CN102887916A - Alkoxy silicon resin intermediate and preparation method thereof - Google Patents

Abstract

The invention relates to an alkoxy silicone resin intermediate and a preparation method thereof, wherein the alkoxy content of the alkoxy silicone resin intermediate is 8 to 15%, and the viscosity of the alkoxy silicone resin intermediate is 10~500mm ² /S. The preparation method of the organosilicon resin intermediate of the present invention comprises the following steps: (1) adding alcohol to the organochlorosilane to carry out alcoholysis reaction; (2) adding a catalyst to the alcoholysis product and condensing at 50-200°C React for 1~8h to get the condensation product; (3) Add water to the condensation product, hydrolyze at 30~100°C; (4) Neutralize the pH value to 6~8, remove the methanol in the product, decolorize and filter , in alkoxy silicone resin intermediates. The alkoxy silicone resin intermediate of the present invention can be applied to modify organic resins containing active hydroxyl functional groups and can also be directly mixed with curing agents for coil steel coatings, electrical paints and other high temperature resistant products, etc., the by-product of its preparation method Less, economical and environmentally friendly.

Description

A kind of alkoxy silicone resin intermediate and preparation method thereof

technical field

The invention relates to a resin intermediate and a preparation method thereof, in particular to an alkoxy-containing silicone resin intermediate and a preparation method thereof.

Background technique

The basic structural unit (main chain) of traditional silicone polymers is composed of Si-O chain links, and the side chains are connected to various other organic groups through silicon atoms. Therefore, the structure of silicone products contains both "organic groups" and "inorganic structures". This special composition and molecular structure makes it integrate the characteristics of organic substances and the functions of inorganic substances, and has high and low temperature resistance , weather aging resistance, electrical insulation, ozone resistance, water repellency, flame retardant, non-toxic, non-corrosive and physiologically inert, and many other excellent properties, and some varieties also have oil resistance, solvent resistance, and radiation resistance. Compared with other polymer materials, the Si-O bond energy (450KJ/mol) in silicone resin is much greater than the C-C bond energy (345KJ/mol) and C-O bond energy (351KJ/mol). Therefore, the most prominent properties of silicone products are excellent temperature resistance, dielectric properties, weather resistance, physiological inertia and low surface tension, etc. Therefore, silicone products have been widely used in the fields of coatings, adhesives and high temperature resistant resins. application.

Due to the excellent performance of silicone products, they are widely used to modify other organic resins. There are two main types of silicone products used for modification: hydroxyl-containing silicone resin intermediates and alkoxy-containing silicone resin intermediates. When the hydroxyl-containing silicone resin intermediate reacts with the organic resin, the hydroxyl group not only reacts with the hydroxyl group of the organic resin, but also undergoes a condensation reaction, which makes the reaction difficult to control, and sometimes the product is turbid. For example, the hydroxyl silicone resin intermediate reacts with E-44, and after adding a solvent, a transparent product can be obtained, and occasionally a turbid product; and it is difficult to obtain a transparent product by reacting with E-20. And when preparing hydroxyl-containing organic silicon resin intermediates, organochlorosilanes are mainly used to hydrolyze in the presence of solvents such as toluene and xylene, and then separate acid water, and wash the resin liquid to neutrality. This method will produce a large amount of low-concentration acid water 1. The use of organic solvents and the like brings environmental pollution, and the obtained silanol needs to be preserved in a solvent, so there are many defects. However, the technology for preparing silicone resin intermediates containing alkoxy groups is not yet mature, and there is no effective method for preparing silicone resin intermediates containing certain alkoxy groups.

Contents of the invention

In order to overcome the above defects, the present invention provides an economical and environment-friendly alkoxy silicone resin intermediate with few by-products and a preparation method thereof.

In the alkoxy silicone resin of the present invention, the alkoxy content of the alkoxy silicone resin intermediate is 8-15%, and the viscosity of the alkoxy silicone resin intermediate is 10-500mm ² /S .

Wherein, the viscosities mentioned in the present invention are all measured at 25° C. with a Pinnacle viscometer.

Wherein, the alkoxy group is a methoxy group or an ethoxy group.

The present invention also provides a kind of preparation method of alkoxy silicone resin intermediate, it comprises the following steps:

(1) Add alcohol to organochlorosilane for alcoholysis reaction;

(2) Add a catalyst to the alcoholysis product, and conduct a condensation reaction at 50-200°C for 1-8 hours to obtain a condensation product;

(3) Add water to the condensation product and perform hydrolysis reaction at 30~100°C;

(4) Neutralize to a pH value of 6-8, remove impurities, decolorize, and filter to obtain an alkoxy silicone resin intermediate.

Wherein, in step (1), the molar ratio of alcohol to chlorine in the organochlorosilane is (0.3~1.5): 1; the organochlorosilane is methyltrichlorosilane, phenyltrichlorosilane, methylphenyldichlorosilane One or more of chlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, silicon tetrachloride, methyl vinyl dichlorosilane; the molar ratio of the alcohol to the chlorine in the organochlorosilane is (0.5~1.2):1.

