CN109824904B

CN109824904B - Modified MQ silicon resin and preparation method and application thereof

Info

Publication number: CN109824904B
Application number: CN201811558600.4A
Authority: CN
Inventors: 刘志锋; 张聪颖; 穆建涛; 封玲珑; 马伟; 曹骏; 杨继朋; 邱化敏
Original assignee: Wanhua Chemical Group Co Ltd; Wanhua Chemical Ningbo Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd; Wanhua Chemical Ningbo Co Ltd
Priority date: 2018-12-19
Filing date: 2018-12-19
Publication date: 2021-09-03
Anticipated expiration: 2038-12-19
Also published as: CN109824904A

Abstract

The invention belongs to the technical field of synthesis of MQ resin, and particularly relates to modified MQ silicon resin and a preparation method and application thereof; the modified MQ silicon resin is shown as the general formula (I) (M)^AM^B)m(M^VI) nQ; wherein m is 0.025-0.375 and n is 0.05-0.75, based on the amount of Q-mer substance as 1. The modified MQ silicon resin prepared by the method can be added into a pressure-sensitive adhesive system to replace or partially replace the conventional prime coat process, so that the pressure-sensitive adhesive manufacturing process is simplified, and the cost is reduced; when the organic silicon pressure-sensitive adhesive is mixed with all the components of the organic silicon pressure-sensitive adhesive, the mixture is clear and transparent and is not turbid; the pressure-sensitive adhesive product with high quality can be obtained, and the requirement on the transparency of the pressure-sensitive adhesive product can be met.

Description

Modified MQ silicon resin and preparation method and application thereof

Technical Field

The invention belongs to the technical field of synthesis of MQ resin, and particularly relates to modified MQ silicon resin and a preparation method and application thereof.

Background

In recent years, the demand of pressure-sensitive adhesives keeps increasing rapidly, high-performance special pressure-sensitive adhesives develop rapidly, the production and sales volume of the pressure-sensitive adhesives continuously and greatly rise, and the pressure-sensitive adhesives become the pressure-sensitive adhesive variety with the highest sales volume in the global range. However, in China, the application of the high-performance special pressure-sensitive adhesive is far lower than the international level due to the restriction of technology. With the ever-increasing performance, it is expected that the growth of high performance specialty pressure sensitive adhesives will be fastest.

The organic silicon pressure-sensitive adhesive has higher chemical resistance, temperature resistance and dielectric property than other organic pressure-sensitive adhesives, has the highest temperature resistance (the short-term use temperature can reach 300 ℃) and the widest use temperature range (-75-260 ℃) in all pressure-sensitive adhesives, and is mainly used for manufacturing electric and electronic adhesive tapes and other occasions needing temperature resistance. Silicone pressure sensitive adhesives can withstand multiple cycles of cold and heat, which are not comparable to other pressure sensitive adhesives. In addition, it can be used for adhering various difficult-to-adhere materials, such as polyolefin, fluoroplastic, polyimide, polycarbonate, etc. without surface treatment.

At present, the silicone pressure-sensitive adhesive on the market and imported needs to use a primer (for example, silicone pressure-sensitive adhesive of Dow Corning company needs to use a matched primer, and silicone pressure-sensitive adhesive tape of 3M company is detected to be coated with the primer), otherwise, the pressure-sensitive adhesive can fall off from a base material in the using process, and the use is seriously influenced. However, when the silicone pressure-sensitive adhesive is used, a plurality of processes are added to the production by using the primer, and the cost is increased.

In summary, although the research on silicone pressure-sensitive adhesives is still going on, there are some problems, such as insufficient adhesion and adhesion of the adhesives to the substrate. How to improve the adhesion and adhesion of the silicone pressure-sensitive adhesive to the substrate without using a primer is an important subject to be researched.

Disclosure of Invention

The invention aims to provide a modified MQ silicon resin and a preparation method thereof, wherein the modified MQ silicon resin is added into a pressure-sensitive adhesive, so that the adhesive and a pressure-sensitive adhesive base material have good adhesion and adhesive force, a conventional prime coat procedure can be replaced or partially replaced, the pressure-sensitive adhesive manufacturing process is simplified, and the cost is reduced.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a modified MQ silicon resin is shown in formula (I) (M)^AM^B)m(M^VI) nQ; wherein m is 0.025 to 0.375, preferably 0.2 to 0.35, based on the amount of Q-mer substance of 1; n is 0.05 to 0.75, preferably 0.05 to 0.15;

the chemical structure of the modified MQ silicon resin is shown as follows:

wherein M is^AThe chemical structural formula of (A) is:

wherein the value of P is an integer of 1 to 10, preferably an integer of 1 to 3; the value of X is 2, 4, 6, and preferably 4;

M^Bthe chemical structural formula of (A) is:

wherein the value of P is an integer of 1 to 10, preferably an integer of 1 to 3;

M^VIthe chemical structural formula of (A) is:

according to the modified MQ silicon resin provided by the invention, preferably, in the general formula (I), m/n is 0.03-7.5, and more preferably 2.3-7.0.

Another object of the present invention is to provide a method for preparing the modified MQ silicone resin as described above, comprising the steps of:

(1) vinyl MQ resin synthesis: mixing silicate ester, tetramethyl divinyl disiloxane, alcohol solvent and aromatic hydrocarbon solvent, contacting with an aqueous solution of acid catalyst, and reacting at 70-80 ℃, preferably for 1-3 h; then heating to 110-140 ℃ for reflux reaction, preferably reacting for 3-5h to obtain vinyl MQ resin;

(2) synthesis of modified MQ silicon resin:

1) contacting hydrogen-terminated silicone oil with a platinum catalyst, and mixing to form a mixture; mixing an epoxy alkene and vinyl acetate to form a pre-mixture; then contacting the obtained pre-mixture with the obtained mixture, and reacting for 1-3h to obtain a modified hydrogen-terminated silicone oil prepolymer;

2) contacting the vinyl MQ resin prepared in the step (1) with an aromatic hydrocarbon solvent, and uniformly mixing to form a mixture of the vinyl MQ resin and the aromatic hydrocarbon solvent; contacting the prepared modified hydrogen-terminated silicone oil prepolymer with a mixture of vinyl MQ resin and aromatic hydrocarbon solvent, reacting for 3-5h, heating to 75-85 ℃, performing reflux reaction for 3-5h, heating to 95-105 ℃, and performing reflux reaction for 1-3 h; and carrying out post-treatment to obtain the modified MQ silicon resin.

According to the preparation method provided by the invention, preferably, the raw material components are used in the following amounts, based on 100 wt% of the total weight of the raw material components in the reaction system of the step (1):

silicate is 25 to 50 wt%, more preferably 29 to 42 wt%,

10 to 20 wt%, more preferably 12 to 15 wt%,

10 to 25 wt%, more preferably 14 to 18 wt%,

10 to 30 wt%, more preferably 15 to 20 wt%,

the aqueous solution of the acid catalyst is 10 to 25 wt%, more preferably 16 to 21 wt%.

Preferably, in the aqueous solution of the acid catalyst, the mass ratio of the acid catalyst to water is 0.5-1: 1, more preferably 0.6 to 0.8: 1.

in the step (1), preferably, the silicate is one or more selected from the group consisting of methyl orthosilicate, polycondensate of methyl orthosilicate, ethyl orthosilicate, polycondensate of propyl orthosilicate, and more preferably, is ethyl orthosilicate.

Preferably, the alcoholic solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol and n-butanol, more preferably ethanol.

Preferably, the aromatic hydrocarbon solvent is selected from one or more of benzene, toluene and xylene, more preferably xylene.

Preferably, the acid catalyst is selected from one or more of p-toluenesulfonic acid, concentrated sulfuric acid of 95-99 wt% and concentrated hydrochloric acid of 30-38 wt%; more preferably 36 wt% concentrated hydrochloric acid.

In the step (1), preferably, silicate, tetramethyldivinyldisiloxane, an alcohol solvent, and an aromatic hydrocarbon solvent are mixed, and contacted with an aqueous solution of an acid catalyst while being heated to 50 to 60 ℃.

Preferably, the step (1) further comprises extracting, washing and distilling (for example, rotary steaming) the product solution (the solution containing the vinyl MQ resin) after the reaction is finished to obtain the vinyl MQ resin; the extractant for extraction is selected from one or more of toluene, xylene, hexane, cyclohexane and n-heptane, more preferably from xylene and/or n-heptane. In the present invention, the extraction and rotary evaporation processes are all conventional operations in the field.

According to the preparation method provided by the invention, preferably, the raw material components are used in the following amounts, based on 100 wt% of the total weight of the raw material components in the reaction system of the step (2):

the mixture of the vinyl MQ resin and the aromatic hydrocarbon solvent is 51 to 90 wt%, more preferably 70 to 75 wt%;

hydrogen-terminated silicone oil is 4-35 wt%, more preferably 26-29 wt%;

0.05 to 0.3 wt%, more preferably 0.1 to 0.2 wt%,

the pre-mixture of the epoxy alkene and vinyl acetate is 2-20 wt%, more preferably 4-16 wt%.

