in tandem, limiting the use of organotin compounds.
The invention patent with Chinese patent application number 200610035149.9 discloses a method for synthesizing polyoxosilane, which comprises the steps of adding reaction monomers, a catalyst and water into a reactor, stirring at normal temperature, placing the reactor in a microwave reaction field for reaction, and adding a terminator to obtain a polymerization product polysiloxane, wherein the terminator is carbon dioxide, sulfuric acid or hydrochloric acid, and the catalyst is potassium hydroxide or sodium hydroxide and the like. The comparison document replaces the traditional heating synthesis method with a microwave irradiation method, and no additional water is needed to carry out degradation reaction in the reaction process. However, the comparison document has the following disadvantages: 1. microwave irradiation is required, so that the synthesis cost is increased; 2. the synthesis method must use a terminator, so that the difficulty of reactant separation is increased; 3. the condensation reaction of the silane coupling agent is difficult to control by using an alkaline substance as a catalyst, which is not favorable for large-scale production.
The invention patent with Chinese patent application number 201210594059.9 discloses chloromethyl-containing polyoxosilane and a synthesis method thereof, wherein the selected reactants are octamethylcyclotetrasiloxane, chloromethyl ring bodies, an end-capping reagent and a catalyst, wherein the catalyst is concentrated sulfuric acid, hydrochloric acid and the like, and the end-capping reagent is hexamethyldisiloxane, 1, 3-divinyl tetramethyl disiloxane and the like; and (3) dehydrating the two reaction monomers, adding an end-capping reagent and a catalyst to carry out polymerization reaction, heating, removing micromolecular low-boiling-point substances in the materials in a vacuum state, and cooling to obtain the chloromethyl polysiloxane. However, the comparison document needs to use a blocking agent, so that the separation difficulty of reactants is increased; concentrated sulfuric acid or hydrochloric acid is used as a catalyst, the catalysis speed is too high, the reaction process cannot be controlled, the quality of the product containing chloromethyl polysiloxane is difficult to ensure, and the product yield is low.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a catalytic synthesis method of polysiloxane, has the advantages of high processing efficiency, high finished product yield, simple and mature process, low production cost, high economic benefit and the like, and is suitable for large-scale production and sale of polysiloxane.
The invention also aims to provide the polyoxosilane which has the characteristics of good thermal stability, good weather resistance and good high and low temperature resistance in view of the defects in the prior art.
The purpose of the invention is realized by the following technical scheme.
A method for the catalytic synthesis of polysiloxanes comprises the following steps.
(1) Adding an organic solvent, a reactant gamma- (2, 3-epoxy propoxy) propyl trimethoxy silane and a reactant dimethyl diethoxy silane into a reaction device, wherein the molar ratio of the reactant gamma- (2, 3-epoxy propoxy) propyl trimethoxy silane to the reactant dimethyl diethoxy silane is 1: 12-5: 3.
the organic solvent is used for dissolving the reactant gamma- (2, 3-epoxy propoxy) propyl trimethoxy silane and the reactant dimethyl diethoxy silane, thereby creating conditions for the next catalytic reaction. Wherein, the reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and the reactant dimethyl diethoxy silane are common commercial products.
(2) Stirring the mixture consisting of the reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and the reactant dimethyl diethoxy silane at room temperature for 1-60 minutes, heating to 40-80 ℃ in a water bath or oil bath, dropwise adding an organic solvent, an organic dilute acid and deionized water one by taking the organic dilute acid as a catalyst, wherein the total molar ratio of the organic solvent to the mixture is 1: 1-1: 3, wherein the total molar ratio of the organic dilute acid to the mixture is 0.01: 1-1: 1, the total molar ratio of the deionized water to the mixture is 1: 1-2: 1, and after the dropwise addition is finished, the constant-temperature reaction is carried out for 2-12 hours.
The organic dilute acid is used as a catalyst to provide protonic acid for reactants, promote chemical reaction between the reactants, accelerate the reaction rate and improve the production efficiency. The deionized water has the function of promoting alkoxy hydrolysis, but water is generated in the reaction process, so that the dosage of the deionized water is controlled to ensure that the total molar ratio of the deionized water to the mixture is 1: 1-2: 1, and the excessive water is prevented from inhibiting the reaction.
