阅读说明：本技术 一种对称四苯基的苯基乙烯基硅油及其制备方法 (Symmetrical tetraphenyl phenyl vinyl silicone oil and preparation method thereof ) 是由 郭书利 李娜 孙洪涛 史胜南 高博 陈栋 何晓峰 于 2021-09-14 设计创作，主要内容包括：本发明属于高分子材料领域,具体涉及一种对称四苯基的苯基乙烯基硅油及其制备方法,利用四苯基环戊二烯酮和多乙烯基硅油在氯萘的常压开放式体系中的合成了对称四苯基的苯基乙烯基硅油。合成的对称四苯基的苯基乙烯基硅油主要用于硅橡胶和硅树脂胶黏剂的耐高温助剂和耐辐照助剂。在硅橡胶硫化时,对称四苯基的苯基乙烯基硅油可以参与硅橡胶的交联反应,键接到硅橡胶大分子链上,对称分布的四苯基的苯基的作用相当于纳米尺度的增强相,具有较强的抗热变形能力、抗热老化能力、耐高温性、耐辐照性、耐溶剂性；对称四苯基的苯基乙烯基硅油在硅树脂胶黏剂中,用来提高胶黏剂的粘结强度、抗剪强度和耐高温性。(The invention belongs to the field of high polymer materials, and particularly relates to symmetrical tetraphenyl phenyl vinyl silicone oil and a preparation method thereof. The synthesized symmetrical tetraphenyl phenyl vinyl silicone oil is mainly used as a high-temperature-resistant auxiliary agent and an irradiation-resistant auxiliary agent of silicone rubber and silicone resin adhesives. When the silicon rubber is vulcanized, the symmetrical tetraphenyl phenyl vinyl silicone oil can participate in the cross-linking reaction of the silicon rubber and is bonded to a silicon rubber macromolecular chain, and the symmetrically distributed tetraphenyl phenyl groups have the functions of a nano-scale reinforcing phase and have stronger thermal deformation resistance, thermal aging resistance, high temperature resistance, irradiation resistance and solvent resistance; the symmetrical tetraphenyl phenyl vinyl silicone oil is used in silicone adhesive to raise the adhesive strength, shearing strength and high temperature resistance.)

1. The symmetrical tetraphenyl phenyl vinyl silicone oil is characterized by comprising the following raw materials in parts by weight: 5-20 parts of tetraphenylcyclopentadienone, 20-50 parts of polyvinyl silicone oil, 1-5 parts of catalyst and 50-100 parts of solvent.

2. The symmetrical tetraphenyl phenyl vinyl silicone oil of claim 1 wherein the tetraphenylcyclopentadienone is a purple colored particle made by reacting acenaphthenequinone with dibenzyl ketone to remove two molecules of water and one molecule of potassium hydroxide.

3. The symmetrical tetraphenyl phenyl vinyl silicone oil of claim 1 wherein the solvent is one of xylene, toluene, chlorotoluene, and dichlorotoluene.

4. The symmetrical tetraphenyl phenyl vinyl silicone oil according to claim 1, wherein said polyvinyl silicone oil is a polymethylsilicone oil having a vinyl group content of 0.04mol/L to 0.068 mol/L.

5. The symmetrical tetraphenyl phenyl vinyl silicone oil of claim 1 wherein the catalyst is one of alpha-chloronaphthalene and beta-chloronaphthalene.

6. A preparation method of symmetrical tetraphenyl phenyl vinyl silicone oil is characterized by comprising the following steps:

step 1, adding tetraphenylcyclopentadienone and a solvent into a reactor, and magnetically stirring until the tetraphenylcyclopentadienone is dissolved;

step 2, adding polyvinyl silicone oil and a catalyst into the reactor, fully and uniformly stirring, introducing nitrogen into the system, opening a heating device, heating to 140-280 ℃ for continuous reaction, heating to 210-280 ℃ for continuous reaction for 8-15 hours when the color of the reaction system is changed from dark green to orange and transparent, and stopping the reaction;

and 3, cooling the product to a certain temperature, transferring the solution into a separating funnel, standing for layering, collecting an upper-layer product, washing the collected upper-layer transparent product with methanol, and carrying out reduced pressure distillation to remove methanol and redundant unreacted raw material polyvinyl silicone oil to obtain the symmetrical tetraphenyl phenyl vinyl silicone oil.

7. The method for preparing symmetrical tetraphenyl phenyl vinyl silicone oil according to claim 6 wherein the dissolution temperature in step 1 is 50-105 ℃.

