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CN118085290B - A preparation method and application of MQ resin - Google Patents

A preparation method and application of MQ resin Download PDF

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Publication number
CN118085290B
CN118085290B CN202410320651.2A CN202410320651A CN118085290B CN 118085290 B CN118085290 B CN 118085290B CN 202410320651 A CN202410320651 A CN 202410320651A CN 118085290 B CN118085290 B CN 118085290B
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resin
low
vinyl
acid
pressure
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CN118085290A (en
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赵玉东
张创
张鹏飞
鲍冉
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Wuhan Zhongke Advanced Material Technology Co Ltd
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Wuhan Zhongke Advanced Material Technology 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic 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
    • C08G77/04—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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • 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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a preparation method and application of MQ resin, and belongs to the field of organic silicon resin. The method comprises the steps of reacting a solvent, water, tetraethoxysilane and a class of end-capping agents under an acidic catalyst, neutralizing to obtain an MQ resin solution, adding a class-II end-capping agents under an alkaline catalyst, reacting, neutralizing, and removing low-pressure to obtain the MQ resin. The MQ resin prepared by the invention combines the compounding performance of two products of the conventional high vinyl content MQ resin and the methyl MQ resin, improves the compatibility and the reactivity of the MQ resin in a pressure-sensitive adhesive system, and further improves the stripping force of the pressure-sensitive adhesive, the stability of the stripping force after double-85 ageing and the light transmittance. The prepared modified MQ resin with low vinyl content and low hydroxyl value can replace a commercially available anchoring agent, and solves the problem of silicon transfer of the pressure-sensitive adhesive in the long-term use process.

Description

Preparation method and application of MQ resin
Technical Field
The invention relates to the field of organic silicon resin, in particular to a preparation method and application of MQ resin.
Background
At present, the organic silicon pressure-sensitive adhesive is used as a silicon adhesive, and has better high and low temperature resistance (-50 ℃ to 200 ℃ for long-term use), chemical resistance (solvent resistance) and low dielectric property, and good adhesiveness to low-surface energy materials compared with the traditional pressure-sensitive adhesive. The organic silicon pressure-sensitive adhesive tape is widely applied to industrial production and electronic industry in the forms of splicing tapes, electrical tapes, shielding tapes, protective films and the like. The organic silicon pressure-sensitive adhesive is mainly prepared by mixing raw silicone rubber, MQ silicone resin and a solvent according to a certain proportion. The silicone rubber can increase the fluidity of the pressure-sensitive adhesive, so that the interfacial adhesion is increased, and the initial tackiness is strong and is used as a crosslinking curing main body. And the MQ silicone resin is used as a reinforcing agent to have a larger influence on the adhesive property of the pressure-sensitive adhesive, and the adhesion strength of the organic silicon pressure-sensitive adhesive can be obviously improved through the adhesion and reinforcement of the MQ silicone resin. Along with the increase of market competition, more stringent requirements are also put on the performance of the organic silicon pressure-sensitive adhesive, such as the requirement of the organic silicon pressure-sensitive adhesive with higher peeling strength (> 1000 g/inch), stronger high-low temperature resistance (-75-260 ℃) and lower silicon transfer and high light transmittance, and one important way for improving the performance of the organic silicon pressure-sensitive adhesive is to improve the performance of MQ silicone resin and the performance of an anchoring agent, and the anchoring agent sold in the market is usually a small molecular monomer, has poor stability and high volatile matters, and is easy to migrate and pollute the surface of an adherend.
The conventional commercial methyl MQ resin has the problems of low stripping force and poor stripping force stability after aging caused by high hydroxyl content and poor compatibility, and most of vinyl MQ resin is more than 2wt% in vinyl content, so that the cohesive strength of the pressure-sensitive adhesive is improved, but the pressure-sensitive adhesive cannot be independently used as a tackifying resin material instead of methyl MQ resin.
In addition, due to poor compatibility of the conventional MQ resin and the silicone oil silicone rubber system, the light transmittance is reduced when the MQ resin is added into the pressure-sensitive adhesive, so that the application of the MQ resin in the high-end optical field is affected.