(3) Distilling under reduced pressure to remove the organic solvent, adding solvent toluene until the product is dissolved again, and then adding alkaline solid powder to neutralize the reaction liquid to neutrality.
The purpose of this step is to neutralize the acid in the reaction, the formed organic dilute acid salt is insoluble in toluene and can be removed, the toluene can dissolve organic matters such as K-D, etc., but can not dissolve inorganic matters, thus facilitating the separation of the two; the toluene is selected to further react the unreacted reactants, and the total molar ratio of the product to the toluene is as follows: 1: 1-1: 3.
(4) vacuum-filtering to remove insoluble substances, and then carrying out vacuum distillation to remove toluene, thus obtaining the reaction product polysiloxane K-D.
The chemical name of the reaction product polysiloxane K-D? Is its characteristic or advantage?
In the step (1), the molar ratio of the reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane to the reactant dimethyl diethoxy silane is 1: 4-3: 2.
wherein, in the step (2), the organic solvent is at least one of tetrahydrofuran, ethanol or methanol.
Preferably, the organic solvent is tetrahydrofuran, and the tetrahydrofuran can form hydrogen bonds with the intermediate product in the reaction process, so that the reaction rate is inhibited, and the viscosity of the generated product is not too high. Wherein the intermediate product is a product obtained by breaking one silicon-oxygen bond in reactant KH-560 to react with reactant DEDMS, or a product obtained by breaking two silicon-oxygen bonds in reactant KH-560 to react with reactant DEDMS.
Tetrahydrofuran is a heterocyclic organic compound which is one of the most polar ethers and is used as a moderately polar solvent in chemical reactions and extractions. It is colorless transparent liquid with ether-like smell, relative density of 0.89, molecular weight of 72.11, melting point of-108.5 deg.c, boiling point of 66 deg.c, flash point of-17.2 deg.c, self-ignition point of 321.1 deg.c and refractive index of 1.407. Tetrahydrofuran (THF) is a colorless, water-miscible, less viscous organic liquid at ordinary temperature and pressure, and the formula of this heterocyclic compound can be written as (CH)2)4O, a commonly used one because it is a liquid with a long rangeA moderately polar aprotic solvent. Its main use is as a precursor of high molecular polymers. Tetrahydrofuran is an important organic synthetic raw material and is a solvent with excellent performance, is particularly suitable for dissolving PVC, polyvinylidene chloride and butylaniline, and is widely used as surface coating, anticorrosive coating and printingPrinting inkAnd solvents for magnetic tapes and film coatings, and as reaction solvents.
The molecular formula of the ethanol is C2H5OH, one of alcohols, is a main component of wine, is commonly called alcohol, is flammable and volatile colorless transparent liquid at normal temperature and normal pressure, and has special and pleasant fragrance and slight irritation in an aqueous solution. Ethanol is a very good solvent, and can dissolve a lot of ethanolInorganic substanceAnd can also dissolve a plurality of organic matters, so that ethanol is commonly used for dissolving plant pigments or medicinal components in the plant pigments, and the ethanol is also commonly used as a solvent for reaction, so that the organic matters and inorganic matters which participate in the reaction can be dissolved, the contact area is enlarged, and the reaction rate is improved. The physical properties of ethanol are mainly related to the properties of its lower linear alcohols. Hydroxyl groups in the molecule may formHydrogen bondsTherefore, the viscosity of ethanol is very high and is not close to that of ethanolRelative molecular massIs/are as followsOrganic compoundsThe polarity is large. At room temperature, ethanol is a colorless, flammable, and specially scented volatile liquid. As a solvent, ethanol is volatile and can be mixed with water,Acetic acid、Acetone (II)Benzene, benzene,Carbon tetrachlorideChloroform, diethyl ether,Ethylene glycolGlycerin, nitroMethane、Pyridine compoundAndtolueneAnd the like.