8. The method for preparing symmetrical tetraphenyl phenyl vinyl silicone oil according to claim 6 wherein the nitrogen rate in step 2 is 0.5-5 m/s.

9. The method for preparing symmetrical tetraphenyl phenyl vinyl silicone oil according to claim 6 wherein the cooling temperature in step 3 is 20-30 ℃.

Technical Field

The invention belongs to the field of high polymer materials, particularly relates to symmetrical tetraphenyl phenyl vinyl silicone oil and a preparation method thereof, and particularly relates to a method for synthesizing symmetrical tetraphenyl phenyl vinyl by using tetraphenylcyclopentadienone and polyvinyl silicone oil in a chloronaphthalene normal-pressure open system.

Background

The silicone oil is a linear structure oily substance formed by carrying out hydrolytic polycondensation on an organic silicon monomer with double functional groups or single functional groups, and is chain-shaped silicone oil with different polymerization degrees. The structural formula is as follows:

wherein n is the degree of polymerization, R is a hydrocarbon group such as methyl, ethyl, phenyl, etc., and X is hydroxyl or hydrogen. The other silicone oil is modified silicone oil, the molecular main chain is not completely composed of Si-O-Si bonds, and a certain amount of silicon heterochains are contained. We can classify them into two classes of linear silicone oils and modified silicone oils according to R, R'. Linear silicone oils include both non-functional and functional silicone oils; the modified silicone oil comprises three types of carbon functional silicone oil, copolymerized silicone oil and main chain modified silicone oil. The silicone oil (Wangchunjiang, Wangyang. production status and development trend of organosilicon compounds [ J ]. Jiangsu chemical industry, 2002,30(2): 16-21) is mainly a linear silicone oil using Si-O-Si as main chain, and the organosilicon compounds with low molecular weight or even high molecular weight and alkyl, aryl or active groups connected to silicon atoms have small intermolecular force and large distance, and the molecules are in spiral structures, so that the special structure endows the silicone oil with excellent characteristics, and the silicone oil is an important product in organosilicon high polymers. It is colorless, tasteless, nontoxic, nonvolatile, and non-corrosive silicone oil liquid oil with various viscosities, and has the dual properties of glass and quartz. Silicone oils have many specific properties due to their specific structure. Such as good heat resistance, water resistance, low viscosity-temperature coefficient, low surface tension, electrical insulation, oxygen resistance, physiological inertia, flexibility and the like, and has good surface activity and excellent film forming property (Wangduon. development and application progress of modified silicone oil [ J ] Shanghai Ma technology, 2012 (3): 21-26). The silicone oil is classified into methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen-containing silicone oil, methyl phenyl silicone oil, and the like according to chemical structures.

However, these conventional silicone oils cannot be used under special conditions, for example, under extreme conditions such as aerospace and nuclear industries, the silicone oils are required to have tetraphenyl or fused ring groups, and substances containing multiple benzene rings can absorb radiation energy of high-energy rays more easily, disperse the energy in a large conjugated system, and then emit the energy to the surrounding environment in the form of light and heat. Besides the functions, the uniformly distributed tetraphenyl groups have less influence on the performance protection and the process of a system due to the uniform distribution of the tetraphenyl groups, and have practical significance advantages.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention provides the symmetrical tetraphenyl phenyl vinyl silicone oil and the preparation method thereof, the tetraphenyl cyclopentadienone and the polyvinyl silicone oil are utilized to prepare the symmetrical tetraphenyl phenyl vinyl silicone oil in a normal-pressure open system of chloronaphthalene, and an auxiliary agent with excellent performance is provided for preparing high-temperature-resistant and irradiation-resistant silicone rubber or silicone resin adhesive.

In order to achieve the purpose, the invention adopts the following technical scheme.

The symmetrical tetraphenyl phenyl vinyl silicone oil comprises the following raw materials in parts by weight: 5-20 parts of tetraphenylcyclopentadienone, 20-50 parts of polyvinyl silicone oil, 1-5 parts of catalyst and 50-100 parts of solvent.

Further, the tetraphenylcyclopentadienone is purple particles, and is prepared by removing two molecules of water and one molecule of potassium hydroxide through the reaction of acenaphthenequinone and dibenzyl ketone.

Further, the solvent is one of xylene, toluene, chlorotoluene and dichlorotoluene.

Further, the polyvinyl silicone oil is polymethyl silicone oil with a vinyl content of 0.04mol/L-0.068 mol/L.

Further, the catalyst is one of alpha-chloronaphthalene and beta-chloronaphthalene.

A preparation method of symmetrical tetraphenyl phenyl vinyl silicone oil comprises the following steps:

step 1, adding tetraphenylcyclopentadienone and a solvent into a reactor, and magnetically stirring until the tetraphenylcyclopentadienone is dissolved.

