CN110408034B - Synthetic method of phenyl block silicone resin - Google Patents
Synthetic method of phenyl block silicone resin Download PDFInfo
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- CN110408034B CN110408034B CN201910759133.XA CN201910759133A CN110408034B CN 110408034 B CN110408034 B CN 110408034B CN 201910759133 A CN201910759133 A CN 201910759133A CN 110408034 B CN110408034 B CN 110408034B
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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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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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
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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Abstract
The invention provides phenyl block silicon resin, which is prepared from phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, a solvent and dihydroxy polytrifluoropropylmethylsiloxane through hydrolysis, prepolymerization, washing with water, dewatering, condensation and desolventizing. The introduction of fluorine group makes phenyl silicone resin have lower surface energy, oil resistance, antifouling property and excellent anti-sticking property. The synthetic silicone resin can be cured into a transparent film at room temperature, and the prepared coating adhesive has the tensile strength of more than 2.5Mpa and the Shore hardness of 75A. The combination of the branched silicone resin and the linear siloxane provides the silicone resin with better flexibility and flexibility, and provides possibility for application materials requiring certain toughness in high-temperature occasions.
Description
Technical Field
The invention relates to a synthetic method of phenyl block silicone resin, belonging to the technical field of chemical production.
Background
The organic silicon resin has many excellent physical and chemical properties, such as high and low temperature resistance, radiation resistance, oxidation resistance, high air permeability, weather resistance, mold release property, hydration resistance, physiological inertia and the like. The method is widely applied to the fields of electronic and electrical appliance chemical industry, metallurgy, building, aerospace, aviation, medical materials and the like. The organic silicon resin is used as a necessary raw material of some high-end organic silicon products, although the dosage is not large, the organic silicon resin is indispensable, the production of domestic silicon resin is less at present, foreign products carry out technical blockade on the silicon resin, and under the international environment, the independent development of the production process of the silicon resin is particularly important.
The common silicone resin has a highly cross-linked network structure, high hardness and strength, but poor toughness; the silicone rubber has a spiral long-chain structure and good elasticity, but is low in crosslinking degree and hardness and easy to scratch. The present patent does not solve the above problems and develop a phenyl block silicone resin having both a chain-like and a network-like structure.
CN107459652A provides a room temperature curable heat resistant silicone resin and a preparation method thereof. The invention firstly synthesizes an alkoxy silane compound containing a hexafluoro butyl-containing aryl ether structure, and then prepares alkoxy-terminated organic silicon resin (R1SiO1.5) a (R2R 3 SiO) b (R2R 3Si-R4-R2R3 SiO) C by copolymerizing with trifunctional silicon resin prepolymer and hydroxy silicone oil, wherein R1 is aryl, R2R3 is methyl, aryl or saturated alkyl with 2-10 carbon atoms, and R4 is hexafluoro butyl-containing aryl ether group; a + b + c =1, the value of a ranges from 0 to 0.5, the value of b ranges from 0 to 1 earlier, the value of c ranges from 0 to 1 earlier, and the mass content of the alkoxy groups ranges from 0.1% to 10%. The organic silicon resin can be cured at room temperature to reach 450 ℃ after being mixed with trialkoxysilane and a curing catalyst, and has an elastic-plastic silicon resin material. However, the silicone resin material obtained by the method has the defects of low hardness, scratch resistance and the like, so that the application condition of the material is narrow.
CN104327289B provides a preparation method and application of an organic functional group end-capped block optical transparent organic silicon resin containing trapezoidal polysilsesquioxane. This patent uses organotin as a catalyst, which is a fatal drawback of this patent. Organotin belongs to a severe poison and should be strictly prohibited.
The common silicone resin has a highly cross-linked network structure, high hardness and strength, but poor toughness; the silicone rubber has a spiral long-chain structure and good elasticity, but is low in crosslinking degree and hardness and easy to scratch.
Disclosure of Invention
The invention adopts hydroxyl-terminated trapezoidal polysilsesquioxane to initiate the ring-opening polymerization of cyclosiloxane to prepare the vinyl-containing block silicone resin prepolymer. And then uniformly mixing the prepolymer, the catalyst and the cross-linking agent according to a certain proportion, defoaming in vacuum, and curing and molding under set conditions to obtain the optically transparent organic silicon resin. The method improves the mechanical property and flexibility of the silicone resin, and has the characteristics of low shrinkage rate, cold and heat shock resistance, ultraviolet radiation resistance, high light transmittance and the like. The block optical transparent organic silicon resin can be used for packaging electronic components represented by LED packaging.
