WO2022140877A1 - Addition-type silicone rubber having high adhesive strength and preparation method therefor - Google Patents

Abstract

Disclosed are an addition-type silicone rubber having high adhesive strength and a preparation method therefor. On the basis of parts by weight, the addition-type silicone rubber is prepared from raw materials comprising the following components: 100 parts of a terminal vinyl silicone oil, 20-40 parts of a fumed silica, 10-40 parts of a methoxy-modified vinyl silicone oil, 5-20 parts of an epoxy-modified hydrogen-containing silicone oil, 1-5 parts of a silane coupling agent, and 0.01-0.1 parts of an inhibitor. On the basis of the mass of platinum, the preparation raw materials of the addition-type silicone rubber further comprise 10-30 ppm of a platinum catalyst. The methoxy-modified vinyl silicone oil is prepared by a silicon-hydrogen addition reaction of a polyvinyl silicone oil and a trimethoxysilane, the epoxy-modified hydrogen-containing silicone oil is prepared by a silicon-hydrogen addition reaction of a pendant hydrogen-containing silicone oil and allyl glycidyl ether, and the silane coupling agent comprises N,N-dimethyl-3-aminopropyltrimethoxysilane. The addition-type silicone rubber has high adhesive strength to various substrates.

Description

A kind of addition type silicone rubber with high bonding strength and preparation method thereof technical field

The invention relates to the technical field of silicone rubber, in particular to an addition type silicone rubber with high bonding strength and a preparation method thereof.

Background technique

Due to the high mechanical strength of the addition type silicone rubber, it does not release small molecules during curing, the curing shrinkage rate is extremely low, and its temperature-sensitive curing method can control the curing speed by adjusting the temperature, so it has incomparable properties of condensation type silicone rubber. With many advantages, it has a wide range of applications in LED, electronic appliances and other fields. However, the adhesion of addition silicone rubber is far inferior to that of condensation silicone rubber. Addition silicone rubber generally improves adhesion in the following three ways: (1) Surface treatment of the substrate with a primer; (2) Addition of a tackifier with a special structure; (3) Reinforcing powder modification . In addition, addition silicone rubber often requires a long time of high temperature baking to achieve good adhesion. CN109401669A discloses an addition type liquid silicone rubber which is cured and bonded at medium and low temperature. It is self-made containing silicon hydrogen group and acryloxysiloxane as tackifier, which has limitations on the bonding of substrates. CN106751907A discloses an addition type silicone rubber with low curing temperature, short curing time and high bonding strength. The powder is modified by silane oligomer, the process is relatively complicated, it is not easy to control, and it is difficult to popularize in large-scale industry.

SUMMARY OF THE INVENTION

Based on this, the present invention provides an addition type silicone rubber with high applicability to the bonding substrate and high bonding strength, which does not need to add a tackifier with a special structure in the formula, nor does it need to carry out special modification to the powder. , and can achieve high-strength bonding of most substrates without long-term high-temperature baking.

For achieving the above object, the present invention adopts the following scheme:

An addition type silicone rubber with high bonding strength, calculated in parts by weight, is prepared from raw materials comprising the following components:

In terms of the mass of platinum, the preparation raw material of the addition type silicone rubber also includes 10-30 ppm of platinum catalyst;

The methoxy-modified vinyl silicone oil is prepared from polyvinyl silicone oil and trimethoxysilane through hydrosilylation reaction, and the methoxy-modified vinyl silicone oil has the structure shown in formula (I):

Described polyvinyl silicone oil has the structure shown in formula (II):

a, b and c in formula (I) and formula (II) are positive integers;

The epoxy group-modified hydrogen-containing silicone oil is prepared from side hydrogen-containing silicone oil and allyl glycidyl ether through hydrosilylation reaction, and the epoxy group-modified hydrogen-containing silicone oil has the structure shown in formula (III):

The side hydrogen-containing silicone oil has the structure shown in formula (IV):

m, n and p in formula (III) and formula (IV) are positive integers;

The silane coupling agent contains N,N-dimethyl-3-aminopropyltrimethoxysilane.

In some of these embodiments, in parts by weight, the addition type silicone rubber with high adhesive strength is prepared from raw materials comprising the following components:

In some of these embodiments, in parts by weight, the addition type silicone rubber with high adhesive strength is prepared from raw materials comprising the following components:

In some of the embodiments, in terms of the mass of platinum, the preparation raw material of the addition type silicone rubber further includes 10-15 ppm of platinum catalyst.

