CN112646545A - Self-adhesive liquid silicone rubber preparation capable of spraying and preparation method thereof - Google Patents
Self-adhesive liquid silicone rubber preparation capable of spraying and preparation method thereof Download PDFInfo
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- 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
- C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09J187/005—Block or graft polymers not provided for in groups C09J101/00 - C09J185/04
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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Abstract
The invention discloses a sprayable self-adhesive liquid silicone rubber preparation and a preparation method thereof, wherein the liquid silicone rubber preparation is prepared by taking 100-120 parts of polydimethylsiloxane as a base material, mixing 40-60 parts of hydrogenated styrene-isoprene block copolymer as a modifier, 30-40 parts of fumed silica, 0.8-2 parts of trimethylolpropane triacrylate, 0.6-1.5 parts of styrene, 0.1-0.5 part of catalyst hydrogen peroxide, adding 0.02-0.1 part of platinum catalyst and 20-45 parts of water. The preparation and the method improve the adhesive property and stability of the liquid silicone rubber by improving the formula of the liquid silicone rubber, and particularly meet the adhesive property between ceramic and glass products.
Description
Technical Field
The invention relates to the technical field of organic adhesives, in particular to a sprayable self-adhesive liquid silicone rubber preparation and a preparation method thereof.
Background
The silicone rubber is an elastomer formed by compounding and vulcanizing linear polysiloxane serving as a basic polymer (raw rubber) and a crosslinking agent, a reinforcing filler and other compounding agents. The silicone rubber is classified into two types, namely mixing silicone rubber and liquid silicone rubber, according to the commercial forms of the silicone rubber. The liquid silicone rubber is different from the mixed silicone rubber, and is a base material with self-leveling property or thixotropy prepared by taking linear polyorganosiloxane with medium polymerization degree as a base polymer and matching with filler, various auxiliaries and additives. The liquid silicone rubber is also called two-component addition silicone rubber.
The liquid silicone rubber is widely used in a plurality of fields such as electronics, machinery, cultural relics, artware, automobiles, aerospace and the like. Such as silica gel products used for forming molds, injection molding processes, cake molds and the like of crystal glue, polyurethane, epoxy resin and the like, are widely used as coating and encapsulating materials for moisture prevention, consignment and insulation of electronic components in the electronic industry, and play roles in dust prevention, moisture prevention, shock prevention and insulation protection of electronic components and assemblies. If the transparent gel is adopted to encapsulate the electronic components, the device can play a role in shockproof and waterproof protection, the components can be seen, the failure of the components can be detected by using a probe, the components can be replaced, and the damaged silica gel can be encapsulated and repaired again. It can also be used for making products of gypsum, wax, epoxy resin, polyester resin, polyurethane resin and low-melting point alloy, etc., and can be used for high-frequency embossing of artificial leather, surface and bottom modeling of shoes, manufacturing of industrial art, ceramics, toy industry, duplication of furniture and household appliances and electronic components, molding of gypsum and cement materials, molding of wax products, manufacturing of models, molding of materials, etc.
However, because of its poor adhesion, when used as potting, coating and embedding materials, the base material is usually required to be subjected to priming treatment or added with a tackifier, so that the liquid silicone rubber is not applied in the field of adhesives, and relatively speaking, the preparation process is complex, the use cost is high, and particularly, the adhesion performance is poor, so that the application of the liquid silicone rubber is limited.
Chinese patent application 2016106421624 discloses a preparation method of self-adhesive liquid silicone rubber capable of spraying, which comprises the following steps: mixing a silicon-hydrogen compound containing a silicon-hydrogen bond and two substances containing an epoxy group allyl compound and having a carbon-carbon double bond molar ratio of 1:5-5:1, heating to 60 ℃, and introducing nitrogen for protection to obtain a mixed solution for later use; taking 100g of mixed solution, adding 0.1-2g of polymerization inhibitor, and uniformly stirring; after stirring evenly, mixing 5-10g of toluene with 0.02-0.1g of 2000ppm platinum catalyst, slowly dripping into the reactor, and heating while stirring; after the dripping is finished, controlling the reaction temperature between 60 and 100 ℃ and reacting for 1 to 5 hours; adding 1-3g of activated carbon for adsorption for 0.5-2h, and finally, carrying out suction filtration on the reactant to remove low molecules to obtain a coupling agent; the coupling agent, the coupling agent containing epoxy groups and the vinyl coupling agent are mixed according to the mass ratio of 100: 5-40: 4-35 to obtain the tackifier; adding 0.5-10g of tackifier into 100g of liquid silicone rubber, uniformly mixing, diluting to 20-40% of solid content by using a solvent, and thus obtaining the self-adhesive liquid silicone rubber for spraying.
