CN102492143A - Preparation method for high-temperature-resistant silicon resin - Google Patents
Preparation method for high-temperature-resistant silicon resin Download PDFInfo
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- CN102492143A CN102492143A CN2011104037552A CN201110403755A CN102492143A CN 102492143 A CN102492143 A CN 102492143A CN 2011104037552 A CN2011104037552 A CN 2011104037552A CN 201110403755 A CN201110403755 A CN 201110403755A CN 102492143 A CN102492143 A CN 102492143A
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Abstract
The invention relates to a preparation method for high-temperature-resistant silicon resin, in particular to a preparation method for high-temperature methylphenyl silicon resin. The method is characterized by comprising the following steps of: dissolving an acetic acid derivative into methylbenzene; reflowing for removing water; mixing chlorosilane serving a raw material, and dropwise adding slowly; stirring; adding methanol; continually stirring and reflowing; recovering fractions which are in the temperature range of 67-80 DEG C; cooling, adding water and washing till the pH is equal to 6-7; removing a solvent under a negative pressure in vacuum; and cooling to obtain a solid finished product. The silicon solid methylphenyl silicon resin prepared by using the method has the characteristics of transparence, high-low temperature resistance, weather resistance, insulation and the like, and is environmentally-friendly.
Description
Technical field
The present invention relates to a kind of preparation method of high temperature resistant silicon resin, a kind of specifically preparation method of high-temperature resisting methyl phenyl polysiloxane.
Background technology
Silicone resin is to have highly cross-linked cancellated polymkeric substance; Both contained organic group in the structure; Contain inorganic structure again; This special composition and molecular structure are that it integrates organism and inorganics characteristic, have unique physicochemical property, make it be widely used in the base-material of heat resisting coating, weather-resistant coating and electrically insulating material.Methyl phenyl silicone resin makes its weathering resistance, electric insulating quality except having common silicone resin because of the introducing of phenyl siliconoxygen bond.Outside water-proof breathable properties and the physiology inertia, also have superpower high and low temperature resistance, higher specific refractory power can be widely used in high-temperature resistant coating paint etc.
At present; The temperature tolerance that has heatproof powder coating preferably on the market only about 180 ℃, reach higher heat resistance, then adopts organosilicon coating; And the preparation of traditional silicone resin is the toluene solution that is processed into about 50%, sells with the solvent type resin form.The heatproof temperature of the high-temperature resistant coating that this solvent-type organosilicon resin is modulated into is generally at 200～300 ℃, and then need cooperate the high temperature requirement that just can reach more than 300 ℃ with other fillers such as ceramic glaze or magnetic porcelains for the coating of higher temperature.These methods have bigger toxicity in operating process, and environmental pollution is serious.Special procure the main dependence on import product of the fire resistant resin that needs higher temperature in the field for aerospace, big aircraft etc.
The compound method of methyl phenyl silicone resin mainly contains two kinds at present:
A kind of is to adopt the methyl chlorosilane of different functionality and phenyl chlorosilane monomer to generate silicone resin through step reaction such as hydrolysis, washing, filtration, condensations.A kind of chlorosilane monomer hydrolysis that utilizes different functional groups is disclosed in patent CN101508776B, in the method for organic amine catalytic preparation silicone resin.CN101343365.A discloses a kind of method of utilizing the chlorosilane monomer under the alkaline catalysts effect, to prepare phenyl polysiloxane.This method production efficiency is low, and reaction is fierce, and product is complicated.Most importantly produce a large amount of hydrogenchloride, corrosive equipment and contaminate environment in the reaction process.
Another kind be with the methylsiloxane of different functionality and phenyl siloxane be hydrolyzed, step reaction such as underpressure distillation, polycondensation generate silicone resin.This reaction does not produce hydrogenchloride, reacting balance, and the formation efficiency advantages of higher, but the raw material that this method is produced is various, and reaction is complicated, and temperature tolerance is relatively poor etc.
Summary of the invention
The present invention is intended to disclose a kind of preparation method of high-temperature resistant organic silicon resin of special use; This high-temperature resistant organic silicon resin normal temperature is solid and tack-free, and environmental pollution is little, can be ground into powder; About 100 ℃, can soften fusion, at the methyl phenyl silicone resin of 180 ℃ of ability curing moldings.