In some embodiments, the viscosity of the polyvinyl silicone oil at 25° C. is 100-1000 mPa.s, the vinyl content is 2-5 wt %, and the vinyl content of the methoxy-modified vinyl silicone oil is 1 -3 wt%, and the ratio of the vinyl content in the polyvinyl silicone oil to the vinyl content in the methoxy-modified vinyl silicone oil is 1.5-2.4:1.

In some of these embodiments, the viscosity of the polyvinyl silicone oil at 25° C. is 400-600 mPa.s, the vinyl content is 2.5-3.5 wt %, and the vinyl content of the methoxy-modified vinyl silicone oil is 1-2 wt%, and the ratio of the vinyl content in the polyvinyl silicone oil to the vinyl content in the methoxy-modified vinyl silicone oil is 1.8-2.0:1.

In some of the embodiments, the viscosity of the side hydrogen-containing silicone oil at 25° C. is 50-150 mPa.s, the hydrogen content is 0.3-1.0 wt %, and the hydrogen content of the epoxy group-modified hydrogen-containing silicone oil is 0.2-0.5wt%, and the ratio of the hydrogen content of the side hydrogen-containing silicone oil to the hydrogen content of the epoxy group-modified hydrogen-containing silicone oil is 1.3-2.0:1.

In some of these embodiments, the viscosity of the side hydrogen-containing silicone oil at 25° C. is 100-120 mPa.s, the hydrogen content is 0.4-0.6 wt %, and the hydrogen content of the epoxy group-modified hydrogen-containing silicone oil is 0.2-0.4 wt %, and the ratio of the hydrogen content of the side hydrogen-containing silicone oil to the hydrogen content of the epoxy group-modified hydrogen-containing silicone oil is 1.6-1.8:1.

In some of these embodiments, the preparation method of the methoxy-modified vinyl silicone oil comprises the following steps: stirring the polyvinyl silicone oil represented by formula (II), toluene and the Carstel platinum catalyst uniformly, and then adding dropwise Trimethoxysilane, the reaction temperature was kept at 55-65°C during the dropwise addition, and the reaction was continued for 2-4h at a temperature of 55-65°C after the dropwise addition to remove toluene, unreacted trimethoxysilane and catalyst in the reaction product. , that is, the methoxy-modified vinyl silicone oil is obtained.

In some of these embodiments, the mass ratio of the polyvinyl silicone oil and trimethoxysilane is 100:9-13.

In some of the embodiments, the preparation method of the epoxy group-modified hydrogen-containing silicone oil comprises the following steps: stirring the side-side hydrogen-containing silicone oil represented by the formula (IV), toluene and the Calsturt platinum catalyst uniformly, and then Allyl glycidyl ether was added dropwise, the reaction temperature was kept at 55-65°C during the dropwise addition, and the reaction was continued for 2-4h at a temperature of 55-65°C after the dropwise addition to remove toluene and unreacted allyl in the reaction product. base glycidyl ether and catalyst to obtain the epoxy group-modified hydrogen-containing silicone oil.

In some of these embodiments, the mass ratio of the side hydrogen-containing silicone oil and allyl glycidyl ether is 100:20-30.

In some embodiments, the silane coupling agent is selected from N,N-dimethyl-3-aminopropyltrimethoxysilane, γ-glycidyl etheroxypropyltrimethoxysilane, γ-glycidyl Etheroxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3 - of isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, methacryloxypropyltrimethoxysilane and methacryloxypropyltriethoxysilane At least one, and at least one, is N,N-dimethyl-3-aminopropyltrimethoxysilane.

In some embodiments, the silane coupling agent is composed of coupling agent A and coupling agent B, and the coupling agent A is N,N-dimethyl-3-aminopropyltrimethoxysilane, The coupling agent B is selected from γ-glycidyl etheroxypropyltrimethoxysilane, γ-glycidyl etheroxypropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane At least one of propyltriethoxysilane, methacryloxypropyltrimethoxysilane, and methacryloxypropyltriethoxysilane.