In conclusion, the pressure-sensitive adhesive obtained after the MQ resin in the prior art is added into a silicone oil silicone rubber system has low light transmittance, low peeling force and poor peeling force stability after aging, and silicon transfer is easy to occur in the use process.
Disclosure of Invention
The invention aims to overcome the technical defects, and provides a preparation method and application of MQ resin, which solve the technical problems of low light transmittance, low stripping force, poor stability of stripping force after aging and silicon transfer in the use process of the pressure-sensitive adhesive in the prior art.
In order to achieve the technical purpose, the technical scheme of the invention provides a preparation method of MQ resin, which comprises the following steps:
(1) Adding a solvent, deionized water and an acid catalyst into a reaction container, uniformly stirring, adding tetraethoxysilane, uniformly stirring, and reacting for 0.2-1h, adding a blocking agent into the reaction solution of the reaction, and reacting for 1-4h at 25-40 ℃;
(2) Adding a second-class end-capping reagent and an alkaline catalyst into the low-vinyl MQ resin solution, carrying out high-temperature reflux reaction to remove water molecules generated in the system until no water is generated, adding acid into the system for neutralization, washing the system to be neutral, taking an upper-layer organic phase solution, and removing low-boiling substances through decompression to obtain the MQ resin.
Further, the addition amounts of the substances in the step (1) are calculated according to mass fractions respectively as follows:
100 parts of ethyl orthosilicate;
1-10 parts, preferably 2-6 parts, of a class A end-capping agent;
40-80 parts, preferably 50-70 parts, of a class B end-capping agent;
0.5 to 2 parts, preferably 0.7 to 1.5 parts, of an acidic catalyst;
30-70 parts of deionized water, preferably 40-60 parts;
50-100 parts of solvent, preferably 60-80 parts;
further, the addition amounts of the substances in the step (2) are respectively calculated as mass fractions:
100 parts of MQ resin solution (without solvent);
10-30 parts, preferably 15-25 parts, of a second type of end-capping agent;
0.2 to 1 part, preferably 0.4 to 0.8 part, of basic catalyst;
further, the acid catalyst in the step (1) is one or more of formic acid, acetic acid, hydrochloric acid, fluorosulfonic acid, sulfuric acid, hydrobromic acid, hydrofluoric acid and p-phenylmethane sulfonic acid, preferably hydrochloric acid;
Further, the solvent in the step (1) comprises any one or more of methanol, ethanol, n-propanol and isopropanol, preferably ethanol;
Further, the blocking agent in the step (1) includes a blocking agent A and a blocking agent B, wherein the blocking agent A is one or more of vinyl dimethyl ethoxy silane, vinyl methyl dimethoxy silane, vinyl methyl diethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane and tetramethyl divinyl disiloxane, and the blocking agent B is one or more of methoxy trimethyl silane, ethoxy trimethyl silane, dimethoxy dimethyl silane, diethoxy dimethyl silane, methyl trimethoxy silane, methyl triethoxy silane and hexamethyldisiloxane, preferably a mixture of tetramethyl divinyl disiloxane and hexamethyldisiloxane.
Further, the extractant in the step (1) is any one or more of cyclohexane, toluene and xylene, preferably toluene;
Further, the second-class end-capping agent in the step (2) is one or more of methoxytrimethylsilane, trimethylethoxysilane and trimethylchlorosilane, preferably methoxytrimethylsilane;
Further, the basic catalyst in the step (2) is one or more of potassium hydroxide, sodium hydroxide, tetramethyl ammonium hydroxide and triethylamine, preferably tetramethyl ammonium hydroxide;
the MQ resin obtained by the invention is MQ resin with low vinyl content and low hydroxyl value, and has the following structural formula;
Wherein M is vinyl, hydroxyl, alkoxy and trimethylsiloxy, the ratio M/Q of the number of siloxane units to the number of tetraphenylsiloxane units in the MQ resin structure is 0.6-1.0, preferably 0.7-0.9, the weight average molecular weight of the MQ resin is 3000-9000, preferably 4000-8000, the vinyl content is 0.02-0.24%, preferably 0.04-0.15%, the hydroxyl content is 0.3-2.0%, preferably 0.5-1.5%.
