CN113025053A

CN113025053A - High-temperature-resistant self-leveling methyl phenyl silicone rubber and preparation method thereof

Info

Publication number: CN113025053A
Application number: CN202110259945.5A
Authority: CN
Inventors: 窦国梁; 张迪; 王凯; 葛佳男; 陈怀良; 毕旺杰
Original assignee: Shandong Baolongda New Materials Co ltd
Current assignee: Shandong Baolongda New Materials Co ltd
Priority date: 2021-03-10
Filing date: 2021-03-10
Publication date: 2021-06-25

Abstract

The invention relates to the technical field of preparation of organosilicon dealcoholization sealants, in particular to high-temperature-resistant self-leveling methyl phenyl silicone rubber and a preparation method thereof.

Description

High-temperature-resistant self-leveling methyl phenyl silicone rubber and preparation method thereof

Technical Field

The invention relates to the technical field of preparation of organic silicon dealcoholized sealant, in particular to high-temperature-resistant self-leveling methyl phenyl silicone rubber and a preparation method thereof.

Background

The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.

The silicone rubber has excellent performances in the aspects of weather resistance, high and low temperature resistance, electrical insulation, physiological compatibility and the like, and has wide application in the fields of aerospace, buildings, electronics, medical treatment and the like. The room temperature vulcanized methyl silicone rubber is divided into a condensation type and an addition type. The condensed silicone rubber can be divided into dealcoholized, deacidified, ketoxime, deamidated and other products according to byproducts released in vulcanization, and the dealcoholized silicone rubber has no peculiar smell, basically has no corrosion to bonding base materials, has little influence on human health, has good environmental protection property and is more and more widely applied because the byproducts are alcohol substances. However, in the traditional dealcoholized silicone rubber, 107 silicone rubber is used as a base rubber, a filler, a plasticizer, a crosslinking agent, a catalyst and the like are added for matching and preparation, and organic tin is used as a catalyst, so that the rubber material can be unvulcanized after being stored for a long time, and the stability is poor; the titanate is used as a catalyst, and a viscosity peak is caused by the reaction of titanate and hydroxyl of the base adhesive in the production process, so that the production is not facilitated; in addition, the dealcoholized silicone rubber has the defects of poor transparency, easy yellowing and the like, and is not favorable for popularization and application in the market. However, the traditional dealcoholized silicone rubber has no obvious advantages in the fields of high temperature resistance, low temperature resistance, radiation resistance and the like. The phenyl silicone rubber has good high and low temperature resistance, electrical insulation, radiation resistance and the like, and is widely applied to the fields of electronics, machinery, aerospace and the like.

The invention patent (201510630806.3) reports that the fluorine-containing phenyl silicone rubber is room-temperature cured, and the fluorine-containing phenyl silicone rubber prepared by hydroxyl-terminated fluorine-containing phenyl silicone oil has the advantages of excellent oil resistance, solvent resistance, high and low temperature resistance and radiation resistance. However, the inventors found that the methods for producing the ketoxime-type and amide-type polymers are not environmentally friendly, and the problem of high viscosity of the colloidal system is not solved in the production process of the dealcoholization process, and the storage stability of the colloidal system is not satisfactory.

Disclosure of Invention

In order to solve the problems in the prior art, the disclosure provides a high-temperature-resistant self-leveling methyl phenyl silicone rubber and a preparation method thereof, the room-temperature vulcanized methyl phenyl silicone rubber with an alkoxy end capping replaces hydroxyl end capping polydimethylsiloxane to be used as a base rubber, so that the problem of viscosity peak generated in the production process is solved, and the product has excellent performances such as higher temperature resistance, lower temperature resistance, radiation aging resistance, viscoelastic damping performance and the like.

Specifically, the technical scheme of the present disclosure is as follows:

in a first aspect of the present disclosure, a high temperature resistant self-leveling type methylphenyl silicone rubber comprises a methylphenyl polysiloxane.

In a second aspect of the present disclosure, a method for preparing a high temperature resistant self-leveling type methyl phenyl silicone rubber comprises: and (3) stirring the components containing the methyl phenyl polysiloxane by using a powerful dispersing machine, and discharging the materials after emptying.