Chinese patent application 201910800917.2 discloses a self-lubricating addition type liquid silicone rubber, which comprises the following raw materials in parts by weight: 120-200 parts of an alkenyl-containing polysiloxane; 1-15 parts of hydrogenated polysiloxane; 30-80 parts of fumed silica; 10-30 parts of silazane white carbon black treating agent; 1-30 parts of methyl phenyl silicone oil; 0.004-0.06 part of Si-H addition catalyst; 0.03-0.6 parts of inhibitor. According to the invention, the types and the amounts of the alkenyl-containing polysiloxane and the hydrogenated polysiloxane in the base rubber, the component A and the component B are screened, and the oil penetration rate and the product performance are controlled through raw material screening and formula design, so that the addition type liquid silicone rubber with high tear strength (more than or equal to 45kN/m) and low permanent compression deformation rate (less than or equal to 20%) is provided, and meanwhile, the oil penetration is stable, and the long-term self-lubricating effect can be kept.
Further, as disclosed in chinese patent application 202010690113.4, a method for preparing an addition type liquid silicone rubber tackifier comprises the steps of: reacting hydrogenpolysiloxane with ester compound containing styryl under the action of platinum-containing catalyst, and adding inhibitor after the reaction is completed to obtain the tackifier.
Although the addition type adhesive liquid silicone rubber is applied more at home at present, the application of the patent mostly focuses on the preparation of polysiloxane and derivatives thereof as base materials, although the cost of siloxane is low, the siloxane also has the characteristic of poor adhesive property, and often needs to be matched with a tackifier for use, the tackifier has complex components or is not friendly to a catalyst, and meanwhile, the tackifier has poor stability at high temperature, so that the adhesive property is reduced, and the production and popularization of the addition type adhesive liquid silicone rubber are seriously influenced. Particularly, for ceramic or glass products, a liquid silicone rubber adhesive which is environment-friendly and has good adhesive property and stability is needed.
Disclosure of Invention
Aiming at the defects in the technology, the invention provides a sprayable self-adhesive liquid silicone rubber preparation and a preparation method thereof.
Another object of the present invention is to provide a sprayable self-adhesive liquid silicone rubber formulation and a method for preparing the same, which has high temperature stability, can maintain good adhesive property at 50-80 ℃, and has a sprayable characteristic, and is convenient to use.
To achieve the above object, the present invention is realized by:
a sprayable self-adhesive liquid silicone rubber preparation is characterized in that the liquid silicone rubber preparation is prepared by taking 100-120 parts of polydimethylsiloxane as a base material, mixing 40-60 parts of hydrogenated styrene-isoprene block copolymer as a modifier, 30-40 parts of fumed silica, 0.8-2 parts of modified monomer trimethylolpropane triacrylate, 0.6-1.5 parts of auxiliary monomer styrene, 0.1-0.5 part of catalyst hydrogen peroxide, adding 0.02-0.1 part of 2000ppm platinum catalyst and 20-45 parts of water.
In the liquid silicone rubber preparation, the molecular chain of the hydrogenated styrene-isoprene block copolymer after reaction is in a star shape without the main chain and the side chain, and meanwhile, the polydimethylsiloxane is used for carrying out a grafting reaction with the hydrogenated styrene-isoprene block copolymer and is used as a branched chain of the hydrogenated styrene-isoprene block copolymer, so that the molecular weight of the liquid silicone rubber is increased, and the branched chain increases the adhesive property of the preparation on the basis of stable star shape, thereby greatly improving the adhesive property of the liquid silicone rubber preparation and having enough adsorption force and adhesive property on smooth surfaces of ceramics, glass and the like.