Further, the second-class end-capping agent in the step (2) is one or more of gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma- (methacryloyloxy) propyl trimethoxysilane, gamma- (methacryloyloxy) propyl triethoxysilane, 2- (3, 4 epoxycyclohexyl) ethyl trimethoxysilane, 2- (3, 4 epoxycyclohexyl) ethyl triethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane and aminophenyl propyl trimethoxysilane, preferably gamma-glycidoxypropyl trimethoxysilane.
The MQ resin obtained by the invention is modified MQ resin with low vinyl content and low hydroxyl value, the structural formula is as follows,
Wherein M is one or more of vinyl, trimethylsiloxy and hydroxyl, alkoxy, epoxy, acetoxy, amino, preferably vinyl, trimethoxysiloxy, hydroxyl and epoxy, the ratio M/Q of the number of siloxane units to tetraphenylsiloxane units in the MQ resin structure is 0.6-1.0, preferably 0.7-0.9, the weight average molecular weight of the MQ resin is 3000-9000, preferably 4000-8000, the vinyl content is 0.02-0.24%, preferably 0.04-0.15%, the hydroxyl content is 0.3-2.0%, preferably 0.5-1.5%. The content of functional groups (such as epoxy, alkoxy, acetoxy, amino, etc.) is 0.3-1.5%, preferably 0.5-1.0%.
The application of the MQ resin comprises the steps of mixing the low-vinyl-content low-hydroxyl-value modified MQ resin serving as an anchoring agent with methyl vinyl silicone rubber, vinyl silicone oil, hydrogen-containing silicone oil, an inhibitor, a platinum catalyst and a solvent to prepare a pressure-sensitive adhesive, and coating the pressure-sensitive adhesive on a substrate to obtain a pressure-sensitive adhesive product.
The base material can be one selected from TPU, PET, CPP and BOPP, the methyl vinyl silicone rubber has a molecular weight of 40-70 ten thousand, a vinyl content of 0.1-0.5 wt%, the hydrogen content of hydrogen-containing silicone oil can be selected from 0.8-1.6 wt% and a volatile content less than or equal to 2.0%, the commercially available anchoring agent is Dow Corning 297, the inhibitor is acetylene cyclohexanol, and the catalyst is 5000ppm platinum catalyst.
The preparation method of the MQ resin has the beneficial effects that the preparation method is simple in operation method and mild in condition, the low-vinyl MQ resin is subjected to re-end capping through the end capping agent, and the end capped product is the low-vinyl-content low-hydroxyl-value MQ resin or the low-vinyl-content low-hydroxyl-value modified MQ resin with a double-layer spherical structure, so that the problem of high hydroxyl content in the silicon resin prepared by the prior art is solved, and meanwhile, the preparation method can replace a compound system of the vinyl MQ resin and the methyl MQ resin in the field of organosilicon pressure-sensitive adhesives, and is beneficial to large-scale production. The MQ resin effectively improves the peeling strength, the light transmittance and the aging adhesive force stability of the organic silicon pressure-sensitive adhesive.
The prepared low-vinyl-content low-hydroxyl-value modified MQ resin is introduced into a functional monomer (such as epoxy group, alkoxy group, acetoxy group, amino group and the like) to replace an anchoring agent in the prior art, and the silicon transfer problem of the pressure-sensitive adhesive in the long-term use process is solved on the basis of meeting the requirement of improving the adhesive force of a substrate.
The pressure-sensitive adhesive provided by the invention is coated on a substrate and cured at 120-160 ℃ for 60-120 seconds, and the prepared pressure-sensitive adhesive product has higher peel strength, aging adhesive force stability and light transmittance.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The sources of the raw materials in the following examples were all purchased from Aladin.
The molecular weight and distribution in the examples were measured by gel chromatography (GPC) using toluene as the mobile phase.
The silicon hydroxyl content test method of the MQ resin sample is nuclear magnetic resonance silicon spectrum.