In some embodiments, the silane coupling agent consists of coupling agent A, coupling agent B1 and coupling agent B2, and coupling agent A is N,N-dimethyl-3-aminopropyl Trimethoxysilane, the coupling agent B1 is 3-isocyanatopropyltrimethoxysilane and/or 3-isocyanatopropyltriethoxysilane, and the coupling agent B2 is γ-glycidyl ether oxygen Propyltrimethoxysilane and/or gamma-glycidyloxypropyltriethoxysilane.

In some of the embodiments, the mass ratio of the coupling agent A, the coupling agent B1 and the coupling agent B2 is 1:3-7:2-6.

In some of these embodiments, the weight part of the N,N-dimethyl-3-aminopropyltrimethoxysilane is 0.1-0.5 parts.

In some of these embodiments, the vinyl-terminated silicone oil has a viscosity of 1000-20000 mPa.s at 25°C.

In some of these embodiments, the vinyl-terminated silicone oil has a viscosity of 1000-10000 mPa.s at 25°C.

In some of these embodiments, the fumed silica has a specific surface area of 100-400 m ² /g.

In some of these embodiments, the inhibitor is selected from 1-ethynyl-1-cyclohexanol, tetramethyltetravinylcyclotetrasiloxane, 2-methyl-3-butynyl-2-ol , at least one of 3-methyl-1-pentynyl-3-ol, 3,5-dimethyl-1-hexynyl-3-ol and 3-methyl-1-dodecyn-3-ol A sort of.

In some embodiments, the platinum catalyst is selected from at least one of chloroplatinic acid, chloroplatinic acid-isopropanol complex, and chloroplatinic acid-divinyltetramethyldisiloxane complex .

The present invention also provides a method for preparing the above-mentioned addition type silicone rubber with high adhesive strength.

The specific technical solutions are as follows:

A preparation method of the above-mentioned high-bond-strength addition silicone rubber, comprising the steps:

a. Mix the vinyl-terminated silicone oil and the fumed silica evenly, heat up to 120-150° C. and vacuumize to obtain a base material;

b, mixing the base material, methoxy-modified vinyl silicone oil and epoxy-modified hydrogen-containing silicone oil;

c. Add the silane coupling agent and inhibitor, and stir;

d. Finally, add the catalyst, vacuumize, and stir to obtain the addition type silicone rubber with high bonding strength.

In some of these embodiments, the preparation method of the high-bond-strength addition silicone rubber comprises the following steps:

a. Add the vinyl-terminated silicone oil into the kneader, then add the fumed silica in batches, mix at room temperature for 1-2 hours, heat up to 120-150° C. and vacuumize for 1-3 hours to obtain the base material;

b. At room temperature, add the base material into a planetary mixer or a high-speed dispersing mixer, and then add the methoxy-modified vinyl silicone oil and epoxy-modified hydrogen-containing silicone oil into the planetary mixer or high-speed dispersing mixer Mix with the base material for 10-30min;

c. Add the silane coupling agent and inhibitor, and stir for 10-20min;

d. Finally, add the catalyst, vacuumize, and stir for 5-15 minutes to obtain the addition type silicone rubber with high bonding strength.

Compared with the prior art, the present invention has the following beneficial effects:

In the present invention, a certain amount of methoxy-modified vinyl silicone oil is introduced on the basis of conventional vinyl-terminated silicone oil as a base polymer, and a certain amount of side-hydrogen-containing silicone oil containing an epoxy group is used as a cross-linking agent. The amount of fumed silica, silane coupling agent, inhibitor and platinum catalyst can make the obtained addition type silicone rubber have high bonding strength to various base materials at lower curing temperature and curing time. The introduction of the methoxy group in the methoxy-modified vinyl silicone oil and the epoxy group in the epoxy group-modified hydrogen-containing silicone oil greatly improves the polarity of the polymer body of the addition type silicone rubber system, improves the reactivity, reduces the the curing reaction temperature. The methoxy-modified vinyl silicone oil can not only participate in the cross-linking reaction through the vinyl group, but also the methoxy group contained in it can react with the hydroxyl group on the surface of the substrate, thereby promoting adhesion and improving the bond strength. At the same time, on the one hand, the Si-H group of epoxy group-modified hydrogen-containing silicone oil undergoes cross-linking reaction with terminal vinyl silicone oil and methoxy-modified vinyl silicone oil; -Under the action of dimethyl-3-aminopropyltrimethoxysilane, the ring is opened, and then a chemical reaction can occur between the substrate and the silane coupling agent, thereby further promoting the bonding and improving the bonding strength. Therefore, the addition type silicone rubber with high bonding strength of the present invention has the characteristics of wide bonding range and high bonding strength, and has excellent bonding properties to glass, stainless steel, aluminum, PBT, PC and other substrates.

