CN107915843B - Modified MQ silicon resin and preparation method thereof - Google Patents

Modified MQ silicon resin and preparation method thereof Download PDF

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CN107915843B
CN107915843B CN201711122797.2A CN201711122797A CN107915843B CN 107915843 B CN107915843 B CN 107915843B CN 201711122797 A CN201711122797 A CN 201711122797A CN 107915843 B CN107915843 B CN 107915843B
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CN107915843A (en
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刘志锋
李书同
颜和祥
穆建涛
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

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Abstract

The invention belongs to the technical field of synthesis of MQ resin, and provides modified MQ silicon resin and a preparation method thereof; the modified MQ silicon resin is shown as a general formula (I) (M)AMB)m(MH) nQ, wherein m is 0.25-0.40, n is 0.25-0.40; wherein M isAThe structural formula of (A) is:
Figure DDA0001467739010000011
MBthe structural formula of (A) is:
Figure DDA0001467739010000012
MHthe structural formula of (A) is:

Description

Modified MQ silicon resin and preparation method thereof
Technical Field
The invention belongs to the technical field of synthesis of MQ resin, and particularly relates to modified MQ silicon resin for tackifying pressure-sensitive adhesive and a preparation method thereof.
Background
In recent years, the demand of pressure-sensitive adhesives keeps a faster growth rate, high-performance special pressure-sensitive adhesives develop particularly rapidly, the production and the sales are continuously and greatly increased, and the pressure-sensitive adhesives become the pressure-sensitive adhesive varieties with the highest sales volume in the global range. But in China, the application of the method is far lower than the international level due to the restriction of technology. With the increasing performance, it is expected that the growth of such 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. The organic silicon pressure-sensitive adhesive can withstand multiple cycles of cold and heat, which is incomparable with 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, the silicone pressure-sensitive adhesive of Dow Corning company needs to use a matched primer, and the silicone pressure-sensitive adhesive tape of 3M company is coated with the primer by detection), otherwise, the pressure-sensitive adhesive can fall off from a base material in the using process, and the use is seriously influenced. The use of the primer adds a plurality of working procedures to the production and increases the cost.
Although the research on the organic silicon pressure-sensitive adhesive is continuous, the problems exist, and the adhesive force and the adhesion force of the adhesive to the substrate are not enough.
Disclosure of Invention
The invention aims to provide a modified MQ silicon resin for tackifying pressure-sensitive adhesive and a preparation method thereof, aiming at the problems that the prior pressure-sensitive adhesive has insufficient adhesive force to a base material, needs to use a primer to increase working procedures, cost and the like; the obtained resin is added into the pressure-sensitive adhesive, so that the adhesive and the pressure-sensitive adhesive base material have good adhesion and adhesive force, the 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 above object, the present invention provides a modified MQ silicone resin, which is represented by the general formula (I) (M)AMB)m(MH) nQ, wherein the m value is 0.25-0.40, preferably 0.25-0.30, based on the molar weight of the Q chain link of 1; n has a value of 0.25 to 0.40, preferably 0.25 to 0.30;
the chemical structure is as follows:
Figure BDA0001467739000000021
wherein M isAThe structural formula of (A) is:
Figure BDA0001467739000000022
MBthe structural formula of (A) is:
Figure BDA0001467739000000031
MHthe structural formula of (A) is:
Figure BDA0001467739000000032
MQ silicone resin is a very unique siloxane, is a silicone resin consisting of tetrafunctional siloxane condensation chain links (Q) and monofunctional siloxane chain links (M), and the molar mass of the silicone resin is generally 1000-8000g/mol, and the number ratio of the M chain links to the Q chain links in the molecular structure and the structure determine the properties and the application range of the resin.
In the invention, the chemical structure of the Q chain link is a structure known in the field, and the details are shown in Chinese patent document CN 103524741A.
In the present invention, (M)AMB) The ratio of the amount (molar) of the material of the mer to the Q mer is M, MHThe ratio of the amount (molar) of the material of mer to Q mer is n.
According to the modified MQ silicone resin provided by the invention, m/n is preferably 0.8-1.2.
The invention also provides a preparation method of the modified MQ silicon resin, which comprises the following steps:
(1) synthesis of hydrogen-containing MQ resin: contacting silicate ester, tetramethyl dihydrodisiloxane, acid catalyst and aromatic hydrocarbon solvent; heating to 40-60 deg.C, adding organic monobasic acid; heating for reaction, distilling to generate ethyl acetate and ethanol, cooling to 40-60 ℃, and adding organic acid anhydride for reaction to obtain hydrogen-containing MQ resin;
(2) synthesis of modified MQ resin: contacting allyl glycidyl ether, vinyl silane compounds and platinum catalyst, and heating to 40-60 ℃ to form a mixture; premixing the hydrogen-containing MQ resin and aromatic hydrocarbon solvent to form a premix; controlling the temperature to be 45-55 ℃, contacting the premix with the mixture system, and heating for reaction to obtain the modified MQ resin.
According to the preparation method provided by the invention, preferably, the following components are used according to the total weight of the components in the reaction system of the step (1) being 100 wt%:
the silicate is 30 to 55 wt%, more preferably 33.60 to 52.26 wt%,
5 to 12 wt%, more preferably 8.49 to 11.81 wt%,
the acid catalyst is present in an amount of 0.1 to 0.2 wt%, more preferably 0.12 to 0.17 wt%,
5 to 14 wt%, more preferably 9.88 to 13.74 wt%,
20 to 35 wt%, more preferably 22.79 to 32.66 wt%,
the organic acid anhydride is 5 to 12 wt%, more preferably 6.46 to 10.54 wt%.
Preferably, the following components are used, based on the total weight of the components in the reaction system of the step (2) being 100 wt%:
allyl glycidyl ether in an amount of 10 to 20 wt.%, more preferably 11.44 to 17.48 wt.%,
10 to 25 wt%, more preferably 15.03 to 22.71 wt%, of the vinyl silane compound,
the platinum catalyst is 0.001-0.002, more preferably 0.0013-0.0019 wt%,
the premix of the hydrogen-containing MQ resin and the aromatic hydrocarbon solvent is 55 to 80 wt%, more preferably 69 to 75 wt%.
Preferably, the hydrogen containing MQ resin is 55 to 67 wt%, more preferably 59.80 to 63.42 wt%, and the aromatic hydrocarbon solvent is 33 to 45 wt%, more preferably 33.96 to 38.76 wt%, based on the total weight of the premix being 100 wt%.
According to the preparation method provided by the invention, in the step (1), preferably, the silicate is selected from methyl orthosilicate or a polycondensate thereof, ethyl orthosilicate or a polycondensate thereof, propyl orthosilicate or a polycondensate thereof, and more preferably, ethyl orthosilicate.
Preferably, the acid catalyst is selected from one or more of p-toluenesulfonic acid, 95-98 wt% concentrated sulfuric acid and 98-99 wt% trifluoromethanesulfonic acid; more preferably 98-99 wt% of trifluoromethanesulfonic acid.
Preferably, the aromatic hydrocarbon solvent is selected from one or more of benzene, toluene and xylene, more preferably xylene.