In a third aspect of the disclosure, a high-temperature-resistant self-leveling type methyl phenyl silicone rubber and/or a preparation method of the high-temperature-resistant self-leveling type methyl phenyl silicone rubber is applied to the fields of vehicles, household appliances, electronic appliances, aerospace and the like.

One or more technical schemes in the disclosure have the following beneficial effects:

(1) the characteristic of lower activity of alkoxy-terminated polymethylphenylsiloxane as a base adhesive is utilized, and the sealant is controlled to have better fluidity mainly by adding a cross-linking agent, a proper reinforcing filler, a catalyst and the like, so that the alkoxy-terminated polymethylphenylsiloxane can play excellent effects of high temperature resistance, oxidation resistance, water resistance and corrosion resistance when being applied to coating electromagnetic electronic elements.

(2) The dealcoholized sealant produced by using the chelated tin and titanium chelate as a catalyst has stable storage property.

(3) The method has the advantages of simple process, low toxicity, environmental protection, no corrosion and no odor, and the product released in the vulcanization is alcohol substance, has no corrosion to most base materials and has little influence on human health.

Detailed Description

The disclosure is further illustrated with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present disclosure. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, and/or combinations thereof, unless the context clearly indicates otherwise.

At present, the problems of high viscosity and poor storage stability of a colloid system are not solved in the production process of the existing dealcoholization process, and in order to solve the problems, the disclosure provides a high-temperature-resistant self-leveling methyl phenyl silicone rubber and a preparation method thereof.

In one embodiment of the present disclosure, a high temperature resistant self-leveling type methylphenyl silicone rubber comprises methylphenyl polysiloxane.

Further, the viscosity of the methylphenylpolysiloxane was 10000-80000 mPas.

Further, the methyl phenyl polysiloxane is selected from any one or two or more of methyl dimethoxy terminated polymethylphenylsiloxane, methyl diethoxy terminated polymethylphenylsiloxane, vinyl dimethoxy terminated polymethylphenylsiloxane and vinyl diethoxy terminated polymethylphenylsiloxane; preferred is methyl dimethoxy terminated polymethylphenylsiloxane.

In the existing silicon rubber preparation using hydroxy end-capping or alkoxy end-capping polydimethylsiloxane as basic glue, can be used in-60-250 deg.C range for a long period of time. However, the properties of the methyl silicone rubber are sharply reduced when the rubber is used at a higher temperature, and the use at a high temperature is not satisfactory. The methyl phenyl silicone rubber is used as a base rubber, and the temperature resistance of the silicone rubber can be effectively improved through the phenyl group in the structure.

In certain embodiments, the high temperature resistant self-leveling type methylphenyl silicone rubber further comprises a tin catalyst and a titanium catalyst.

Further, the tin catalyst is selected from any one, two or more of dibutyltin dilaurate, dipentyl tin dilaurate, dihexyl tin dilaurate, dioctyltin dilaurate, dimethoxydibutyltin, dimethoxydipentyl tin, dimethoxydihexyltin, dimethoxydioctyltin, diethoxydibutyltin, diethoxydimethyltin, dipropoxydibutyltin, dipropoxydiethyltin, dipropoxydehexyltin, dipropoxydioctyltin, dibutoxybutyldtyltin, dibutoxydiethyltin, dibutoxybutyldimethyltin, dibutoxybutyldimethyltine, dibutoxybutyldtyltin, dibutoxybutyldimethyltine, dibutyltin diacetylacetonate, stannous octoate, and chelated tin; tin chelates are preferred.

Further, the titanium catalyst is selected from any one, two or more of tetraisopropyl titanate, tetrabutyl titanate, titanate chelate, n-butyl titanate and tetraethyl titanate; preferred are titanate chelates.

In particular, the inventor finds that by adding the chelated tin and the titanate chelate, a stable framework is provided for the sealant, so that the stability of a final product is greatly improved.

