阅读说明：本技术 一种含超支化聚碳硅烷的有机硅脱模剂的制备方法及其应用 (Preparation method and application of organic silicon release agent containing hyperbranched polycarbosilane ) 是由 杨雄发 吴于飞 刘江玲 程飞 焦晓皎 于 2019-01-07 设计创作，主要内容包括：本发明涉及有机硅技术领域,为解决现有橡胶轮胎脱模剂耐温性不够好,导致橡胶轮胎制品上残留一些比较脏的黄色物质,严重影响产品质量的问题,本发明提出了一种含超支化聚碳硅烷的有机硅脱模剂的制备方法,将超支化含氢聚碳硅烷、超支化乙烯基碳硅烷、聚硅氧烷、乳化剂、铂催化剂、增稠剂预混合后,加入去离子水乳化,制备成含超支化聚碳硅烷的有机硅脱模剂。制备方法简单,得到的脱模剂具有耐高温和耐磨性。(The invention relates to the technical field of organic silicon, and aims to solve the problems that the existing rubber tire release agent has poor temperature resistance, so that dirty yellow substances are remained on a rubber tire product, and the product quality is seriously influenced. The preparation method is simple, and the obtained release agent has high temperature resistance and wear resistance.)

1. A preparation method of an organic silicon release agent containing hyperbranched polycarbosilane is characterized in that the preparation method comprises the steps of premixing hyperbranched hydrogenous polycarbosilane, hyperbranched vinyl carbosilane, polysiloxane, an emulsifier, a platinum catalyst and a thickening agent, and adding deionized water for emulsification to prepare the organic silicon release agent containing hyperbranched polycarbosilane.

2. The method for preparing the organic silicon release agent containing the hyperbranched polycarbosilane as claimed in claim 1, wherein the hyperbranched vinyl polycarbosilane is one or more of hyperbranched polyvinyl carbosilanes with different generations and silicon vinyl groups at the tail ends; the hyperbranched polycarbosilane containing hydrogen is one or more of hyperbranched polycarbosilanes containing hydrogen and with different generations and silicon hydrogen at the tail end.

3. The method for preparing the organic silicon release agent containing the hyperbranched polycarbosilane as claimed in claim 1 or 2, wherein the hyperbranched hydrogenpolycarbosilane and the hyperbranched vinyl polycarbosilane are used according to the molar ratio of silicon hydrogen to silicon vinyl of 0.7 ~ 1.5.5: 1.

4. The method for preparing the organic silicon release agent containing the hyperbranched polycarbosilane as claimed in claim 1, wherein the polysiloxane is one or more selected from hydroxyl-terminated polydimethylsiloxane, hydroxyl-terminated methylphenyl siloxane, copolymer of hydroxyl-terminated dimethyl siloxane and methyl trifluoropropyl siloxane, and the using amount of the polysiloxane is 0.5 ~ 4 times of the sum of the masses of the hyperbranched hydrogenpolycarbosilane and the hyperbranched vinyl polycarbosilane.

5. The method for preparing the silicone release agent containing the hyperbranched polycarbosilane as claimed in claim 4, wherein the viscosity of the polysiloxane is 2000 ~ 200000 cp.

6. The method for preparing the silicone mold release agent containing the hyperbranched polycarbosilane as claimed in claim 1, wherein the emulsifier is one or more selected from sodium dodecylbenzene sulfonate, OP-7, OP-10, basf TO-3, basf TO-7 and basf TO-10, and the amount of the emulsifier is 10 ~ 30% of the total mass of the polysiloxane and the hyperbranched polycarbosilane.

7. The method for preparing the organic silicon release agent containing the hyperbranched polycarbosilane as claimed in claim 1, wherein the platinum complex is selected from H₂PtCl₆Isopropyl alcohol solution of (1), H₂PtCl₆Tetrahydrofuran solution of (2), methyl ethyleneOne or more of a platinum complex coordinated by siloxane, a platinum complex coordinated by diethyl phthalate and a platinum complex coordinated by dicyclopentadiene platinum dichloride, wherein the amount of the platinum complex is 6 ~ 80ppm of the mass of a platinum metal element of all components.