And 2, adding polyvinyl silicone oil and a catalyst into the reactor, fully and uniformly stirring, introducing nitrogen into the system, opening a heating device, heating to 140-280 ℃ for continuous reaction, heating to 210-280 ℃ for continuous reaction for 8-15 hours when the color of the reaction system is changed from dark green to orange and transparent, and stopping the reaction.

And 3, cooling the product to a certain temperature, transferring the solution into a separating funnel, standing for layering, collecting an upper-layer product, washing the collected upper-layer transparent product with methanol, and carrying out reduced pressure distillation to remove methanol and redundant unreacted raw material polyvinyl silicone oil to obtain the symmetrical tetraphenyl phenyl vinyl silicone oil.

Further, the dissolving temperature in the step 1 is 50-105 ℃.

Further, the nitrogen velocity in the step 2 is 0.5-5 m/s.

Further, the cooling temperature in the step 3 is 20-30 ℃.

Compared with the prior art, the invention has the beneficial effects of.

1. The synthesis process is an open system and is carried out at normal pressure, which is favorable for the smooth implementation of the synthesis.

2. The synthesized symmetrical tetraphenyl phenyl vinyl silicone oil is mainly used as a high-temperature-resistant auxiliary agent and an irradiation-resistant auxiliary agent of silicone rubber and silicone resin adhesives. When the silicon rubber is vulcanized, the symmetrical tetraphenyl phenyl vinyl silicone oil can participate in the cross-linking reaction of the silicon rubber and is bonded to a silicon rubber macromolecular chain, and the symmetrically distributed tetraphenyl phenyl groups have the functions of a nano-scale reinforcing phase and have stronger thermal deformation resistance, thermal aging resistance, high temperature resistance, irradiation resistance and solvent resistance. The symmetrical tetraphenyl phenyl vinyl silicone oil can also be used in a silicone resin adhesive to improve the adhesive strength, the shear strength and the high temperature resistance of the adhesive.

Drawings

FIG. 1 is a flow chart of a preparation process of symmetrical tetraphenyl phenyl vinyl silicone oil.

FIG. 2 is an infrared spectrum of a symmetrical tetraphenyl phenyl vinyl silicone oil prepared in example 1.

FIG. 3 shows the nuclear magnetic spectrum of the symmetrical tetraphenyl phenyl vinyl silicone oil prepared in example 1.

FIG. 4 is a reaction mechanism diagram of the preparation of symmetrical tetraphenyl phenyl vinyl silicone oil.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

Example 1.

Placing 5 parts of tetraphenylcyclopentadienone powder and 50 parts of dimethylbenzene into a 200ml three-necked bottle with a condensing reflux device, a magnetic stirring device and an aeration device, keeping the temperature at 50 ℃, heating to 75 ℃ after the tetraphenylcyclopentadienone is completely dissolved, slowly adding polyvinyl silicone oil (containing 0.04mol/L of vinyl) containing 20 parts into the system, stirring for 5min after the dropwise addition is finished, slowly dropwise adding 1 part of alpha-chloronaphthalene into the three-necked bottle within 20min, introducing nitrogen (the speed is 1 m/s), heating to 155 ℃ for continuous reaction, heating to 220 ℃ for continuous reaction for 15 hours when the color of the reaction system is changed into an orange transparent solution, stopping the reaction, slowly cooling the product to 20 ℃, placing the product into a separating funnel, standing for layering, collecting an upper layer product, washing the collected upper layer product with methanol to be transparent, carrying out reduced pressure distillation to remove the normethanol and unreacted polyvinyl silicone oil (containing 0.04mol/L of vinyl), the product was obtained as a clear oily liquid.

Example 2.

Placing 5 parts of tetraphenylcyclopentadienone powder and 60 parts of xylene into a 200ml three-necked bottle with a condensing reflux device, a magnetic stirring device and an aeration device, keeping the temperature at 50 ℃, heating to 85 ℃ after the tetraphenylcyclopentadienone is completely dissolved, slowly adding 25 parts of polyvinyl silicone oil (containing 0.04mol/L of vinyl) into the system, stirring for 5min after the dropwise addition is finished, slowly dropwise adding 1.5 parts of alpha-chloronaphthalene into the three-necked bottle within 20min, introducing nitrogen (the speed is 1.5 m/s), heating to 165 ℃ for continuous reaction, heating to 220 ℃ for continuous reaction for 15 hours when the color of the reaction system is changed into dark green transparent solution, stopping the reaction, slowly cooling the product to 20 ℃, placing the product into a separating funnel, standing for layering, collecting an upper layer product, washing the collected upper layer product with methanol to be transparent, and distilling under reduced pressure to remove the methanol and unreacted polyvinyl norsilicone oil (containing 0.04mol/L of vinyl), the product was obtained as a clear oily liquid.