The pressure-sensitive adhesive sample preparation and testing method comprises the following steps:
1. the preparation of the rubber comprises MQ resin, vinyl methyl silicone rubber, hydrogen-containing silicone oil, an inhibitor, an anchoring agent, a platinum catalyst and a solvent.
2. And (3) preparing a sample, namely uniformly coating the mixed pressure-sensitive adhesive sample on a PET film after corona by using a 70-micrometer coating rod, baking for 2 minutes by using a 150 ℃ oven, and then cutting into adhesive tapes to be stuck on a steel plate.
3. Testing pressure sensitive adhesive peel force was tested by a tensile machine according to the GB/T2792-2014 method.
4. Aging, namely aging the sample by using a constant temperature and humidity box at the temperature of 85 ℃ and RH of 85% for 72 hours, and testing the stripping force after aging.
5. Light transmittance, namely testing by using a light transmittance haze tester;
6. and (3) transferring silicon, namely aging the sample in a constant temperature and humidity box at 85 ℃ and 85% RH for 72 hours, and observing the surface pollution state of the adherend.
Example 1
Adding 210g of water, 200g of isopropanol and 2.0g of concentrated hydrochloric acid into a reactor, stirring uniformly, adding 400g of ethyl orthosilicate into the reactor A, stirring and reacting for 10min at 25 ℃, adding 320g of hexamethyldisiloxane and 4g of tetramethyl divinyl disiloxane, reacting for 2h at 25 ℃, adding 300g of toluene, standing and layering after stirring uniformly, adding sodium bicarbonate for neutralization, retaining an upper organic phase MQ resin solution, adding 70g of trimethylethoxysilane and 1.8g of sodium hydroxide, refluxing at a high temperature of 110 ℃ for 2h, removing water molecules generated in the system until no water is generated, adding hydrochloric acid for neutralization, washing to neutrality, taking an upper organic phase solution, and carrying out decompression and low-pressure dehydration to obtain the low-vinyl-content low-hydroxyl-value MQ resin. The M/Q ratio of the test specimen was 1.0, the weight average molecular weight was 3385, the hydroxyl content was 2.0% by weight, and the vinyl content was 0.02% by weight. 40g of the MQ powder sample is uniformly stirred with 20g of commercial vinyl methyl silicone rubber, 60g of dimethylbenzene, 0.8g of hydrogen-containing silicone oil, 0.6g of commercial anchoring agent, 0.1g of ethynyl cyclohexanol and 0.4g of catalyst with 5000ppm of platinum content in the same batch to obtain an organosilicon pressure-sensitive adhesive component sample 1.
In this example, hexamethyldisiloxane is replaced with one of methoxytrimethylsilane and ethoxytrimethylsilane in an equivalent manner, tetramethyldivinyl disiloxane is replaced with one of vinyldimethylmethoxysilane and vinyldimethylethoxysilane in an equivalent manner, and trimethylethoxysilane is replaced with methoxytrimethylsilane or trimethylchlorosilane in an equivalent manner, so that the performance of the prepared organosilicon pressure-sensitive adhesive is similar to that of sample 1.
Example 2
Adding 280g of water, 200g of isopropanol and 8.0g of concentrated hydrochloric acid into a reactor, stirring uniformly, adding 400g of ethyl orthosilicate into the reactor A, stirring and reacting for 10min at 25 ℃, adding 160g of hexamethyldisiloxane and 40g of tetramethyl divinyl disiloxane, reacting for 2h at 25 ℃, adding 300g of toluene, standing and layering after stirring uniformly, adding sodium bicarbonate for neutralization, retaining an upper organic phase MQ resin solution, adding 120g of trimethylethoxysilane and 4.0g of sodium hydroxide, refluxing at a high temperature of 110 ℃ for 2h, removing water molecules generated in the system until no water is generated, adding hydrochloric acid for neutralization, washing to neutrality, taking an upper organic phase solution, and carrying out decompression and low-pressure dehydration to obtain the MQ resin with low vinyl content and low hydroxyl value. The M/Q ratio of the test specimen was 0.60, the weight average molecular weight was 8985, the hydroxyl content was 1.50% by weight, and the vinyl content was 0.24% by weight. 40g of the MQ powder sample is uniformly stirred with 20g of commercial vinyl methyl silicone rubber, 60g of dimethylbenzene, 0.8g of hydrogen-containing silicone oil, 0.6g of commercial anchoring agent, 0.1g of ethynyl cyclohexanol and 0.4g of catalyst with 5000ppm of platinum content in the same batch to obtain an organosilicon pressure-sensitive adhesive component sample 2.