8. The preparation method of the organic silicon release agent containing the hyperbranched polycarbosilane as claimed in claim 1, characterized in that the thickening agent is one or more selected from hydroxyethyl cellulose, hydroxypropyl methylcellulose, methylcellulose and polyacrylamide, and the usage amount is 0.1-3% of the total mass of the polysiloxane and the hyperbranched polycarbosilane polymer.

9. The preparation method of the silicone release agent containing the hyperbranched polycarbosilane as claimed in claim 1, wherein the temperature is controlled at 20 ~ 60 ℃ during emulsification, the emulsification time is 2 ~ 8h, and the solid content of the silicone emulsion is 8 ~ 40%.

10. The preparation method of the organic silicon release agent containing the hyperbranched polycarbosilane, as claimed in claim 1, and the application of the prepared organic silicon release agent containing the hyperbranched polycarbosilane in the manufacture of tire products.

Technical Field

The invention relates to the technical field of organic silicon, in particular to a preparation method and application of an organic silicon release agent containing hyperbranched polycarbosilane.

Background

Tires are one of the essential parts of automobiles. With the development of the automobile industry, the automobile keeping quantity in China is continuously increased, and the requirement of the domestic tire replacement market is strong. It is expected that the car inventory will remain at a rate of more than 10% increase from 2017 to 2020, which will undoubtedly push the overall market for tire matching and replacement to continue to grow rapidly. In the manufacture of tires, some compounds adhere very strongly to the mold during heat and pressure vulcanization, and if a mold release agent is not used, they are damaged by hot tearing during demolding, or production is interrupted by the tire remaining in the mold. Thus, without a good release agent, it is not possible to produce acceptable tires quickly and efficiently.

The organosilicon release agent is the tire release agent which is most widely applied and used at present, and has the advantages of less coating, good surface performance of a workpiece, no corrosion to a mold and the like. However, the existing silicone tire release agent has some defects, such as poor temperature resistance, which causes some dirtier yellow substances to remain on rubber tire products, and seriously affects the product quality.

Disclosure of Invention

In order to solve the problem that the temperature resistance of the existing rubber tire release agent is not good enough, so that some dirty yellow substances are left on rubber tire products, and the product quality is seriously influenced, the invention provides a preparation method of an organic silicon release agent containing hyperbranched polycarbosilane, the preparation method is simple, and the obtained release agent has high temperature resistance and wear resistance.

The invention also provides application of the organic silicon release agent containing the hyperbranched polycarbosilane in manufacturing tire products.

The invention is realized by the following technical scheme: a preparation method of an organic silicon release agent containing hyperbranched polycarbosilane comprises the steps of premixing hyperbranched hydrogenous polycarbosilane, hyperbranched vinyl carbosilane, polysiloxane, an emulsifier, a platinum catalyst and a thickening agent, and adding deionized water for emulsification to prepare the organic silicon release agent containing hyperbranched polycarbosilane.

The hyperbranched vinyl polycarbosilane is one or more of hyperbranched polyvinyl carbosilanes with different generations and silicon vinyl at the tail end, and is marked as G0-Vi, G1-Vi, G2-Vi and G3-Vi respectively.

The preparation method of G0-Vi comprises the following steps: putting Mg scraps (3g, 125mmol) and 0.1-0.5 g of iodine into a clean three-necked bottle in an anhydrous and oxygen-free state, adding 50ml of diethyl ether, and slowly dropwise adding a mixed solution of 20ml of diethyl ether and 12.6g (105mmol) of allyl bromide when the temperature of the mixed solution is reduced to 0-5 ℃ through an ice bath. And after the dropwise addition is finished, reacting for 2 hours at 0-5 ℃ to obtain an ether solution of the allyl bromide Grignard reagent. Then 3.5g of methyltrichlorosilane (23.4 mmol) was dissolved in 30ml of diethyl ether, and the obtained diethyl ether solution of allyl bromide Grignard reagent was slowly added dropwise at 0-5 ℃ in an ice bath. After the addition was complete, the reaction was stirred at room temperature overnight and then worked up: and transferring the supernatant into a separating funnel, performing vacuum filtration on the precipitate through a Buchner funnel, washing and washing a filter cake by using 60ml of diethyl ether for three times, combining the filtrate and the supernatant, and dropwise adding about 200ml of 0-5 ℃ saturated ammonium chloride aqueous solution to quench the reaction until no bubbles and precipitate are generated. The organic phase was washed successively with a saturated aqueous solution of sodium chloride and ice water three times, dried over anhydrous magnesium sulfate overnight, and the ether was removed by rotary evaporation at 60 ℃ and distilled under reduced pressure at 105 ℃ under 130mmHg to obtain a colorless transparent liquid, the yield was about 83%, and the purity was 96.0%.