Detailed ways

The technical solutions of the present invention are further described below through specific embodiments. It should be understood by those skilled in the art that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used in the description of the present invention are only for the purpose of describing specific embodiments, and are not used to limit the present invention.

The terms "comprising" and "having" and any variations thereof of the present invention are intended to cover a non-exclusive inclusion. For example, a process, method, apparatus, product or device comprising a series of steps is not limited to the listed steps or modules, but optionally also includes unlisted steps, or optionally also includes steps for these processes, other steps inherent in the method, product or device.

The "plurality" mentioned in the present invention means two or more. "And/or", which describes the association relationship of the associated objects, means that there can be three kinds of relationships, for example, A and/or B, which can mean that A exists alone, A and B exist at the same time, and B exists alone. The character "/" generally indicates that the associated objects are an "or" relationship.

The following are specific examples.

The viscosity mentioned in the following examples refers to the viscosity at a temperature of 25°C.

The preparation method of methoxy-modified vinyl silicone oil (MOMVS) of the present invention comprises the following steps:

Among them, a, b, and c are positive integers.

a. In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, first add 100 parts of polyvinyl silicone oil (viscosity 500mPa.s, vinyl content 3wt%), 300 parts of toluene and 20ppm of Kalster Platinum catalyst, stir evenly;

b. Slowly add 11 parts of trimethoxysilane dropwise to the above mixed solution, keep the reaction temperature at 60°C during the dropwise addition, and continue to react for 3h after the dropping (reaction temperature is kept at 60°C);

c. The reaction product is evaporated under reduced pressure to remove toluene and unreacted trimethoxysilane, and activated carbon adsorbs and removes the catalyst to obtain methoxy-modified vinyl silicone oil (MOMVS).

It was determined that the vinyl content of the prepared methoxy-modified vinyl silicone oil (MOMVS) was 1.55 wt %.

The preparation method of epoxy group-modified hydrogen-containing silicone oil (EPMHS) of the present invention comprises the following steps:

Among them, m, n, p are positive integers;

a. In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, first add 100 parts of side hydrogen-containing silicone oil (viscosity 110mPa.s, hydrogen content 0.5wt%), 300 parts of toluene and 20ppm of Karls Teplatin catalyst, stir evenly;

b. Slowly add 25 parts of allyl glycidyl ether dropwise to the above-mentioned mixed solution, keep the reaction temperature at 60°C during the dropwise addition, and continue to react for 3h after the dropping (the reaction temperature is kept at 60°C);

c. The reaction product is evaporated under reduced pressure to remove toluene and unreacted allyl glycidyl ether, and activated carbon adsorbs and removes the catalyst to obtain epoxy-modified hydrogen-containing silicone oil (EPMHS).

It was determined that the hydrogen content of the prepared epoxy-modified hydrogen-containing silicone oil (EPMHS) was 0.30 wt %.

Example 1

A kind of addition type silicone rubber, its composition is as follows (in parts by weight):

The preparation method includes the following steps:

a. Add 100 parts of the vinyl-terminated silicone oil into the kneader, then add fumed silica in batches, mix at room temperature for 1.5 hours, heat up to 130° C. and vacuumize for 2 hours to obtain the base material;

b, at room temperature, the base material is added to the planetary mixer or the high-speed dispersing mixer, and then MOMVS and EPMHS are added to the planetary mixer or the high-speed dispersing mixer to mix with the base material for 20min;

c. Add the silane coupling agent and inhibitor, and stir for 15min;

d. Finally, add the catalyst, vacuumize, and stir for 10 min to obtain.

Example 2

A kind of addition type silicone rubber, its composition is as follows (in parts by weight):

The preparation method includes the following steps:

a. Add 100 parts of the vinyl-terminated silicone oil into the kneader, then add fumed silica in batches, mix at room temperature for 1.5 hours, heat up to 130° C. and vacuumize for 2 hours to obtain the base material;

b, at room temperature, the base material is added to the planetary mixer or the high-speed dispersing mixer, and then MOMVS and EPMHS are added to the planetary mixer or the high-speed dispersing mixer to mix with the base material for 20min;

c. Add the silane coupling agent and inhibitor, and stir for 15min;

d. Finally, add the catalyst, vacuumize, and stir for 10 min to obtain.