This patent developed phenyl block silicone resins having both chain and network structures. In order to achieve the purpose, the invention adopts the following technical scheme:
a synthetic method of phenyl block silicone resin comprises the following steps:
(1) adding a silicone resin raw material, a solvent and dihydroxy polytrifluoropropylmethylsiloxane into a container, uniformly stirring to obtain a mixed solution, dropwise adding the mixed solution into water, reacting at room temperature for 0.5-2 hours after dropwise adding, and performing hydrolysis reaction to obtain a silanol solution; the mass concentration of the hydrolyzed silanol is 30-70%;
(2) heating the obtained silanol solution to 70-90 ℃, carrying out prepolymerization for 2-6h, and washing a prepolymerization product to be neutral to obtain a silicone resin prepolymer;
(3) and (3) after dewatering the obtained silicone resin prepolymer, adding a polycondensation catalyst to perform dehydration condensation reaction for 2-5 hours, washing the condensation product to be neutral, dewatering and desolventizing to obtain the phenyl block silicone resin.
The solvent in the step (1) comprises one or more of toluene, xylene and methyl isobutyl ketone.
The viscosity of the dihydroxy polytrifluoropropylmethylsiloxane is 100-10000 mPa.s, and the fluorine content of the dihydroxy polytrifluoropropylmethylsiloxane is 20-50%.
The silicon resin raw materials are phenyl trichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane and methylphenyl dichlorosilane; the dihydroxy polytrifluoropropylmethylsiloxane accounts for 50-80% of the mass of the silicone resin raw material; the mass ratio of phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane and methylphenyldichlorosilane is 1: 0.2-0.65: 0.18-0.55: 0.2-0.6.
The polycondensation catalyst in the step (3) is one or more of potassium hydroxide, sodium hydroxide, cesium hydroxide, lithium hydroxide and tetramethylammonium hydroxide; the addition amount of the polycondensation catalyst is 1-20% of the mass of the prepolymer of the silicone resin.
The water washing adopts one of distilled water, deionized water and ultrapure water.
Compared with the prior art, the invention has the following beneficial effects:
(1) the addition of the dihydroxy polytrifluoropropylmethylsiloxane introduces fluorine groups, so that the phenyl silicone resin has lower surface energy, oil resistance, antifouling property and excellent anti-sticking property. The method has better application to preventing high-voltage creepage and preventing the deposition of the photovoltaic panel.
(2) The synthetic silicone resin can be cured into a transparent film at room temperature, and the prepared coating adhesive has tensile strength of more than 2.5Mpa and Shore hardness of 75A, meets the requirement of surface coating of industrial electronic instruments and electronic circuit boards, and plays a role in three prevention.
(3) The dihydroxy polytrifluoropropylmethylsiloxane has terminal hydroxyl groups, so that branched silicone resin and linear silicone resin are combined, the silicone resin has better flexibility and flexibility, and application materials needing certain toughness in high-temperature occasions provide possibility.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
(1) 54.2g of phenyltrichlorosilane, 28g of dimethyldichlorosilane, 23.4g of diphenyldichlorosilane, 24.8 g of methylphenyldichlorosilane, 100g of toluene and 15g of 1500mPa.s dihydroxy polytrifluoropropylmethylsiloxane are added into a 500ml three-neck flask, stirred and mixed uniformly, the mixed solution is added into water by a constant-pressure dropping funnel, the titration time is about 30min, the mixture reacts for 1h at room temperature after the dropping is finished, the hydrolysis is finished, and then the prepolymerization is carried out for 3h at 80 ℃.
(2) Standing and layering, separating lower acid water layer, washing upper hydrolysate with hot distilled water to neutrality to obtain a silicone prepolymer, then dewatering the silicone prepolymer at 110 ℃ for 1h, adding 2g of tetramethylammonium hydroxide after dewatering for condensation reaction for 4h, washing with hot distilled water to neutrality after reaction is finished, and then dewatering to obtain a phenyl silicone resin product, wherein the resin can be cured into a film, and is transparent and elastic after curing.
