CN105585713A - Method for preparing alcohol-solubility methyl silicone resin - Google Patents
Method for preparing alcohol-solubility methyl silicone resin Download PDFInfo
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- CN105585713A CN105585713A CN201610168766.XA CN201610168766A CN105585713A CN 105585713 A CN105585713 A CN 105585713A CN 201610168766 A CN201610168766 A CN 201610168766A CN 105585713 A CN105585713 A CN 105585713A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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Abstract
The invention discloses a method for preparing alcohol-solubility methyl silicone resin. The method is simple, stable and environmentally friendly in technology. The method includes the steps that methyltrialkoxysilane, dimethyldialkoxysilane, an alcohol solvent and a molecule control assistant are mixed, an acid catalyst is added, deionized water is dropwise added at the temperature of 50-70 DEG C, the dropwise-adding time is controlled to range 0.5 hour to 3 hours, the reaction continues to be conducted for 3-4 hours after the dropwise-adding process is finished, carbonate is added to neutralize the acid catalyst till the solution is neutral, the solution is heated to remove the alcohol solvent and the water in the solution and heated to 140 DEG C, the temperature is maintained for 0.5 hour, the solution is cooled, an alcohol solvent is added, an alcohol solution in a certain proportion is prepared, and the alcohol-solubility methyl silicone resin is obtained through filtering. According to the preparing method, the cost of the adopted raw materials is low; in the production process, gel is not prone to occurrence, wastewater is avoided, and the produced methyl silicone resin has good solubility in the alcohol solvent.
Description
Technical field
The present invention relates to organic chemical synthesis field, be specifically related to a kind of preparation method of methyl silicon resin of alcohol dissolubility.
Background technology
Organic siliconresin is the thermosetting polysiloxanes system with highly cross-linked structure, has both contained organic group in its structureGroup, contains again inorganic structure, and this special composition and molecular structure make it have Characteristics of Organic and inorganic matter function concurrently, haveGood heat endurance, oxidation stability, excellent hydrophobicity etc., be used as high temperature resistant micarex adhesive.
Organic group number in organic siliconresin can have a huge impact the performance of organic siliconresin, along with R/Si'sIncrease, the heat resistance of organic siliconresin, lower hardness, bending, pliability increases, and therefore in the application of micarex adhesive, needsWant the product that R/Si is low. At present, people process organic siliconresin for the solvent with environmental protection, carry out constantly exploring,In 2010, Cao Wanrong etc. delivered at " insulating materials " in the research of low weightless organic silicon adhesive " high temperature resistant, " literary composition and have carriedArrive, adopt MTES, dimethyldiethoxysilane and ethyl orthosilicate under the catalysis of hydrochloric acid, to react 4 littleTime, remove unnecessary alcohol and water, obtain methyl silicon resin, at the solid content that is formulated to 50% with toluene and isopropyl alcohol, its R/Si ratioBetween 1-1.2, there is high temperature and be fuming less and the few feature of thermal weight loss. But solubilizer not in the method hydrolytic process, was hydrolyzedThe difficult control of journey is prone to gel, improper suitability for industrialized production, and last process for preparation adopts toluene Mixed Solvent, has certain poisonProperty, environmental protection not.
In addition, in the patent that is CN201310198353.2 at notification number, inventor has proposed employing ethyl orthosilicate, firstEthyl triethoxy silicane alkane, dimethyl diethoxy silane and toluene, at 50-70 DEG C, use atlapulgite as catalyst, dripDeionized water is hydrolyzed, and removes by filter catalysts and solvents, at 105-115 DEG C, reacts 10-15min, adds toluene to mixSolution obtains methyl silicon resin, prepares the methyl silicon resin of R/Si < 1. But the atlapulgite activity adopting in this preparation methodLow, hydrolysis degree is not high, is difficult to obtain bonding good methyl silicon resin, and in polycondensation process easy gel, be not suitable for workIndustryization is produced, and in the toluene mixture of use, toluene has certain toxicity, environmental protection not.
Summary of the invention
The object of the invention is to overcome the shortcoming existing in prior art, provide a kind of technique succinct, stable, environmental protectionThe preparation method of the methyl silicon resin of alcohol dissolubility, the cost of raw material that this preparation method uses is low, is difficult in process of production solidifyingGlue, without waste water produce, the methyl silicon resin of producing has good dissolubility in alcoholic solvent.
