CN101508776A - Method of preparing methyl phenyl polysiloxane - Google Patents

Abstract

The invention discloses a method for synthesizing organic silicon, specifically referring to a method for preparing a methylphenyl silicone resin which itself has a low curing temperature and does not stick back. In the present invention, by using monomers such as methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, methylphenyldichlorosilane and diphenyldichlorosilane, the ratio of raw materials is adjusted to control the appropriate reaction Temperature and polymerization time, hydrolysis reaction, polycondensation reaction and other processes are carried out to obtain a methyl phenyl silicone resin with low curing temperature and no back-sticking of the paint film after curing. The advantage of the present invention is that the methylphenyl silicone resin prepared by the method has the characteristics of low curing temperature, no sticking back, clarity, high and low temperature resistance, weather resistance, insulation, etc., and is especially suitable for impregnating varnishes above H level. It is suitable for the preparation of insulating varnishes, weather-resistant varnishes, and high-temperature-resistant varnishes above H level, used as high-temperature-resistant mold release agents, and can also be used in some demanding fields such as oil drilling, high-temperature resistance, water resistance and sand prevention.

Description

A kind of preparation method of methylphenyl silicone resin

technical field

The invention relates to a method for synthesizing organosilicon, in particular to a method for preparing methylphenyl silicone resin which itself has a low curing temperature and does not stick back.

Background technique

At present, there are general-purpose methylphenyl silicone resins of existing brands at home and abroad, such as 1153, 1053 and other methylphenyl silicone resins. Their curing temperature needs to be ≥ 200°C, and the cured paint film has weak adhesion to the substrate and cannot be cured. The paint film is easy to stick back and other shortcomings. Some brands of silicone resins with low-temperature curing characteristics mainly rely on external crosslinking agents, catalysts and other components to strengthen the curing reaction. As a result, the heat resistance of the cured silicone resin is reduced, especially the high-temperature flexibility deterioration and storage Stability, but still can not completely overcome the phenomenon of sticking back after curing.

The methylphenyl silicone resin of the present invention has excellent properties, such as low curing temperature, no stickiness, clarity, high and low temperature resistance, weather resistance, insulation, etc. Insulating varnishes, weather-resistant varnishes, and high-temperature-resistant varnishes above grade H are used as high-temperature-resistant mold release agents, and can also be used in some demanding fields such as oil drilling, high-temperature resistance, water resistance, and sand prevention.

Contents of the invention

The invention aims at the deficiencies in the prior art. The invention proposes a convenient preparation method, which can realize the methyl phenyl silicone resin itself with low curing temperature and no sticking back.

The present invention is achieved through the following technical solutions:

A preparation method of methyl phenyl silicone resin is characterized in that it is carried out according to the following steps:

(1) Methyltrichlorosilane (MeSiCl ₃ ), dimethyldichlorosilane (Me ₂ SiCl ₂ ), phenyltrichlorosilane (PhSiCl ₃ ), methylphenyldichlorosilane (MePhSiCl ₂ ) and two Any two or more monomers in phenyldichlorosilane (Ph ₂ SiCl ₂ ) are dissolved in toluene to form a chlorosilane toluene solution, which is subjected to a hydrolysis reaction to obtain a silanol toluene solution; preferably, the hydrolysis reaction temperature is 30°C to 70°C; preferably, the concentration of the silanol toluene solution is 40% to 60%, calculated based on the mass of the silanol in the solution;

(2) Then wash with hot water at 40°C to 70°C until neutral;

(3) add organic amine or other organic bases to carry out polycondensation reaction as a catalyst, and react for 1 to 6 hours; preferably, the polycondensation reaction is carried out at a reaction temperature of 50 to 60°C and a vacuum of -0.07 to 0.08MPa; as Preferably, the catalyst is triethanolamine, triethylenediamine, triethylenetetramine, tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrabutylammonium hydroxide; as a better choice, the catalyst is Butanol is made into a 10% solution, prepared by mass percentage; the amount of catalyst is 0.05‰～2‰ of silanol, calculated by mass;

(4) add stabilizer again, can obtain methylphenyl silicone resin; As preferably, described stabilizer is phosphoric acid, acetic acid, acetic anhydride; As a better choice, the ratio of described stabilizer and catalyst is 1 : 0.1～1.0, calculated by mass ratio.