Example 3
Adding 160g of water, 320g of isopropanol and 6.0g of concentrated hydrochloric acid into a reactor, stirring uniformly, adding 400g of ethyl orthosilicate into the reactor A, stirring and reacting for 10min at 25 ℃, adding 280g of hexamethyldisiloxane and 8.0g of tetramethyl divinyl disiloxane, reacting for 2h at 25 ℃, adding 300g of toluene, standing and layering after stirring uniformly, adding sodium bicarbonate for neutralization, retaining an upper organic phase MQ resin solution, adding 60g of trimethylethoxysilane and 1.6g of sodium hydroxide, refluxing at a high temperature of 110 ℃ for 2h, removing water molecules generated in the system until no water is generated, adding hydrochloric acid for neutralization, washing to neutrality, taking an upper organic phase solution, and carrying out decompression and low-pressure dehydration to obtain the MQ resin with low vinyl content and low hydroxyl value. The M/Q ratio of the test specimen was 0.70, the weight average molecular weight was 7985, the hydroxyl group content was 0.52% by weight, and the vinyl content was 0.04% by weight. 40g of the MQ powder sample is uniformly stirred with 20g of commercial vinyl methyl silicone rubber, 60g of dimethylbenzene, 0.8g of hydrogen-containing silicone oil, 0.6g of commercial anchoring agent, 0.1g of ethynyl cyclohexanol and 0.4g of catalyst with 5000ppm of platinum content in the same batch to obtain an organosilicon pressure-sensitive adhesive component sample 3.
Example 4
Adding 200g of water, 280g of isopropanol and 4.2g of concentrated hydrochloric acid into a reactor, stirring uniformly, adding 400g of tetraethoxysilane into the reactor A, stirring and reacting for 10min at 25 ℃, adding 240g of hexamethyldisiloxane and 16g of tetramethyl divinyl disiloxane, reacting for 2h at 35 ℃, adding 300g of toluene, refluxing and reacting for 2h, stopping stirring, standing and layering, adding sodium bicarbonate for neutralization, retaining an upper organic phase MQ resin solution, adding 100g of trimethylethoxysilane and 1g of potassium hydroxide, refluxing and reacting for 2h at 110 ℃ at a high temperature, removing water molecules generated in the system until no water is generated, adding hydrochloric acid for neutralization, washing to neutrality, taking an upper organic phase solution, and decompressing and removing low content of vinyl to obtain the low hydroxyl value MQ resin. The M/Q ratio of the test specimen was 0.71, the weight average molecular weight was 5964, the hydroxyl content was 0.94% by weight, and the vinyl content was 0.09% by weight. 40g of the MQ powder sample is uniformly stirred with 20g of commercial vinyl methyl silicone rubber, 60g of dimethylbenzene, 0.8g of hydrogen-containing silicone oil, 0.6g of commercial anchoring agent, 0.1g of ethynyl cyclohexanol and 0.4g of catalyst with 5000ppm of platinum content in the same batch to obtain an organosilicon pressure-sensitive adhesive component sample 4.