Preferably, the organic monobasic acid is selected from one or more of formic acid, acetic acid and propionic acid, more preferably acetic acid.
Preferably, the organic anhydride is selected from acetic anhydride and/or phthalic anhydride, more preferably acetic anhydride.
Preferably, in step (1), the hydrogen-containing MQ resin is of formula (II) (M)H) aQ is shown; wherein a is 0.75 to 0.85 based on the molar amount of the Q mer of 1. a represents MHMolar ratio to Q.
Preferably, the hydrogen content of the hydrogen-containing MQ resin is from 0.6 wt% to 0.8 wt%, more preferably from 0.65 wt% to 0.75 wt%.
In the step (1), silicate ester, tetramethyl dihydrodisiloxane, acid catalyst and xylene are added into a three-neck flask which is provided with a stirrer, a thermometer and a condenser according to the weight ratio, stirring is started, and the stirring speed is controlled to be 260 r/min. Then heating and dripping acetic acid; preferably, the organic monobasic acid is added dropwise when the temperature is raised to 45-55 ℃.
In the step (1), after the organic monoacid is dripped, carrying out reflux reaction for 1-3h, and then heating for reaction; preferably, after the organic monoacid is dripped, the temperature of the system is raised to 70-90 ℃ for reaction, and the reaction time is 1-3 h.
After the temperature rise reaction, distilling the generated ethyl acetate and ethanol to 90-100 ℃, continuing to distill for 1-3h, and then cooling; preferably, the organic anhydride is added dropwise when the temperature is reduced to 45-55 ℃ and the reaction is carried out for 1-3h, more preferably for 2 h.
After the reaction is finished, closing the heating and stirring system, cooling to room temperature, transferring the liquid in the bottle to a separating funnel, and adding an extracting agent for extraction; preferably, in step (1), the extractant is selected from one or more of toluene, xylene, hexane, cyclohexane and n-heptane. More preferably from xylene and/or n-heptane.
Adding an extracting agent for extraction, washing with distilled water until the pH value is 7, adding anhydrous sodium sulfate to adsorb water until the liquid is clear and transparent, filtering to obtain colorless and transparent filtrate, and rotationally evaporating the extracting agent to obtain white powdery solid, namely the hydrogen-containing MQ resin.
According to the preparation method provided by the invention, in the step (2), preferably, the vinyl silane compound is selected from one or more of vinyl trimethoxy silane, vinyl triethoxy silane and methyl vinyl diethoxy silane, and more preferably vinyl trimethoxy silane.
Preferably, the aromatic hydrocarbon solvent is selected from one or more of benzene, toluene and xylene, more preferably xylene.
Preferably, the platinum catalyst is selected from the group consisting of Karster catalysts having a platinum content of 5000 ppm.
In the step (2), the allyl glycidyl ether, the vinyl silane compound and the platinum catalyst are contacted, stirring is started, the stirring speed is controlled to be 220-260r/min, the temperature is raised to 40-50 ℃, and stirring is carried out for 1-2 h. Preferably, the premixed mixture of the hydrogen-containing MQ resin and the aromatic hydrocarbon solvent is dripped into a reaction system, the reaction temperature is controlled to react for 3 to 5 hours, the temperature is increased to 70 to 90 ℃, the reflux reaction is carried out for 3 to 5 hours, the temperature is increased to 95 to 115 ℃, and the reflux reaction is carried out for 1 to 3 hours. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3-5 parts by weight of activated carbon for adsorption for 5-8h, filtering to obtain colorless filtrate, and rotary evaporating aromatic hydrocarbon solvent to obtain white solid.
According to the preparation method provided by the invention, preferably, the hydrogen content of the modified MQ silicon resin is 0.1-0.2 wt%.
In the present invention, the part M in the hydrogen-containing MQ resin is modifiedHQuilt MAAnd MBAnd (4) substituting to obtain the modified MQ resin. Whereby (M) of the general formula (II)H) The a value in aQ is equivalent to the M/Q value in the modified MQ silicon resin. Preferably, the molar ratio of M/Q in the modified MQ silicone resin is from 0.75 to 0.85.
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 modified MQ silicon resin is used as a formula raw material of the pressure-sensitive adhesive.
The technical scheme of the invention has the following beneficial effects:
1) the modified MQ silicon resin prepared by the method is white solid powder, and is clear, transparent and not turbid when being mixed with each component of the organic silicon pressure-sensitive adhesive;
2) the modified MQ resin 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, thereby simplifying the pressure-sensitive adhesive manufacturing process and reducing the cost;
3) according to the preparation method, the hydrogen content of the obtained modified MQ resin is 0.1-0.2 wt%, contains Si-H active groups, and can continuously participate in other reactions; and the M/Q is 0.75-0.85, so that the epoxy resin is very suitable for reinforcing pressure-sensitive adhesive.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below by way of examples. While the examples describe preferred embodiments of the invention, it should be understood that the invention can be embodied in various forms and should not be construed as limited to the embodiments set forth herein.
The test method comprises the following steps:
1. number average molecular weight of the product measured by WATERS gel permeation chromatograph: dissolving the sample in tetrahydrofuran, separating by gel chromatography, and measuring the molecular weight and molecular weight distribution of the MQ class silicon resin material sample by making a standard curve by using a standard PS (polystyrene) and relatively correcting.
2. Measuring the hydrogen content of the product by a hydrogen content titration method: accurately weighing 0.1000-0.3000 g (hydrogen content is lower than 0.2%, maximum sampling amount is 0.3g) of sample in a 250ml iodine measuring flask, and adding 20ml of carbon tetrachloride for dissolving; then adding 10ml of 0.2mol/L bromine-acetic acid solution and 0.5ml of water, covering a plug, shaking up, sealing the bottle mouth with carbon tetrachloride liquid, and placing in the dark for reaction for 30 min; after the reaction is completed, adding 25ml of potassium iodide solution with the mass fraction of 10%, forcibly shaking for 2-3 min, and washing the bottle mouth with deionized water; titrating with 0.1mol/L sodium thiosulfate standard solution, adding 3 drops of starch solution when the solution changes from dark red to bright red, and continuing to titrate, wherein the end point is determined when the solution just changes from blue to colorless. And simultaneously carrying out a blank experiment, carrying out parallel titration for 2 times in the blank experiment, taking an average value, and if the difference value of the two titration results is large, carrying out titration again.
Calculation formula of hydrogen content:
Figure BDA0001467739000000081
WH-the mass fraction of hydrogen,
C——Na2S2O3the molar concentration of (a) is mol/L,
V0blank experiment consuming Na2S2O3The volume of the solution is ml, and the volume of the solution,
V1titration of the sample to consume Na2S2O3The volume of the solution is ml, and the volume of the solution,
m-mass of sample g.
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.