Methanol (molecular formula CH)3OH) is an organic compound, the simplest alcohol. Methanol is very light, highly volatile, colorless, flammable and toxic. Are commonly used as solvents, antifreeze, fuels or neutralizers. Alias: xylitol, wood essence. Appearance and properties: colorless clear liquid with pungent odor. Has little ethanol-like smell, is easy to volatilize and flow, has no smoke and blue flame during combustion, can be mutually dissolved with organic solvents such as water, alcohol, ether and the like, can form an azeotropic mixture with various compounds, can form a solvent mixture with various compounds, and has solubilityCan be superior to ethanol, and can dissolve various inorganic salts, such as sodium iodide,Calcium chloride、Ammonium nitrateCopper sulfate, copper sulfate,Silver nitrateAmmonium chloride and sodium chloride, and the like.
Wherein, in the step (2), the organic dilute acid catalyst is dilute sulfuric acid or dilute hydrochloric acid.
Preferably, the organic dilute acid is 25% by mass of dilute sulfuric acid or 17% by mass of dilute sulfuric acid, provides protonic acid for reactants, is favorable for promoting the reactants to perform chemical reaction, improves the reaction rate, and has weaker volatility than dilute hydrochloric acid.
The reaction mechanism (1) of the present invention is:
wherein,。
the reaction mechanism (2) of the present invention is:
wherein,。
in the step (2), the stirring time is 1-30 minutes, the temperature of the water bath or oil bath is 50-70 ℃, and the constant-temperature reaction time is 5-10 hours, so that the reactants are ensured to fully react.
In the step (2), the total molar ratio of the organic solvent to the mixture is 1: 1-1: 2.5, the total molar ratio of the organic dilute acid to the mixture is 0.01: 1-0.05: 1, and the total molar ratio of the deionized water to the mixture is 1: 1-1.5: 1.
Wherein in the step (3), the alkaline solid powder is at least one of sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or calcium hydroxide.
The alkaline solid powder is used for neutralizing organic dilute acid in the reaction, and the formed organic dilute acid salt is insoluble in toluene and is removed.
Sodium bicarbonate, commonly known as "baking soda", "soda ash" or "bicarbonates", is a white fine crystal, having a solubility in water lower than that of sodium carbonate. Sodium bicarbonate starts to work to liberate carbon dioxide (CO) after binding with water2) And exhibits weak alkalinity when dissolved in water. Sodium bicarbonate, a white alkaline powder readily soluble in water, begins to act upon water to liberate carbon dioxide, CO2The reaction is faster in acidic liquids, and the effect of the evolved gas is faster as the ambient temperature increases.
The sodium carbonate is white powder or granule, has no odor, is alkaline salt, and has water absorption. Begin to lose at 400 DEG CCarbon dioxideIt can be decomposed and effervesced in the presence of acid, is soluble in water and glycerin, and is insoluble in water and glycerinEthanol. The water solution is in strong alkalinity,pH11.6, relative density 2.53, melting point 851 ℃ and pungency.
Chemical formula K of potassium carbonate2CO3138.19, relative molecular mass, property: colorless crystals or white particles. It has hygroscopic property. When the water content is sufficient, the water-soluble organic compound is not hygroscopic, is easily soluble in water and is hardly soluble in ethanol. The aqueous solution is strongly alkaline and irritant.
The molecular formula of the sodium hydroxide is NaOH, the sodium hydroxide has strong corrosivity, the water solution of the sodium hydroxide is strong alkaline, the pure sodium hydroxide is white solid available particles and has hygroscopicity, and the sodium hydroxide is dissolved in ethanol and methanol and can be subjected to neutralization reaction with acid.
Potassium hydroxide (formula: KOH), commonly known as caustic potash, is a white solid that is soluble in water, alcohols, but insoluble in ethers. Is extremely hygroscopic and deliquescent in air. Can react with carbon dioxide to generate potassium carbonate, and can generate acid-base neutralization reaction with acid.