Preferably, in the pre-mixture formed by the epoxy alkene and the vinyl acetate, the mass ratio of the epoxy alkene to the vinyl acetate is 0.5-3: 1, more preferably 1-2: 1;

preferably, in the mixture of the vinyl MQ resin and the aromatic hydrocarbon solvent, the mass ratio of the vinyl MQ resin to the aromatic hydrocarbon solvent is 0.5-3: 1, more preferably 1-2: 1.

in the step (2), the chemical structural formula of the hydrogen-terminated silicone oil is as follows:

in the formula, P is an integer of 1 to 10, preferably an integer of 1 to 3.

The chemical structural formula of the epoxy alkene is as follows:

the value of X is 2, 4, 6, preferably 4. Preferably, the alkylene oxide is selected from one or more of 1, 2-epoxy-5-hexene, 1, 2-epoxy-7-octene and 1, 2-epoxy-9-decene, more preferably 1, 2-epoxy-7-octene.

Preferably, the platinum catalyst is selected from the group consisting of Karster catalysts having a platinum content of 3000-8000 ppm.

In the step (2), before or after mixing, the hydrogen-terminated silicone oil and the platinum catalyst are heated to enable the temperature of the reaction system to reach 45-55 ℃. The purpose of raising the temperature here is to bring the temperature of the system close to or at the temperature required for the modification reaction.

Before or after mixing the vinyl MQ resin prepared in the step (1) and the aromatic hydrocarbon solvent, heating to ensure that the temperature of a reaction system reaches 45-55 ℃ so as to ensure that the modified hydrogen-terminated silicone oil prepolymer, the vinyl MQ resin and the aromatic hydrocarbon solvent can react at the required temperature.

The post-treatment in the step (2) comprises adsorption, filtration and rotary evaporation. These work-up procedures are conventional in the art.

According to the preparation method provided by the invention, preferably, the vinyl MQ resin in the step (1) is shown as a general formula (II) (M)^VI) aQ is shown; wherein a is 0.75 to 0.85 based on 1 of the Q-mer substance.

Preferably, the vinyl content of the modified MQ silicone resin of step (2) is from 0.1 wt% to 15 wt%, more preferably from 0.3 wt% to 12 wt%.

The invention also provides application of the modified MQ silicon resin or the modified MQ silicon resin prepared by the preparation method in pressure-sensitive adhesives.

The technical scheme of the invention has the beneficial effects of one or more of the following aspects:

1) the modified MQ silicon resin obtained by the invention is added into a pressure-sensitive adhesive system, so that the adhesive and the pressure-sensitive adhesive base material have good adhesion and adhesive force after curing, and can replace or partially replace the conventional primary coating process in pressure-sensitive adhesive manufacturing, thereby simplifying the pressure-sensitive adhesive manufacturing process and reducing the cost; and the synthetic method of the modified MQ silicon resin is simple and feasible, and becomes another option for realizing industrialization.

2) The modified MQ silicon resin prepared by the method is white solid powder, and is clear and transparent and not turbid when being mixed with each component of the organic silicon pressure-sensitive adhesive; the pressure-sensitive adhesive product with high quality can be obtained, and the requirement on the transparency of the pressure-sensitive adhesive product can be met.

3) According to the preparation method, the vinyl content of the obtained modified MQ silicon resin is 0.3 wt% -12 wt%, and if a certain amount of vinyl active groups are contained in the MQ silicon resin, the modified MQ silicon resin can continuously participate in other chemical reactions; and the M/Q is 0.75-0.85, so that the modified MQ silicone resin is very suitable for reinforcing pressure-sensitive adhesives, and the application of the obtained modified MQ silicone resin is expanded.

Detailed Description

In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.

In some examples of the invention, the modified MQ silicone resin is of the general formula (I) (M)^AM^B)m(M^VI) nQ; wherein m is 0.025 to 0.375, e.g., 0.05, 0.1, 0.15, 0.2, 0.25, 0.275, 0.3, 0.325, 0.35, based on the amount of Q-mer substance as 1; n is 0.05-0.75, e.g., 0.06, 0.08, 0.15、0.18、0.2、0.4、0.5、0.7；

The chemical structure of the modified MQ silicon resin is shown as follows:

wherein M is^AThe chemical structural formula of (A) is:

wherein P is an integer from 1 to 10, e.g., 2, 4, 6, 8; the value of X is 2, 4, 6;

M^Bthe chemical structural formula of (A) is:

wherein P is an integer from 1 to 10, e.g., 2, 4, 6, 8;

M^VIthe chemical structural formula of (A) is:

MQ silicone resin is a very unique siloxane, which is a silicone resin consisting of tetrafunctional siloxane condensation chain links (Q) and monofunctional siloxane chain links (M), the molar mass of the silicone resin is generally 1000-20000g/mol, and the number (molar mass) ratio of the M chain links and the Q chain links in the molecular structure and the structure determine the properties and application range of the resin. In the present invention, M^AChain link and M^BThe number (molar weight) of the chain links is represented by M, M^VIThe number of segments (molar mass) is denoted by n.

In the present invention, the chemical structure of Q is a structure known in the art, which is a tetrafunctional network of Si-O-Si segments.

In a preferred embodiment, in formula (I), m/n is 0.03 to 7.5, e.g., 0.05, 0.1, 0.17, 0.3, 0.5, 1.0, 2.0, 3.5, 5.0, 6.0, 6.5, 7.0.

In some examples, a method of preparing a modified MQ silicone resin as described above, comprising the steps of:

(1) vinyl MQ resin synthesis: mixing silicate ester, tetramethyldivinyldisiloxane, alcohol solvent and aromatic hydrocarbon solvent, premixing with acid catalyst and water to form aqueous solution of acid catalyst, and reacting at 70-80 deg.C (such as 75 deg.C) for 1-3h (such as 2 h); then heating to 110-140 ℃ (for example, 120 ℃) for reflux reaction to obtain the vinyl MQ resin.

In a preferred embodiment, silicate ester, tetramethyldivinyldisiloxane, an alcohol solvent, an aromatic hydrocarbon solvent are mixed and contacted with an aqueous solution of an acid catalyst while being heated to 50 to 60 ℃ (e.g., 55 ℃); then the temperature is raised to 110-140 ℃ for reflux reaction for 3-5h (for example, 4 h).

The total weight of the raw material components in the reaction system in the step (1) is 100 wt%, and the dosage of the raw material components is as follows:

silicate is from 25 to 50% by weight, for example 27%, 30%, 35%, 40%, 45%,

tetramethyldivinyldisiloxane in an amount of 10 to 20% by weight, for example 11%, 13%, 15%, 18%,

alcohol solvents are 10 to 25 wt%, for example, 11 wt%, 13 wt%, 15 wt%, 18 wt%, 22 wt%,

the aromatic hydrocarbon solvent is 10 to 30% by weight, for example, 12%, 15%, 20%, 25%, 28%,

the aqueous solution of the acid catalyst is 10 to 25 wt%, for example, 13 wt%, 15 wt%, 20 wt%, 22 wt%.

In the aqueous solution of the acid catalyst, the mass ratio of the acid catalyst to water is 0.5-1: 1, e.g., 0.55:1, 0.65:1, 0.75:1, 0.85: 1.

In some preferred embodiments, the silicate is selected from one or more of methyl orthosilicate, polycondensate of methyl orthosilicate, ethyl orthosilicate, polycondensate of ethyl orthosilicate, propyl orthosilicate, and polycondensate of propyl orthosilicate, preferably ethyl orthosilicate.

The alcohol solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol and n-butanol, preferably ethanol. The aromatic hydrocarbon solvent is selected from one or more of benzene, toluene and xylene, and is preferably xylene.

The acid catalyst is selected from one or more of p-toluenesulfonic acid, 95 to 99 wt% (e.g., 98 wt%) concentrated sulfuric acid, and 30 to 38 wt% (e.g., 36 wt%) concentrated hydrochloric acid; preferably 36 wt% concentrated hydrochloric acid.

In some examples, step (1) further comprises: after the reaction is finished, closing the heating and stirring system, cooling the product solution (the solution containing the vinyl MQ resin) after the reaction is finished to room temperature, transferring the product solution into a separating funnel, and extracting, washing and distilling to obtain the resin containing the vinyl MQ; in some examples, the extractive extractant is selected from one or more of toluene, xylene, hexane, cyclohexane and n-heptane, preferably from xylene and/or n-heptane. For example, washing with deionized water until PH 7, adding anhydrous sodium sulfate to adsorb water until the liquid is clear and transparent, filtering to give a colorless and transparent filtrate, and rotary evaporating the extractant to give a white powder solid. The extraction, washing and distillation described herein are all conventional in the art.