The reaction raw material sources are as follows:
tetraethoxysilane, caruncle morning light chemical ltd, AR;
tetramethyldihydrodisiloxane, AR, chemical ltd, waveriridaceae, beijing;
trifluoromethanesulfonic acid, alatin reagent, AR;
xylene, juju gaku corporation, AR;
acetic acid, cromion chemical agents ltd, AR;
acetic anhydride, cromion chemical reagents ltd, AR;
n-heptane, AR, juju de science ltd;
anhydrous sodium sulfate, AR, cropland science ltd;
allyl glycidyl ether, shanghai meier, AR;
vinyltrimethoxysilane, shanghai meier, AR;
vinyltriethoxysilane, shanghai meirel, AR;
methylvinyldiethoxysilane, shanghai meier, AR;
5000ppm of a platinum catalst, an aniba;
formic acid, cromion chemical reagents ltd, AR;
propionic acid, cromion chemical reagents ltd, AR;
phthalic anhydride, cromet chemical reagents ltd, AR;
concentrated sulfuric acid, cromion chemical reagents ltd, AR;
dow Corning7657, Dow Corning;
PI film, Hangzhou Dahua plastics Co.
Example 1:
(1) synthesis of hydrogen-containing MQ resin: 166.67g of tetraethoxysilane, 42.98g of tetramethyldihydrodisiloxane, 0.63g of trifluoromethanesulfonic acid, and 50g of xylene were charged in a three-necked flask equipped with a stirrer, a thermometer, and a condenser; stirring is started, and the stirring speed is controlled to be 260 r/min. Heating to 50 ℃, dripping 115.30g of acetic acid, carrying out reflux reaction for 2h after dripping is finished, heating to 85 ℃, carrying out reflux reaction for 2h, distilling the generated ethyl acetate and ethanol to 100 ℃, continuing to distill for 2h, cooling to 60 ℃, dripping 32.68g of acetic anhydride, and carrying out reaction for 2 h. 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 distilled water until PH 7, anhydrous sodium sulfate was added to adsorb water until the liquid was clear and transparent, and filtration was carried out to obtain a colorless and transparent filtrate, and xylene and n-heptane were rotary-distilled off to obtain 86.43g of a white powdery solid with a yield of 95%.
The specific molecular formula of the product is as follows: (M)H) aQ, wherein a has a value of 0.8. The product has a number average molecular weight of 5069g/mol, Mw/ml as determined by WATERS gel permeation chromatographyMn is 1.38. The hydrogen content of the product, determined by means of a hydrogen content titration method, was 0.69% by weight, which was close to the theoretical hydrogen content of 0.70% by weight.
(2) Synthesis of modified MQ resin: 21.68g of allyl glycidyl ether, 28.16g of vinyl trimethoxy silane and 0.0025g of 5000ppm of Karster platinum catalyst are added into a three-neck flask provided with a stirrer, a thermometer and a condenser, stirring is started, the stirring speed is controlled to be 260r/min, the temperature is raised to 50 ℃, stirring is carried out for 1h, 86.43g of hydrogen-containing MQ resin and 50g of xylene are premixed, and the mixture is added into the three-neck flask dropwise. Controlling the reaction temperature to be 55 ℃, finishing the dropwise adding for 1h, reacting for 4h, heating to 80 ℃, carrying out reflux reaction for 4h, heating to 100 ℃, and carrying out reflux reaction for 2 h. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and performing rotary evaporation on xylene to obtain a white solid.
The specific molecular formula of the product is as follows: (M)AMB)m(MH) nQ, wherein m is 0.25 and n is 0.3. The product was found to have a number average molecular weight of 7861g/mol and an Mw/Mn of 1.38 by WATERS gel permeation chromatography. The hydrogen content of the transparent product, determined by means of a hydrogen content titration method, was 0.16% by weight, which was close to the theoretical hydrogen content of 0.17% by weight.
Example 2:
(1) synthesis of hydrogen-containing MQ resin: 166.67g of tetraethoxysilane, 40.30g of tetramethyldihydrodisiloxane, 0.63g of trifluoromethanesulfonic acid and 50g of xylene are charged into a three-necked flask equipped with a stirrer, a thermometer and a condenser; stirring is started, and the stirring speed is controlled to be 260 r/min. Heating to 50 ℃, dropwise adding 114.10g of acetic acid, carrying out reflux reaction for 2h after dropwise adding, then heating to 85 ℃, carrying out reflux reaction for 2h, distilling the generated ethyl acetate and ethanol to 100 ℃, continuing to distill for 2h, then cooling to 60 ℃, dropwise adding 30.63g of acetic anhydride, and carrying out reaction for 2 h. 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 distilled water until PH 7, anhydrous sodium sulfate was added to adsorb water until the liquid was clear and transparent, and filtration was carried out to obtain a colorless and transparent filtrate, and xylene and n-heptane were rotary-distilled off to obtain 81.23g of a white powdery solid with a yield of 92%.
The specific molecular formula of the product is as follows:(MH) aQ, wherein a has a value of 0.75. The product number average molecular weight was 5509g/mol and Mw/Mn 1.39 as determined by WATERS gel permeation chromatography. The hydrogen content of the product, determined by means of a hydrogen content titration method, was 0.66% by weight, which was similar to the theoretical hydrogen content of 0.68% by weight.
(2) Synthesis of modified MQ resin: 20.78g of allyl glycidyl ether, 26.99g of vinyltrimethoxysilane and 0.0025g of 5000ppm of Karster platinum catalyst are added into a three-neck flask provided with a stirrer, a thermometer and a condenser, stirring is started, the stirring speed is controlled to be 260r/min, the temperature is raised to 50 ℃, stirring is carried out for 1h, 81.23g of hydrogen-containing MQ resin and 50g of dimethylbenzene are premixed, and the mixture is added into the three-neck flask dropwise. Controlling the reaction temperature to be 55 ℃, finishing the dropwise adding for 1h, reacting for 4h, heating to 80 ℃, carrying out reflux reaction for 4h, heating to 100 ℃, and carrying out reflux reaction for 2 h. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and performing rotary evaporation on xylene to obtain a white solid.
The specific molecular formula of the product is as follows: (M)AMB)m(MH) nQ, wherein m is 0.25 and n is 0.25. The product number average molecular weight was 8748g/mol as determined by WATERS gel permeation chromatography, Mw/Mn 1.39. The hydrogen content of the clear product, determined by means of a hydrogen content titration method, was 0.12% by weight, which was similar to the theoretical hydrogen content of 0.14% by weight.
Example 3:
(1) synthesis of hydrogen-containing MQ resin: 166.67g of tetraethoxysilane, 45.67g of tetramethyldihydrodisiloxane, 0.63g of trifluoromethanesulfonic acid and 50g of xylene are charged into a three-necked flask equipped with a stirrer, a thermometer and a condenser; stirring is started, and the stirring speed is controlled to be 260 r/min. Heating to 50 ℃, dripping 116.50g of acetic acid, carrying out reflux reaction for 2h after dripping is finished, heating to 85 ℃, carrying out reflux reaction for 2h, distilling the generated ethyl acetate and ethanol to 100 ℃, continuing to distill for 2h, cooling to 60 ℃, dripping 34.71g of acetic anhydride, and carrying out reaction for 2 h. 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 distilled water until PH was 7, anhydrous sodium sulfate was added to adsorb moisture until the liquid was clear and transparent, and colorless and transparent filtrate was obtained by filtration, and xylene and n-hexane were rotary-distilled off to obtain 88.05g of a white powder solid with a yield of 94%.