The preparation method of the methyl silicon resin of alcohol dissolubility of the present invention follows these steps to realize:
(1) methyl trialkoxysilane, dimethyl dialkoxy silicane are mixed to form to solution A, described methyl tri-alkoxy siliconThe mol ratio of alkane and dimethyl dialkoxy silicane is 20:1～4:1;
(2) in solution A, add the alcoholic solvent of 0.5～1.0 times of amount, and add consumption be solution A total amount 0.5%～3% pointSon is controlled 0.05%～0.1% the acidic catalyst that auxiliary agent and consumption are solution A total amounts, obtains solution B;
(3) solution B is heated to 50～70 DEG C and maintain at this temperature and drip deionized water, time for adding is controlled at0.5～3 hour, dropwise rear maintenance temperature and continue reaction 3～4 hours, obtain solution C, the consumption of described deionized water withThe mol ratio of the alkoxy base sum in solution A is 1.1～1.8:1;
(4) in solution C, add carbonate, the acidic catalyst in neutralization solution B, to neutral, obtains solution D;
(5) solution D is heated, be warming up to 140 DEG C and holding temperature half an hour, remove alcoholic solvent and water wherein, coolingAdd alcoholic solvent, be mixed with a certain proportion of alcoholic solution, filter the methyl silicon resin that obtains alcohol dissolubility.
As the further scheme of the present invention, methyl trialkoxysilane is MTMS or methyl three ethoxiesBase silane, dimethyl dialkoxy silicane is dimethyldimethoxysil,ne or dimethyldiethoxysilane.
As preferred embodiments of the present invention, alcoholic solvent is one or more in methyl alcohol, ethanol, isopropyl alcohol and n-butanol.
As the further scheme of the present invention, molecular Control auxiliary agent is surfactant.
As further preferred scheme of the present invention, molecular Control auxiliary agent be Tween 80, polysorbas20, class of department 80, OP-10,One or more in class of department 20, polyether modified silicon oil.
As preferred embodiments of the present invention, the consumption of molecular Control auxiliary agent is 1%～2% of solution A total amount.
As the further scheme of the present invention, acidic catalyst is organic acid or inorganic acid.
As the further preferred scheme of the present invention, acidic catalyst is the one in hydrochloric acid, acetic acid, formic acid.
As the further scheme of the present invention, carbonate is the one in sodium acid carbonate, saleratus, sodium carbonate.
The invention has the beneficial effects as follows: in the present invention, raw material used is all the conventional reagent of this area, is purchased price lowHonest and clean, building-up process is simple, has well handlingly, is suitable for large-scale production. Be difficult in process of production gel,Produce without waste water, the activity of the acidic catalyst of use is strong, and the R/Si of prepared methyl silicon resin is low, and dissolves in environmental protectionAlcoholic solvent.
Detailed description of the invention
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment for the present invention is described, stillShould be appreciated that these are described is in order to further illustrate the features and advantages of the present invention, instead of to the claims in the present inventionRestriction.
Embodiment 1
In the four-hole boiling flask of 1000ml, add 272 grams of MTMSs, 12 grams of dimethyldimethoxysil,ne, 142Gram methyl alcohol, 142 grams of n-butanols, 8.52 grams of Tween 80s and 0.142 gram of hydrochloric acid, be heated to 50 DEG C, drips deionized water 119.2Gram, the mol ratio of the consumption of deionized water and MTMS and dimethyldimethoxysil,ne alkoxy base sumFor 1.1:1, time for adding is controlled at 3 hours, dropwises rear continuation reaction 4 hours, uses in sodium acid carbonate extremely molten with hydrochloric acidIt is neutral that liquid is, and heat temperature raising is removed methyl alcohol and n-butanol and the water in solution, is warming up to 140 DEG C and holding temperature half an hour,After cooling, add methyl alcohol to be mixed with the alcoholic solution of 50% solid content, filter and obtain the methyl silicon resin methanol solution of R/Si=1.05.
Embodiment 2
In the four-hole boiling flask of 1000ml, add 356 grams of MTESs, 74 grams of dimethyldiethoxysilanes, 215Gram ethanol, 80 and 0.43 grams of acetic acid of 2.15 grams of classes of department, be heated to 70 DEG C, drips 226.8 grams of deionized waters, deionized waterThe mol ratio of consumption and MTES and dimethyldiethoxysilane alkoxy base sum is 1.8:1, dripsTime is controlled at 0.5 hour, dropwises rear continuation reaction 3 hours, uses in sodium carbonate and is neutral, heating with acetic acid to solutionThe second alcohol and water in solution is removed in intensification, is warming up to 140 DEG C and holding temperature half an hour, adds ethanol to be mixed with 50% after coolingThe alcoholic solution of solid content, filters and obtains the methyl silicon resin ethanolic solution of R/Si=1.2.