The preparation method is characterized in that two reaction processes are adopted, firstly, a polypropylene structural unit on a molecular chain of the hydrogenated styrene-isoprene block copolymer is cracked to form a free radical in the presence of peroxide, and the free radical reacts with a polyfunctional modified monomer trimethylolpropane triacrylate in the presence of an auxiliary monomer styrene to form a star-shaped polymer copolymer, and carbonyl on the molecule is not grafted on a block but is used as an arm of the copolymer to play a role in branching, so that the stability and the bonding performance of the preparation can be improved; and secondly, the polydimethylsiloxane is subjected to a grafting reaction with the hydrogenated styrene-isoprene block copolymer, and the polydimethylsiloxane is grafted on an alkyl part of the hydrogenated styrene-isoprene block copolymer as a branched chain, so that the length and the branched chain of a molecular chain are increased, the bonding performance is greatly improved, sufficient bonding force can be realized under the condition of low concentration, and the good bonding performance can be guaranteed after spraying.
The polydimethylsiloxane is polydimethylsiloxane having a viscosity of 3 to 8 ten thousand.
The hydrogenated styrene-isoprene block copolymer has a number average molecular weight of 10 to 30 ten thousand.
The platinum catalyst was 2000ppm Karstedt's catalyst.
Further, the preparation can also be added with a coupling agent, wherein the coupling agent is any one or any combination of KH-560, KH-566 and KH-567.
A preparation method of a sprayable self-adhesive liquid silicone rubber preparation is characterized by comprising the following steps:
dissolving a copolymer, namely crushing a hydrogenated styrene-isoprene block copolymer into small particles, wherein the outer diameter of the particles is not more than 1cm, adding base material polydimethylsiloxane into a reaction kettle, then adding the hydrogenated styrene-isoprene block copolymer particles in batches, controlling the temperature to be not more than 130 ℃, and starting a stirrer;
step two, preparing a star-shaped copolymer, heating to 160-.
And step three, grafting, then cooling to 100-120 ℃, adding 30-40 parts of fumed silica, 0.02-0.1 part of 2000ppm platinum catalyst and 20-45 parts of water, mixing and continuously stirring for 45-60min, and discharging to obtain the self-adhesive liquid silicon rubber preparation. In the step, polydimethylsiloxane and hydrogenated styrene-isoprene block copolymer are subjected to a grafting reaction, and the polydimethylsiloxane is grafted on the hydrogenated styrene-isoprene block copolymer as a branched chain, so that the length of a molecular chain and the number of branched chains are increased, and the bonding performance can be improved.
In the preparation method, firstly, the star-shaped copolymer is prepared by taking hydrogen peroxide as a catalyst, at the moment, the condition that the proper temperature is kept is the premise of promoting the smooth reaction (generally more than 150 ℃), the styrene can play a role in inhibiting the crosslinking (due to the particularity of the molecular structure), the reaction can be promoted to be carried out towards the direction of generating the star-shaped polymer under the catalysis of the hydrogen peroxide, the occurrence of the crosslinking reaction is prevented or reduced, and the star-shaped copolymer is successfully prepared.
After the star-shaped copolymer is prepared, a platinum catalyst is added, so that polydimethylsiloxane is attached to the hydrogenated styrene-isoprene block copolymer, and the-O-bond of the polydimethylsiloxane and the alkyl of the hydrogenated styrene-isoprene block can perform a grafting reaction, so that the molecular chain length and the number of branched chains of the star-shaped copolymer are increased, and the bonding performance of the preparation is improved on the basis of ensuring the stability.
The water is added according to the concentration of all the conditions, and the best amount is 30-35 parts.
And in the third step, the coupling agent is further added, the fumed silica, the platinum catalyst and the water are added, the coupling agent is added to increase the viscosity of the preparation, the mixture is mixed and stirred for a period of time, and then the material can be discharged, so that the bonding performance is further improved.
Compared with the prior art, the invention has the following beneficial effects:
1) the silicone rubber preparation prepared from the viscous liquid has strong adsorption capacity, can be well adhered to glass, ceramics and other materials, is high-temperature resistant, and can keep good adhesion performance at 50-80 ℃.
2) The preparation synthesized by the invention has a stable structure, can have good compatibility with liquid silicone rubber, and can improve the mechanical property of the silicone rubber.