The specific molecular formula of the product is as follows: (M)H) aQ, wherein the value of a is 0.85. The number average molecular weight of the product was 4306g/mol and Mw/Mn was 1.41 as determined by WATERS gel permeation chromatography. The hydrogen content of the product, determined by means of a hydrogen content titration method, was 0.72% by weight, which was similar to the theoretical hydrogen content of 0.73% by weight.
(2) Synthesis of modified MQ resin: 25.74g of allyl glycidyl ether, 33.44g of vinyltrimethoxysilane and 0.0025g of 5000ppm of Karster platinum catalyst are added into a three-neck flask provided with a stirrer, a thermometer and a condenser, stirring is started, the stirring speed is controlled to be 260r/min, the temperature is raised to 50 ℃, stirring is carried out for 1h, 88.05g of hydrogen-containing MQ resin and 50g of dimethylbenzene are premixed, and the mixture is dripped into the three-neck flask. Controlling the reaction temperature to be 55 ℃, finishing the dropwise adding for 1h, reacting for 4h, heating to 80 ℃, carrying out reflux reaction for 4h, heating to 100 ℃, and carrying out reflux reaction for 2 h. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and performing rotary evaporation on xylene to obtain a white solid.
The specific molecular formula of the product is as follows: (M)AMB)m(MH) nQ, wherein m is 0.3 and n is 0.25. The number average molecular weight of the product was 7200g/mol as determined by WATER gel permeation chromatography, and Mw/Mn was 1.41. The hydrogen content of the transparent product, determined by means of a hydrogen content titration method, was 0.12% by weight, which was close to the theoretical hydrogen content of 0.13% by weight.
Example 4:
(1) synthesis of hydrogen-containing MQ resin: 122.30g of methyl orthosilicate, 42.98g of tetramethyldihydrodisiloxane, 0.63g of p-toluenesulfonic acid and 50g of xylene are added into a three-neck flask equipped with a stirrer, a thermometer and a condenser; stirring is started, and the stirring speed is controlled to be 260 r/min. Heating to 50 ℃, dripping 115.30g of acetic acid, carrying out reflux reaction for 2h after dripping, heating to 85 ℃, carrying out reflux reaction for 2h, distilling the generated methyl acetate and methanol to 100 ℃, continuing to distill for 2h, cooling to 60 ℃, dripping 32.68g of acetic anhydride, and carrying out reaction for 2 h. 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 distilled water until PH was 7, anhydrous sodium sulfate was added to adsorb water until the liquid was clear and transparent, and filtration was carried out to obtain a colorless and transparent filtrate, and xylene and n-heptane were rotary-distilled off to obtain 84.61g as a white powdery solid with a yield of 93%.
The specific molecular formula of the product is as follows: (M)H) aQ, wherein a has a value of 0.8. The product number average molecular weight was 5060g/mol, Mw/Mn 1.40 as determined by WATERS gel permeation chromatography. The hydrogen content of the product, determined by means of a hydrogen content titration method, was 0.69% by weight, which was close to the theoretical hydrogen content of 0.70% by weight.
(2) Synthesis of modified MQ resin: 21.22g of allyl glycidyl ether, 27.57g of vinyltrimethoxysilane and 0.0025g of 5000ppm of Karster platinum catalyst are added into a three-neck flask provided with a stirrer, a thermometer and a condenser, stirring is started, the stirring speed is controlled to be 260r/min, the temperature is raised to 50 ℃, stirring is carried out for 1h, 84.61g of hydrogen-containing MQ resin and 50g of dimethylbenzene are premixed, and the mixture is added into the three-neck flask dropwise. Controlling the reaction temperature to be 55 ℃, finishing the dropwise adding for 1h, reacting for 4h, heating to 80 ℃, carrying out reflux reaction for 4h, heating to 100 ℃, and carrying out reflux reaction for 2 h. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and performing rotary evaporation on xylene to obtain a white solid.
The specific molecular formula of the product is as follows: (M)AMB)m(MH) nQ, wherein m is 0.25 and n is 0.3. The product number average molecular weight was 7855g/mol and Mw/Mn was 1.42 as determined by WATERS gel permeation chromatography. The hydrogen content of the transparent product, determined by means of a hydrogen content titration method, was 0.16% by weight, which was close to the theoretical hydrogen content of 0.17% by weight.
Example 5:
(1) synthesis of hydrogen-containing MQ resin: 211.23g of propyl orthosilicate, 42.98g of tetramethyldihydrodisiloxane, 0.63g of concentrated sulfuric acid and 50g of xylene are added into a three-neck flask provided with a stirrer, a thermometer and a condenser; stirring is started, and the stirring speed is controlled to be 260 r/min. Heating to 50 ℃, dripping 115.30g of acetic acid, carrying out reflux reaction for 2h after dripping is finished, heating to 85 ℃, carrying out reflux reaction for 2h, distilling the generated propyl acetate and propanol to 100 ℃, continuing to distill for 2h, cooling to 60 ℃, dripping 32.68g of acetic anhydride, and carrying out reaction for 2 h. 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 distilled water until PH 7, anhydrous sodium sulfate was added to adsorb water until the liquid was clear and transparent, and filtration was carried out to obtain a colorless and transparent filtrate, and xylene and n-heptane were rotary-distilled off to obtain 83.70g of a white powdery solid with a yield of 92%.
The specific molecular formula of the product is as follows: (M)H) aQ, wherein a has a value of 0.8. The product number average molecular weight was 5063g/mol, Mw/Mn 1.38 as determined by WATERS gel permeation chromatography. The hydrogen content of the product, determined by means of a hydrogen content titration method, was 0.69% by weight, which was close to the theoretical hydrogen content of 0.70% by weight.
(2) Synthesis of modified MQ resin: 21.00g of allyl glycidyl ether, 27.27g of vinyltrimethoxysilane and 0.0025g of 5000ppm of a Karster catalyst are added into a three-neck flask provided with a stirrer, a thermometer and a condenser, stirring is started, the stirring speed is controlled to be 260r/min, the temperature is raised to 50 ℃, stirring is carried out for 1h, 83.70g of hydrogen-containing MQ resin and 50g of xylene are premixed, and the mixture is dripped into the three-neck flask. Controlling the reaction temperature to be 55 ℃, finishing the dropwise adding for 1h, reacting for 4h, heating to 80 ℃, carrying out reflux reaction for 4h, heating to 100 ℃, and carrying out reflux reaction for 2 h. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and performing rotary evaporation on xylene to obtain a white solid.
The specific molecular formula of the product is as follows: (M)AMB)m(MH) nQ, wherein m is 0.25 and n is 0.3. The product was found to have a number average molecular weight of 7851g/mol and an Mw/Mn of 1.38 by WATERS gel permeation chromatography. The hydrogen content of the transparent product, determined by means of a hydrogen content titration method, was 0.16% by weight, which was close to the theoretical hydrogen content of 0.17% by weight.