The invention is a methyl phenyl silicone resin with low curing temperature, non-sticky, clear and transparent, high and low temperature resistance, weather resistance, insulation and other characteristics, which is used for impregnating varnishes above H level and for preparing insulating varnishes above H level , weather-resistant paint, high-temperature-resistant paint, high-temperature-resistant mold release agent, and can also be used in some demanding fields such as oil drilling, high-temperature resistance, water resistance and sand prevention.

Polymerization general formula of the present invention is as follows:

Note: R=Me, Ph.

Beneficial effects: the methylphenyl silicone resin prepared by the method of the present invention has the characteristics of low curing temperature, no stickiness, clarity, high and low temperature resistance, weather resistance, insulation, etc., and is especially suitable for impregnating varnishes above H level. It is suitable for the preparation of insulating varnishes, weather-resistant varnishes, and high-temperature-resistant varnishes above H level, used as high-temperature-resistant mold release agents, and can also be used in some demanding fields such as oil drilling, high-temperature resistance, water resistance and sand prevention. The obtained methylphenyl silicone resin has an R/Si of 1.20-1.70 (molar ratio), a Ph/R of 0.1-0.6 (molar ratio), and a curing temperature of ≤100°C.

Detailed ways

The implementation of the present invention is described in detail below:

The preparation process of the present invention is as follows:

a. Add various monomers and toluene in proportion to the mixing kettle, mix evenly, add toluene and water into the reaction kettle, stir and heat up to 30-65°C, start adding the mixed monomer solution dropwise, and control the temperature at 30-65°C The dropwise addition is completed within 1.5 to 3 hours at 70°C, and then keep the temperature for half an hour to react;

b, static stratification, put down a layer of acidic water;

c. Wash with hot water at 40-70°C until neutral;

d. Concentrate it to 40% to 60% (mass percentage) under high vacuum conditions and at a temperature not exceeding 60°C;

e. Adding an appropriate amount of catalyst, polycondensation reaction at a vacuum of -0.07 to -0.08MPa and a temperature of 50 to 60°C for 1 to 6 hours, and adding a corresponding amount of stabilizer to obtain a methylphenyl silicone resin.

Example 1:

Add 149.5g of methyltrichlorosilane, 37.5g of dimethyldichlorosilane, 38.1g of phenyltrichlorosilane and 286g of toluene into the mixing tank and mix well. Add 184g of toluene and 950g of water into the reaction kettle, stir and heat up to 65°C, start adding the mixed monomers dropwise, control the reaction temperature at 65-70°C within 3 hours, and finish the reaction for half an hour. After resting, remove the lower acidic water layer, then wash the silanol toluene solution with 65-70°C hot water until neutral, and concentrate under reduced pressure to a solid content of 60%. Take 100g of this silanol solution, add 0.03g of 10% triethylenetetraminebutanol solution as a catalyst, and then add 0.003g of acetic acid stabilizer at a vacuum degree of -0.08MPa and control the temperature at 50°C for 6 hours to obtain a viscosity of 15s (Apply 4 cups), methyl phenyl silicone resin (R/Si=1.2, Ph/R=0.1) that cures at 40°C for 1 hour and does not retack.

Example 2:

Add 195g of diphenyldichlorosilane, 105.8g of phenyltrichlorosilane, 81.3g of dimethyldichlorosilane, 15g of methyltrichlorosilane and 354g of toluene into the mixing tank and mix well. Add 189g of toluene and 1240g of water into the reaction kettle, stir and heat up to 30°C, start to add the mixed monomers dropwise, control the reaction temperature at 30-35°C for 1.5 hours, then stir the reaction for half an hour. After static separation, the lower acidic water layer was removed, and the silanol toluene solution was washed with warm water at 40-45°C until neutral, and then concentrated under reduced pressure to a solid content of 40%. Take 100 g of this silanol solution, add 0.12 g of 10% tetraethylammonium hydroxide butanol solution as a catalyst, and react at a vacuum degree of -0.07 MPa at 60° C. for 1 hour, then add 0.0012 g of acetic anhydride stabilizer, A methylphenyl silicone resin (R/Si=1.7, Ph/R=0.6) with a viscosity of 25 s (coating 4 cups), cured at 100° C. for 2 hours and no retack was obtained.