Example 3

A kind of addition type silicone rubber, its composition is as follows (in parts by weight):

The preparation method includes the following steps:

a. Add 100 parts of the vinyl-terminated silicone oil into the kneader, then add fumed silica in batches, mix at room temperature for 1.5 hours, heat up to 130° C. and vacuumize for 2 hours to obtain the base material;

b, at room temperature, the base material is added to the planetary mixer or the high-speed dispersing mixer, and then MOMVS and EPMHS are added to the planetary mixer or the high-speed dispersing mixer to mix with the base material for 20min;

c. Add the silane coupling agent and inhibitor, and stir for 15min;

d. Finally, add the catalyst, vacuumize, and stir for 10 min to obtain.

Example 4

A kind of addition type silicone rubber, its composition is as follows (in parts by weight):

The preparation method includes the following steps:

a. Add 100 parts of the vinyl-terminated silicone oil into the kneader, then add fumed silica in batches, mix at room temperature for 1.5 hours, heat up to 130° C. and vacuumize for 2 hours to obtain the base material;

b, at room temperature, the base material is added to the planetary mixer or the high-speed dispersing mixer, and then MOMVS and EPMHS are added to the planetary mixer or the high-speed dispersing mixer to mix with the base material for 20min;

c. Add the silane coupling agent and inhibitor, and stir for 15min;

d. Finally, add the catalyst, vacuumize, and stir for 10 min to obtain.

Example 5

A kind of addition type silicone rubber, its composition is as follows (in parts by weight):

The preparation method includes the following steps:

a. Add 100 parts of the vinyl-terminated silicone oil into the kneader, then add fumed silica in batches, mix at room temperature for 1.5 hours, heat up to 130° C. and vacuumize for 2 hours to obtain the base material;

b, at room temperature, the base material is added to the planetary mixer or the high-speed dispersing mixer, and then MOMVS and EPMHS are added to the planetary mixer or the high-speed dispersing mixer to mix with the base material for 20min;

c. Add the silane coupling agent and inhibitor, and stir for 15min;

d. Finally, add the catalyst, vacuumize, and stir for 10 min to obtain.

Example 6

A kind of addition type silicone rubber, its composition is as follows (in parts by weight):

The preparation method includes the following steps:

a. Add 100 parts of the vinyl-terminated silicone oil into the kneader, then add fumed silica in batches, mix at room temperature for 1.5 hours, heat up to 130° C. and vacuumize for 2 hours to obtain the base material;

b, at room temperature, the base material is added to the planetary mixer or the high-speed dispersing mixer, and then MOMVS and EPMHS are added to the planetary mixer or the high-speed dispersing mixer to mix with the base material for 20min;

c. Add the silane coupling agent and inhibitor, and stir for 15min;

d. Finally, add the catalyst, vacuumize, and stir for 10 min to obtain.

Example 7

A kind of addition type silicone rubber, its composition is as follows (in parts by weight):

The preparation method includes the following steps:

a. Add 100 parts of the vinyl-terminated silicone oil into the kneader, then add fumed silica in batches, mix at room temperature for 1.5 hours, heat up to 130° C. and vacuumize for 2 hours to obtain the base material;

b, at room temperature, the base material is added to the planetary mixer or the high-speed dispersing mixer, and then MOMVS and EPMHS are added to the planetary mixer or the high-speed dispersing mixer to mix with the base material for 20min;

c. Add the silane coupling agent and inhibitor, and stir for 15min;

d. Finally, add the catalyst, vacuumize, and stir for 10 min to obtain.

Comparative Example 1

A kind of addition type silicone rubber, its composition is as follows (in parts by weight):

The preparation method includes the following steps:

a. Add 100 parts of the vinyl-terminated silicone oil into the kneader, then add fumed silica in batches, mix at room temperature for 1.5 hours, heat up to 130° C. and vacuumize for 2 hours to obtain the base material;

b. At room temperature, the base material is added to the planetary mixer or the high-speed dispersing mixer, and then the polyvinyl silicone oil and the side hydrogen-containing silicone oil are added to the planetary mixer or the high-speed dispersing mixer and mixed with the base material for 20min;

c. Add the silane coupling agent and inhibitor, and stir for 15min;

d. Finally, add the catalyst, vacuumize, and stir for 10 min to obtain.