Example 6:
(1) synthesis of hydrogen-containing MQ resin: 166.67g of tetraethoxysilane, 42.98g of tetramethyldihydrodisiloxane, 0.63g of trifluoromethanesulfonic acid, and 50g of xylene were charged in a three-necked flask equipped with a stirrer, a thermometer, and a condenser; stirring is started, and the stirring speed is controlled to be 260 r/min. Heating to 50 ℃, dropwise adding 84.4g of formic acid, carrying out reflux reaction for 2h after dropwise adding, then heating to 85 ℃, carrying out reflux reaction for 2h, distilling the generated ethyl formate and ethanol to 100 ℃, continuing to distill for 2h, then cooling to 60 ℃, dropwise adding 32.68g of acetic anhydride, and carrying out reaction for 2 h. 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 distilled water until PH was 7, anhydrous sodium sulfate was added to adsorb water until the liquid was clear and transparent, and filtration was carried out to obtain a colorless and transparent filtrate, and xylene and n-heptane were rotary-distilled off to obtain 84.61g as a white powdery solid with a yield of 93%.
The specific molecular formula of the product is as follows: (M)H) aQ, wherein a has a value of 0.8. The product number average molecular weight was 5065g/mol, Mw/Mn 1.38 as determined by WATERS gel permeation chromatography. The hydrogen content of the product, determined by means of a hydrogen content titration method, was 0.69% by weight, which was close to the theoretical hydrogen content of 0.70% by weight.
(2) Synthesis of modified MQ resin: 21.22g of allyl glycidyl ether, 27.57g of vinyltrimethoxysilane and 0.0025g of 5000ppm of Karster platinum catalyst are added into a three-neck flask provided with a stirrer, a thermometer and a condenser, stirring is started, the stirring speed is controlled to be 260r/min, the temperature is raised to 50 ℃, stirring is carried out for 1h, 84.61g of hydrogen-containing MQ resin and 50g of dimethylbenzene are premixed, and the mixture is added into the three-neck flask dropwise. Controlling the reaction temperature to be 55 ℃, finishing the dropwise adding for 1h, reacting for 4h, heating to 80 ℃, carrying out reflux reaction for 4h, heating to 100 ℃, and carrying out reflux reaction for 2 h. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and performing rotary evaporation on xylene to obtain a white solid.
The specific molecular formula of the product is as follows: (M)AMB)m(MH) nQ, wherein m is 0.25 and n is 0.3. The product was found to have a number average molecular weight of 7857g/mol and an Mw/Mn of 1.38 by WATERS gel permeation chromatography. The hydrogen content of the transparent product, determined by means of a hydrogen content titration method, was 0.16% by weight, which was close to the theoretical hydrogen content of 0.17% by weight.
Example 7:
(1) synthesis of hydrogen-containing MQ resin: 166.67g of tetraethoxysilane, 42.98g of tetramethyldihydrodisiloxane, 0.63g of trifluoromethanesulfonic acid, and 50g of xylene were charged in a three-necked flask equipped with a stirrer, a thermometer, and a condenser; stirring is started, and the stirring speed is controlled to be 260 r/min. Heating to 50 ℃, dropwise adding 142.08g of propionic acid, carrying out reflux reaction for 2h after the dropwise adding is finished, then heating to 85 ℃, carrying out reflux reaction for 2h, distilling the generated ethyl propionate and ethanol, heating to 100 ℃, continuing to distill for 2h, then cooling to 60 ℃, dropwise adding 32.68g of acetic anhydride, and carrying out reaction for 2 h. 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 distilled water until PH 7, anhydrous sodium sulfate was added to adsorb water until the liquid was clear and transparent, and filtration was carried out to obtain a colorless and transparent filtrate, and xylene and n-heptane were rotary-distilled off to obtain 85.52g of a white powdery solid with a yield of 94%.
The specific molecular formula of the product is as follows: (M)H) aQ, wherein a has a value of 0.8. The product number average molecular weight was 5064g/mol, Mw/Mn 1.38 as determined by WATERS gel permeation chromatography. The hydrogen content of the product, determined by means of a hydrogen content titration method, was 0.69% by weight, which was close to the theoretical hydrogen content of 0.70% by weight.
(2) Synthesis of modified MQ resin: 21.45g of allyl glycidyl ether, 27.86g of vinyltrimethoxysilane and 0.0025g of 5000ppm of Karster platinum catalyst are added into a three-neck flask provided with a stirrer, a thermometer and a condenser, stirring is started, the stirring speed is controlled to be 260r/min, the temperature is raised to 50 ℃, stirring is carried out for 1h, 85.52g of hydrogen-containing MQ resin and 50g of dimethylbenzene are premixed, and the mixture is added into the three-neck flask dropwise. Controlling the reaction temperature to be 55 ℃, finishing the dropwise adding for 1h, reacting for 4h, heating to 80 ℃, carrying out reflux reaction for 4h, heating to 100 ℃, and carrying out reflux reaction for 2 h. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and performing rotary evaporation on xylene to obtain a white solid.
The specific molecular formula of the product is as follows: (M)AMB)m(MH) nQ, wherein m is 0.25 and n is 0.3. The product number average molecular weight was 7856g/mol and Mw/Mn was 1.38 as determined by WATERS gel permeation chromatography. The hydrogen content of the transparent product, determined by means of a hydrogen content titration method, was 0.16% by weight, which was close to the theoretical hydrogen content of 0.17% by weight.
Example 8:
(1) synthesis of hydrogen-containing MQ resin: 166.67g of tetraethoxysilane, 42.98g of tetramethyldihydrodisiloxane, 0.63g of trifluoromethanesulfonic acid, and 50g of xylene were charged in a three-necked flask equipped with a stirrer, a thermometer, and a condenser; stirring is started, and the stirring speed is controlled to be 260 r/min. Heating to 50 ℃, dropwise adding 142.08g of acetic acid, carrying out reflux reaction for 2h after the dropwise adding is finished, then heating to 85 ℃, carrying out reflux reaction for 2h, distilling the generated ethyl propionate and ethanol, heating to 100 ℃, continuing to distill for 2h, then cooling to 60 ℃, dropwise adding 47.43g of phthalic anhydride, and carrying out reaction for 2 h. 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 distilled water until PH 7, anhydrous sodium sulfate was added to adsorb water until the liquid was clear and transparent, and filtration was carried out to obtain a colorless and transparent filtrate, and xylene and n-heptane were rotary-distilled off to obtain 83.70g of a white powdery solid with a yield of 92%.
The specific molecular formula of the product is as follows: (M)H) aQ, wherein a has a value of 0.8. The product number average molecular weight was 5067g/mol, Mw/Mn 1.38 as determined by WATERS gel permeation chromatography. The hydrogen content of the product, determined by means of a hydrogen content titration method, was 0.69% by weight, which was close to the theoretical hydrogen content of 0.70% by weight.