Synthetic route of G0-Vi:

the preparation method of the G1-Vi comprises the following steps: 1.6G G0-Vi (9.62mmol), 7.22G trichlorosilane (53.3mmol), 60mL redistilled THF and 0.2. mu.L platinic acid catalyst were added in sequence to a 250mL clean three-necked flask under nitrogen protection, and after 6 hours of reaction at 60 ℃, tetrahydrofuran and excess trichlorosilane were removed under reduced pressure to give G1-C1 (572.67G/mol). Dissolving the obtained G1-C1 in 20ml of anhydrous ether, slowly dropwise adding the obtained solution into a new allyl bromide Grignard reagent with the temperature of about 125mmol 0-5 ℃, stirring the reaction system at room temperature overnight after dropwise adding, and performing aftertreatment with the same G0-Vi to obtain a colorless transparent liquid G1-Vi (623.27G/mol) with the yield of about 80%.

The preparation method of the G2-Vi comprises the following steps: the second generation hyperbranched polycarbosilane G2-Vi with allyl double bond at the end is prepared by the same method by taking G1-Vi as a core, and is transparent flowable liquid with the yield of about 52 percent.

The preparation method of the G3-Vi comprises the following steps: the third generation hyperbranched polycarbosilane G3-Vi with allyl double bond at the end is prepared by the same method by taking G2-Vi as a core, and is transparent flowable liquid with the yield of about 35 percent.

The synthesis routes of the hyperbranched vinyl polycarbosilane G1-Vi, G2-Vi and G3-Vi are shown as follows:

polycarbosilane is a class of organosilicon high molecular compounds, the main chain of which generally consists of silicon and carbon atoms in an alternating way, and the silicon and carbon atoms are connected with hydrogen or organic groups, so that the polycarbosilane is resistant to high temperature, corrosion and abrasion. The hyperbranched polycarbosilane has the advantages of polycarbosilane, and has good fluidity brought by a hyperbranched structure. The usage amount of the hyperbranched hydrogenous polycarbosilane and the hyperbranched vinyl polycarbosilane is 0.7-1.5: 1 according to the molar ratio of silicon hydrogen to silicon vinyl.

The hyperbranched hydrogenous polycarbosilane is one or more of hyperbranched hydrogenous polycarbosilanes with different generations and silicon hydride at the tail end, and is marked as G1-H, G2-H and G3-H respectively.

The preparation method of G1-H comprises the following steps: under the protection of anhydrous oxygen-free nitrogen, adding lithium aluminum hydride (2.38G, 62.8mmol and one-time excess) into a 500mL three-necked bottle, vacuumizing for three times, adding 100mL of diethyl ether, stirring for 30 minutes, slowly dropwise adding G1-Cl (2G, 3.49mmol) to dissolve in 20mL of redistilled diethyl ether solution, after stirring the mixture at room temperature overnight, slowly dropwise adding 200mL of ice-cold 2N HCl hydrochloric acid solution, taking the water layer twice by using diethyl ether, washing the combined organic layer twice by using saturated NaCl aqueous solution, using anhydrous magnesium sulfate overnight, and removing the solvent at 60 ℃ under reduced pressure to obtain the primary hydrogenated hyperbranched polycarbosilane (G1-H), wherein the product is light green transparent oily liquid, and the crude yield is about 80.3%.