(3) The coating rubber prepared by using the silicon resin product has the elongation at break of 400%, the tensile strength of 5.12MPa and the Shore hardness of 75A.
Example 2
(1) 74.5 phenyltrichlorosilane, 21.02 dimethyldichlorosilane, 17.5 diphenyldichlorosilane, 18.5 methylphenyldichlorosilane, 100g toluene and 15g700g mPa.s dihydroxy polytrifluoropropylmethylsiloxane were added into a 500ml three-neck flask, stirred for 10 minutes, the above mixture was added into water by a constant pressure dropping funnel, the titration time was about 30 minutes, and after completion of the dropping, the mixture was reacted at room temperature for 1 hour, after completion of the hydrolysis, and then prepolymerized at 80 ℃ for 3 hours.
(2) And (3) washing to be neutral to obtain a silicone resin prepolymer, adding sodium sulfate to remove water, adding 3g of sodium hydroxide to perform dehydration condensation reaction for 3 hours, washing to be neutral, removing water at high temperature, and desolventizing to obtain the phenyl block silicone resin. The resin can be cured to form a film, and is transparent and elastic after being cured
(3) The coating glue prepared by using the silicone resin product has the elongation at break of 350 percent and the tensile strength of 4.3MPa,
the Shore hardness is 72A.
Example 3
(1) 54.2g of phenyltrichlorosilane, 28g of dimethyldichlorosilane, 23.4g of diphenyldichlorosilane, 24.8 g of methylphenyldichlorosilane and 100g of toluene are added into a 500ml three-neck flask by a constant pressure dropping funnel, the mixed solution is added into water, the titration time is about 30min, the mixture reacts at room temperature for 1h after the dripping is finished, the hydrolysis is finished, and then the prepolymerization is carried out for 3h at 80 ℃.
(2) Standing and layering, separating lower acid water layer, washing upper hydrolysate with hot distilled water to be neutral to obtain a silicone prepolymer, then removing water from the silicone prepolymer at 110 ℃ for 1h, adding 2g of tetramethylammonium hydroxide after water removal for condensation reaction for 4h, washing with hot distilled water to be neutral after reaction is finished, and removing water to obtain a phenyl silicone resin product. The resin is brittle and does not form a film after curing.
(3) The elongation at break of the coating rubber prepared by using the silicon resin product is 50%, and the Shore hardness is 70A.
Example 4
(1) 74.5 phenyltrichlorosilane, 21.02 dimethyldichlorosilane, 17.5 diphenyldichlorosilane, 18.5 methylphenyldichlorosilane and 100g toluene are added into a 500ml three-neck flask, stirred for 10 minutes, the mixed solution is added into water by a constant pressure dropping funnel, the titration time is about 30 minutes, the mixture reacts for 1 hour at room temperature after the dropping is finished, the hydrolysis is finished, and then the prepolymerization is carried out for 3 hours at 80 ℃.
(2) And (3) washing to be neutral to obtain a silicone resin prepolymer, adding sodium sulfate to remove water, adding 3g of sodium hydroxide to perform dehydration condensation reaction for 3 hours, washing to be neutral, removing water at high temperature, and desolventizing to obtain the phenyl block silicone resin. The resin is brittle and does not form a film after curing.
(3) The elongation at break of the coating rubber prepared by using the silicon resin product is 70%, and the Shore hardness is 67A.
Example 5
(1) 100g of phenyltrichlorosilane, 20g of dimethyldichlorosilane, 30g of diphenyldichlorosilane, 20g of methylphenyldichlorosilane, 100g of toluene and 15g of 2000mPa.s dihydroxy polytrifluoropropylmethylsiloxane are added into a 500ml three-neck flask, stirred and mixed uniformly, the mixed solution is added into water by a constant pressure dropping funnel, the titration time is about 30min, the mixture reacts for 1h at room temperature after the dropping is finished, the hydrolysis is finished, and then the prepolymerization is carried out for 3h at 80 ℃.