Calcium hydroxide of the formula Ca (OH)2Commonly known as hydrated lime, limewater, or slaked lime, a white solid, slightly soluble in water, and an aqueous solution thereof, commonly known as limewater, is basic. The air is modified by absorbing carbon dioxide, water and the like, and is generally called as water-absorbing, and calcium hydroxide can react with acid to generate salt and water. Wherein, in the step (1), the reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane has a structural formula as follows:，
the structural formula of reactant dimethyldiethoxysilane is as follows:。
the reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is named as silane coupling agent KH-560, is colorless transparent liquid, is easily dissolved in various organic solvents, is easy to hydrolyze, is condensed to form polysiloxane, is easy to polymerize in the presence of overheat, illumination and peroxide, and has the boiling point of 120 ℃ and the quality standard: the appearance is colorless transparent liquid, the two materials can be coupled, the mechanical strength of the product is improved, the electrical property, the weather resistance and the corrosion resistance of the composite material are improved, and the composite material is suitable for glass fiber reinforced plastic/adhesives and the like.
Reactant dimethyldiethoxysilane (DEDMS) with molecular formula of (CH)3)2Si(C2H5O)2And colorless transparent liquid. The preparation method is mainly used for a structure control agent in the preparation of silicon rubber, a chain extender in the synthesis of an organic silicon product and a silicon oil synthesis raw material. Chinese alias: diethoxydimethylsilane, molecular formula: (CH)3)2Si(C2H5O)2Molecular weight 148.28, property: a colorless transparent liquid.
The other purpose of the invention is realized by the following technical scheme.
A polysiloxane having the formula:
wherein,。
wherein the viscosity of the polyoxosilane is 1000 to 5000 cps. Preferably, the viscosity is 1300 to 4500 cps.
The invention has the beneficial effects that:
(1) the catalyst is 25 percent of dilute sulfuric acid or 17 percent of dilute hydrochloric acid by mass, the use of toxic organic tin is avoided, the solvent is low in price, simple and easy to obtain, the post-treatment process is simple, and the method is suitable for large-scale production.
(2) The viscosity of the prepared polysiloxane K-D reaches 1000-5000 cps, the yield is 45-75%, and the polysiloxane K-D has the characteristics of good thermal stability, weather resistance and high and low temperature resistance, and has a good effect when being applied to an electronic packaging technology.
(3) The method has the advantages of mature and simple process, stable reaction, contribution to general popularization and application and high economic benefit.
(4) The polysiloxane K-D prepared by the method of the invention can be blended with epoxy resin to prepare products with the characteristics of good transparency, high and low temperature resistance (the glass transition temperature is reduced along with the increase of the content of the K-D, as shown in Table 1), weather resistance, thermal stability (as shown in Table 2) and the like.
TABLE 1 glass transition temperature of K-D modified bisphenol A epoxy resin 828.
TABLE 2 thermogravimetric parameters of unmodified bisphenol A epoxy 828 and K-D modified bisphenol A epoxy 828.
| Numbering | Td5%(℃) | Td50%(℃) | R750(%) |
| Unmodified epoxy resin 828 | 355 | 412 | 13.5 |
| P-5%K-D | 452 | 495 | 24.3 |
| P-15%K-D | 429 | 493 | 26.5 |
Detailed Description
The invention is further described with reference to the following examples.
Example 1.
A method for the catalytic synthesis of polysiloxanes, comprising the steps of:
(1) adding a reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and a reactant dimethyl diethoxy silane into a four-neck flask with a reflux condenser, a thermometer, a dropping funnel and a stirring paddle, wherein the molar ratio of the reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane to the reactant dimethyl diethoxy silane is 1: 12;
(2) stirring the reaction mixture at room temperature for 1 minute, heating the reaction mixture to 80 ℃ in a water bath or an oil bath, slowly dropwise adding an organic solvent tetrahydrofuran, 25% of dilute sulfuric acid and deionized water by using 25% of mass fraction as a catalyst by using a dropping funnel, wherein the total molar ratio of the organic solvent to the mixture is 1:1.07, the total molar ratio of the dilute sulfuric acid to the mixture is 0.01:1, the total molar ratio of the deionized water to the mixture is 1:1, and reacting at constant temperature for 2 hours after the dropwise adding is finished;
(3) distilling under reduced pressure to remove the organic solvent, adding a solvent toluene until the product is dissolved again, and then adding alkaline solid powder sodium bicarbonate to neutralize the reaction liquid to be neutral;
(4) vacuum-filtering to remove insoluble substances, and then carrying out vacuum distillation to remove toluene, thus obtaining the reaction product polysiloxane K-D.