In addition, the alcohol is methanol or ethanol; the alcoholysis temperature is 0-100°C, and the alcoholysis time is 3-5h. Wherein, the temperature of the alcoholysis is preferably 0-30°C, especially preferably 10-20°C.

In addition, in step (1), the method of adding alcohol is dropwise, and the dropping rate is 10-120kg/h.

In addition, in step (2), the dosage of the catalyst is 0.01-0.5% of the weight of the organochlorosilane; the catalyst is ferric chloride, boric acid, sulfuric acid, trifluoromethanesulfonic acid, zinc chloride, zinc octoate , zinc naphthenate, zinc naphthenate, cobalt naphthenate, boric acid, tin chloride, dibutyltin dilaurate, aluminum trichloride or zinc isooctanoate.

In addition, in step (3), the amount of water added is 0.5-25% of the weight of the condensation product, the adding method is dropwise, and the dropping rate is 5-30kg/h. In addition, the amount of water added is preferably 4-20% of the weight of the condensation product.

In addition, in step (4), the pH value is neutralized with sodium methoxide, sodium ethoxide or pyridine.

In addition, the present invention removes volatile components at 60~180°C and -0.06~-0.1MPa. Moreover, activated carbon, acid clay and other decolorizing agents can be used to decolorize the product. And the product is preferably dried at 60-150°C for 1-5 hours, more preferably at 80-130°C for 1-4 hours.

The invention prepares a silicone resin intermediate containing an alkoxy group, specifically a silicone resin intermediate containing a methoxy group or an ethoxy group, which can be used to modify an organic resin containing an active hydroxyl functional group (such as: epoxy resin, saturated Polyester, alkyd resin, etc.) to form a modified copolymer to improve its heat resistance, weather resistance, toughness and other comprehensive properties; it can also be used to produce silicone products; it can also be directly mixed with curing agent for coil steel Coatings, electrical paints and other high-temperature-resistant products; expand the application field of silicone products, and provide high-quality raw materials for obtaining excellent modified products.

In addition, the intermediate preparation method of the alkoxysilicone resin of the present invention uses organochlorosilane alcoholysis, and the by-products produced can be absorbed by circulating water, and the concentration of acid water can be increased to more than 25% by the treatment of the tail gas system. in other fields. Moreover, no other organic solvents are used in the production process, and the product is solvent-free, which is convenient for storage and transportation. The invention has the advantages of environment-friendly production, few by-products, recyclable utilization, and no harmful solvents such as benzene and toluene. The invention fills up the gap in domestic production, and the product reaches the international level.

Detailed ways

The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

Example 1

Add 150g of methyltrichlorosilane, 230g of phenyltrichlorosilane, and 20g of methylphenyldichlorosilane into the reactor, stir evenly, then add 115g of methanol dropwise into the reactor at a rate of 10Kg/h, and react at 10°C After 3 hours, the temperature was raised to 40°C, 0.04 g of zinc octylate was added, and the reaction was carried out at 90°C for 5 hours to obtain about 250 g of a crude product. Cool down to 80°C, add 20g of water dropwise at a rate of 30Kg/h, react at 80°C for 2 hours, neutralize with sodium methoxide to pH 7, remove volatiles under reduced pressure, maximum temperature 80°C, pressure -0.095Mpa, Add 2 g of activated carbon and filter to obtain about 200 g of the product. The appearance of the product is a colorless transparent liquid with a viscosity of 150 mm ² /s and an alkoxy content of 8%.

Example 2

Add 150g of methyltrichlorosilane, 230g of phenyltrichlorosilane, and 365.2g of dimethyldichlorosilane into the reactor, stir evenly, then add 165g of ethanol dropwise to the reactor at a rate of 120Kg/h, and react at 10°C After 5h, 3.73g of ferric chloride was added and reacted at 200°C for 1 hour to obtain about 450g of crude product. Cool down to 80°C, add 20g of water dropwise at a rate of 5Kg/h, react at 100°C for 2 hours, neutralize with sodium ethoxide to pH 8, remove volatiles under reduced pressure, maximum temperature 80°C, pressure -0.095Mpa, Add gac 2g, filter, obtain product 360g, product appearance is colorless transparent liquid, viscosity 120mm ^/ s, alkoxyl content 15% (.

Example 3

Add 301.31g of diphenyldichlorosilane into the reactor, stir evenly, then drop 165g of ethanol into the reactor at a rate of 50Kg/h, react at 0°C for 3h, raise the temperature to 40°C, add 0.6g of zinc naphthalate, React at 50°C for 8 hours, get 320g of the crude product, cool down to 80°C, add 15g of water dropwise at a rate of 10Kg/h, react at 50°C for 3 hours, neutralize with sodium methoxide to pH 6, and decompress to remove volatilization The highest temperature is 180°C, the pressure is -0.1Mpa, 2g of activated carbon is added and filtered to obtain 260g of the product. The appearance of the product is a colorless transparent liquid with a viscosity of 10mm ² /s and the content of alkoxy groups in the product is 15%.