(2) Synthesis of modified MQ silicon resin:

1) contacting hydrogen-terminated silicone oil with a platinum catalyst, and heating to 45-55 ℃ to mix to form a mixture; mixing an epoxy alkene and vinyl acetate to form a pre-mixture; then the obtained pre-mixture is contacted with the obtained mixture, the mixture reacts for 1 to 3 hours (for example, 2 hours) at the temperature of between 45 and 55 ℃, the heating is stopped, and the temperature is reduced to the room temperature, so that the modified hydrogen-terminated silicone oil prepolymer is obtained;

2) contacting the vinyl MQ resin prepared in the step (1) with an aromatic hydrocarbon solvent, heating to 45-55 ℃, and uniformly mixing to form a mixture of the vinyl MQ resin and the aromatic hydrocarbon solvent; contacting the prepared modified hydrogen-terminated silicone oil prepolymer with a mixture of vinyl MQ resin and aromatic hydrocarbon solvent, reacting at 45-55 ℃ for 3-5h (e.g., 4h), heating to 75-85 ℃ (e.g., 80 ℃) and then refluxing for 3-5h (e.g., 4h), heating to 95-105 ℃ (e.g., 100 ℃) and then refluxing for 1-3h (e.g., 2 h); after the reaction is stopped, the temperature is reduced to 25 ℃, and then colorless filtrate is obtained by absorption (for example, 3g of activated carbon is added for absorption for 6 hours), and white solid, namely the modified MQ silicon resin, is obtained after the solvent is evaporated in a rotary mode.

The total weight of the raw material components in the reaction system in the step (2) is 100 wt%, and the dosage of the raw material components is as follows:

the vinyl MQ resin solution is 51 to 90 wt%, for example, 55 wt%, 60 wt%, 65 wt%, 68 wt%, 72 wt%, 80 wt%, 90 wt%;

hydrogen-terminated silicone oil is 4 to 35 wt%, for example, 10 wt%, 20 wt%, 25 wt%, 28 wt%, 30 wt%;

platinum catalyst in an amount of 0.05 to 3 wt%, e.g., 0.08 wt%, 0.1 wt%, 0.15 wt%, 0.25 wt%,

the pre-mixture of the epoxy alkene and vinyl acetate is 2-20 wt%, e.g., 3 wt%, 5 wt%, 8 wt%, 10 wt%, 15 wt%.

In the premix formed by the epoxy alkene and the vinyl acetate, the mass ratio of the epoxy alkene to the vinyl acetate is 0.5-3: 1, e.g., 1:1, 1.5:1, 2:1, 2.5: 1;

in the mixture of the vinyl MQ resin and the aromatic hydrocarbon solvent, the mass ratio of the vinyl MQ resin to the aromatic hydrocarbon solvent is 0.5-3: 1, e.g., 1:1, 1.5:1, 2:1, 2.5: 1.

In a preferred embodiment, the alkylene oxide is selected from one or more of 1, 2-epoxy-5-hexene, 1, 2-epoxy-7-octene and 1, 2-epoxy-9-decene, preferably 1, 2-epoxy-7-octene. The aromatic hydrocarbon solvent is selected from one or more of benzene, toluene and xylene, and is preferably xylene. The platinum catalyst is selected from a Karster catalyst with the platinum content of 5000 ppm.

In some examples, the vinyl MQ resin of step (1) is of formula (II) (M)^VI) aQ is shown; wherein a is 0.75 to 0.85 based on 1 of the Q-mer substance. The vinyl content of the modified MQ silicone resin of step (2) is 0.1 wt% to 15 wt%, for example, 0.2 wt%, 0.5 wt%, 1 wt%, 2 wt%, 5 wt%, 10 wt%, 13 wt%.

In other examples, the modified MQ silicone resin as described above, or the modified MQ silicone resin prepared by the preparation method as described above, may be applied to a pressure sensitive adhesive.

< sources of raw materials >

Tetraethoxysilane, caruncle morning light chemical ltd, AR;

methyl orthosilicate, caruncle chenopodium chemicals ltd, AR;

propyl orthosilicate, caruncle chenopodium chemicals ltd, AR;

tetramethyldivinyldisiloxane, caruncle cheng photonics, inc, AR;

ethanol, available from Shigaku corporation, AR;

36 wt% concentrated hydrochloric acid, AR, west longa science ltd;

98 wt% concentrated sulfuric acid, Kemi Euro Chemicals, Inc., AR;

p-toluenesulfonic acid, cromion chemical reagents ltd, AR;

xylene, juju gaku corporation, AR;

n-heptane, cromion chemical agents ltd, AR;

anhydrous sodium sulfate, AR, cropland science ltd;

hydrogen-terminated silicone oil with a hydrogen content of 0.96% and a molar mass of 208g/mol (i.e. the value of P is 1), AR, ibiya special silicone limited;

1, 2-epoxy-7-octene, shanghai vas chemical, AR;

1, 2-epoxy-5-hexene, Hubei Qifei medicine, AR;

1, 2-epoxy-9-decene, shanghai si chemical, AR;

vinyl acetate, Gelest, AR;

5000ppm of Karster platinum catalyst, Anbia-characteristic organosilicon, Inc.;

dow Corning7657, Dow Corning;

PI film, Hangzhou Dahua plastics Co.

< test methods >

1. Number average molecular weight of the product measured by WATERS gel permeation chromatograph: and dissolving the sample in tetrahydrofuran, performing gel chromatography separation, and preparing a standard curve by using a standard PS (polystyrene) to relatively correct and measure the molecular weight and the molecular weight distribution of the obtained modified MQ silicon resin material sample.

2. The vinyl content of the product was determined by vinyl titration method: carrying out addition reaction on excess IBr and the vinyl of the product, sealing, and reacting at 40-45 ℃ for 1.5h to ensure that the vinyl is completely reacted; then adding excessive KI to convert the excessive IBr into the simple substance I₂(ii) a With 0.1mol/L Na₂S₂O₃The standard solution was titrated and a blank run was run in parallel. Na consumed in two groups of experiments₂S₂O₃Half of the difference in the amount of species of (a), is the amount of species of IBr that react with vinyl groups, i.e. the amount of species of vinyl groups in the product. The reaction formula is as follows:

-CH＝CH₂+IBr→-CHI-CH₂Br；

IBr+KI＝KBr+I_2；

I₂+2Na₂S₂O₃＝2NaI+Na₂S₄O₆。

the calculation formula is as follows:

wherein:

W_Vi-the mass percentage of the vinyl groups in the sample,

27-molar mass of vinyl groups,

C——Na₂S₂O₃the concentration of the solution is controlled by the concentration of the solution,

V₀blank titration consumes Na₂S₂O₃The volume of (a) to (b),

v-sample titration consumes Na₂S₂O₃The volume of (a) to (b),

m-mass of the sample taken.

3. 180 degree peel strength of the resulting substrate: GB2792-1998 pressure sensitive adhesive tape 180 peeling strength test method is adopted.

4. Adhesion of the resulting substrate: rubbing the rubber surface and the base material with fingers, and observing the adhesion and adhesion conditions of the rubber surface and the base material.

Example 1:

(1) vinyl MQ resin synthesis: into a three-necked flask equipped with a stirrer, a thermometer and a condenser were charged 208.33g of tetraethoxysilane, 74.56g of tetramethyldivinyldisiloxane, 90g of ethanol and 100g of xylene, and stirring and mixing were started with controlling a stirring speed at 260 r/min. And (3) heating to 60 ℃, dropwise adding a mixed solution prepared from 57.6g of deionized water and 44g of 36 wt% concentrated hydrochloric acid, heating to 75 ℃ after dropwise adding, carrying out reflux reaction for 2 hours, and then heating to 120 ℃ for reflux reaction for 4 hours to obtain a solution containing the vinyl MQ resin. Then the heating and stirring system was turned off, the temperature was reduced to room temperature, the liquid in the bottle was transferred to a separatory funnel, xylene and n-heptane were added for extraction, the mixture was washed with deionized water until PH 7, anhydrous sodium sulfate was added to adsorb moisture until the liquid was clear and transparent, colorless and transparent filtrate was obtained by filtration, and xylene and n-heptane were rotary distilled off to obtain 127.83g of a white powder solid, i.e., vinyl MQ resin, with a yield of 95%.

The Mw of the product obtained from this step was 7304g/mol, Mw/Mn 1.70, as measured by WATERS gel permeation chromatography. The vinyl content of the product was determined by the vinyl content titration method to be 16.00% which is similar to the theoretical vinyl content of 16.05%. Vinyl (VI) being derived only from M^VIThe group, determining the vinyl content, can calculate M^VITo determine the value of a. The specific molecular formula of the vinyl MQ resin product is as follows: (M)^VI) aQ, wherein a has a value of 0.8.

(2) Synthesis of modified MQ silicon resin:

1) adding 72.8g of hydrogen-terminated silicone oil (with hydrogen content of 0.96%) and 0.3g of Kaster platinum catalyst into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 300r/min, and stirring for 0.5 h; premixing 22.08g of 1, 2-epoxy-7-octene and 15.06g of vinyl acetate, dropwise adding into a three-neck flask for reaction, controlling the reaction temperature to be not more than 55 ℃, finishing dropwise adding for 1h, reacting for 2h, stopping heating, introducing nitrogen, and cooling to room temperature to obtain a modified hydrogen-terminated silicone oil prepolymer;

2) adding 67.28g of the vinyl MQ resin powder obtained in the step (1) and 50g of xylene into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 260r/min, and stirring for 1 h; dropwise adding the modified hydrogen-terminated silicone oil prepolymer obtained in the step 1) into a three-neck flask for reaction, controlling the reaction temperature not to exceed 55 ℃, and reacting for 4 hours after dropwise adding is completed within 0.5 hour; then heating to 80 ℃, and carrying out reflux reaction for 4 h; then the temperature is raised to 100 ℃, and the reflux reaction is carried out for 2 hours. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and rotationally evaporating xylene to obtain white solid modified MQ silicon resin.