The product polysiloxane K-D prepared by the invention has a viscosity of 1085cps and a yield of 74.6%.
Example 2.
A method for the catalytic synthesis of polysiloxanes, comprising the steps of:
(1) adding a reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and a reactant dimethyl diethoxy silane into a four-neck flask with a reflux condenser, a thermometer, a dropping funnel and a stirring paddle, wherein the molar ratio of the reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane to the reactant dimethyl diethoxy silane is 5: 12;
(2) stirring the reaction mixture at room temperature for 15 minutes, heating the reaction mixture to 70 ℃ in a water bath or an oil bath, slowly dropwise adding an organic solvent ethanol, 17% by mass of dilute hydrochloric acid and deionized water by using a dropping funnel by taking 17% by mass of dilute hydrochloric acid as a catalyst, wherein the total molar ratio of the organic solvent to the mixture is 1: 1.53, the total molar ratio of the dilute hydrochloric acid to the mixture is 0.03:1, the total molar ratio of the deionized water to the mixture is 1.2:1, and the mixture reacts for 5 hours at constant temperature after the dropwise addition;
(3) distilling under reduced pressure to remove the organic solvent, adding a solvent toluene until the product is dissolved again, and then adding alkaline solid powder sodium carbonate to neutralize the reaction liquid to be neutral;
(4) vacuum-filtering to remove insoluble substances, and then carrying out vacuum distillation to remove toluene, thus obtaining the reaction product polysiloxane K-D.
The product polysiloxane K-D prepared by the invention has the viscosity of 1365cps and the yield of 69.2%.
Example 3.
A method for the catalytic synthesis of polysiloxanes, comprising the steps of:
(1) in a four-neck flask with reflux condenser, thermometer, dropping funnel and stirring paddle, the mole ratio of the reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane to the reactant dimethyldiethoxy silane is 5: 6;
(2) stirring the reaction mixture at room temperature for 30 minutes, heating the reaction mixture to 60 ℃ in a water bath or an oil bath, slowly dropwise adding an organic solvent methanol, 25% of dilute sulfuric acid and deionized water by using a dropping funnel by using 25% of dilute sulfuric acid as a catalyst, wherein the total molar ratio of the organic solvent to the mixture is 1: 1.96, the total molar ratio of the dilute sulfuric acid to the mixture is 0.05:1, the total molar ratio of the deionized water to the mixture is 1.5:1, and after the dropwise addition is finished, the constant-temperature reaction is carried out for 7 hours;
(3) distilling under reduced pressure to remove the organic solvent, adding a solvent toluene until the product is dissolved again, and then adding alkaline solid powder potassium carbonate to neutralize the reaction liquid to be neutral;
(4) vacuum-filtering to remove insoluble substances, and then carrying out vacuum distillation to remove toluene, thus obtaining the reaction product polysiloxane K-D.
The product polysiloxane K-D prepared by the invention has the viscosity of 2871cps and the yield of 49.6%.
Example 4.
A method for the catalytic synthesis of polysiloxanes, comprising the steps of:
(1) adding a reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and a reactant dimethyl diethoxy silane into a four-neck flask with a reflux condenser, a thermometer, a dropping funnel and a stirring paddle, wherein the molar ratio of the reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane to the reactant dimethyl diethoxy silane is 5: 4;
(2) stirring the reaction mixture at room temperature for 45 minutes, heating the reaction mixture to 50 ℃ in a water bath or an oil bath, slowly dropwise adding an organic solvent tetrahydrofuran, 25% of dilute sulfuric acid and deionized water by using a dropping funnel by using 25% of dilute sulfuric acid in mass fraction as a catalyst, wherein the total molar ratio of the organic solvent to the mixture is 1: 2.19, the total molar ratio of the dilute sulfuric acid to the mixture is 0.08:1, the total molar ratio of the deionized water to the mixture is 1.7:1, and the mixture reacts for 9 hours at constant temperature after the dropwise addition;
(3) distilling under reduced pressure to remove the organic solvent, adding a solvent toluene until the product is dissolved again, and then adding alkaline solid powder sodium hydroxide to neutralize the reaction solution to neutrality;
(4) vacuum-filtering to remove insoluble substances, and then carrying out vacuum distillation to remove toluene, thus obtaining the reaction product polysiloxane K-D.