Comparative Example 2

A kind of addition type silicone rubber, its composition is as follows (in parts by weight):

The preparation method includes the following steps:

a. Add 100 parts of the vinyl-terminated silicone oil into the kneader, then add fumed silica in batches, mix at room temperature for 1.5 hours, heat up to 130° C. and vacuumize for 2 hours to obtain the base material;

b. At room temperature, the base material is added to the planetary mixer or the high-speed dispersing mixer, and then MOMVS and side hydrogen-containing silicone oil are added to the planetary mixer or the high-speed dispersing mixer to mix with the base material for 20min;

c. Add the silane coupling agent and inhibitor, and stir for 15min;

d. Finally, add the catalyst, vacuumize, and stir for 10 min to obtain.

Comparative Example 3

A kind of addition type silicone rubber, its composition is as follows (in parts by weight):

The preparation method includes the following steps:

a. Add 100 parts of the vinyl-terminated silicone oil into the kneader, then add fumed silica in batches, mix at room temperature for 1.5 hours, heat up to 130° C. and vacuumize for 2 hours to obtain the base material;

b. At room temperature, the base material is added to the planetary mixer or the high-speed dispersing mixer, and then polyvinyl silicone oil and EPMHS are added to the planetary mixer or the high-speed dispersing mixer to mix with the base material for 20min;

c. Add the silane coupling agent and inhibitor, and stir for 15min;

d. Finally, add the catalyst, vacuumize, and stir for 10 min to obtain.

Comparative Example 4

A kind of addition type silicone rubber, its composition is as follows (in parts by weight):

The preparation method includes the following steps:

a. Add 100 parts of the vinyl-terminated silicone oil into the kneader, then add fumed silica in batches, mix at room temperature for 1.5 hours, heat up to 130° C. and vacuumize for 2 hours to obtain the base material;

b, at room temperature, the base material is added to the planetary mixer or the high-speed dispersing mixer, and then MOMVS and EPMHS are added to the planetary mixer or the high-speed dispersing mixer to mix with the base material for 20min;

c. Add the silane coupling agent and inhibitor, and stir for 15min;

d. Finally, add the catalyst, vacuumize, and stir for 10 min to obtain.

Table 1 lists the formula compositions of the addition silicone rubbers described in Examples 1-7 and Comparative Examples 1-4.

Formulation composition of table 1 addition type silicone rubber (by weight)

a: The silane coupling agent in Comparative Example 4 does not contain N,N-dimethyl-3-aminopropyltrimethoxysilane.

The addition type silicone rubber prepared by the above-mentioned Examples 1-7 and Comparative Examples 1-4 was applied to glass, metal (aluminum, stainless steel) according to GB/T 7124 "Determination of Tensile Shear Strength of Adhesives (Rigid Material to Rigid Material)". ) and plastic (PBT, PC) substrates for sample preparation, curing conditions 80 ℃/30min, testing tensile shear strength, the test results are as follows:

Table 2 Adhesion test results

It can be seen from Table 2 that the addition-type silicone rubber prepared in Examples 1-7 has good adhesion to glass, metal (aluminum, stainless steel) and plastic (PBT, PC) substrates, and the tensile shear strength is >2MPa , the cohesive failure rate is greater than or equal to 80%, and the tensile shear strength of most substrates is close to or exceeds 3MPa, and the cohesive failure is 100%. In contrast, Comparative Example 1 did not use MOMVS and EPMHS, and the tensile shear strength was less than 1 MPa, even only 0.3 MPa for PBT and PC substrates, and there was no cohesive failure; When MOMVS or EPMHS is added to the formula, although the adhesiveness is improved to a certain extent, the tensile shear strength is only about 1MPa, and the cohesive failure rate is less than 50%. Comparative Example 4 uses MOMVS and EPMHS, but does not use N,N-dimethyl-3-aminopropyltrimethoxysilane, and its adhesiveness is worse than that of Comparative Examples 1-3, but not as good as the examples.

The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity, all possible combinations of the technical features in the above-described embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be regarded as the scope described in this specification.