Example 3.

Putting 10 parts of tetraphenylcyclopentadienone powder and 80 parts of xylene into a 200ml three-necked bottle with a condensing reflux device, a magnetic stirring device and an aeration device, keeping the temperature at 50 ℃, heating to 75 ℃ after the tetraphenylcyclopentadienone is completely dissolved, slowly adding polyvinyl silicone oil (containing 0.054mol/L of vinyl) containing 20 parts into the system, stirring for 5min after the dropwise addition is finished, slowly dropwise adding 2 parts of alpha-chloronaphthalene into the three-necked bottle within 30min, introducing nitrogen (the speed is 1.5 m/s), heating to 155 ℃ for continuous reaction, heating to 230 ℃ for continuous reaction for 10 hours when the color of the reaction system is changed into dark green transparent solution, stopping the reaction, slowly cooling the product to room temperature, placing the product into a separating funnel, standing for layering, collecting an upper layer product, washing the collected upper layer product with methanol to be transparent, and carrying out reduced pressure distillation to remove the polyvinyl norsilicone oil (containing 0.4 mol/L of vinyl) and unreacted polyvinyl silicone oil (containing 0.054mol/L of vinyl), the product was obtained as a clear oily liquid.

Example 4.

Putting 10 parts of tetraphenylcyclopentadienone powder and 90 parts of dimethylbenzene into a 200ml three-necked bottle with a condensing reflux device, a magnetic stirring device and an aeration device, keeping the temperature at 50 ℃, heating to 95 ℃ after the tetraphenylcyclopentadienone is completely dissolved, slowly adding polyvinyl silicone oil (containing 0.054mol/L of vinyl) containing 20 parts into the system, stirring for 5min after the dropwise addition is finished, slowly dropwise adding 3 parts of alpha-chloronaphthalene into the three-necked bottle within 30min, introducing nitrogen (the speed is 3 m/s), heating to 165 ℃ for continuous reaction, heating to 230 ℃ for continuous reaction for 10 hours when the color of the reaction system is changed into an orange transparent solution, stopping the reaction, slowly cooling the product to 20 ℃, placing the product into a separating funnel, standing for layering, collecting an upper layer product, washing the collected upper layer product with methanol to be transparent, carrying out reduced pressure distillation to remove the normethanol and unreacted polyvinyl silicone oil (containing 0.054mol/L of vinyl), the product was obtained as a clear oily liquid.

Example 5.

Placing 20 parts of tetraphenylcyclopentadienone powder and 100 parts of dimethylbenzene into a 200ml three-necked bottle with a condensing reflux device, a magnetic stirring device and an aeration device, keeping the temperature at 50 ℃, heating to 75 ℃ after the phenyltetracyclopentadienone is completely dissolved, slowly adding 45 parts of polyvinyl silicone oil (containing 0.068mol/L of vinyl) into the system, stirring for 5min after the dropwise addition is finished, slowly dropwise adding 5 parts of alpha-chloronaphthalene into the three-necked bottle within 30min, introducing nitrogen (the speed is 5 m/s), heating to 155 ℃ for continuous reaction, heating to 250 ℃ for continuous reaction for 8 hours when the black color of the reaction system is changed into a green transparent solution, stopping the reaction, slowly cooling the product to 20 ℃, placing the product into a separating funnel, standing for layering, collecting an upper layer product, washing the collected upper layer product with methanol to be transparent, and distilling under reduced pressure to remove the normethanol and unreacted polyvinyl silicone oil (containing 0.068mol/L of vinyl), the product was obtained as a clear oily liquid.

From FIG. 2, it can be seen that 1400-1600cm is obtained compared with the infrared spectrum of polyvinyl silicone oil^-1The absorption peak of phenyl is increased in the region, and the tetraphenylcyclopentadienone is 1710cm^-1The absorption peak at C = O disappeared, confirming the successful introduction of tetraphenylcyclopentadienone onto the vinyl group, confirming that the synthesis was the expected product.

As is clear from FIG. 3, part of the vinyl groups on the polyvinyl silicone oil were replaced with tetraphenyl groups, so that a proton peak was observed at a chemical shift of 6.8 to 7.6ppm, which was known as a proton peak of a phenyl group of a symmetrical tetraphenyl group, and the results of the infrared spectroscopy were consistent.