(2) Standing and layering, separating lower acid water, washing an upper hydrolysate to be neutral by using hot distilled water to obtain a silicone prepolymer, then dehydrating the silicone prepolymer at 110 ℃ for 1h, adding 4g of potassium hydroxide after the dehydration is finished to perform a condensation reaction for 4h, washing the silicone prepolymer to be neutral by using the hot distilled water after the reaction is finished, and then dehydrating to obtain a phenyl silicone resin product, wherein the resin can be cured into a film, and is transparent and elastic after being cured.
(3) The elongation at break of the coating rubber prepared by using the silicon resin product is 370%, the tensile strength is 4.80MPa, and the Shore hardness is 74A.
Claims (6)
1. A synthetic method of phenyl block silicone resin is characterized in that:
(1) adding a silicone resin raw material, a solvent and dihydroxy polytrifluoropropylmethylsiloxane into a container, uniformly stirring to obtain a mixed solution, dropwise adding the mixed solution into water, reacting at room temperature for 0.5-2 hours after dropwise adding, and performing hydrolysis reaction to obtain a silanol solution; the silicon resin raw materials are phenyl trichlorosilane, dimethyldichlorosilane, diphenyl dichlorosilane and methyl phenyl dichlorosilane, and the mass ratio of the phenyl trichlorosilane, the dimethyldichlorosilane, the diphenyl dichlorosilane and the methyl phenyl dichlorosilane is 1: 0.2-0.65: 0.18-0.55: 0.2-0.6;
(2) heating the obtained silanol solution to 70-90 ℃, carrying out prepolymerization for 2-6h, and washing a prepolymerization product to be neutral to obtain a silicone resin prepolymer;
(3) and (3) after dewatering the obtained silicone resin prepolymer, adding a polycondensation catalyst to perform dehydration condensation reaction for 2-5 hours, washing the condensation product to be neutral, dewatering and desolventizing to obtain the phenyl block silicone resin.
2. The method for synthesizing phenyl-block silicone resin according to claim 1, wherein the solvent in step (1) comprises one or more of toluene, xylene, and methyl isobutyl ketone.
3. The method for synthesizing phenyl block silicone resin according to claim 1, wherein the viscosity of dihydroxy polytrifluoropropylmethylsiloxane is 100mpa.s to 10000 mpa.s.
4. The method for synthesizing phenyl block silicone resin according to claim 1, wherein the mass concentration of silanol after hydrolysis is 30 to 70%.
5. The method for synthesizing phenyl block silicone resin according to claim 1, wherein the polycondensation catalyst in step (3) is one or more of potassium hydroxide, sodium hydroxide, cesium hydroxide, lithium hydroxide, tetramethylammonium hydroxide; the addition amount of the polycondensation catalyst is 1-20% of the mass of the prepolymer of the silicone resin.
6. The method for synthesizing phenyl block silicone resin according to claim 1, wherein the water washing is performed with one of distilled water, deionized water, and ultrapure water.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009119253A1 (en) * | 2008-03-28 | 2009-10-01 | 新日鐵化学株式会社 | Silanol-group-containing curable cage-type silsesquioxane compound, cage-structure-containing curable silicone copolymer, processes for producing these, and curable resin composition |
| CN105199105A (en) * | 2015-09-29 | 2015-12-30 | 广州有色金属研究院 | Method for preparing phenyl silicone oil with fluorine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009119253A1 (en) * | 2008-03-28 | 2009-10-01 | 新日鐵化学株式会社 | Silanol-group-containing curable cage-type silsesquioxane compound, cage-structure-containing curable silicone copolymer, processes for producing these, and curable resin composition |
| CN105199105A (en) * | 2015-09-29 | 2015-12-30 | 广州有色金属研究院 | Method for preparing phenyl silicone oil with fluorine |
Non-Patent Citations (1)
| Title |
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| 含亚苯基甲基苯基硅树脂的合成及表征;李伟，贾梦秋，吴超波，高大海;《化工新型材料》;20100115;第38卷(第1期);第49-54页 * |
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Effective date of registration: 20191204 Address after: 66-2 No. 443007 Hubei city of Yichang province located in Xiaoting District Road Applicant after: Hubei Xingrui silicon material Co., Ltd. Applicant after: Zhaoshun Technology (Guangdong) Co., Ltd Address before: 66-2 No. 443007 Hubei city of Yichang province located in Xiaoting District Road Applicant before: Hubei Xingrui silicon material Co., Ltd. |
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