The preparation method of high-temperature resisting methyl phenyl polysiloxane of the present invention comprises the following steps: acetic acid derivative is dissolved in the toluene, and backflow is anhydrated; With slowly dripping after the chlorosilane raw materials mix, stir, add methyl alcohol again; Continue stirring and refluxing, reclaim the cut of cut in 67～80 ℃ of scopes, add water washing after the cooling to pH=6～7; Remove solvent under the negative pressure of vacuum, get the solid finished product after the cooling, said acetic acid derivative is selected from Potassium ethanoate, sodium-acetate or acetic anhydride; Said chlorosilane raw material be selected from dimethyldichlorosilane(DMCS), the METHYL TRICHLORO SILANE at least a and be selected from mixture at least a in diphenyl dichlorosilane, the phenyl-trichloro-silicane.
Wherein in the chlorosilane raw material, when methyl chlorosilane and phenyl chlorosilane mix, preferably press R/Si:0.25～1.0, Ph/ (Ph+Me): 0.5～0.75 mixed with organosilicon functional group and Siliciumatom.Wherein R and Me represent methylidene, Si represents silicon, and Ph represents phenyl.
Preferred 1: 1～1: 1.2 of the mol ratio of the cl ions in the consumption of acetic acid derivative and the chlorosilane raw material.
Preferred 1: 1～1: 1.2 of the mol ratio of the cl ions in the consumption of methyl alcohol and the chlorosilane raw material.
Solution temperature preferably is controlled at 30～50 ℃ when dripping the chlorosilane raw material.
Solution temperature preferably is controlled at 45～60 ℃ when adding methyl alcohol.
Preferably drip again to stir after 2～3 hours behind the chlorosilane raw material and add methyl alcohol again.
Restir refluxed 1～2 hour after preferably adding methyl alcohol.
Preparing method of the present invention does not produce hydrogen chloride gas in reaction process, little to corrodibility such as equipment.
Characteristics such as that the silicon solid methyl phenyl silicone resin of the inventive method preparation has is transparent, high-low temperature resistant, weather-proof, insulation; Environmental pollution is little, and this resin can soften fusion about 100 ℃, at the methyl phenyl silicone resin of 180 ℃ of ability curing moldings; Silicone resin with this method preparation can be applicable to prepare anti-various heat resisting coating more than-90～+ 800 ℃; It is bonding to can be applicable to the heat accumulation type solar chip, Nuclear power plants refractory coating, solid crystalline substance of great power LED new light sources and lens material; The invisible coating carrier of military aircraft, Military Ship, big aircraft project, guided missile, spaceship etc.
Embodiment
Embodiment 1
640g Potassium ethanoate and 1700ml toluene add in the four-hole boiling flask, and temperature rising reflux anhydrates.Phenyl-trichloro-silicane and METHYL TRICHLORO SILANE were mixed 424g in 3: 1 in molar ratio, slowly drip in the four-hole boiling flask, control reaction temperature dropwises continued and stirs 2hr about 40 ℃; Add 209g methyl alcohol to four-hole boiling flask, control reaction temperature is at 50 ℃, after dropwising; Continue to stir 1hr, be warming up to 70 ℃ of backflow 2hr, reclaim the cut below 78 ℃; Distillate 484ml, add tap water and wash, intensification low-pressure distillation toluene to pH=7.Get 210g solid methyl phenyl silicone resin, detect solid content 99.5%, gel time 28 minutes and 30 seconds.
Embodiment 2
588g sodium-acetate and 1700ml toluene add in the four-hole boiling flask, and temperature rising reflux anhydrates.Phenyl-trichloro-silicane, METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS) were mixed 426g in 3: 1: 1 in molar ratio, slowly drip in the four-hole boiling flask, control reaction temperature dropwises continued and stirs 2hr about 42 ℃; Add 215g methyl alcohol to four-hole boiling flask, control reaction temperature is at 60 ℃, after dropwising; Continue to stir 1hr, be warming up to 68 ℃ of backflow 2hr, reclaim the cut below 80 ℃; Distillate 496ml, add tap water and wash, intensification low-pressure distillation toluene to pH=7.Get 200g solid methyl phenyl silicone resin, detect solid content 99.8%, gel time 18 minutes and 47 seconds.
Embodiment 3
671g acetic anhydride and 1700ml toluene add in the four-hole boiling flask, and temperature rising reflux anhydrates.Diphenyl dichlorosilane, METHYL TRICHLORO SILANE were mixed 575g in 3: 2 in molar ratio, slowly drip in the four-hole boiling flask, control reaction temperature dropwises continued and stirs 2hr about 45 ℃; Add 215g methyl alcohol to four-hole boiling flask, control reaction temperature is at 60 ℃, after dropwising; Continue to stir 1hr, be warming up to 71 ℃ of backflow 2hr, reclaim the cut below 80 ℃; Distillate 476ml, add tap water and wash, intensification low-pressure distillation toluene to pH=7.Get 215g solid methyl phenyl silicone resin, detect solid content 99.2%, gel time 30 minutes and 15 seconds.