The number average molecular weight Mw of the product was 19122g/mol and Mw/Mn was 1.71 as determined by water gel permeation chromatography. The vinyl content of the clear product was determined by the vinyl titration method to be 0.76%, similar to the theoretical vinyl content of 0.77%. The value of a in the vinyl MQ resin is obtained through the step (1); modified by the step (2), part of M^VIBecome M^AAnd/or M^BFor the rest M^VIAnd (4) performing a vinyl test to clarify the value of n, and calculating the value of m according to the value of a. The specific molecular formula of the modified MQ silicon resin product is as follows: (M)^AM^B)m(M^VI) nQ, wherein m is 0.35 and n is 0.1.

Example 2:

(1) vinyl MQ resin synthesis: into a three-necked flask equipped with a stirrer, a thermometer and a condenser were charged 208.33g of tetraethoxysilane, 69.9g of tetramethyldivinyldisiloxane, 90g of ethanol and 100g of xylene, and stirring and mixing were started with the stirring speed controlled at 260 r/min. And (3) heating to 60 ℃, dropwise adding a mixed solution prepared from 57.6g of deionized water and 44g of 36 wt% concentrated hydrochloric acid, heating to 75 ℃ after dropwise adding, carrying out reflux reaction for 2 hours, and then heating to 120 ℃ for reflux reaction for 4 hours to obtain a solution containing the vinyl MQ resin. Then the heating and stirring system was turned off, the temperature was reduced to room temperature, the liquid in the bottle was transferred to a separatory funnel, xylene and n-heptane were added for extraction, the mixture was washed with deionized water until PH 7, anhydrous sodium sulfate was added to adsorb moisture until the liquid was clear and transparent, colorless and transparent filtrate was obtained by filtration, and xylene and n-heptane were rotary distilled off to obtain 118.21g of a white powder solid, i.e., vinyl MQ resin, with a yield of 91%.

The Mw of the product was 7811g/mol and the Mw/Mn was 1.69 as measured by WATERS gel permeation chromatography. The vinyl content of the product was determined by the vinyl content titration method to be 14.95%, similar to the theoretical vinyl content of 15.05%. The specific molecular formula of the vinyl MQ resin product is as follows: (M)^VI) aQ, wherein a has a value of 0.75.

(2) Synthesis of modified MQ silicon resin:

2) adding 64.95g of the vinyl MQ resin powder obtained in the step (1) and 50g of xylene into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 260r/min, and stirring for 1 h; dropwise adding the modified hydrogen-terminated silicone oil prepolymer obtained in the step 1) into a three-neck flask for reaction, controlling the reaction temperature not to exceed 55 ℃, and reacting for 4 hours after dropwise adding is completed within 0.5 hour; then heating to 80 ℃, and carrying out reflux reaction for 4 h; then the temperature is raised to 100 ℃, and the reflux reaction is carried out for 2 hours. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and rotationally evaporating xylene to obtain white solid modified MQ silicon resin.

The number average molecular weight Mw of the product is 20903g/mol and Mw/Mn is 1.71 by a WATERS gel permeation chromatograph test. The vinyl content of the transparent product was determined by the vinyl content titration method to be 0.90%, similar to the theoretical vinyl content of 0.93%. The specific molecular formula of the modified MQ silicon resin product is as follows: (M)^AM^B)m(M^VI) nQ, wherein m is 0.35 and n is 0.05.

Example 3:

(1) vinyl MQ resin synthesis: into a three-necked flask equipped with a stirrer, a thermometer and a condenser were charged 208.33g of tetraethoxysilane, 79.22g of tetramethyldivinyldisiloxane, 90g of ethanol and 100g of xylene, and stirring and mixing were started with controlling a stirring speed at 260 r/min. And (3) heating to 60 ℃, dropwise adding a mixed solution prepared from 57.6g of deionized water and 44g of 36 wt% concentrated hydrochloric acid, heating to 75 ℃ after dropwise adding, carrying out reflux reaction for 2 hours, and then heating to 120 ℃ for reflux reaction for 4 hours to obtain a solution containing the vinyl MQ resin. Then the heating and stirring system was turned off, the temperature was reduced to room temperature, the liquid in the bottle was transferred to a separatory funnel, xylene and n-heptane were added for extraction, the mixture was washed with deionized water until PH 7, anhydrous sodium sulfate was added to adsorb moisture until the liquid was clear and transparent, colorless and transparent filtrate was obtained by filtration, and xylene and n-heptane were rotary distilled off to obtain 125.30g of a white powder solid, i.e., vinyl MQ resin, with a yield of 90%.

The Mw of the product was 6407g/mol and Mw/Mn was 1.65 as measured by WATERS gel permeation chromatography. The vinyl content of the product was determined by vinyl content titration to be 16.98% which was similar to the theoretical vinyl content of 17.06%. The specific molecular formula of the vinyl MQ resin product is as follows: (M)^VI) aQ, wherein the value of a is 0.85.

(2) Synthesis of modified MQ silicon resin:

2) adding 69.61g of the vinyl MQ resin powder obtained in the step (1) and 50g of dimethylbenzene into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 260r/min, stirring for 1h, adding the modified terminal hydrosilicon oil drops obtained in the step 1) into the three-neck flask for reaction, controlling the reaction temperature not to exceed 55 ℃, and reacting for 4h after the dropwise addition is finished for 0.5 h; then heating to 80 ℃, and carrying out reflux reaction for 4 h; then the temperature is raised to 100 ℃, and the reflux reaction is carried out for 2 hours. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and rotationally evaporating xylene to obtain white solid modified MQ silicon resin.

The number average molecular weight Mw of the product is 16427g/mol and Mw/Mn is 1.66 by a WATERS gel permeation chromatograph test. The vinyl content of the transparent product was determined by the vinyl content titration method to be 1.10%, similar to the theoretical vinyl content of 1.13%. The specific molecular formula of the modified MQ silicon resin product is as follows: (M)^AM^B)m(M^VI) nQ, wherein m is 0.35 and n is 0.15.

Example 4:

(1) vinyl MQ resin synthesis: a three-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 152.22g of methyl orthosilicate, 74.56g of tetramethyldivinyldisiloxane, 90g of ethanol and 100g of xylene, and stirred and mixed with stirring while controlling the stirring speed at 260 r/min. And (3) heating to 60 ℃, dropwise adding a mixed solution prepared from 57.6g of deionized water and 44g of 36 wt% concentrated hydrochloric acid, heating to 75 ℃ after dropwise adding, carrying out reflux reaction for 2 hours, and then heating to 120 ℃ for reflux reaction for 4 hours to obtain a solution containing the vinyl MQ resin. Then the heating and stirring system was turned off, the temperature was reduced to room temperature, the liquid in the bottle was transferred to a separatory funnel, xylene and n-heptane were added for extraction, the mixture was washed with deionized water until PH 7, anhydrous sodium sulfate was added to adsorb moisture until the liquid was clear and transparent, colorless and transparent filtrate was obtained by filtration, and xylene and n-heptane were rotary distilled off to obtain 123.80g of a white powder solid, i.e., vinyl MQ resin, with a yield of 92%.

The Mw of the product was 7334g/mol, and Mw/Mn was 1.72 as determined by WATERS gel permeation chromatography. The vinyl content of the product was determined by the vinyl content titration method to be 15.90% which is similar to the theoretical vinyl content of 16.05%. The specific molecular formula of the vinyl MQ resin product is as follows: (M)^VI) aQ, wherein a has a value of 0.8.

(2) Synthesis of modified MQ silicon resin:

1) adding 62.40g of hydrogen-terminated silicone oil (with hydrogen content of 0.96%) and 0.3g of Kaster platinum catalyst into a three-neck flask equipped with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 300r/min, and stirring for 0.5 h; premixing 18.93g of 1, 2-epoxy-7-octene and 12.91g of vinyl acetate, dropwise adding into a three-neck flask for reaction, controlling the reaction temperature to be not more than 55 ℃, finishing dropwise adding for 1h, reacting for 2h, stopping heating, introducing nitrogen, and cooling to room temperature to obtain a modified hydrogen-terminated silicone oil prepolymer;

2) adding 67.28g of the vinyl MQ resin powder obtained in the step (1) and 50g of xylene into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 260r/min, and stirring for 1 h; adding the modified hydrogen-terminated silicone oil drops obtained in the step 1) into a three-neck flask for reaction, controlling the reaction temperature not to exceed 55 ℃, and reacting for 4 hours after dropwise adding is completed within 0.5 hour; then heating to 80 ℃, and carrying out reflux reaction for 4 h; then the temperature is raised to 100 ℃, and the reflux reaction is carried out for 2 hours. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and rotationally evaporating xylene to obtain white solid modified MQ silicon resin.