(2) Synthesis of modified MQ resin: 21.00g of allyl glycidyl ether, 27.27g of vinyltrimethoxysilane and 0.0025g of 5000ppm of Karster platinum catalyst are added into a three-neck flask provided with a stirrer, a thermometer and a condenser, stirring is started, the stirring speed is controlled to be 260r/min, the temperature is raised to 50 ℃, stirring is carried out for 1h, 83.70g of hydrogen-containing MQ resin and 50g of dimethylbenzene are premixed, and the mixture is added into the three-neck flask dropwise. Controlling the reaction temperature to be 55 ℃, finishing the dropwise adding for 1h, reacting for 4h, heating to 80 ℃, carrying out reflux reaction for 4h, heating to 100 ℃, and carrying out reflux reaction for 2 h. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and performing rotary evaporation on xylene to obtain a white solid.
The specific molecular formula of the product is as follows: (M)AMB)m(MH) nQ, wherein m is 0.25 and n is 0.3. The product number average molecular weight was 7856g/mol and Mw/Mn was 1.38 as determined by WATERS gel permeation chromatography. The hydrogen content of the transparent product, determined by means of a hydrogen content titration method, was 0.16% by weight, which was close to the theoretical hydrogen content of 0.17% by weight.
Example 9:
(1) synthesis of hydrogen-containing MQ resin: 166.67g of tetraethoxysilane, 42.98g of tetramethyldihydrodisiloxane, 0.63g of trifluoromethanesulfonic acid, and 50g of xylene were charged in a three-necked flask equipped with a stirrer, a thermometer, and a condenser; stirring is started, and the stirring speed is controlled to be 260 r/min. Heating to 50 ℃, dropwise adding 142.08g of acetic acid, carrying out reflux reaction for 2h after the dropwise adding is finished, then heating to 85 ℃, carrying out reflux reaction for 2h, distilling the generated ethyl propionate and ethanol, heating to 100 ℃, continuing to distill for 2h, then cooling to 60 ℃, dropwise adding 32.68g of acetic anhydride, and carrying out reaction for 2 h. 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 distilled water until PH 7, anhydrous sodium sulfate was added to adsorb water until the liquid was clear and transparent, and filtration was carried out to obtain a colorless and transparent filtrate, and xylene and n-heptane were rotary-distilled off to obtain 86.43g of a white powdery solid with a yield of 95%.
The specific molecular formula of the product is as follows: (M)H) aQ, wherein a has a value of 0.8. The product number average molecular weight was 5069g/mol, Mw/Mn 1.38 as determined by WATERS gel permeation chromatography. The hydrogen content of the product, determined by means of a hydrogen content titration method, was 0.69% by weight, which was close to the theoretical hydrogen content of 0.70% by weight.
(2) Synthesis of modified MQ resin: 21.00g of allyl glycidyl ether, 26.16g of vinyl triethoxysilane and 0.0025g of 5000ppm of Karster platinum catalyst are added into a three-neck flask provided with a stirrer, a thermometer and a condenser, stirring is started, the stirring speed is controlled to be 260r/min, the temperature is raised to 50 ℃, stirring is carried out for 1h, 86.43g of hydrogen-containing MQ resin and 50g of xylene are premixed, and the mixture is added into the three-neck flask dropwise. Controlling the reaction temperature to be 55 ℃, finishing the dropwise adding for 1h, reacting for 4h, heating to 80 ℃, carrying out reflux reaction for 4h, heating to 100 ℃, and carrying out reflux reaction for 2 h. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and performing rotary evaporation on xylene to obtain a white solid.
The specific molecular formula of the product is as follows: (M)AMB)m(MH) nQ, wherein m is 0.25 and n is 0.3. The number average molecular weight of the product was 7903g/mol as determined by WATERS gel permeation chromatography, and Mw/Mn was 1.38. The hydrogen content of the transparent product, determined by means of a hydrogen content titration method, was 0.16% by weight, which was close to the theoretical hydrogen content of 0.17% by weight.
Example 10:
(1) synthesis of hydrogen-containing MQ resin: 166.67g of tetraethoxysilane, 42.98g of tetramethyldihydrodisiloxane, 0.63g of trifluoromethanesulfonic acid, and 50g of xylene were charged in a three-necked flask equipped with a stirrer, a thermometer, and a condenser; stirring is started, and the stirring speed is controlled to be 260 r/min. Heating to 50 ℃, dropwise adding 142.08g of acetic acid, carrying out reflux reaction for 2h after the dropwise adding is finished, then heating to 85 ℃, carrying out reflux reaction for 2h, distilling the generated ethyl propionate and ethanol, heating to 100 ℃, continuing to distill for 2h, then cooling to 60 ℃, dropwise adding 32.68g of acetic anhydride, and carrying out reaction for 2 h. 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 distilled water until PH 7, anhydrous sodium sulfate was added to adsorb water until the liquid was clear and transparent, and filtration was carried out to obtain a colorless and transparent filtrate, and xylene and n-heptane were rotary-distilled off to obtain 86.43g of a white powdery solid with a yield of 95%.
The specific molecular formula of the product is as follows: (M)H) aQ, wherein a has a value of 0.8. The product number average molecular weight was 5069g/mol, Mw/Mn 1.38 as determined by WATERS gel permeation chromatography. The hydrogen content of the product, determined by means of a hydrogen content titration method, was 0.69% by weight, which was close to the theoretical hydrogen content of 0.70% by weight.
(2) Synthesis of modified MQ resin: 21.00g of allyl glycidyl ether, 25.12g of methyl vinyl diethoxysilane (Shanghai Merrill, AR) and 0.0025g of platinum catalyst were added to a three-neck flask equipped with a stirrer, a thermometer and a condenser, stirring was started, the stirring speed was controlled at 260r/min, the temperature was raised to 50 ℃, stirring was carried out for 1 hour, 86.43g of hydrogen-containing MQ resin and 50g of xylene were premixed, and the mixture was added dropwise to the three-neck flask. Controlling the reaction temperature to be 55 ℃, finishing the dropwise adding for 1h, reacting for 4h, heating to 80 ℃, carrying out reflux reaction for 4h, heating to 100 ℃, and carrying out reflux reaction for 2 h. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and performing rotary evaporation on xylene to obtain a white solid.
The specific molecular formula of the product is as follows: (M)AMB)m(MH) nQ, wherein m is 0.25 and n is 0.3. The product number average molecular weight was 7887g/mol and Mw/Mn was 1.38 as determined by WATERS gel permeation chromatography. Determination of the Permeability by means of a Hydrogen content titration methodThe hydrogen content of the product is close to the theoretical hydrogen content of 0.17 wt%.
Comparative example 1
The synthesis of only the hydrogen-containing MQ resin was carried out in the same manner as in step (1) of example 1; no modification of the hydrogen containing MQ resin was performed.
Comparative example 2
(1) Synthesis of hydrogen-containing MQ resin: the same as example 1;
(2) synthesis of modified MQ resin: 43.36g of allyl glycidyl ether and 0.0025g of 5000ppm Karster platinum catalyst are added into a three-neck flask provided with a stirrer, a thermometer and a condenser, stirring is started, the stirring speed is controlled to be 260r/min, the temperature is raised to 50 ℃, stirring is carried out for 1h, 86.43g of hydrogen-containing MQ resin and 50g of xylene are premixed, and the mixture is dripped into the three-neck flask. Controlling the reaction temperature to be 55 ℃, finishing the dropwise adding for 1h, reacting for 4h, heating to 80 ℃, carrying out reflux reaction for 4h, heating to 100 ℃, and carrying out reflux reaction for 2 h. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and performing rotary evaporation on xylene to obtain a white solid.