Example 5
Adding 240g of water, 240g of isopropanol and 2.8g of concentrated hydrochloric acid into a reactor, stirring uniformly, adding 400g of ethyl orthosilicate into the reactor A, stirring and reacting for 60min, adding 200g of hexamethyldisiloxane and 24g of tetramethyl divinyl disiloxane, reacting for 4h at 25 ℃, adding 200g of toluene, refluxing and reacting for 2h, stopping stirring, standing and layering, adding sodium bicarbonate for neutralization, retaining an upper organic phase MQ resin solution, adding 80g of trimethylethoxysilane and 1g of tetramethylammonium hydroxide, refluxing and reacting for 2h at a high temperature of 110 ℃, removing water molecules generated in the system until no water is generated, adding hydrochloric acid for neutralization, washing to neutrality, taking an upper organic phase solution, and decompressing and removing low to obtain the low-vinyl-content low-hydroxyl-value MQ resin. The M/Q ratio of the test specimen was 0.77, the weight average molecular weight was 4012, the hydroxyl content was 0.61% by weight, and the vinyl content was 0.14% by weight. 40g of the MQ powder sample is uniformly stirred with 20g of commercial vinyl methyl silicone rubber, 60g of dimethylbenzene, 0.8g of hydrogen-containing silicone oil, 0.6g of commercial anchoring agent, 0.1g of ethynyl cyclohexanol and 0.4g of catalyst with 5000ppm of platinum content in the same batch to obtain an organosilicon pressure-sensitive adhesive component sample 5.
Example 6
180G of water, 250g of isopropanol and 6.2g of concentrated hydrochloric acid are added into a reactor, stirring is carried out uniformly, 400g of tetraethoxysilane is added into a reactor A, stirring is carried out for 30min, 285g of hexamethyldisiloxane and 15g of tetramethyl divinyl disiloxane are added, the temperature is 35 ℃, the reaction is carried out for 1h, 200g of toluene is added, the reflux reaction is carried out for 2h, stirring is stopped, standing and layering are carried out, sodium bicarbonate is added for neutralization, an upper organic phase MQ resin solution is reserved, 72g of gamma-glycidoxypropyl trimethoxysilane and 1g of tetramethyl ammonium hydroxide are added, the high-temperature reflux reaction at 110 ℃ is carried out for 2h, the generated water molecules in the system are eliminated until no water is generated, hydrochloric acid is added for neutralization, the upper organic phase solution is taken, and the low-vinyl content low-hydroxyl value modified MQ resin is obtained through decompression and low-pressure removal. The M/Q ratio of the test specimen was 0.81, the weight average molecular weight was 5312, the hydroxyl content was 0.56% by weight, the vinyl content was 0.08% by weight, and the epoxy content was 0.78% by weight.
The silicone pressure-sensitive adhesive component sample 6 is obtained by uniformly stirring 1g of the low vinyl content and low hydroxyl value modified MQ resin powder sample prepared in the embodiment, 40g of the MQ resin sample synthesized in the embodiment 2, 20g of commercial vinyl methyl silicone rubber in the same batch, 60g of dimethylbenzene, 0.8g of hydrogen-containing silicone oil, 0.1g of ethynyl cyclohexanol and 0.4g of catalyst with 5000ppm of platinum content.
The performance of the prepared silicone pressure-sensitive adhesive sample was similar to sample 6, except that the gamma-glycidoxypropyl trimethoxysilane in this example was replaced with an equivalent amount of one of gamma-glycidoxypropyl triethoxysilane, gamma- (methacryloyloxy) propyl trimethoxysilane, gamma- (methacryloyloxy) propyl triethoxysilane, 2- (3, 4 epoxycyclohexenyl) ethyl trimethoxysilane, 2- (3, 4 epoxycyclohexenyl) ethyl triethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, and aminophenylpropyl trimethoxysilane.
Example 7
40G of commercial methyl MQ resin (molecular weight 3822, hydroxyl content 0.52%) is taken and evenly stirred with 20g of commercial vinyl methyl silicone rubber, 60g of dimethylbenzene, 0.8g of hydrogen-containing silicone oil, 0.6g of low vinyl content and low hydroxyl value modified MQ resin synthesized in example 6, 0.1g of ethynyl cyclohexanol and 0.4g of catalyst with platinum content of 5000ppm in the same batch to obtain an organosilicon pressure-sensitive adhesive component sample 7.
Comparative example 1
40G of commercial methyl MQ resin (molecular weight 3822, hydroxyl content 0.52%) is taken and evenly stirred with 20g of commercial vinyl methyl silicone rubber, 60g of dimethylbenzene, 0.8g of hydrogen-containing silicone oil, 0.6g of commercial anchoring agent, 0.1g of ethynyl cyclohexanol and 0.4g of catalyst with platinum content of 5000ppm in the same batch to obtain an organosilicon pressure-sensitive adhesive component sample 8.