In certain embodiments, the high temperature resistant self-leveling type methylphenyl silicone rubber further comprises any one or a combination of any two or more of a cross-linking agent, a plasticizer, a chain extender, a reinforcing filler or an adhesion promoter.

Further, the cross-linking agent is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane; preferred is phenyltrimethoxysilane.

Further, the plasticizer is one or two of dimethyl silicone oil and methyl phenyl silicone oil; preferably methyl phenyl silicone oil.

Further, the chain extender is selected from one or two of methyldimethoxysilane, methyldiethoxysilane, phenyl dimethoxysilane and phenyl diethoxysilane; preferred is phenyldimethoxysilane.

Further, the reinforcing filler is selected from one or two of hydrophilic white carbon black and hydrophobic white carbon black; preferably hydrophobic white carbon black.

Further, the tackifier is selected from one or two of KH-560, KH-550, KH-570, KH792 and KH-602; preferably KH-560.

Preferably, the methyl phenyl polysiloxane accounts for 90-110 parts; further preferably 100 parts.

Preferably, the tin catalyst is 0.5-3 parts; further preferably 1 part.

Preferably, the titanium catalyst is 2-6 parts; further preferably 4 parts.

Preferably, the cross-linking agent is 7-15 parts; further preferably 10 parts.

Preferably, the plasticizer is 30-50 parts; further preferably 40 parts.

Preferably, the chain extender is 1-20 parts; further preferably 5 parts.

Preferably, the reinforcing filler is 6 to 20 parts; further preferably 10 parts.

Preferably, the tackifier is 0.4-2 parts; further preferably 1 part.

In one embodiment of the present disclosure, a method for preparing a high temperature resistant self-leveling type methyl phenyl silicone rubber comprises: and (3) stirring the components containing the methyl phenyl polysiloxane by using a powerful dispersing machine, and discharging the materials after emptying.

In certain embodiments, the method of making comprises: firstly, adding methyl phenyl polysiloxane, a cross-linking agent, a plasticizer and a chain extender into a powerful dispersion machine, and stirring; then, after emptying, adding a reinforcing filler, and stirring; and finally, emptying, adding the tackifier, the tin catalyst and the titanium catalyst, stirring, emptying and discharging.

Furthermore, in the preparation method, in order to uniformly disperse the reinforcing filler in the system, the methyl phenyl polysiloxane, the cross-linking agent, the plasticizer and the chain extender are firstly mixed, and then the reinforcing filler is added; otherwise, when the reinforcing filler is added together with the cross-linking agent, the plasticizer and the chain extender, the reinforcing filler is partially agglomerated and cannot be dispersed, so that the colloid strength performance is reduced.

Furthermore, in the preparation method, if the catalyst is added in advance, part of the materials in the system can participate in the reaction in advance, and the performances of surface dryness, viscosity elimination, stability and the like of the colloid can be influenced.

Further, in the above preparation method, the stirring is divided into two parts: stirring for 20-40 min, vacuumizing, and stirring for 20-40 min.

In one embodiment of the disclosure, a high-temperature-resistant self-leveling type methyl phenyl silicone rubber and/or a preparation method of the high-temperature-resistant self-leveling type methyl phenyl silicone rubber is applied to the fields of vehicles, household appliances, electronic appliances, aerospace and the like.

In order to make the technical solutions of the present disclosure more clearly understood by those skilled in the art, the technical solutions of the present disclosure will be described in detail below with reference to specific embodiments.

Example 1

(1) Firstly, 100 parts of methyl dimethoxy terminated polymethylphenylsiloxane, 10 parts of phenyl trimethoxy silane, 40 parts of methyl phenyl silicone oil and 5 parts of phenyl dimethoxy silane are added into a powerful dispersing machine, stirring is started for 20 minutes, and then vacuumizing is carried out to continue stirring for 40 minutes.

(2) After emptying, 10 parts of hydrophobic white carbon black is added, stirring is started for 30 minutes, and then vacuumizing and stirring are carried out for 30 minutes.

(3) After emptying, adding 1 part of KH-560, 1 part of chelated tin and 4 parts of titanate chelate, starting stirring for 40 minutes, vacuumizing, continuing stirring for 40 minutes, emptying and discharging.