Embodiment 3
In the four-hole boiling flask of 1000ml, add 272 grams of MTMSs, 29.6 grams of dimethyldiethoxysilanes,100 grams of methyl alcohol, 126.2 grams of isopropyl alcohols, 1.5 grams of polysorbas20s, 1.5 grams of polyether modified silicon oils and 0.23 gram of formic acid, be heated to65 DEG C, drip 172 grams of deionized waters, the consumption of deionized water and MTMS and dimethyldiethoxysilane alkaneThe mol ratio of oxygen base group sum is 1.5:1, and time for adding is controlled at 3.5 hours, dropwises rear continuation reaction 3.5 hours,Use in saleratus and be neutral with hydrochloric acid to solution, heat temperature raising is removed methyl alcohol and isopropyl alcohol and the water in solution, heats upTo 140 DEG C and holding temperature half an hour, add isopropyl alcohol to be mixed with the alcoholic solution of 50% solid content after cooling, filter and obtain R/Si=1.09 methyl silicon resin aqueous isopropanol.
Embodiment 4
In the four-hole boiling flask of 1000ml, add 356 grams of MTESs, 36 grams of dimethyldimethoxysil,ne, 235Gram methyl alcohol, 3 grams of 20,4.84 grams of OP-10 of class of department and 0.31 gram of hydrochloric acid, be heated to 60 DEG C, drips 166.3 grams of deionized waters,The mol ratio of the consumption of deionized water and MTES and dimethyldimethoxysil,ne alkoxy base sum is1.4:1, time for adding is controlled at 1 hour, dropwises rear continuation reaction 3.5 hours, uses in sodium acid carbonate extremely molten with hydrochloric acidIt is neutral that liquid is, and heat temperature raising is removed the first alcohol and water in solution, is warming up to 140 DEG C and holding temperature half an hour, adds after coolingMethyl alcohol and isopropyl alcohol mixed liquor are mixed with the alcoholic solution of 50% solid content, filter and obtain R/Si=1.13 methyl silicon resin methyl alcohol andAqueous isopropanol.
The embodiments of the invention that it should be pointed out that foregoing description. But the technical staff of art technology should be appreciated that,The present invention is not restricted to the described embodiments, and that in above-described embodiment, describes just illustrates principle of the present invention, is not departing from thisUnder the prerequisite of invention scope, the present invention also has multiple changes and improvements, and these changes and improvements all fall into claimed thisIn bright scope.
Claims (9)
1. a preparation method for the methyl silicon resin of alcohol dissolubility, is characterized in that the preparation method of the methyl silicon resin of alcohol dissolubilityFollow these steps to realize:
(1) methyl trialkoxysilane, dimethyl dialkoxy silicane are mixed to form to solution A, described methyl tri-alkoxy siliconThe mol ratio of alkane and dimethyl dialkoxy silicane is 20:1～4:1;
(2) in solution A, add the alcoholic solvent of 0.5～1.0 times of amount, and add consumption be solution A total amount 0.5%～3% pointSon is controlled 0.05%～0.1% the acidic catalyst that auxiliary agent and consumption are solution A total amounts, obtains solution B;
(3) solution B is heated to 50～70 DEG C and maintain at this temperature and drip deionized water, time for adding is controlled at0.5～3 hour, dropwise rear maintenance temperature and continue reaction 3～4 hours, obtain solution C, the consumption of described deionized water withThe mol ratio of the alkoxy base sum in solution A is 1.1～1.8:1;
(4) in solution C, add carbonate, the acidic catalyst in neutralization solution B, to neutral, obtains solution D;
(5) solution D is heated, remove alcoholic solvent and water wherein, also holding temperature half is little to continue to be heated to 140 DEG CTime, cooling adds alcoholic solvent, is mixed with a certain proportion of alcoholic solution, filters the methyl silicon resin that obtains alcohol dissolubility.
2. the preparation method of the methyl silicon resin of a kind of alcohol dissolubility according to claim 1, is characterized in that: described methylTrialkoxy silane is MTMS or MTES, and described dimethyl dialkoxy silicane is diformazanBase dimethoxy silane or dimethyldiethoxysilane.