The specific molecular formula of the product is as follows: (M)A)m(MH) nQ, wherein m is 0.5 and n is 0.3. The product was found to have a number average molecular weight of 7851g/mol and an Mw/Mn of 1.38 by WATERS gel permeation chromatography. The hydrogen content of the transparent product, determined by means of a hydrogen content titration method, was 0.16% by weight, which was close to the theoretical hydrogen content of 0.17% by weight.
Comparative example 3
(1) Synthesis of hydrogen-containing MQ resin: same as example 1
(2) Synthesis of modified MQ resin: 56.26g of vinyltrimethoxysilane and 0.0025g of 5000ppm of Karster platinum catalyst are added into a three-neck flask provided with a stirrer, a thermometer and a condenser, stirring is started, the stirring speed is controlled to be 260r/min, the temperature is raised to 50 ℃, stirring is carried out for 1h, 86.43g of hydrogen-containing MQ resin and 50g of dimethylbenzene are premixed, and the mixture is dripped into the three-neck flask. Controlling the reaction temperature to be 55 ℃, finishing the dropwise adding for 1h, reacting for 4h, heating to 80 ℃, carrying out reflux reaction for 4h, heating to 100 ℃, and carrying out reflux reaction for 2 h. Stopping heating, introducing nitrogen, cooling to room temperature, adding 3g of activated carbon for adsorption for 6h, filtering to obtain colorless filtrate, and performing rotary evaporation on xylene to obtain a white solid.
The specific molecular formula of the product is as follows: (M)B)m(MH) nQ, wherein m is 0.5 and n is 0.3. The product was found to have a number average molecular weight of 7871g/mol and an Mw/Mn of 1.38 by WATERS gel permeation chromatography. The hydrogen content of the transparent product, determined by means of a hydrogen content titration method, was 0.16% by weight, which was close to the theoretical hydrogen content of 0.17% by weight.
Test example
(1) The hydrogen-containing MQ resin obtained in comparative example 1 was added to the silicone pressure-sensitive adhesive made of dow corning7657 at a mass fraction of 1%, and the modified MQ resin of example 1 at different mass fractions (1%, 1.5%, 2%, 3%, and 5%) and added to the PI film to make a silicone pressure-sensitive adhesive tape, and the 180 degree peel strength test of the pressure-sensitive adhesive on the PI substrate was examined to indirectly test the adhesion property to the substrate. The results are shown in table 1, where the blank sample is a silicone pressure sensitive adhesive made by Dow Corning7657 without the addition of any kind of MQ resin.
TABLE 1 Silicone pressure sensitive adhesive tape Properties
Figure BDA0001467739000000221
As can be seen from Table 1, as the addition amount of the modified MQ resin in the silicone pressure-sensitive adhesive increases, the 180-degree peel strength of the silicone pressure-sensitive adhesive gradually increases, namely the 180-degree peel strength indirectly reflects the increase of the adhesive force of the silicone pressure-sensitive adhesive, and can replace the priming process. The 180-degree peel strength of the silicone pressure-sensitive adhesive prepared by adding the unmodified hydrogen-containing MQ resin in the comparative example 1 is lower than that of the silicone pressure-sensitive adhesive added with the modified MQ resin in the embodiment 1 of the invention.
In addition, no primer is added in the preparation process of the silicone pressure-sensitive adhesive prepared by adding any MQ resin and unmodified hydrogen-containing MQ resin, and a large amount of residual adhesive exists in the 180-degree peel strength test; the organic silicon pressure-sensitive adhesive added with the modified MQ resin does not contain a primer, and no adhesive residue occurs when a 180-degree peel strength test is carried out. Therefore, the modified MQ resin is added, and under the condition of ensuring normal use of the pressure-sensitive adhesive, a primer is not required to be coated, so that the production process and the cost are saved.
(2) Examples 1-10 the synthesized modified MQ resin was added to a silicone pressure sensitive adhesive made by Dow Corning7657 at an addition level of 3% by mass and added to a silicone pressure sensitive adhesive tape made of PI film, and the adhesive properties to the substrate were indirectly tested by examining the 180 degree peel strength test of the pressure sensitive adhesive on the PI substrate, with the results shown in table 2:
TABLE 2 Silicone pressure sensitive adhesive tape Properties
Figure BDA0001467739000000231
As can be seen from Table 2, with MA，MBThe 180-degree peel strength thereof is significantly increased with an increase in the addition amount (refer to examples 1 to 3); mBThe variation also has an effect on the 180 degree peel strength (see examples 8-10).
(3) The MQ resins obtained in comparative examples 1 to 3 and the modified MQ resin of example 1 were added to a silicone pressure-sensitive adhesive prepared from Dow Corning7657 at a mass fraction of 1% and applied to a silicone pressure-sensitive adhesive tape prepared from a PI film, and the 180-degree peel strength test of the pressure-sensitive adhesive on a PI substrate was examined to indirectly test the adhesion property to the substrate. The results are shown in Table 3.
TABLE 3 Silicone pressure sensitive adhesive tape Properties
Figure BDA0001467739000000232
As can be seen from Table 3, there is no M in the MQ resinA、MBOnly M isHIn the case of (1) (as in comparative example), the 180 degree peel strength was poor without primer coating, i.e., the indirect adhesion was poor. In the presence of M aloneA(comparative example 2) or MBIn the case of comparative example 3, the adhesive force was not as good as the adhesive force in the case where both were present (example 1). This indicates that M is contained togetherAAnd MBThe hydrogen-containing MQ resin has better adhesive force and adhesive force.
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 (47)

1. A modified MQ silicon resin is characterized in that the modified MQ silicon resin is shown as a general formula (I) (M)AMB)m(MH) nQ, wherein the m value is 0.25-0.40 based on the molar weight of the Q chain link as 1; n is 0.25-0.40;
the chemical structure is as follows:
Figure FDA0002487098700000011
wherein M isAThe structural formula of (A) is:
Figure FDA0002487098700000012
MBthe structural formula of (A) is:
Figure FDA0002487098700000013
MHthe structural formula of (A) is:
Figure FDA0002487098700000021
2. the modified MQ silicone resin according to claim 1, wherein the value of m is from 0.25 to 0.30.