3) The preparation synthesized by the invention has the characteristics of spraying, convenient use and simple synthesis process, and can meet the requirements of industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The applicant researches and discovers that the bonding performance of the adhesive is closely related to the length of a molecular chain of the adhesive, and in general, the longer the molecular chain is, the better the bonding performance is, and the shorter the molecular chain is, the poorer the bonding performance is, so that the adhesive has enough molecular chains to maintain good bonding performance; meanwhile, for a molecular chain with a certain length, the stability is also problematic, and generally, the longer the molecular chain is, the poorer the stability is, which in turn may bring negative effects to the adhesive property, so that maintaining the adhesive stability and the adhesive property is a major problem faced by the liquid silicone rubber adhesive at present.
Based on the technical scheme, the liquid silicone rubber adhesive is realized from two aspects of stability and improvement of molecular chain length, so that the liquid silicone rubber adhesive has good adhesive property and sufficient stability.
Based on the above, the sprayable self-adhesive liquid silicone rubber preparation realized by the invention is prepared by taking 100-120 parts of polydimethylsiloxane as a base material, mixing 40-60 parts of hydrogenated styrene-isoprene block copolymer as a modifier, 30-40 parts of fumed silica, 0.8-2 parts of modified monomer trimethylolpropane triacrylate, 0.6-1.5 parts of auxiliary monomer styrene, 0.1-0.5 part of catalyst hydrogen peroxide, and adding 0.02-0.1 part of 2000ppm platinum catalyst and 20-45 parts of water.
Wherein the preparation steps comprise:
dissolving a copolymer, namely crushing a hydrogenated styrene-isoprene block copolymer into small particles, wherein the outer diameter of the particles is not more than 1cm, adding base material polydimethylsiloxane into a reaction kettle, then adding the hydrogenated styrene-isoprene block copolymer particles in batches, controlling the temperature to be not more than 130 ℃, and starting a stirrer;
step two, preparing a star-shaped copolymer, heating to 160-.
And step three, grafting, then cooling to 100-120 ℃, adding 30-40 parts of fumed silica, 0.02-0.1 part of 2000ppm platinum catalyst and 20-45 parts of water, mixing and continuously stirring for 45-60min, and discharging to obtain the self-adhesive liquid silicon rubber preparation. In the step, polydimethylsiloxane and hydrogenated styrene-isoprene block copolymer are subjected to a grafting reaction, and the polydimethylsiloxane is grafted on the hydrogenated styrene-isoprene block copolymer as a branched chain, so that the length of a molecular chain and the number of branched chains are increased, and the bonding performance can be improved.
In the second step, when the star-shaped copolymer is prepared, it should be noted that the styrene can only play a role in inhibiting crosslinking (due to the particularity of the molecular structure) at a high temperature (usually above 150 ℃), so that the reaction can be promoted to proceed toward the direction of generating the star-shaped polymer under the catalysis of peroxide, thereby preventing or reducing the occurrence of the crosslinking reaction, and thus the star-shaped copolymer can be successfully prepared.
In the third step, a coupling agent can be added, for example, after fumed silica, platinum catalyst and water are added, the coupling agent is added to increase the viscosity of the preparation, and the mixture is mixed and stirred for a period of time to discharge, so that the bonding performance is further improved.
Example 1.
Dissolving a copolymer, namely crushing a hydrogenated styrene-isoprene block copolymer into small particles, wherein the outer diameter of the particles is not more than 1cm, adding 100 parts of base polydimethylsiloxane into a reaction kettle, then adding 40 parts of hydrogenated styrene-isoprene block copolymer particles in total in batches, controlling the temperature to be not more than 130 ℃, and starting a stirrer;
step two, preparing a star-shaped copolymer, heating to 160-.
And step three, grafting, then cooling to 100-120 ℃, adding 30 parts of fumed silica, 0.02 part of 2000ppm platinum catalyst and 20 parts of water, mixing and continuously stirring for 45-60min, and discharging to obtain the self-adhesive liquid silicon rubber preparation.
Diluting at a certain proportion, spraying on a glass bottle, and curing at 150 deg.C for 10 min. The basic properties and adhesion of the compound were tested. As shown in table 1.
Example 2.
Dissolving a copolymer, namely crushing a hydrogenated styrene-isoprene block copolymer into small particles, wherein the outer diameter of the particles is not more than 1cm, adding 120 parts of base material polydimethylsiloxane into a reaction kettle, then adding 60 parts of hydrogenated styrene-isoprene block copolymer particles in total in batches, controlling the temperature to be not more than 130 ℃, and starting a stirrer;
step two, preparing a star-shaped copolymer, heating to 160-.