Example 4

Add 126.6g of dimethyldichlorosilane and 70.53g of methylvinyldichlorosilane into the reactor, stir evenly, then drop 90g of ethanol into the reactor at a rate of 80Kg/h, react at 0°C for 3h, and heat up to At 60°C, add 0.2g of zinc naphthenate and react at 100°C for 4 hours to obtain 160g of crude product. Cool down to 60°C, add 30g of water dropwise at a rate of 20Kg/h, react at 30°C for 4 hours, neutralize with sodium ethoxide to pH 8, remove volatiles under reduced pressure, maximum temperature 60°C, pressure -0.06Mpa, Add 2 g of acid clay and filter to obtain 130 g of the product, which is a colorless transparent liquid with a viscosity of 105 mm ² /s and an alkoxy content of 9%.

Example 5

Add 230g of phenyltrichlorosilane and 42.60g of dimethyldichlorosilane into the reactor, stir evenly, then drop 150g of methanol into the reactor at a rate of 10Kg/h, react at 80°C for 3h, and heat up to 60°C. Add 1.01g of dibutyltin dilaurate, react at 90°C for 5 hours to obtain 231g of crude product, cool down to 80°C, add 10g of water dropwise at a rate of 10Kg/h, react at 80°C for 2 hours, and neutralize with sodium methoxide When the pH value is 7, add 2g of activated carbon, filter, add 0.01g of concentrated hydrochloric acid, then dropwise add 40g of water, react at 50°C for 2h, remove volatiles under reduced pressure, the maximum temperature is 80°C, and the pressure is -0.095Mpa to obtain 190g of the product , the appearance of the product is a colorless transparent liquid with a viscosity of 425mm ² /s and an alkoxy content of 8%.

Example 6

Add 286.7g of methylphenyldichlorosilane, 193.53g of dimethyldichlorosilane, and 167.41g of methyltrichlorosilane into the reactor, stir evenly, then add 150g of methanol dropwise to the reactor at a speed of 10Kg/h. React at 100°C for 3 hours, raise the temperature to 40°C, add 0.59 g of trifluoromethanesulfonic acid, and react at 120°C for 5 hours to obtain 400 g of crude product. Cool down to 80°C, add 10g of water dropwise at a rate of 15Kg/h, react at 80°C for 2 hours, neutralize with sodium methoxide to pH 7, remove volatiles under reduced pressure, maximum temperature 80°C, pressure -0.095Mpa, Add 2 g of activated carbon and filter to obtain 360 g of the product, which is a colorless transparent liquid with a viscosity of 95 mm ² /s and an alkoxy content of 14%.

Claims (9)

1. an alkoxyl silicone resin intermediate is characterized in that, the content of alkoxyl group is 8 ~ 15% in the described alkoxyl silicone resin intermediate, and the viscosity of described alkoxyl silicone resin intermediate is 10 ~ 500mm ²/ S.

2. silicone resin intermediate according to claim 1 is characterized in that, described alkoxyl group is methoxy or ethoxy.

3. the preparation method of an alkoxyl silicone resin intermediate according to claim 1 and 2 is characterized in that, comprises the steps:

(1) in organochlorosilane, adds alcohol, carry out alcoholysis reaction;

(2) in alcoholysis product, add catalyzer, in 50 ~ 200 ℃ of condensation reaction 1 ~ 8h, obtain condensation product;

(3) in condensation product, add entry, in 30 ~ 100 ℃ of hydrolysis reaction;

(4) being neutralized to the pH value is 6 ~ 8, imurity-removal, and decolour, filter, get the alkoxyl silicone resin intermediate.

4. method according to claim 3 is characterized in that, in the step (1), the mol ratio of chlorine is (0.3 ~ 1.5) in alcohol and the organochlorosilane: 1; Described organochlorosilane is one or more in METHYL TRICHLORO SILANE, phenyl-trichloro-silicane, dichloromethyl phenylsilane, dimethyldichlorosilane(DMCS), diphenyl dichlorosilane, silicon tetrachloride, the methyl ethylene dichlorosilane; The mol ratio of chlorine is (0.5 ~ 1.2) in described alcohol and the organochlorosilane: 1.

5. method according to claim 3 is characterized in that, described alcohol is methyl alcohol or ethanol; The temperature of described alcoholysis is that 0 ~ 100 ℃, time of alcoholysis are 3 ~ 5h.

6. method according to claim 3 is characterized in that, in step (1), adds the mode of alcohol for dripping, and rate of addition is 10 ~ 120kg/h.

7. method according to claim 3 is characterized in that, in step (2), the consumption of described catalyzer is 0.01 ~ 0.5% of organochlorosilane weight; Described catalyzer is a kind of in iron trichloride, boric acid, sulfuric acid, trifluoromethanesulfonic acid, zinc chloride, zinc octoate, naphthalene acid zinc, zinc naphthenate, cobalt naphthenate, boric acid, tin chloride, dibutyl tin dilaurate, aluminum chloride or the isocaprylic acid zinc.

8. method according to claim 3 is characterized in that, in step (3), the amount that adds entry is 0.5 ~ 25% of condensation product weight, and the adding mode is dropping, and rate of addition is 5 ~ 30kg/h.

9. method according to claim 3 is characterized in that, in step (4), with in sodium methylate, sodium ethylate or the pyridine and the pH value.