The number average molecular weight Mw of the product is 15505g/mol and Mw/Mn is 1.75 by testing the product by a WATERS gel permeation chromatograph. The vinyl content of the clear product was determined by the ethylene titration method to be 1.65%, similar to the theoretical vinyl content of 1.68%. The specific molecular formula of the modified MQ silicon resin product is as follows: (M)^AM^B)m(M^VI) nQ, wherein m is 0.3 and n is 0.2.

Example 5:

(1) vinyl MQ resin synthesis: a three-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 264.33g of propyl orthosilicate, 74.56g of tetramethyldivinyldisiloxane, 90g of ethanol and 100g of xylene, and stirring and mixing were started with the stirring speed controlled at 260 r/min. And (3) heating to 60 ℃, dropwise adding a mixed solution prepared from 57.6g of deionized water and 44g of 36 wt% concentrated hydrochloric acid, heating to 75 ℃ after dropwise adding, carrying out reflux reaction for 2 hours, and then heating to 120 ℃ for reflux reaction for 4 hours to obtain a solution containing the vinyl MQ resin. Then the heating and stirring system was turned off, the temperature was reduced to room temperature, the liquid in the bottle was transferred to a separatory funnel, xylene and n-heptane were added for extraction, washing was performed with deionized water until PH 7, anhydrous sodium sulfate was added to adsorb moisture until the liquid was clear and transparent, filtration was performed to obtain a colorless and transparent filtrate, and xylene and n-heptane were spin-evaporated to obtain 119.76g of a white powder solid, i.e., vinyl MQ resin, with a yield of 89%.

The Mw of the product was 7324g/mol and Mw/Mn was 1.70 as determined by WATERS gel permeation chromatography. The vinyl content of the product was determined by the vinyl content titration method to be 15.89%, similar to the theoretical vinyl content of 16.05%. The specific molecular formula of the vinyl MQ resin product is as follows: (M)^VI) aQ, wherein a has a value of 0.8.

(2) Synthesis of modified MQ silicon resin:

1) adding 52.00g of hydrogen-terminated silicone oil (with hydrogen content of 0.96%) and 0.3g of Kaster platinum catalyst into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 300r/min, and stirring for 0.5 h; 15.77g of 1, 2-epoxy-7-octene and 10.76g of vinyl acetate were premixed and added dropwise to a three-necked flask for reaction. Controlling the reaction temperature to be not more than 55 ℃, reacting for 2 hours after 1 hour of dropwise addition, stopping heating, introducing nitrogen, and cooling to room temperature to obtain a modified hydrogen-terminated silicone oil prepolymer;

The number average molecular weight Mw of the product was 15789g/mol and Mw/Mn was 1.69 as measured by WATERS gel permeation chromatography. Tong (Chinese character of 'tong')The vinyl content of the clear product was determined by the vinyl content titration method to be 2.75% and similar to the theoretical vinyl content of 2.79%. The specific molecular formula of the modified MQ silicon resin product is as follows: (M)^AM^B)m(M^VI) nQ, wherein m is 0.25 and n is 0.3.

Example 6:

(1) vinyl MQ resin synthesis: into a three-necked flask equipped with a stirrer, a thermometer and a condenser were charged 208.33g of tetraethoxysilane, 74.56g of tetramethyldivinyldisiloxane, 90g of ethanol and 100g of xylene, and stirring and mixing were started with controlling a stirring speed at 260 r/min. And (3) heating to 60 ℃, dropwise adding a mixed solution prepared from 57.6g of deionized water and 44g of 36 wt% concentrated sulfuric acid, heating to 75 ℃ after dropwise adding, carrying out reflux reaction for 2 hours, and then heating to 120 ℃ for reflux reaction for 4 hours to obtain a solution containing the vinyl MQ resin. Then the heating and stirring system was turned off, the temperature was reduced to room temperature, the liquid in the bottle was transferred to a separatory funnel, xylene and n-heptane were added for extraction, washing was performed with deionized water until PH 7, anhydrous sodium sulfate was added to adsorb moisture until the liquid was clear and transparent, filtration was performed to obtain a colorless and transparent filtrate, and xylene and n-heptane were rotary distilled off to obtain 126.49g of a white powder solid, i.e., vinyl MQ resin, with a yield of 94%.

The Mw of the product was 7354g/mol and the Mw/Mn was 1.65 as measured by WATERS gel permeation chromatography. The vinyl content of the product was determined by the vinyl content titration method to be 15.85% which is similar to the theoretical vinyl content of 16.05%. The specific molecular formula of the vinyl MQ resin product is as follows: (M)^VI) aQ, wherein a has a value of 0.8.

(2) Synthesis of modified MQ resin:

1) adding 41.60g of hydrogen-terminated silicone oil (with hydrogen content of 0.96%) and 0.3g of Kaster platinum catalyst into a three-neck flask equipped with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 300r/min, and stirring for 0.5 h; 12.62g of 1, 2-epoxy-7-octene and 8.609g of vinyl acetate were premixed and added dropwise to a three-necked flask for reaction. Controlling the reaction temperature to be not more than 55 ℃, reacting for 2 hours after 1 hour of dropwise addition, stopping heating, introducing nitrogen, and cooling to room temperature to obtain a modified hydrogen-terminated silicone oil prepolymer;

The number average molecular weight Mw of the product is 14154g/mol, and Mw/Mn is 1.65 by WATERS gel permeation chromatography. The vinyl content of the clear product was determined by the vinyl content titration method to be 4.10% which is similar to the theoretical vinyl content of 4.17%. The specific molecular formula of the modified MQ silicon resin product is as follows: (M)^AM^B)m(M^VI) nQ, wherein m is 0.2 and n is 0.4.

Example 7:

(1) vinyl MQ resin synthesis: into a three-necked flask equipped with a stirrer, a thermometer and a condenser were charged 208.33g of tetraethoxysilane, 74.56g of tetramethyldivinyldisiloxane, 90g of ethanol and 100g of xylene, and stirring and mixing were started with controlling a stirring speed at 260 r/min. And (3) heating to 60 ℃, dropwise adding a mixed solution prepared from 57.6g of deionized water and 44g of p-toluenesulfonic acid, heating to 75 ℃ after dropwise adding, carrying out reflux reaction for 2h, and then heating to 120 ℃ for reflux reaction for 4h to obtain a solution containing the vinyl MQ resin. Then the heating and stirring system was turned off, the temperature was reduced to room temperature, the liquid in the bottle was transferred to a separatory funnel, xylene and n-heptane were added for extraction, the mixture was washed with deionized water until PH 7, anhydrous sodium sulfate was added to adsorb moisture until the liquid was clear and transparent, colorless and transparent filtrate was obtained by filtration, and xylene and n-heptane were rotary distilled off to obtain 122.45g of a white powder solid, i.e., vinyl MQ resin, with a yield of 91%.

The Mw of the product was 7324g/mol and the Mw/Mn was 1.66 as measured by WATERS gel permeation chromatography. By vinyl radicalsThe product was determined to have a vinyl content of 15.96% by content titration method, similar to the theoretical vinyl content of 16.05%. The specific molecular formula of the vinyl MQ resin product is as follows: (M)^VI) aQ, wherein a has a value of 0.8.

(2) Synthesis of modified MQ silicon resin:

1) adding 31.20g of hydrogen-terminated silicone oil (with the hydrogen content of 0.96%) and 0.3g of Kaster platinum catalyst into a three-neck flask equipped with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 300r/min, stirring for 0.5h, premixing 9.46g of 1, 2-epoxy-7-octene and 6.46g of vinyl acetate, dropwise adding into the three-neck flask for reaction, controlling the reaction temperature not to exceed 55 ℃, completing dropwise addition for 1h, reacting for 2h, stopping heating, introducing nitrogen, and cooling to room temperature to obtain a modified hydrogen-terminated silicone oil prepolymer;

2) adding 67.28g of vinyl MQ resin powder obtained in the step (1) and 50g of dimethylbenzene into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 260r/min, stirring for 1h, adding modified terminal hydrosilicon oil drops obtained in the step 1) into the three-neck flask for reaction, controlling the reaction temperature not to exceed 55 ℃, and reacting for 4h after the dropwise addition is finished for 0.5 h; then heating to 80 ℃, and carrying out reflux reaction for 4 h; then the temperature is raised to 100 ℃, and the reflux reaction is carried out for 2 hours. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and rotationally evaporating xylene to obtain white solid modified MQ silicon resin.

The number average molecular weight Mw of the product was 12402g/mol and Mw/Mn was 1.71 as measured by WATERS gel permeation chromatography. The vinyl content of the clear product was determined by vinyl content titration to be 5.88%, similar to the theoretical vinyl content of 5.92%. The specific molecular formula of the modified MQ silicon resin product is as follows: (M)^AM^B)m(M^VI) nQ, wherein m is 0.15 and n is 0.5.