The synthetic route of the hyperbranched carbosilane G1-H is shown as follows:

the same operation steps are carried out by using G2-C1, so that the second-generation hydrogenated hyperbranched polycarbosilane (G2-H) which is transparent yellowish liquid and has a crude yield of about 64.4 percent can be obtained, the third-generation hydrogenated hyperbranched polycarbosilane (G3-H) which is light yellow liquid and has a crude yield of about 45.8 percent can be obtained, the second-generation hydrogenated hyperbranched polycarbosilane (G2-H) and the third-generation hydrogenated hyperbranched polycarbosilane (G3-H) have the following structural formulas:

the polysiloxane is selected from one or more of hydroxyl-terminated polydimethylsiloxane, hydroxyl-terminated methylphenyl siloxane, copolymer of hydroxyl-terminated dimethyl siloxane and methyl trifluoropropyl siloxane, and the using amount of the polysiloxane is 0.5-4 times of the sum of the masses of the hyperbranched hydrogen-containing polycarbosilane and the hyperbranched vinyl polycarbosilane. Preferably, the usage amount is 1-2 times of the sum of the usage amounts of the hyperbranched hydrogenous polycarbosilane and the hyperbranched vinyl polycarbosilane.

The viscosity of the polysiloxane is 2000-200000 cp, preferably 5000-60000 cp.

The emulsifier is selected from one or more of sodium dodecyl benzene sulfonate, OP-7, OP-10, basf TO-3, basf TO-7 and basf TO-10, and the using amount of the emulsifier is 10-30% of the total mass of the polysiloxane and the hyperbranched polycarbosilane.

The platinum complex is selected from H₂PtCl₆Isopropyl alcohol solution of (1), H₂PtCl₆The solvent is one or more of tetrahydrofuran solution, platinum complex coordinated by methyl vinyl siloxane, platinum complex coordinated by diethyl phthalate and platinum complex coordinated by dicyclopentadiene platinum dichloride, the dosage of the platinum complex is 6-80 ppm of the mass of the platinum metal element of all the components, and preferably, the dosage of the platinum complex is 6-40 ppm of the mass of the platinum metal element of all the components.

The thickening agent is selected from one or more of hydroxyethyl cellulose, hydroxypropyl methylcellulose, methylcellulose and polyacrylamide, and the using amount of the thickening agent is 0.1-3% of the total mass of the polysiloxane and the hyperbranched polycarbosilane polymer. Preferably, the amount of the polysiloxane-modified polycarbosilane polymer is 0.1-1% of the total mass of the polysiloxane-modified polycarbosilane polymer.

The temperature is controlled to be 20-60 ℃ in the emulsification process, the emulsification time is 2-8 h, the solid content of the organic silicon emulsion is regulated and controlled by adding deionized water, and the solid content of the organic silicon emulsion is 8-40%.

The preparation method comprises the steps of premixing hyperbranched hydrogenous polycarbosilane, hyperbranched vinyl carbosilane, polysiloxane, an emulsifier, a platinum catalyst and a thickening agent uniformly, and adding deionized water for emulsification to prepare the organic silicon emulsion. The solid content of the obtained organosilicon emulsion is 8-40%.

The organic silicon release agent containing the hyperbranched polycarbosilane prepared by the invention is applied to the manufacture of tire products. Can be used for demoulding rubber tyres. The release agent has excellent high temperature resistance and wear resistance, has very good adsorbability with tire capsule molds and the like, has less transferability, thereby having good release effect, and tire products manufactured by using the release agent have clear stripes, basically have no cracks, have no yellow pollutant residue, and have high product yield.

Compared with the prior art, the invention has the beneficial effects that:

(1) the release agent prepared by the invention has excellent high temperature resistance and wear resistance, has very good adsorbability with tire capsule molds and the like, and has less transferability, thereby having very good release effect;

(2) the tire product manufactured by the release agent has clear stripes, basically has no cracks, has no residual yellow pollutants, and has high product yield.

Drawings

FIG. 1 is a 1H-NMR spectrum of G1-H;

FIG. 2 is a 1H-NMR spectrum of G2-H;

FIG. 3 is a 1H-NMR spectrum of G0-Vi;

FIG. 4 is a 1H-NMR spectrum of G1-Vi;

FIG. 5 is a 1H-NMR spectrum of G2-Vi;

FIG. 6 is a 1H-NMR spectrum of G3-Vi;

figure 7 is a TGA analysis of example 1.

Detailed Description

The present invention is further illustrated by the following examples, which are not intended to limit the scope of the present invention. The starting materials used in the examples are either commercially available or prepared by conventional methods.