3. The modified MQ silicone resin according to claim 1, wherein the value of n is from 0.25 to 0.30.
4. The modified MQ silicone resin of any of claims 1 to 3, wherein m/n is from 0.8 to 1.2.
5. A process for the preparation of modified MQ silicone resins as claimed in any of claims 1 to 4, characterized in that it comprises the following steps:
(1) synthesis of hydrogen-containing MQ resin: contacting silicate ester, tetramethyl dihydrodisiloxane, acid catalyst and aromatic hydrocarbon solvent; heating to 40-60 deg.C, adding organic monobasic acid; heating for reaction, distilling to generate ethyl acetate and ethanol, cooling to 40-60 ℃, and adding organic acid anhydride for reaction to obtain hydrogen-containing MQ resin;
(2) synthesis of modified MQ resin: contacting allyl glycidyl ether, vinyl silane compounds and platinum catalyst, and heating to 40-60 ℃ to form a mixture; premixing the hydrogen-containing MQ resin and aromatic hydrocarbon solvent to form a premix; controlling the temperature to be 45-55 ℃, contacting the premix with the mixture system, and heating for reaction to obtain modified MQ resin;
the vinyl silane compound is vinyl trimethoxy silane.
6. The preparation method according to claim 5, wherein the following components are used, based on 100 wt% of the total weight of the components in the reaction system of the step (1):
30-55 wt% of silicate ester,
5-12 wt% of tetramethyl dihydrodisiloxane,
0.1-0.2 wt% of acid catalyst,
5-14 wt% of aromatic hydrocarbon solvent,
20-35 wt% of organic monobasic acid,
the organic acid anhydride is 5-12 wt%.
7. The method of claim 6, wherein the silicate is 33.60-52.26 wt%.
8. The method according to claim 6, wherein the tetramethyldihydrodisiloxane is 8.49 to 11.81 wt%.
9. The production method according to claim 6, wherein the acid catalyst is 0.12 to 0.17 wt%.
10. The method according to claim 6, wherein the aromatic hydrocarbon solvent is 9.88 to 13.74 wt%.
11. The production method according to claim 6, wherein the organic monobasic acid is 22.79 to 32.66 wt%.
12. The production method according to claim 6, wherein the organic acid anhydride is 6.46 to 10.54 wt%.
13. The preparation method according to claim 5, wherein the following components are used, based on 100 wt% of the total weight of the components in the reaction system of the step (2):
10-20 wt% of allyl glycidyl ether,
10-25 wt% of vinyl silane compound,
the platinum catalyst is 0.001-0.002,
the premix of the hydrogen-containing MQ resin and the aromatic hydrocarbon solvent is 55-80 wt%.
14. The method of claim 13, wherein the allyl glycidyl ether is 11.44 to 17.48 wt%.
15. The production method according to claim 13, wherein the vinyl silane compound is 15.03 to 22.71 wt%.
16. The production method according to claim 13, wherein the platinum catalyst is 0.0013 to 0.0019 wt%.
17. The preparation method according to claim 13, wherein the pre-mixture of the hydrogen-containing MQ resin and the aromatic hydrocarbon solvent is 69-75 wt%.
18. The preparation method according to claim 5, wherein the hydrogen-containing MQ resin is 55 to 67 wt% and the aromatic hydrocarbon solvent is 33 to 45 wt%, based on 100 wt% of the total weight of the premix.
19. The preparation method of claim 18, wherein the hydrogen-containing MQ resin is 59.80-63.42 wt%.
20. The method according to claim 18, wherein the aromatic hydrocarbon solvent is 33.96 to 38.76 wt%.
21. The production method according to claim 5, wherein in the step (1), the silicate is selected from methyl orthosilicate or a polycondensate thereof, ethyl orthosilicate or a polycondensate thereof, and propyl orthosilicate or a polycondensate thereof.
22. The production method according to claim 21, wherein the silicate is tetraethoxysilane.
23. The production process according to claim 5, wherein in the step (1), the acid catalyst is one or more selected from the group consisting of p-toluenesulfonic acid, 95 to 98 wt% of concentrated sulfuric acid and 98 to 99 wt% of trifluoromethanesulfonic acid.
24. The production method according to claim 23, wherein the acid catalyst is 98 to 99 wt% of trifluoromethanesulfonic acid.
25. The production method according to claim 5, wherein in the step (1), the aromatic hydrocarbon solvent is one or more selected from the group consisting of benzene, toluene and xylene.
26. The production method according to claim 25, wherein the aromatic hydrocarbon solvent is xylene.
27. The production method according to claim 5, wherein in the step (1), the organic monobasic acid is one or more selected from formic acid, acetic acid and propionic acid.
28. The production method according to claim 27, wherein the organic monobasic acid is acetic acid.
29. The production method according to claim 5, wherein in the step (1), the organic acid anhydride is selected from acetic anhydride and/or phthalic anhydride.
30. The production method according to claim 29, wherein the organic acid anhydride is acetic anhydride.
31. The process according to claim 5, wherein, in step (1), the hydrogen-containing MQ resin is represented by the general formula (II) (M)H) aQ is shown; wherein a is 0.75 to 0.85 based on the molar amount of the Q mer of 1.
32. The preparation method as claimed in claim 31, wherein the hydrogen content of the hydrogen-containing MQ resin is 0.6 wt% to 0.8 wt%.
33. The preparation method as claimed in claim 32, wherein the hydrogen content of the hydrogen-containing MQ resin is 0.65 wt% to 0.75 wt%.
34. The production process according to claim 5, wherein in the step (1), the organic monobasic acid is added dropwise while raising the temperature to 45 to 55 ℃.
35. The preparation process according to claim 34, wherein in the step (1), after the organic monobasic acid is added dropwise, the system is heated to 70-90 ℃ for reaction for 1-3 hours.
36. The production process according to claim 34, wherein in the step (1), the organic acid anhydride is added dropwise when the temperature of the system is reduced to 45 to 55 ℃.
37. The preparation method according to any one of claims 5 to 36, wherein the step (1) further comprises, after adding the organic acid anhydride for reaction, contacting the reaction system with an extracting agent for extraction to obtain a white powdery solid, namely the hydrogen-containing MQ resin.
38. The method of claim 37, wherein the extractant is selected from one or more of toluene, xylene, hexane, cyclohexane, and n-heptane.
39. The method of claim 38, wherein the extractant is selected from xylene and/or n-heptane.
40. The production method according to any one of claims 5 to 36, wherein in the step (2), the aromatic hydrocarbon solvent is selected from one or more of benzene, toluene and xylene.
41. The production method according to claim 40, wherein the aromatic hydrocarbon solvent is xylene.
42. The production method according to any one of claims 5 to 36, wherein in the step (2), the platinum catalyst is selected from the group consisting of Karster catalysts having a platinum content of 5000 ppm.
43. The production method according to any one of claims 5 to 36, wherein, in step (2), the premix is added dropwise to the system of the mixture.
44. The preparation method of claim 43, wherein the reaction conditions for the contacting of the premix and the system of mixtures are as follows: heating to 70-90 ℃, and carrying out reflux reaction for 3-5 h; heating to 95-115 ℃, and carrying out reflux reaction for 1-3 h.
45. The preparation process according to claim 43, wherein the modified MQ silicone resin has a hydrogen content of 0.1 to 0.2 wt.%.
46. The preparation process according to claim 45, wherein the molar ratio of M/Q in the modified MQ silicone resin is from 0.75 to 0.85.
47. Use of a modified MQ silicone resin according to any one of claims 1 to 4, or of a modified MQ silicone resin prepared by the preparation process according to any one of claims 5 to 46, in a pressure-sensitive adhesive.
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