Claims (8)
1. the preparation method of a high-temperature resisting methyl phenyl polysiloxane is characterized in that comprising the following steps: acetic acid derivative is dissolved in the toluene, and backflow is anhydrated; With slowly dripping after the chlorosilane raw materials mix, stir, add methyl alcohol again; Continue stirring and refluxing, reclaim the cut of cut in 67～80 ℃ of scopes, add water washing after the cooling to pH=6～7; Remove solvent under the negative pressure of vacuum, get the solid finished product after the cooling, said acetic acid derivative is selected from Potassium ethanoate, sodium-acetate or acetic anhydride; Said chlorosilane raw material be selected from dimethyldichlorosilane(DMCS), the METHYL TRICHLORO SILANE at least a and be selected from mixture at least a in diphenyl dichlorosilane, the phenyl-trichloro-silicane.
2. the preparation method of claim 1 wherein in the chlorosilane raw material, presses R/Si:0.25～1.0 with organosilicon functional group and Siliciumatom in the mixture, Ph/ (Ph+Me): 0.5～0.75 mixed.
3. the preparation method of claim 1, wherein the mol ratio of the cl ions in the consumption of acetic acid derivative and the chlorosilane raw material is 1: 1～1: 1.2.
4. the preparation method of claim 1, wherein the mol ratio of the cl ions in the consumption of methyl alcohol and the chlorosilane raw material is 1: 1～1: 1.2.
5. the preparation method of claim 1, solution temperature is controlled at 30～50 ℃ when wherein dripping the chlorosilane raw material.
6. the preparation method of claim 1, solution temperature is controlled at 45～60 ℃ when wherein adding methyl alcohol.
7. the preparation method of claim 1 wherein drips to stir after 2～3 hours behind the chlorosilane raw material and adds methyl alcohol again.
8. the preparation method of claim 1, wherein add methyl alcohol after restir refluxed 1～2 hour.
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| CN 201110403755 CN102492143B (en) | 2011-12-07 | 2011-12-07 | Preparation method for high-temperature-resistant silicon resin |
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| CN 201110403755 CN102492143B (en) | 2011-12-07 | 2011-12-07 | Preparation method for high-temperature-resistant silicon resin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204993A (en) * | 2013-04-16 | 2013-07-17 | 江苏大学 | Preparation method of methyl silicone resin |
| CN105111440A (en) * | 2015-09-24 | 2015-12-02 | 唐山三友硅业有限责任公司 | Continuous environment-friendly preparation process of methyl phenyl silicone resin for high-temperature-resistant paint |
| CN106366315A (en) * | 2016-08-31 | 2017-02-01 | 湖北新四海化工股份有限公司 | Powder silicon resin and preparation method thereof |
| CN107141944A (en) * | 2017-06-30 | 2017-09-08 | 浙江永固为华涂料有限公司 | A kind of thin layer storage tank outer wall insulating moulding coating |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423611A (en) * | 2008-12-01 | 2009-05-06 | 金小凤 | Method for preparing high temperature resistant silicone resin |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423611A (en) * | 2008-12-01 | 2009-05-06 | 金小凤 | Method for preparing high temperature resistant silicone resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204993A (en) * | 2013-04-16 | 2013-07-17 | 江苏大学 | Preparation method of methyl silicone resin |
| CN103204993B (en) * | 2013-04-16 | 2015-06-10 | 江苏大学 | Preparation method of methyl silicone resin |
| CN105111440A (en) * | 2015-09-24 | 2015-12-02 | 唐山三友硅业有限责任公司 | Continuous environment-friendly preparation process of methyl phenyl silicone resin for high-temperature-resistant paint |
| CN106366315A (en) * | 2016-08-31 | 2017-02-01 | 湖北新四海化工股份有限公司 | Powder silicon resin and preparation method thereof |
| CN107141944A (en) * | 2017-06-30 | 2017-09-08 | 浙江永固为华涂料有限公司 | A kind of thin layer storage tank outer wall insulating moulding coating |
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| CN102492143B (en) | 2013-05-08 |
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Effective date of registration: 20190628 Address after: 212200 Yihe Road, Sanmao Town, Yangzhong City, Zhenjiang City, Jiangsu Province Patentee after: Jiangsu Pearl Silicone Rubber Material Co., Ltd. Address before: 212200 No. 1 Yihe Road, Pearl Square, Yangzhong City, Zhenjiang City, Jiangsu Province Patentee before: Jiangsu Hongda New Material Co., Ltd. |