Example 2

(1) Adding 90 parts of hydroxyl-terminated polymethylphenylsiloxane, 14 parts of methyltrimethoxysilane, 30 parts of methylphenylsilicone oil and 5 parts of methyldimethoxysilane into a powerful dispersing machine, starting stirring for 20 minutes, vacuumizing, and continuing stirring for 40 minutes.

(2) After emptying, 10 parts of hydrophilic white carbon black is added, stirring is started for 30 minutes, and then vacuumizing and stirring are carried out for 30 minutes.

(3) After emptying, 1 part of KH-560, 1 part of dibutyltin dilaurate and 4 parts of tetraisopropyl titanate are added, stirring is started for 40 minutes, then vacuumizing is carried out, stirring is continued for 40 minutes, and emptying and discharging are carried out.

Example 3

(1) Firstly, 110 parts of vinyl dimethoxy terminated polymethylphenylsiloxane, 14 parts of vinyl triethoxysilane, 30 parts of methyl phenyl silicone oil and 5 parts of phenyl diethoxysilane are added into a powerful dispersing machine, stirring is started for 20 minutes, and then vacuumizing is carried out to continue stirring for 40 minutes.

Example 4

(1) Firstly, 100 parts of methyl dimethoxy terminated polymethylphenylsiloxane, 10 parts of phenyl trimethoxy silane, 40 parts of dimethyl silicone oil and 5 parts of methyl dimethoxy silane are added into a powerful dispersing machine, stirring is started for 20 minutes, and then vacuumizing is carried out to continue stirring for 40 minutes.

(3) After emptying, 1 part of KH-560, 1 part of dimethoxy dioctyltin and 4 parts of tetraethyl titanate are added, stirring is started for 40 minutes, then vacuumizing is carried out, stirring is continued for 40 minutes, and emptying and discharging are carried out.

Comparative example 1:

the difference from example 1 is that in this comparative example 1, hydroxy-terminated polydimethylsiloxane replaces methyldimethoxy-terminated polymethylphenylsiloxane of example 1.

Comparative example 2:

the difference from example 1 is that: in this comparative example 2, no tin oxide was added.

The product performance test results obtained in the above examples 1 to 4 and comparative examples 1 to 2 are shown in the following table 1, and the shore hardness of the test piece is measured according to GB/T531.1-2008 "test method for indentation hardness of rubber pocket durometer", and the tensile strength and elongation at break are measured according to GB/T528-2009 "test for tensile stress strain property of vulcanized rubber or thermoplastic rubber".

TABLE 1 Performance testing of various samples

TABLE 2 stability test of high temperature resistant self-leveling type methyl phenyl silicone rubber

The room temperature vulcanized methyl phenyl silicone rubber with the end capped by the alkoxy group prepared by the components disclosed by the invention is short in curing time, high in tensile strength, high in tensile bonding strength and good in leveling property, and still has high tensile strength and elongation at break after being aged at high temperatures of 300 ℃ for 1000h and 350 ℃ for 1000 h. The method has the advantages of simple process, good storage stability, low toxicity, environmental protection, no corrosion and no odor, and the product released in vulcanization is alcohol substance, has no corrosion to most base materials, and has little influence on human health.

Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A high-temperature-resistant self-leveling methyl phenyl silicone rubber is characterized by comprising methyl phenyl polysiloxane.

2. The high temperature resistant self-leveling type methyl phenyl silicone rubber as claimed in claim 1, wherein the viscosity of the methyl phenyl polysiloxane is 10000-; further, the methyl phenyl polysiloxane is selected from any one or two or more of methyl dimethoxy terminated polymethylphenylsiloxane, methyl diethoxy terminated polymethylphenylsiloxane, vinyl dimethoxy terminated polymethylphenylsiloxane and vinyl diethoxy terminated polymethylphenylsiloxane; preferred is methyl dimethoxy terminated polymethylphenylsiloxane.

3. The high temperature resistant self-leveling methyl phenyl silicone rubber according to claim 1, wherein the high temperature resistant self-leveling methyl phenyl silicone rubber further comprises a tin catalyst and a titanium catalyst.