3. the preparation method of the methyl silicon resin of a kind of alcohol dissolubility according to claim 1, is characterized in that: described alcohol is moltenAgent is one or more in methyl alcohol, ethanol, isopropyl alcohol and n-butanol.
4. the preparation method of the methyl silicon resin of a kind of alcohol dissolubility according to claim 1, is characterized in that: described moleculeControl auxiliary agent is surfactant.
5. the preparation method of the methyl silicon resin of a kind of alcohol dissolubility according to claim 4, is characterized in that: described moleculeControl auxiliary agent is preferably one or more in Tween 80, polysorbas20, class of department 80, OP-10, class of department 20, polyether modified silicon oil.
6. the preparation method of the methyl silicon resin of a kind of alcohol dissolubility according to claim 1, is characterized in that: described moleculeThe consumption of controlling auxiliary agent is preferably 1%～2% of solution A total amount.
7. the preparation method of the methyl silicon resin of a kind of alcohol dissolubility according to claim 1, is characterized in that: described acidityCatalyst is organic acid or inorganic acid.
8. the preparation method of the methyl silicon resin of a kind of alcohol dissolubility according to claim 7, is characterized in that: described acidityCatalyst is preferably the one in hydrochloric acid, acetic acid, formic acid.
9. the preparation method of the methyl silicon resin of a kind of alcohol dissolubility according to claim 1, is characterized in that: described carbonic acidSalt is the one in sodium acid carbonate, saleratus, sodium carbonate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610168766.XA CN105585713A (en) | 2016-03-23 | 2016-03-23 | Method for preparing alcohol-solubility methyl silicone resin |
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| CN201610168766.XA CN105585713A (en) | 2016-03-23 | 2016-03-23 | Method for preparing alcohol-solubility methyl silicone resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144044A (en) * | 2019-05-22 | 2019-08-20 | 浩硅科技(上海)有限公司 | A kind of no-solvent type methyl silicon resin and its manufacture craft |
| CN111040166A (en) * | 2019-11-28 | 2020-04-21 | 湖北新四海化工股份有限公司 | Environment-friendly moisture-curing silicone resin and preparation method thereof |
| CN115340842A (en) * | 2021-05-12 | 2022-11-15 | 中蓝晨光化工研究设计院有限公司 | Bi-component condensed type room temperature vulcanized silicone rubber binder and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047314A (en) * | 1989-05-09 | 1990-11-28 | 化学工业部晨光化工研究院一分院 | Ablative coatings and ablative coatings are with the preparation method of pure dissolubility silicone resin |
| CN1810858A (en) * | 2006-02-27 | 2006-08-02 | 中蓝晨光化工研究院 | Synthesis of organosilicon resin |
| CN105111441A (en) * | 2015-09-24 | 2015-12-02 | 唐山三友硅业有限责任公司 | Process for continuously preparing methyl silicone resin |
-
2016
- 2016-03-23 CN CN201610168766.XA patent/CN105585713A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047314A (en) * | 1989-05-09 | 1990-11-28 | 化学工业部晨光化工研究院一分院 | Ablative coatings and ablative coatings are with the preparation method of pure dissolubility silicone resin |
| CN1810858A (en) * | 2006-02-27 | 2006-08-02 | 中蓝晨光化工研究院 | Synthesis of organosilicon resin |
| CN105111441A (en) * | 2015-09-24 | 2015-12-02 | 唐山三友硅业有限责任公司 | Process for continuously preparing methyl silicone resin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144044A (en) * | 2019-05-22 | 2019-08-20 | 浩硅科技(上海)有限公司 | A kind of no-solvent type methyl silicon resin and its manufacture craft |
| CN111040166A (en) * | 2019-11-28 | 2020-04-21 | 湖北新四海化工股份有限公司 | Environment-friendly moisture-curing silicone resin and preparation method thereof |
| CN115340842A (en) * | 2021-05-12 | 2022-11-15 | 中蓝晨光化工研究设计院有限公司 | Bi-component condensed type room temperature vulcanized silicone rubber binder and preparation method thereof |
| CN115340842B (en) * | 2021-05-12 | 2024-05-07 | 中蓝晨光化工研究设计院有限公司 | Double-component condensed room temperature vulcanized silicone rubber binder and preparation method thereof |
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