Example 8:

(1) vinyl MQ resin synthesis: into a three-necked flask equipped with a stirrer, a thermometer and a condenser were charged 208.33g of tetraethoxysilane, 74.56g of tetramethyldivinyldisiloxane, 90g of ethanol and 100g of xylene, and stirring and mixing were started with controlling a stirring speed at 260 r/min. And (3) heating to 60 ℃, dropwise adding a mixed solution prepared from 57.6g of deionized water and 44g of 36 wt% concentrated hydrochloric acid, heating to 75 ℃ after dropwise adding, carrying out reflux reaction for 2 hours, and then heating to 120 ℃ for reflux reaction for 3 hours to obtain a solution containing the vinyl MQ resin. Then the heating and stirring system was turned off, the temperature was reduced to room temperature, the liquid in the bottle was transferred to a separatory funnel, xylene and n-heptane were added for extraction, the mixture was washed with deionized water until PH 7, anhydrous sodium sulfate was added to adsorb moisture until the liquid was clear and transparent, colorless and transparent filtrate was obtained by filtration, and xylene and n-heptane were rotary distilled off to obtain 118.41g of a white powder solid, i.e., vinyl MQ resin, with a yield of 88%.

The Mw of the product was 6988g/mol and Mw/Mn 1.69 as measured by WATERS gel permeation chromatography. The vinyl content of the product was determined by the vinyl content titration method to be 16.20% which is similar to the theoretical vinyl content of 16.05%. The specific molecular formula of the vinyl MQ resin product is as follows: (M)^VI) aQ, wherein a has a value of 0.8.

(2) Synthesis of modified MQ resin:

1) adding 20.80g of hydrogen-terminated silicone oil (with hydrogen content of 0.96%) and 0.3g of Kaster platinum catalyst into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 300r/min, and stirring for 0.5 h; 6.31g of 1, 2-epoxy-7-octene and 4.30g of vinyl acetate were premixed and added dropwise to a three-necked flask for reaction. Controlling the reaction temperature to be not more than 55 ℃, reacting for 2 hours after 1 hour of dropwise addition, stopping heating, introducing nitrogen, and cooling to room temperature to obtain a modified hydrogen-terminated silicone oil prepolymer;

2) adding 67.28g of mixed solution of the vinyl MQ resin powder obtained in the step (1) and 50g of dimethylbenzene into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 260r/min, and stirring for 1 h; adding the modified hydrogen-terminated silicone oil drops obtained in the step 1) into a three-neck flask for reaction, controlling the reaction temperature not to exceed 55 ℃, and reacting for 4 hours after dropwise adding is completed within 0.5 hour; then heating to 80 ℃, and carrying out reflux reaction for 4 h; then the temperature is raised to 100 ℃, and the reflux reaction is carried out for 2 hours. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and rotationally evaporating xylene to obtain white solid modified MQ silicon resin.

The number average molecular weight Mw of the product was 10218g/mol and Mw/Mn was 1.75 as measured by WATERS gel permeation chromatography. The vinyl content of the clear product was determined by the vinyl content titration method to be 8.00% which is similar to the theoretical vinyl content of 8.23%. The specific molecular formula of the modified MQ silicon resin product is as follows: (M)^AM^B)m(M^VI) nQ, wherein m is 0.1 and n is 0.6.

Example 9:

(1) vinyl MQ resin synthesis: into a three-necked flask equipped with a stirrer, a thermometer and a condenser were charged 208.33g of tetraethoxysilane, 74.56g of tetramethyldivinyldisiloxane, 90g of ethanol and 100g of xylene, and stirring and mixing were started with controlling a stirring speed at 260 r/min. And (3) heating to 60 ℃, dropwise adding a mixed solution prepared from 57.6g of deionized water and 44g of 36 wt% concentrated hydrochloric acid, heating to 75 ℃ after dropwise adding, carrying out reflux reaction for 2 hours, and then heating to 120 ℃ for reflux reaction for 5 hours to obtain a solution containing the vinyl MQ resin. Then the heating and stirring system was turned off, the temperature was reduced to room temperature, the liquid in the bottle was transferred to a separatory funnel, xylene and n-heptane were added for extraction, the mixture was washed with deionized water until PH 7, anhydrous sodium sulfate was added to adsorb moisture until the liquid was clear and transparent, colorless and transparent filtrate was obtained by filtration, and xylene and n-heptane were rotary distilled off to obtain 127.83g of a white powder solid, i.e., vinyl MQ resin, with a yield of 95%.

The Mw of the product was 7309g/mol and Mw/Mn was 1.71 as measured by WATERS gel permeation chromatography. The vinyl content of the product was determined by the vinyl content titration method to be 16.01% which is similar to the theoretical vinyl content of 16.05%. The specific molecular formula of the vinyl MQ resin product is as follows: (M)^VI) aQ, wherein a has a value of 0.8.

(2) Synthesis of modified MQ silicon resin:

1) adding 10.40g of hydrogen-terminated silicone oil (with hydrogen content of 0.96%) and 0.3g of Kaster platinum catalyst into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 300r/min, and stirring for 0.5 h; premixing 3.15g of 1, 2-epoxy-7-octene and 2.15g of vinyl acetate, dropwise adding into a three-neck flask for reaction, controlling the reaction temperature to be not more than 55 ℃, finishing dropwise adding for 1h, reacting for 2h, stopping heating, introducing nitrogen, and cooling to room temperature to obtain a modified hydrogen-terminated silicone oil prepolymer;

The number average molecular weight Mw of the product was 8998g/mol and Mw/Mn was 1.69 as measured by WATERS gel permeation chromatography. The vinyl content of the clear product was determined by the vinyl content titration method to be 11.30%, similar to the theoretical vinyl content of 11.41%. The specific molecular formula of the modified MQ silicon resin product is as follows: (M)^AM^B)m(M^VI) nQ, wherein m is 0.05 and n is 0.7.

Example 10

The reaction process of step (1) is the same as that of step (1) in example 1;

(2) synthesis of modified MQ silicon resin:

1) adding 72.8g of hydrogen-terminated silicone oil (with hydrogen content of 0.96%) and 0.3g of Kaster platinum catalyst into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 300r/min, and stirring for 0.5 h; premixing 17.17g of 1, 2-epoxy-5-octene and 15.06g of vinyl acetate, dropwise adding into a three-neck flask for reaction, controlling the reaction temperature to be not more than 55 ℃, finishing dropwise adding for 1h, reacting for 2h, stopping heating, introducing nitrogen, and cooling to room temperature to obtain a modified hydrogen-terminated silicone oil prepolymer;

The number average molecular weight Mw of the product is 18707g/mol and Mw/Mn is 1.71 as measured by WATERS gel permeation chromatography. The vinyl content of the clear product was determined by the vinyl titration method to be 0.76%, similar to the theoretical vinyl content of 0.78%. The value of a in the vinyl MQ resin is obtained through the step (1); modified by the step (2), part of M^VIBecome M^AAnd/or M^BFor the rest M^VIAnd (4) performing a vinyl test to clarify the value of n, and calculating the value of m according to the value of a. The specific molecular formula of the modified MQ silicon resin product is as follows: (M)^AM^B)m(M^VI) nQ, wherein m is 0.35 and n is 0.1.

Example 11

The reaction process of step (1) is the same as that of step (1) in example 1;

(2) synthesis of modified MQ silicon resin:

1) adding 72.8g of hydrogen-terminated silicone oil (with hydrogen content of 0.96%) and 0.3g of Kaster platinum catalyst into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 300r/min, and stirring for 0.5 h; premixing 17.17g of 1, 2-epoxy-9-decene and 27.00g of vinyl acetate, dropwise adding the premixed mixture into a three-neck flask for reaction, controlling the reaction temperature to be not more than 55 ℃, finishing dropwise adding for 1h, reacting for 2h, stopping heating, introducing nitrogen, and cooling to room temperature to obtain a modified hydrogen-terminated silicone oil prepolymer;

The number average molecular weight Mw of the product was 19773g/mol and Mw/Mn was 1.71 as measured by WATERS gel permeation chromatography. The vinyl content of the clear product was determined by the vinyl titration method to be 0.73%, similar to the theoretical vinyl content of 0.74%. The value of a in the vinyl MQ resin is obtained through the step (1); modified by the step (2), part of M^VIBecome M^AAnd/or M^BFor the rest M^VIAnd (4) performing a vinyl test to clarify the value of n, and calculating the value of m according to the value of a. The specific molecular formula of the modified MQ silicon resin product is as follows: (M)^AM^B)m(M^VI) nQ, wherein m is 0.35 and n is 0.1.

Comparative example 1

Methyl MQ resin synthesis: a three-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 208.33g of ethyl orthosilicate, 64.95g of hexamethyldisiloxane, 90g of ethanol and 100g of xylene, and stirred and mixed while controlling a stirring speed at 260 r/min. And (3) heating to 60 ℃, dropwise adding a mixed solution prepared from 57.6g of deionized water and 44g of 36 wt% concentrated hydrochloric acid, heating to 75 ℃ after dropwise adding, carrying out reflux reaction for 2 hours, and then heating to 120 ℃ for reflux reaction for 4 hours to obtain a solution containing the methyl MQ resin. Then the heating and stirring system was turned off, the temperature was reduced to room temperature, the liquid in the bottle was transferred to a separatory funnel, xylene and n-heptane were added for extraction, the mixture was washed with deionized water until PH 7, anhydrous sodium sulfate was added to adsorb moisture until the liquid was clear and transparent, colorless and transparent filtrate was obtained by filtration, and xylene and n-heptane were rotary distilled off to obtain 118.70g of methyl MQ resin as a white powder solid with a yield of 95%.