Comparative example 2
60G of commercial Dow Corning pressure-sensitive adhesive 7657, 40g of dimethylbenzene, 0.8g of hydrogen-containing silicone oil, 0.6g of commercial anchoring agent and 0.4g of catalyst with the platinum content of 5000ppm are taken and stirred uniformly to obtain an organosilicon pressure-sensitive adhesive component sample 9.
Pressure sensitive adhesive performance tests were carried out on the silicone pressure sensitive adhesive component samples 1 to 9, and the test results are shown in the following table.
The result shows that the low hydroxyl and low vinyl modified MQ resin synthesized by the same method can replace the traditional anchoring agent, and solves the technical problems that silicon is easy to migrate and pollute the surface of an adherend in the long-term use process of the pressure-sensitive adhesive.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.

Claims (4)

  1. The application of the MQ resin in the pressure-sensitive adhesive is characterized by comprising the following steps of mixing the MQ resin with low vinyl content and low hydroxyl value as tackifying resin, the modified MQ resin with low vinyl content and low hydroxyl value as anchoring agent with methyl vinyl silicone rubber, hydrogen-containing silicone oil, inhibitor, platinum catalyst and solvent to prepare an organosilicon pressure-sensitive adhesive;
    the preparation method of the low-vinyl-content low-hydroxyl-number MQ resin or the low-vinyl-content low-hydroxyl-number modified MQ resin comprises the following steps of:
    (1) Adding a solvent, deionized water and an acid catalyst into a reaction container, uniformly stirring, adding tetraethoxysilane, uniformly stirring, and reacting for 0.2-1h, adding a blocking agent into the reaction solution of the reaction, and reacting for 1-4h at 25-40 ℃;
    The blocking agent A is one or more of vinyl dimethyl methoxy silane, vinyl dimethyl ethoxy silane and tetramethyl divinyl disiloxane, and the blocking agent B is one or more of trimethyl methoxy silane, trimethyl ethoxy silane, trimethyl chlorosilane and hexamethyldisiloxane;
    The additive amount of each substance is respectively 100 parts by mass of tetraethoxysilane, 1-10 parts by mass of end capping agent A, 40-80 parts by mass of end capping agent B and 0.5-2 parts by mass of acid catalyst;
    (2) Adding a second-class end-capping reagent and an alkaline catalyst into the MQ resin solution, carrying out high-temperature reflux reaction for 2-6h, removing water molecules generated in the system, adding acid after the reaction is finished for neutralization, washing with water to be neutral, taking an upper-layer organic phase solution, and removing low-boiling substances through decompression to obtain MQ resin;
    The second-class end capping agent is one or more of methoxytrimethylsilane, trimethylethoxysilane and trimethylchlorosilane, and the prepared MQ resin is MQ resin with low vinyl content and low hydroxyl value;
    The second-class end-capping agent is one or more of gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma- (methacryloyloxy) propyl trimethoxysilane, gamma- (methacryloyloxy) propyl triethoxysilane, 2- (3, 4 epoxycyclohexenyl) ethyl trimethoxysilane, 2- (3, 4 epoxycyclohexenyl) ethyl triethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane and aminophenyl propyl trimethoxysilane, and the prepared MQ resin is modified MQ resin with low vinyl content and low hydroxyl value.
  2. 2. The use according to claim 1, wherein the acidic catalyst is one or more of formic acid, acetic acid, hydrochloric acid, fluorosulfonic acid, sulfuric acid, hydrobromic acid, hydrofluoric acid, p-toluenesulfonic acid.
  3. 3. The method according to claim 1, wherein in the step (2), the addition amount of each substance is respectively 100 parts by mass of MQ resin solution, 10-30 parts by mass of the second-class end capping agent and 0.2-1 part by mass of the alkaline catalyst.
  4. 4. The use according to claim 1, wherein the basic catalyst is one or more of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, triethylamine.
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