Example 3:

Add 154g methyltrichlorosilane, 128g dimethyldichlorosilane, 317g phenyltrichlorosilane, 285g methylphenyldichlorosilane and 650g toluene into the mixing tank and mix well. Add 325g of toluene and 1875g of water into the reaction kettle, stir and heat up to 40°C, start to add the mixed monomers dropwise, control the reaction temperature at 40-45°C, and react for half an hour after the drop is completed within 2 hours. After static separation, the lower acidic water layer was removed, the silanol toluene solution was washed with hot water at 55-60°C until neutral, and then concentrated under reduced pressure to a solid content of about 50%. Take 100 g of this silanol solution, add 0.1 g of 10% tetramethylammonium hydroxide butanol solution as a catalyst, and react for 2 hours at a vacuum degree of -0.075 MPa and a temperature of 55 ° C, then add 0.002 g of a phosphoric acid stabilizer, A methylphenyl silicone resin (R/Si=1.5, Ph/R=0.4) with a viscosity of 21 s (coating 4 cups) and curing at 90° C. for 1.5 hours without retack was obtained.

Example 4:

Add 128g of methyltrichlorosilane, 107g of dimethyldichlorosilane, 227g of phenyltrichlorosilane and 520g of toluene into the mixing tank and mix well. Add 337g of toluene and 2997g of water into the reaction kettle, stir and heat up to 50°C, start to add the mixed monomers dropwise, control the reaction temperature at 50-55°C, and react for half an hour after 2.5 hours of dropwise addition. Static layering to remove the acidic water layer, washing the silanol toluene solution with hot water at 60-65°C until neutral, and then concentrating under reduced pressure until the solid content is 45%. Take 100 g of this silanol solution, add 0.18 g of 10% triethanolamine butanol solution as a catalyst, react for 3 hours at a vacuum degree of -0.075 MPa, and a temperature of 50 ° C, and then 0.0022 g of acetic anhydride stabilizer to obtain a viscosity of 18 s (Coat 4 cups) Methylphenyl silicone resin (R/Si=1.3, Ph/R=0.3) that cures at 60°C for 1 hour and does not retack.

Implement pour 5:

Add 127g of methyltrichlorosilane, 274g of dimethyldichlorosilane, 270g of phenyltrichlorosilane and 750g of toluene into the mixing tank and mix well. Add 400g of toluene and 2000g of water into the reaction kettle, stir and heat up to 40°C, start to add the mixed monomers dropwise, control the reaction temperature at 40-45°C within 2 hours and then react for half an hour. Static layering, separation of the acidic water layer, washing the silanol toluene solution with 45-50°C hot water until neutral, and then concentrating under reduced pressure until the solid content is 50%. Take 100 g of this silanol solution, add 0.075 g of 10% tetramethylammonium hydroxide butanol solution as a catalyst, the vacuum degree is -0.07 MPa, and the temperature is controlled at 50 ° C. After reacting for 3.5 hours, add 0.003 g of acetic acid stabilizer to obtain the viscosity It is a methyl phenyl silicone resin (R/Si=1.5, Ph/R=0.2) that cures at 80°C for 1.5 hours in 20s (coating 4 cups) and does not stick back.