And step three, grafting, then cooling to 100-120 ℃, adding 40 parts of fumed silica, 0.1 part of 2000ppm platinum catalyst and 45 parts of water, mixing and continuously stirring for 45-60min, and discharging to obtain the self-adhesive liquid silicon rubber preparation.
Diluting at a certain proportion, spraying on a glass bottle, and curing at 150 deg.C for 10 min. The basic properties and adhesion of the compound were tested. As shown in table 1.
Example 3.
Dissolving a copolymer, namely crushing a hydrogenated styrene-isoprene block copolymer into small particles, wherein the outer diameter of the particles is not more than 1cm, adding 110 parts of base material polydimethylsiloxane into a reaction kettle, then adding 50 parts of hydrogenated styrene-isoprene block copolymer particles in total in batches, controlling the temperature to be not more than 130 ℃, and starting a stirrer;
step two, preparing a star-shaped copolymer, heating to 160-.
And step three, grafting, then cooling to 100-120 ℃, adding 35 parts of fumed silica, 0.08 part of 2000ppm platinum catalyst and 35 parts of water, mixing and continuously stirring for 45-60min, and discharging to obtain the self-adhesive liquid silicon rubber preparation.
Diluting at a certain proportion, spraying on a glass bottle, and curing at 150 deg.C for 10 min. The basic properties and adhesion of the compound were tested. As shown in table 1.
Example 4.
Dissolving a copolymer, namely crushing a hydrogenated styrene-isoprene block copolymer into small particles, wherein the outer diameter of the particles is not more than 1cm, adding 105 parts of base material polydimethylsiloxane into a reaction kettle, then adding 52 parts of hydrogenated styrene-isoprene block copolymer particles in total in batches, controlling the temperature to be not more than 130 ℃, and starting a stirrer;
step two, preparing a star-shaped copolymer, heating to 160-.
And step three, grafting, then cooling to 100-120 ℃, adding 36 parts of fumed silica, 0.07 part of 2000ppm platinum catalyst and 30 parts of water, mixing and continuously stirring for 45-60min, and discharging to obtain the self-adhesive liquid silicon rubber preparation.
Diluting at a certain proportion, spraying on a glass bottle, and curing at 150 deg.C for 10 min. The basic properties and adhesion of the compound were tested. As shown in table 1.
Example 5.
Dissolving a copolymer, namely crushing a hydrogenated styrene-isoprene block copolymer into small particles, wherein the outer diameter of the particles is not more than 1cm, adding 116 parts of base material polydimethylsiloxane into a reaction kettle, then adding 54 parts of hydrogenated styrene-isoprene block copolymer particles in total in batches, controlling the temperature to be not more than 130 ℃, and starting a stirrer;
step two, preparing a star-shaped copolymer, heating to 160-.
And step three, grafting, then cooling to 100-120 ℃, adding 38 parts of fumed silica, 0.06 part of 2000ppm platinum catalyst and 25 parts of water, mixing and continuously stirring for 45-60min, and discharging to obtain the self-adhesive liquid silicon rubber preparation.
Diluting at a certain proportion, spraying on a glass bottle, and curing at 150 deg.C for 10 min. The basic properties and adhesion of the compound were tested. As shown in table 1.
Example 6.
Dissolving a copolymer, namely crushing a hydrogenated styrene-isoprene block copolymer into small particles, wherein the outer diameter of the particles is not more than 1cm, adding 112 parts of base material polydimethylsiloxane into a reaction kettle, then adding 48 parts of hydrogenated styrene-isoprene block copolymer particles in total in batches, controlling the temperature to be not more than 130 ℃, and starting a stirrer;
step two, preparing a star-shaped copolymer, heating to 160-.
And step three, grafting, then cooling to 100-120 ℃, adding 32 parts of fumed silica, 0.04 part of 2000ppm platinum catalyst and 25 parts of water, mixing and continuously stirring for 45-60min, and discharging to obtain the self-adhesive liquid silicon rubber preparation.
Diluting at a certain proportion, spraying on a glass bottle, and curing at 150 deg.C for 10 min. The basic properties and adhesion of the compound were tested. As shown in table 1.
Comparative example the example in a self-adhesive liquid silicone rubber filed by the applicant in 2019 was taken as a comparative example.