The above-mentioned embodiments only represent several embodiments of the present invention, and the descriptions thereof are specific and detailed, but should not be construed as a limitation on the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can also be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (10)

1. An addition type silicone rubber with high bonding strength, characterized in that, in parts by weight, prepared from raw materials comprising the following components:

   

   In terms of the mass of platinum, the preparation raw material of the addition type silicone rubber also includes 10-30 ppm of platinum catalyst;

   The methoxy-modified vinyl silicone oil is prepared from polyvinyl silicone oil and trimethoxysilane through hydrosilylation reaction, and the methoxy-modified vinyl silicone oil has the structure shown in formula (I):

   

   Described polyvinyl silicone oil has the structure shown in formula (II):

   

   a, b and c in formula (I) and formula (II) are positive integers;

   The epoxy group-modified hydrogen-containing silicone oil is prepared from side hydrogen-containing silicone oil and allyl glycidyl ether through hydrosilylation reaction, and the epoxy group-modified hydrogen-containing silicone oil has the structure shown in formula (III):

   

   The side hydrogen-containing silicone oil has the structure shown in formula (IV):

   

   m, n and p in formula (III) and formula (IV) are positive integers;

   The silane coupling agent contains N,N-dimethyl-3-aminopropyltrimethoxysilane.
2. The addition type silicone rubber of high bonding strength according to claim 1 is characterized in that, in parts by weight, it is prepared from the raw material comprising the following components:

   

   Preferably, the high bonding strength addition type silicone rubber, in parts by weight, is prepared from raw materials comprising the following components:

   

   Preferably, the raw material for the preparation of the addition type silicone rubber further comprises 10-15 ppm of platinum catalyst.
3. The addition type silicone rubber with high bonding strength according to claim 1, wherein the viscosity of the polyvinyl silicone oil at 25°C is 100-1000 mPa.s, the vinyl content is 2-5wt%, and the The vinyl content of the methoxy-modified vinyl silicone oil is 1-3 wt%, and the ratio of the vinyl content in the polyvinyl silicone oil to the vinyl content in the methoxy-modified vinyl silicone oil is 1.5 -2.4:1; preferably, the viscosity of the polyvinyl silicone oil at 25°C is 400-600 mPa.s, the vinyl content is 2.5-3.5 wt%, and the vinyl content of the methoxy-modified vinyl silicone oil is is 1-2%, and the ratio of the vinyl content in the polyvinyl silicone oil to the vinyl content in the methoxy-modified vinyl silicone oil is 1.8-2.0:1.
4. The addition type silicone rubber with high adhesive strength according to claim 1, wherein the viscosity of the side hydrogen-containing silicone oil at 25°C is 50-150 mPa.s, the hydrogen content is 0.3-1.0 wt%, and the The hydrogen content of the epoxy group-modified hydrogen-containing silicone oil is 0.2-0.5 wt%, and the ratio of the hydrogen content of the side hydrogen-containing silicone oil to the hydrogen content of the epoxy group-modified hydrogen-containing silicone oil is 1.3 -2.0:1; preferably, the viscosity of the side hydrogen-containing silicone oil at 25°C is 100-120 mPa.s, the hydrogen content is 0.4-0.6 wt%, and the hydrogen content of the epoxy group-modified hydrogen-containing silicone oil is It is 0.2-0.4 wt%, and the ratio of the hydrogen content of the side hydrogen-containing silicone oil to the hydrogen content of the epoxy group-modified hydrogen-containing silicone oil is 1.6-1.8:1.
5. The addition type silicone rubber with high bonding strength according to claim 1, wherein the preparation method of the methoxy-modified vinyl silicone oil comprises the steps of: adding the polyvinyl silicone oil represented by the formula (II) , toluene and Calsturt platinum catalyst are stirred evenly, and then trimethoxysilane is added dropwise. The reaction temperature is kept at 55-65 °C during the dropwise addition. Toluene and unreacted trimethoxysilane and catalyst in the product, to obtain the methoxy-modified vinyl silicone oil; and/or,