4. The high temperature self-leveling type methylphenylsilicone rubber of claim 3, wherein said tin catalyst is selected from any one, two or more of dibutyltin dilaurate, dipentyl tin dilaurate, dihexyltin dilaurate, dioctyltin dilaurate, dimethoxydibutyltin, dimethoxydipentyl tin, dimethoxydihexyltin, dimethoxydioctyltin, diethoxydibutyltin, diethoxydiethyltin, dipropoxydibutyltin, dipropoxydiethyltin, dibutoxybutyldtyltin, dibutoxydiethyltin, dibutoxybutyldimethyltin, dibutoxybutyldimethyldioctyltin, dibutoxybutyldtyltin, diacetylacetonylbutyloxide, stannous octoate, chelated tin; tin chelates are preferred.

5. The high temperature resistant self-leveling methyl phenyl silicone rubber according to claim 3, wherein the titanium catalyst is selected from one, two or more of tetraisopropyl titanate, tetrabutyl titanate, titanate chelate, n-butyl titanate and tetraethyl titanate; preferred are titanate chelates.

6. The high temperature resistant self-leveling methyl phenyl silicone rubber according to claim 1, wherein the high temperature resistant self-leveling methyl phenyl silicone rubber further comprises any one or a combination of any two or more of a cross-linking agent, a plasticizer, a chain extender, a reinforcing filler or a tackifier.

7. The high temperature resistant self-leveling methyl phenyl silicone rubber according to claim 6, wherein the cross-linking agent is selected from one or more of methyl trimethoxysilane, methyl triethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, phenyl trimethoxysilane and phenyl triethoxysilane; preferred are phenyltrimethoxysilane;

further, the plasticizer is selected from dimethyl silicone oil and methyl phenyl silicone oil; preferably methyl phenyl silicone oil;

further, the chain extender is selected from one or two of methyldimethoxysilane, methyldiethoxysilane, phenyl dimethoxysilane and phenyl diethoxysilane; preferred are phenyl dimethoxysilane;

further, the reinforcing filler is selected from one or two of hydrophilic white carbon black and hydrophobic white carbon black; preferably hydrophobic white carbon black;

further, the tackifier is selected from one or two of KH-560, KH-550, KH-570, KH792 and KH-602; preferably KH-560;

8. the high-temperature-resistant self-leveling methyl phenyl silicone rubber according to any one of claims 1 to 7, wherein 90 to 110 parts of methyl phenyl polysiloxane; further preferably 100 parts;

preferably, the tin catalyst is 0.5-3 parts; further preferably 1 part;

preferably, the titanium catalyst is 2-6 parts; further preferably 4 parts;

preferably, the cross-linking agent is 7-15 parts; further preferably 10 parts;

preferably, the plasticizer is 30-50 parts; further preferably 40 parts;

preferably, the chain extender is 1-20 parts; further preferably 5 parts.

Preferably, the reinforcing filler is 6 to 20 parts; further preferably 10 parts;

preferably, the tackifier is 0.4-2 parts; further preferably 1 part.

9. A preparation method of high-temperature-resistant self-leveling methyl phenyl silicone rubber is characterized by comprising the following steps: stirring the components containing the methyl phenyl polysiloxane by using a powerful dispersion machine, emptying and discharging;

or the preparation method comprises the following steps: firstly, adding methyl phenyl polysiloxane, a cross-linking agent, a plasticizer and a chain extender into a powerful dispersion machine, and stirring; then, after emptying, adding a reinforcing filler, and stirring; finally, after emptying, adding the tackifier, the tin catalyst and the titanium catalyst, stirring, emptying and discharging;

further, the stirring is divided into two parts: stirring for 20-40 min, vacuumizing, and stirring for 20-40 min.

10. Use of a high temperature resistant self-leveling methyl phenyl silicone rubber as defined in any one of claims 1 to 7 and/or a method of preparing a high temperature resistant self-leveling methyl phenyl silicone rubber as defined in claim 9 in the fields of vehicles, household appliances, electronic appliances and aerospace.