Comparative example 1
Step S1: 79.2g of 1, 4-butanediol diacrylate, 23.2g of hydroxyethyl acrylate and 0.42g of 4000ppm of platinum catalyst are uniformly stirred to form a mixed solution for later use;
step S2: 220g of tetramethylcyclotetrasiloxane and 0.45g of p-hydroxyphenol are introduced into a four-neck flask with thermometer and reflux condenser, stirred under nitrogen and heated to 60 ℃. And (3) slowly adding the mixed solution obtained in the step (1), continuing to heat to 120 ℃ after the addition, reacting for 4 hours, cooling, and adding 20g of activated carbon for adsorption for 1 hour. Finally, carrying out suction filtration, and removing low molecules to obtain the tackifier 1;
step S3: 50 parts of vinyl-terminated polydimethylsiloxane with the viscosity of 8 ten thousand, 20 parts of 2 ten thousand vinyl-terminated polydimethylsiloxane, 1 part of vinyl silicone oil with the viscosity of 300mPa.s and the mass fraction of 1% of vinyl, 25 parts of fumed silica, 5 parts of hexamethyldisilazane and 1.52 parts of water are added into a kneader and stirred uniformly at room temperature, then the temperature is increased to 180 ℃, the vacuum degree is 0.01MPa, the mixture is treated for 3 hours, after cooling, 0.65 part of hydrogen-containing silicone oil with the hydrogen content of 0.8%, 0.005 part of ethynyl cyclohexanol and 0.5 part of tackifier are sequentially added and stirred uniformly, 0.01 part of platinum catalyst with the hydrogen content of 4000ppm is added and stirred uniformly, and finally, the mixture is solidified for 5min at the temperature of 130 ℃ for forming. The properties of the samples are shown in Table 1.
Comparative example 2
Step S1: 93.6g of 1, 6-butanediol diacrylate and 0.41g of 4000ppm of platinum catalyst are uniformly stirred to form a mixed solution for later use;
step S2: 185g of hydrogen-containing silicone oil having a viscosity of 30mPa.s and a hydrogen content of 1.5% and 0.4g of p-hydroxyphenol were charged into a four-necked flask equipped with a thermometer and a reflux condenser, stirred and warmed to 50 ℃ under a nitrogen blanket. And (3) slowly adding the mixed solution obtained in the step (1), continuing to heat to 90 ℃ after the addition, reacting for 4 hours, cooling, and adding 20g of activated carbon for adsorption for 1 hour. Finally, carrying out suction filtration to remove low molecules to obtain a tackifier 2;
step S3: adding 40 parts of vinyl-terminated polydimethylsiloxane with the viscosity of 8 ten thousand, 20 parts of 2 ten thousand vinyl-terminated polydimethylsiloxane, 2 parts of vinyl silicone oil with the viscosity of 300mPa.s and the mass fraction of 1% of vinyl, 28 parts of fumed silica, 6 parts of hexamethyldisilazane and 1.6 parts of water into a kneader at room temperature, uniformly stirring, then heating to 180 ℃ and the vacuum degree of 0.01MPa, treating for 3 hours, cooling, sequentially adding 0.95 part of hydrogen-containing silicone oil with the hydrogen content of 0.8%, 0.005 part of ethynyl cyclohexanol and 4.5 parts of tackifier, uniformly stirring, adding 0.01 part of platinum catalyst with the hydrogen content of 4000ppm, uniformly stirring, and finally curing at the temperature of 130 ℃ for 5min to form the product. The properties of the samples are shown in Table 1.
Comparative example 3
Step S1: 198g of 1, 4-butanediol diacrylate acrylate compound, 142g of glycidyl methacrylate and 1.6g of 4000ppm of platinum catalyst are uniformly stirred to form a mixed solution for later use;
step S2: 580g of tetramethylcyclotetrasiloxane and 1.0g of p-hydroxyphenol were added to a four-necked flask with a thermometer and a reflux condenser, stirred and heated to 50 ℃ under nitrogen protection. And (3) slowly adding the mixed solution obtained in the step (1), continuing to heat to 90 ℃ after the addition, reacting for 4 hours, cooling, and adding 30g of activated carbon for adsorption for 1 hour. Finally, carrying out suction filtration to remove low molecules to obtain a tackifier 3;
step S3: 60 parts of vinyl-terminated polydimethylsiloxane with the viscosity of 8 ten thousand, 25 parts of 2 ten thousand vinyl-terminated polydimethylsiloxane, 4 parts of vinyl silicone oil with the viscosity of 50mPa.s and the mass fraction of vinyl of 2%, 32 parts of fumed silica, 8 parts of hexamethyldisilazane and 2 parts of water are added into a kneader at room temperature and stirred uniformly, then the mixture is heated to 180 ℃ and the vacuum degree is 0.01MPa, the mixture is treated for 3 hours, after cooling, 2 parts of hydrogen-containing silicone oil with the hydrogen content of 1.1%, 0.005 part of ethynyl cyclohexanol and 1.5 parts of tackifier are sequentially added and stirred uniformly, then 0.01 part of platinum catalyst with the hydrogen content of 4000ppm is added and stirred uniformly, and the properties of the sample are shown in Table 1.