The product polysiloxane K-D prepared by the invention has a viscosity of 3450cps and a yield of 56.8%.
Example 5.
A method for the catalytic synthesis of polysiloxanes, comprising the steps of:
(1) adding a reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and a reactant dimethyl diethoxy silane into a four-neck flask with a reflux condenser, a thermometer, a dropping funnel and a stirring paddle, wherein the molar ratio of the reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane to the reactant dimethyl diethoxy silane is 5: 3;
(2) stirring the reaction mixture at room temperature for 60 minutes, heating the reaction mixture to 40 ℃ in a water bath or oil bath, slowly dropwise adding an organic solvent tetrahydrofuran, 17% by mass of dilute hydrochloric acid and deionized water by using a dropping funnel, wherein the total molar ratio of the organic solvent to the mixture is 1: 2.41, the total molar ratio of the dilute hydrochloric acid to the mixture is 0.09:1, and the total molar ratio of the deionized water to the mixture is 1.95:1, and reacting at constant temperature for 12 hours after the dropwise adding;
(3) distilling under reduced pressure to remove the organic solvent, adding a solvent toluene until the product is dissolved again, and then adding alkaline solid powder potassium hydroxide to neutralize the reaction liquid to neutrality;
(4) vacuum-filtering to remove insoluble substances, and then carrying out vacuum distillation to remove toluene, thus obtaining the reaction product polysiloxane K-D.
The product polysiloxane K-D prepared by the invention has a viscosity of 4480cps and a yield of 44.9%.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (6)
1. A method for the catalytic synthesis of polysiloxanes, comprising the steps of:
(1) adding reactant gamma- (2, 3-epoxy propoxy) propyl trimethoxy silane and reactant dimethyl diethoxy silane into a reaction device, wherein the molar ratio of the reactant gamma- (2, 3-epoxy propoxy) propyl trimethoxy silane to the reactant dimethyl diethoxy silane is 1: 12-5: 3;
(2) stirring the mixture consisting of the reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and the reactant dimethyl diethoxy silane at room temperature for 1-60 minutes, heating to 40-80 ℃ in a water bath or oil bath, dropwise adding an organic solvent, dilute sulfuric acid or dilute hydrochloric acid and deionized water one by taking dilute sulfuric acid or dilute hydrochloric acid as a catalyst, wherein the total molar ratio of the organic solvent to the mixture is 1: 1-1: 3, wherein the total molar ratio of dilute sulfuric acid or dilute hydrochloric acid to the mixture is 0.01: 1-1: 1, the total molar ratio of deionized water to the mixture is 1: 1-2: 1, and after the dropwise addition is finished, the constant-temperature reaction is carried out for 2-12 hours;
(3) distilling under reduced pressure to remove the organic solvent, adding a solvent toluene until the product is dissolved again, and then adding alkaline solid powder to neutralize the reaction liquid to neutrality;
(4) vacuum filtering to remove insoluble substances, and then carrying out vacuum distillation to remove toluene, thus obtaining the reaction product polysiloxane.
2. The process of claim 1, wherein the catalyst comprises: in the step (1), the molar ratio of the reactant gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane to the reactant dimethyl diethoxy silane is 1: 4-3: 2.
3. the process of claim 1, wherein the catalyst comprises: in the step (2), the organic solvent is at least one of tetrahydrofuran, ethanol or methanol.
4. The process of claim 1, wherein the catalyst comprises: in the step (2), the stirring time is 1-30 minutes, the temperature of the water bath or oil bath is 50-70 ℃, and the constant-temperature reaction time is 5-10 hours.
5. The process of claim 1, wherein the catalyst comprises: in the step (2), the total molar ratio of the organic solvent to the mixture is 1: 1-1: 2.5, the total molar ratio of the dilute sulfuric acid or dilute hydrochloric acid to the mixture is 0.01: 1-0.05: 1, and the total molar ratio of the deionized water to the mixture is 1: 1-1.5: 1.
6. The process of claim 1, wherein the catalyst comprises: in the step (3), the alkaline solid powder is at least one of sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or calcium hydroxide.
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