The Mw of the product was 6810g/mol and Mw/Mn was 1.70 as measured by WATERS gel permeation chromatography. The specific molecular formula of the methyl MQ resin product is as follows: MaQ, wherein the value of a is 0.8.

Comparative example 2:

a step (2) of performing only the vinyl MQ resin synthesis step (1) and not performing modification of the vinyl MQ resin; the vinyl MQ resin synthesis procedure was the same as in step (1) of example 1.

The Mw of the product was 7304g/mol, Mw/Mn 1.70 as determined by WATERS gel permeation chromatography. The vinyl content of the product was determined by the vinyl content titration method to be 16.00% which is similar to the theoretical vinyl content of 16.05%. The specific molecular formula of the vinyl MQ resin product is as follows: (M)^VI) aQ, wherein a has a value of 0.8.

Comparative example 3:

(1) vinyl MQ resin synthesis: same as example 1, step (1);

(2) Synthesis of modified MQ silicon resin:

1) adding 72.8g of hydrogen-terminated silicone oil (with hydrogen content of 0.96%) and 0.3g of Kaster platinum catalyst into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 300r/min, and stirring for 0.5 h; dropwise adding 42.00g of 1, 2-epoxy-7-octene into a three-neck flask for reaction, controlling the reaction temperature not to exceed 55 ℃, reacting for 2 hours after dropwise adding is finished for 1 hour, stopping heating, introducing nitrogen, and cooling to room temperature to obtain a modified hydrogen-terminated silicone oil prepolymer;

2) adding 67.28g of resin powder obtained in the step (1) and 50g of dimethylbenzene into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 260r/min, and stirring for 1 h; adding the modified hydrogen-terminated silicone oil drops obtained in the step 1) into a three-neck flask for reaction, controlling the reaction temperature not to exceed 55 ℃, and reacting for 4 hours after dropwise adding is completed within 0.5 hour; then heating to 80 ℃, and carrying out reflux reaction for 4 h; then the temperature is raised to 100 ℃, and the reflux reaction is carried out for 2 hours. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and rotationally evaporating xylene to obtain white solid modified MQ silicon resin.

The number average molecular weight Mw of the product was 19766g/mol and Mw/Mn was 1.71 as measured by WATERS gel permeation chromatography. The vinyl content of the clear product was determined by the vinyl titration method to be 0.71%, similar to the theoretical vinyl content of 0.74%. The specific molecular formula of the modified MQ silicon resin product is as follows: (M)^A)m(M^VI) nQ, wherein m is 0.35 and n is 0.1.

Comparative example 4:

(1) vinyl MQ resin synthesis: same as example 1, step (1);

(2) Synthesis of modified MQ silicon resin:

1) adding 72.8g of hydrogen-terminated silicone oil (with hydrogen content of 0.96%) and 0.3g of Karsted platinum catalyst into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring, controlling the stirring speed to be 300r/min, and stirring for 0.5 h; dropwise adding 30.12g of vinyl acetate into a three-neck flask for reaction, controlling the reaction temperature to be not more than 55 ℃, finishing dropwise adding for 1h, reacting for 2h, stopping heating, introducing nitrogen, and cooling to room temperature to obtain a modified hydrogen-terminated silicone oil prepolymer;

2) adding 67.28g of the mixed solution of the resin powder obtained in the step (1) and 50g of xylene into a three-neck flask provided with a stirrer, a thermometer and a condenser, heating to 50 ℃, starting stirring and mixing, controlling the stirring speed to be 260r/min, and stirring for 1 h; adding the modified hydrogen-terminated silicone oil drops obtained in the step 1) into a three-neck flask for reaction, controlling the reaction temperature not to exceed 55 ℃, and reacting for 4 hours after dropwise adding is completed within 0.5 hour; then heating to 80 ℃, and carrying out reflux reaction for 4 h; then the temperature is raised to 100 ℃, and the reflux reaction is carried out for 2 hours. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and rotationally evaporating xylene to obtain white solid modified MQ silicon resin.

The number average molecular weight Mw of the product was 18572g/mol and Mw/Mn was 1.71 as measured by WATERS gel permeation chromatography. The vinyl content of the clear product was determined by the vinyl titration method to be 0.74%, similar to the theoretical vinyl content of 0.79%. The specific molecular formula of the modified MQ silicon resin product is as follows: (M)^A)m(M^VI) nQ, wherein m is 0.35 and n is 0.1.

Test example:

(1) the methyl MQ resin obtained in comparative example 1 was added to the silicone pressure-sensitive adhesive made of Dow Corning7657 at a mass fraction of 3%, the modified MQ silicone resin obtained in example 1 was added to the silicone pressure-sensitive adhesive made of Dow Corning7657 at different mass fractions (1%, 2%, 3%, 5%, and 10%), and the silicone pressure-sensitive adhesive made of Dow Corning7657 was used as a blank without adding any kind of MQ silicone resin and applied to the PI film to make a silicone pressure-sensitive adhesive tape, respectively. The 180-degree peel strength test of the pressure-sensitive adhesive on the PI base material is examined, and the adhesive property of the pressure-sensitive adhesive on the base material is indirectly tested, and the results are shown in Table 1.

Wherein, the blank sample is coated on the PI film to prepare the silicone pressure sensitive adhesive tape with the number of 0 #; the modified MQ silicone resin prepared in example 1 is added with silicone pressure sensitive adhesive prepared by Dow Corning7657 in different mass fractions (1%, 2%, 3%, 5% and 10%), and the silicone pressure sensitive adhesive is respectively coated on PI films to prepare silicone pressure sensitive adhesive tapes with numbers of 1#, 2#, 3#, 4#, and 5 #; the methyl MQ resin obtained in comparative example 1 was added to a silicone pressure-sensitive adhesive prepared by Dow Corning7657 in a mass fraction of 3% and applied to a PI film to prepare a silicone pressure-sensitive adhesive tape having a No. 6.

Table 1 peel strength test results of silicone pressure sensitive adhesive tapes

As can be seen from Table 1, as the addition amount of the modified MQ silicone resin obtained in the invention in the silicone pressure-sensitive adhesive increases, the 180-degree peel strength of the silicone pressure-sensitive adhesive gradually increases, namely the increase of the adhesive force is indirectly reflected. Whereas the blank samples (silicone pressure sensitive adhesive without any MQ silicone resin) and the silicone pressure sensitive adhesive prepared with methyl MQ resin (unmodified) had lower 180 degree peel strength than the silicone pressure sensitive adhesive with modified MQ silicone resin of example 1 of the present invention.

In addition, in the process of preparing the organic silicon pressure sensitive adhesive tape by adding the methyl MQ resin and a blank sample, when a 180-degree peel strength test is carried out under the condition of not adding a primer, a large amount of residual adhesive exists; in the process of preparing the organic silicon pressure sensitive adhesive tape by adding the modified MQ silicon resin, when 180-degree peel strength test is carried out under the condition of not adding a primer, adhesive residue is avoided, and the peel strength is kept at a high level. Therefore, the modified MQ silicon resin is added, and under the condition of ensuring normal use of the pressure-sensitive adhesive, a primer does not need to be coated, so that the production process and the cost of the pressure-sensitive adhesive are saved.

(2) Adding the modified MQ silicon resin prepared in the examples 1-9 into the organic silicon pressure-sensitive adhesive prepared by Dow Corning7657 according to the addition amount of 3 mass percent, and coating the organic silicon pressure-sensitive adhesive on a PI film to prepare an organic silicon pressure-sensitive adhesive tape; the 180-degree peel strength test of the pressure-sensitive adhesive on the PI base material is examined, the adhesive property of the pressure-sensitive adhesive on the base material is indirectly tested, and the results are shown in the table 2:

table 2 peel strength test results for silicone pressure sensitive tapes

As can be seen from Table 2, M was added in the course of modifying the resin^A、M^BWith an increase in the addition amount (i.e., an increase in the value of m), the 180-degree peel strength of the resulting silicone pressure-sensitive adhesive tape was significantly improved (refer to examples 1 to 9).

(3) The MQ resins obtained in comparative examples 1,2, 3 and 4 and the modified MQ silicone resin obtained in inventive example 1 were added to the silicone pressure-sensitive adhesive prepared by Dow Corning7657 at a mass fraction of 3%, and coated on a PI film to prepare a silicone pressure-sensitive adhesive tape; and (3) inspecting the 180-degree peel strength test of the pressure-sensitive adhesive on the PI base material, and indirectly testing the adhesive property of the pressure-sensitive adhesive on the base material. The results are shown in Table 3:

table 3 peel strength test results of silicone pressure sensitive adhesive tapes

As can be seen from table 3, the silicone pressure sensitive adhesive tape to which the modified MQ silicone resin obtained in example 1 of the present invention was added had a peel strength higher than that of the other resins (comparative examples 1 to 4) when subjected to a 180-degree peel strength test with a primer.