TABLE 1
The product performance test method in table 1 is as follows:
1. hardness, tensile strength and elongation at break were determined according to GB/T-531-1999.
2. Tear strength was determined according to GB/T-529-1999.
3. The adhesion strength to glass was measured according to GBT GBT 7124-2008.
As can be seen from Table 1, examples 1, 2, 3, 4, 5 and 6 have significantly improved adhesion to glass ceramics as compared with comparative examples 1, 2 and 3, and especially the adhesion at 100 ℃ is greatly improved as compared with comparative examples, thus proving that the invention has excellent stability and temperature resistance.
The above disclosure is only for a few specific embodiments of the present invention, but the present invention is not limited thereto, and any variations that can be made by those skilled in the art are intended to fall within the scope of the present invention.
Claims (9)
1. A sprayable self-adhesive liquid silicone rubber preparation is characterized in that the liquid silicone rubber preparation is prepared by taking 100-120 parts of polydimethylsiloxane as a base material, mixing 40-60 parts of hydrogenated styrene-isoprene block copolymer as a modifier, 30-40 parts of fumed silica, 0.8-2 parts of modified monomer trimethylolpropane triacrylate, 0.6-1.5 parts of auxiliary monomer styrene, 0.1-0.5 part of catalyst hydrogen peroxide, adding 0.02-0.1 part of platinum catalyst and 20-45 parts of water.
2. Sprayable self-adhesive liquid silicone rubber formulation according to claim 1, characterized in that the polydimethylsiloxane is a polydimethylsiloxane having a viscosity of 3 to 8 ten thousand.
3. The sprayable self-adhesive liquid silicone rubber formulation according to claim 1, wherein the hydrogenated styrene-isoprene block copolymer has a number average molecular weight of 10 to 30 ten thousand.
4. Sprayable self-adhesive liquid silicone rubber formulation according to claim 1, wherein the platinum catalyst is 2000ppm Karstedt's catalyst.
5. The sprayable self-adhesive liquid silicone rubber formulation according to claim 1, wherein a coupling agent is further added to the formulation, wherein the coupling agent is any one or any combination of KH-560, KH-566 and KH-567.
6. A preparation method of a sprayable self-adhesive liquid silicone rubber preparation is characterized by comprising the following steps:
dissolving a copolymer, namely crushing a hydrogenated styrene-isoprene block copolymer into particles, adding base material polydimethylsiloxane into a reaction kettle, adding the hydrogenated styrene-isoprene block copolymer particles in batches, controlling the temperature to be not more than 130 ℃, and starting a stirrer;
step two, preparing a star-shaped copolymer, heating to 160-;
and step three, grafting, then cooling to 100-120 ℃, adding 30-40 parts of fumed silica, 0.02-0.1 part of 2000ppm platinum catalyst and 20-45 parts of water, mixing and continuously stirring for 45-60min, and discharging to obtain the self-adhesive liquid silicon rubber preparation.
7. The process for producing a sprayable self-adhesive liquid silicone rubber formulation according to claim 6, characterized in that the hydrogenated styrene-isoprene block copolymer has an outer particle diameter of not more than 1 cm.
8. The process for preparing sprayable self-adhesive liquid silicone rubber formulation according to claim 6, wherein the amount of water is from 30 to 35 parts.
9. The method for preparing the sprayable self-adhesive liquid silicone rubber preparation according to claim 6, wherein the third step further comprises adding a coupling agent, adding fumed silica, platinum catalyst and water, then adding the coupling agent, mixing and continuously stirring for a period of time to discharge, and further improving the adhesive property.
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