   The preparation method of the epoxy group-modified hydrogen-containing silicone oil comprises the following steps: stirring the side-hydrogen-containing silicone oil represented by the formula (IV), toluene and Calsturt platinum catalyst evenly, and then adding allyl glycidol dropwise ether, the reaction temperature is kept at 55-65 ℃ during the dropwise addition, and the reaction is continued at a temperature of 55-65 ℃ for 2-4 hours after the dropwise addition, to remove toluene and unreacted allyl glycidyl ether and catalyst in the reaction product, That is, the epoxy group-modified hydrogen-containing silicone oil is obtained.
6. The addition type silicone rubber with high adhesive strength according to claim 5, wherein the mass ratio of the polyvinyl silicone oil and trimethoxysilane is 100:9-13; and/or, the side containing The mass ratio of hydrogen silicone oil and allyl glycidyl ether is 100:20-30.
7. The addition type silicone rubber with high adhesive strength according to claim 1, wherein the silane coupling agent is selected from the group consisting of N,N-dimethyl-3-aminopropyltrimethoxysilane, γ-shrinkage Glyceryl ether oxypropyl trimethoxysilane, γ-glycidyl ether oxypropyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4- Epoxycyclohexyl)ethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, methacryloxypropyltrimethoxysilane and methyl At least one of acryloyloxypropyltriethoxysilane, and at least one of which is N,N-dimethyl-3-aminopropyltrimethoxysilane;

   Preferably, the silane coupling agent consists of a coupling agent A and a coupling agent B, the coupling agent A is N,N-dimethyl-3-aminopropyltrimethoxysilane, and the coupling agent A is N,N-dimethyl-3-aminopropyltrimethoxysilane. Agent B is selected from γ-glycidyl etheroxypropyltrimethoxysilane, γ-glycidyl etheroxypropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethylsilane at least one of oxysilane, methacryloxypropyltrimethoxysilane and methacryloxypropyltriethoxysilane;

   Preferably, the silane coupling agent is composed of coupling agent A, coupling agent B1 and coupling agent B2, and said coupling agent A is N,N-dimethyl-3-aminopropyltrimethoxysilane , the coupling agent B1 is 3-isocyanatopropyltrimethoxysilane and/or 3-isocyanatopropyltriethoxysilane, and the coupling agent B2 is γ-glycidyloxypropyltrimethoxysilane Silane and/or γ-Glycidoxypropyltriethoxysilane;

   Preferably, the mass ratio of the coupling agent A, the coupling agent B1 and the coupling agent B2 is 1:3-7:2-6;

   Preferably, the weight part of the N,N-dimethyl-3-aminopropyltrimethoxysilane is 0.1-0.5 part.
8. The addition type silicone rubber with high adhesive strength according to any one of claims 1-7, wherein the vinyl-terminated silicone oil has a viscosity of 1000-20000 mPa.s at 25°C; and/or,

   The specific surface area of the fumed silica is 100-400 m ² /g; and/or,

   The inhibitor is selected from 1-ethynyl-1-cyclohexanol, tetramethyltetravinylcyclotetrasiloxane, 2-methyl-3-butynyl-2-ol, 3-methyl-1 -At least one of pentynyl-3-ol, 3,5-dimethyl-1-hexynyl-3-ol, and 3-methyl-1-dodecyn-3-ol; and/or,

   The platinum catalyst is selected from at least one of chloroplatinic acid, chloroplatinic acid-isopropanol complex, and chloroplatinic acid-divinyltetramethyldisiloxane complex.
9. A preparation method of the addition-type silicone rubber of high adhesive strength according to any one of claims 1-8, characterized in that, comprising the steps:

   a. Mix the vinyl-terminated silicone oil and the fumed silica evenly, heat up to 120-150° C. and vacuumize to obtain a base material;

   b, mixing the base material, methoxy-modified vinyl silicone oil and epoxy-modified hydrogen-containing silicone oil;

   c. Add the silane coupling agent and inhibitor, and stir;

   d. Finally, add the catalyst, vacuumize, and stir to obtain the addition type silicone rubber with high bonding strength.
10. The preparation method of the addition type silicone rubber of high bonding strength according to claim 9, is characterized in that, comprises the steps:

    a. Add the vinyl-terminated silicone oil into the kneader, then add the fumed silica in batches, mix at room temperature for 1-2 hours, heat up to 120-150° C. and vacuumize for 1-3 hours to obtain the base material;

    b. At room temperature, add the base material into a planetary mixer or a high-speed dispersing mixer, and then add the methoxy-modified vinyl silicone oil and epoxy-modified hydrogen-containing silicone oil into the planetary mixer or high-speed dispersing mixer Mix with the base material for 10-30min;

    c. Add the silane coupling agent and inhibitor, and stir for 10-20 min;

    d. Finally, add the catalyst, vacuumize, and stir for 5-15 minutes to obtain the addition type silicone rubber with high bonding strength.