When the organic silicon pressure sensitive adhesive tape prepared by adding the modified MQ silicon resin obtained in the embodiment 1 of the invention is subjected to 180-degree peel strength test without primer coating, the peel strength value is larger, the residual adhesive amount is small, and even no residual adhesive exists; when the silicone pressure sensitive adhesive tape prepared by adding the unmodified MQ resin is subjected to a 180-degree peel strength test, a large amount of residual adhesive exists, but the peel strength of the vinyl resin is slightly better than that of the methyl resin (comparing example 1 with comparative example 1 and comparative example 2); only carry out M^AOr M^BThe 180 degree peel strength of the pressure sensitive tape prepared from the single modified MQ silicone resin was superior to that of the two simultaneously modified MQ silicone resins (example 1 compared to comparative examples 3 and 4).

Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A modified MQ silicon resin is characterized in that the modified MQ silicon resin is shown as a general formula (I) (M)^AM^B)m(M^VI) nQ; wherein m is 0.025-0.375 based on the amount of Q chain substance as 1; n is 0.05-0.75;

the chemical structure of the modified MQ silicon resin is shown as follows:

wherein M is^AThe chemical structural formula of (A) is:

，

wherein the value of P is an integer from 1 to 10; the value of X is 2, 4, 6;

M^Bthe chemical structural formula of (A) is:

wherein the value of P is an integer from 1 to 10;

M^VIthe chemical structural formula of (A) is:

2. the modified MQ silicone resin of claim 1, wherein m is from 0.2 to 0.35, based on the amount of Q mer material of 1.

3. The modified MQ silicone resin of claim 1, wherein n is from 0.05 to 0.15, based on the amount of Q mer material of 1.

4. The modified MQ silicone resin of claim 1, wherein M is M^AIn the chemical structural formula (2), the value of P is an integer of 1 to 3.

5. The modified MQ silicone resin of claim 1, wherein M is M^AIn the chemical structural formula (2), X is 4.

6. The modified MQ silicone resin of claim 1, wherein M is M^BIn the chemical structural formula (2), the value of P is an integer of 1 to 3.

7. The modified MQ silicone resin of claim 1, wherein in the general formula (I), m/n is from 0.03 to 7.5.

8. The modified MQ silicone resin of claim 7, wherein in the general formula (I), m/n is from 2.3 to 7.0.

9. A method for preparing a modified MQ silicone resin according to any of claims 1 to 8, comprising the steps of:

(1) vinyl MQ resin synthesis: mixing silicate ester, tetramethyl divinyl disiloxane, alcohol solvent and aromatic hydrocarbon solvent, contacting with aqueous solution of acid catalyst, and reacting at 70-80 deg.C; then heating to 110-140 ℃ for reflux reaction to obtain vinyl MQ resin;

(2) synthesis of modified MQ silicon resin:

10. The preparation method according to claim 9, wherein the step (1) comprises mixing silicate, tetramethyldivinyldisiloxane, an alcohol solvent, and an aromatic hydrocarbon solvent, contacting with an aqueous solution of an acid catalyst, and reacting at 70-80 ℃ for 1-3 hours; then heating to 110-140 ℃ for reflux reaction, and reacting for 3-5 h.

11. The preparation method according to claim 9, wherein the raw material components are used in the following amounts, based on 100 wt% of the total weight of the raw material components in the reaction system of step (1):

25 to 50 weight percent of silicate,

10-20 wt% of tetramethyl divinyl disiloxane,

10-25 wt% of alcohol solvent,

10-30 wt% of aromatic hydrocarbon solvent,

the aqueous solution of the acid catalyst is 10 to 25 wt%.

12. The production method according to claim 11, wherein the raw material components are used in the following amounts, based on 100 wt% of the total weight of the raw material components in the reaction system of the step (1):

29 to 42 weight percent of silicate,

12-15 wt% of tetramethyl divinyl disiloxane,

14-18 wt% of alcohol solvent,

15-20 wt% of aromatic hydrocarbon solvent,

the aqueous solution of the acid catalyst is 16 to 21 wt%.

13. The production method according to claim 11, wherein the mass ratio of the acid catalyst to water in the aqueous solution of the acid catalyst is from 0.5 to 1: 1.

14. the production method according to claim 13, wherein the mass ratio of the acid catalyst to water in the aqueous solution of the acid catalyst is from 0.6 to 0.8: 1.

15. the production method according to any one of claims 9 to 14, wherein in the step (1), the silicate is selected from one or more of methyl orthosilicate, polycondensate of methyl orthosilicate, ethyl orthosilicate, polycondensate of propyl orthosilicate, and propyl orthosilicate; and/or

The alcohol solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol and n-butanol; and/or

The aromatic hydrocarbon solvent is selected from one or more of benzene, toluene and xylene; and/or

The acid catalyst is one or more selected from p-toluenesulfonic acid, concentrated sulfuric acid with the weight percent of 95-99% and concentrated hydrochloric acid with the weight percent of 30-38%.

16. The production method according to claim 15, wherein in the step (1), the silicate is tetraethoxysilane; and/or

The alcohol solvent is ethanol; and/or

The aromatic hydrocarbon solvent is xylene; and/or

The acid catalyst was 36 wt% concentrated hydrochloric acid.

17. The production method according to any one of claims 9 to 14 and 16, wherein in the step (1), silicate, tetramethyldivinyldisiloxane, an alcohol solvent and an aromatic hydrocarbon solvent are mixed and contacted with the aqueous solution of the acid catalyst at an elevated temperature of 50 to 60 ℃.

18. The preparation method according to claim 17, wherein the step (1) further comprises extracting, washing and distilling the product solution after the reaction is finished to obtain the vinyl MQ resin; the extracting agent is one or more selected from toluene, xylene, hexane, cyclohexane and n-heptane.

19. The method of claim 18, wherein the extractive extractant is selected from xylene and/or n-heptane.

20. The production method according to any one of claims 9 to 14, 16 and 18 to 19, wherein the following raw material components are used in amounts, based on 100 wt% of the total weight of the raw material components in the reaction system of the step (2):

the mixture of the vinyl MQ resin and the aromatic hydrocarbon solvent is 51 to 90 weight percent;

the hydrogen-terminated silicone oil accounts for 4-35 wt%;

0.05-0.3 wt% of platinum catalyst,

the pre-mixture formed by epoxy alkene and vinyl acetate is 2-20 wt%.

21. The preparation method according to claim 20, wherein the raw material components are used in the following amounts, based on 100 wt% of the total weight of the raw material components in the reaction system of step (2):

the mixture of the vinyl MQ resin and the aromatic hydrocarbon solvent is 70 to 75 weight percent;

the hydrogen-terminated silicone oil accounts for 26-29 wt%;

0.1-0.2 wt% of platinum catalyst,

the pre-mixture of epoxy alkene and vinyl acetate is 4-16 wt%.

22. The method of claim 20, wherein the pre-mixture of the alkylene oxide and the vinyl acetate has a mass ratio of the alkylene oxide to the vinyl acetate of 0.5-3: 1.

23. the method of claim 22, wherein the pre-mixture of the alkylene oxide and the vinyl acetate has a mass ratio of 1-2: 1.

24. the process according to claim 20, wherein the mass ratio of the vinyl MQ resin to the aromatic hydrocarbon solvent in the mixture of the vinyl MQ resin and the aromatic hydrocarbon solvent is from 0.5 to 3: 1.

25. the process according to claim 24, wherein the mass ratio of the vinyl MQ resin to the aromatic hydrocarbon solvent in the mixture of the vinyl MQ resin and the aromatic hydrocarbon solvent is 1 to 2: 1.

26. the production method according to any one of claims 9 to 14, 16, 18 to 19, 21 to 25, wherein in the step (2), the alkylene oxide is selected from one or more of 1, 2-epoxy-5-hexene, 1, 2-epoxy-7-octene, and 1, 2-epoxy-9-decene; and/or

The platinum catalyst is selected from the group consisting of Karster catalysts having a platinum content of 3000-8000 ppm.

27. The production method according to claim 26, wherein in the step (2), the oxyalkylene is 1, 2-epoxy-7-octene; and/or

The aromatic hydrocarbon solvent is xylene.

28. The process according to any one of claims 9 to 14, 16, 18 to 19, 21 to 25 and 27, wherein the vinyl MQ resin of step (1) is of the general formula (II) (M)^VI) aQ is shown; wherein a is 0.75 to 0.85 when the amount of the Q chain member substance is 1;

the vinyl content of the modified MQ silicon resin in the step (2) is 0.1-15 wt%.

29. The preparation method as claimed in claim 28, wherein the vinyl content of the modified MQ silicone resin of step (2) is 0.3 wt% to 12 wt%.

30. Use of a modified MQ silicone resin according to any one of claims 1 to 8, or prepared by the preparation process according to any one of claims 9 to 29, in a pressure sensitive adhesive.