Embodiment 6:

Add 150g of methyltrichlorosilane, 129g of dimethyldichlorosilane, 180g of diphenyldichlorosilane, 332g of phenyltrichlorosilane and 550g of toluene into the mixing tank and mix well. Add 280g of toluene and 1800g of water into the reaction kettle, stir and heat up to 45°C, start to add the mixed monomers dropwise, control the reaction temperature at 45-50°C for 2 hours and then react for half an hour. Static layering, separation of the acidic water layer, washing the silanol toluene solution with hot water at 50-55°C until neutral, and then concentrating under reduced pressure until the solid content is 50%. Take 100g of this silanol solution, add 0.95g of 10% tetrabutylammonium hydroxide butanol solution as a catalyst, the vacuum degree is -0.075MPa, and the temperature is controlled at 55°C. After reacting for 3.5 hours, add 0.004g of phosphoric acid stabilizer to obtain a viscosity of 22s (Coat 4 cups) Methylphenyl silicone resin (R/Si=1.4, Ph/R=0.5) cured at 90°C for 1.5 hours without retack.

Embodiment 7:

Add 90g of methyltrichlorosilane, 43g of dimethyldichlorosilane, 268g of phenyltrichlorosilane, 89g of methylphenyldichlorosilane and 360g of toluene into the mixing tank and mix well. Add 180g of toluene and 1100g of water into the reaction kettle, stir and heat up to 35°C, start to add the mixed monomers dropwise, control the reaction temperature at 35-40°C for 2 hours, then keep the temperature for half an hour. Static layering, separate the acidic water layer, wash the silanol toluene solution with hot water at 50-55°C until neutral, then concentrate under reduced pressure until the solid content is 50%. Take 100g of this silanol solution, add 0.1g of 10% triethylenediaminebutanol solution as a catalyst, the vacuum degree is -0.075MPa, and the temperature is controlled at 55°C. After reacting for 3.5 hours, add 0.003g of acetic acid stabilizer to obtain a viscosity of 21s (Coat 4 cups) Methylphenyl silicone resin (R/Si=1.3, Ph/R=0.5) cured at 95°C for 1.5 hours without retack.

Claims (8)

1, a kind of preparation method of methyl phenyl silicone resin is characterized in that being undertaken by following step:

(1) with METHYL TRICHLORO SILANE (MeSiCl ₃), dimethyldichlorosilane(DMCS) (Me ₂SiCl ₂), phenyl-trichloro-silicane (PhSiCl ₃), dichloromethyl phenylsilane (MePhSiCl ₂) and diphenyl dichlorosilane (Ph ₂SiCl ₂) in any two or more monomers be dissolved in the toluene, form the silicone resin toluene solution; The reaction that is hydrolyzed again, the silanol toluene solution;

(2) use 40 ℃～70 ℃ hot water wash to neutral then;

(3) add organic amine again or other organic bases carries out polycondensation as catalyzer, reacted 1～6 hour;

(4) add an amount of stablizer, can obtain methyl phenyl silicone resin.

2, according to the preparation method of the described a kind of methyl phenyl silicone resin of claim 1, it is characterized in that: described hydrolysising reacting temperature is 30 ℃～70 ℃.

3, according to the preparation method of the described a kind of methyl phenyl silicone resin of claim 1, it is characterized in that: the concentration of described silicone resin toluene solution is 40%～60%, accounts for the Mass Calculation of solution with silanol.

4, according to the preparation method of the described a kind of methyl phenyl silicone resin of claim 1, it is characterized in that: described polycondensation is to be 50～60 ℃ in temperature of reaction, and vacuum tightness is carried out under-0.07～0.08MPa.

5, a kind of method of preparing methyl phenyl polysiloxane according to claim 1 is characterized in that: described catalyzer is trolamine, triethylene diamine, triethylene tetramine, Tetramethylammonium hydroxide, tetraethyl-hydrogen-oxygen ammonium or TBAH.

6, a kind of method of preparing methyl phenyl polysiloxane according to claim 5 is characterized in that: described catalyzer is to be made into 10% solution, preparation by mass percentage with butanols; Catalyst levels is 0.05 ‰～2 ‰ of a silanol, calculates by mass.

7, a kind of method of preparing methyl phenyl polysiloxane according to claim 1 is characterized in that: described stablizer is phosphoric acid, acetic anhydride, acetic acid.

8, a kind of method of preparing methyl phenyl polysiloxane according to claim 7, it is characterized in that: the ratio of described consistent dose and catalyzer is 1:0.1～1.0, presses mass ratio.