CN112961357B - Organic silicon adhesion promoter and preparation method and application thereof - Google Patents

Organic silicon adhesion promoter and preparation method and application thereof Download PDF

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CN112961357B
CN112961357B CN202110160001.2A CN202110160001A CN112961357B CN 112961357 B CN112961357 B CN 112961357B CN 202110160001 A CN202110160001 A CN 202110160001A CN 112961357 B CN112961357 B CN 112961357B
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adhesion promoter
polysiloxane
hydrogen
mass
phenolic hydroxyl
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CN112961357A (en
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赖学军
曾运生
曾幸荣
李红强
刘政宇
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South China University of Technology SCUT
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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
    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses an organic silicon adhesion promoter and a preparation method and application thereof. The organic silicon adhesion promoter is obtained by carrying out hydrosilylation reaction on polysiloxane containing phenolic hydroxyl and acrylate compounds; the polysiloxane containing phenolic hydroxyl is obtained by carrying out hydrosilylation reaction on a phenol compound containing carbon-carbon double bonds and hydrogen-containing polysiloxane. The preparation method of the organic silicon adhesion promoter comprises the following steps: 1) carrying out hydrosilylation reaction of a phenol compound containing carbon-carbon double bonds and hydrogen-containing polysiloxane to obtain polysiloxane containing phenolic hydroxyl groups; 2) and carrying out hydrosilylation reaction of the acrylate compound and the polysiloxane containing the phenolic hydroxyl group to obtain the organic silicon adhesion promoter. The organic silicon adhesion promoter disclosed by the invention is simple to prepare, wide in raw material source, low in cost and easy to realize industrial production, can be used for remarkably improving the adhesion property and mechanical property of ALSR, and can meet the use requirement in a damp and hot environment.

Description

Organic silicon adhesion promoter and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic silicon materials, in particular to an organic silicon adhesion promoter and a preparation method and application thereof.
Background
The addition type liquid silicone rubber (ALSR) has the advantages of good insulativity, good weather resistance, good dimensional stability and the like, and is widely applied to the fields of automobile manufacturing, aerospace, architectural decoration, electronic and electrical appliance pouring sealant and the like. However, the main chain of the ALSR molecular chain is formed by alternately arranging silicon atoms and oxygen atoms, bonding the silicon atoms and the oxygen atoms in a spiral three-dimensional configuration, and a side group is a non-polar organic group, so that the bond polarity can be offset to form a non-polar or weak-polar state, the surface energy is lower, a group with reaction activity is lacked, the bonding performance to plastic and metal substrates is poor, and the further popularization and application of the ALSR molecular chain are greatly limited.
With the rapid development of recent industries such as electronics and transportation, people put higher demands on the adhesion performance of silicone rubber materials in harsh environments, such as: for the bonding and sealing between the lamp shade and the lamp shell of the automobile lamp, the good sealing performance is required to prevent dust and moisture from invading and damaging electronic devices, and the debonding is also required not to occur after a large amount of heat generated by long-time illumination of the high-power lamp in wet rainy season or high temperature in summer. The effect of improving the bonding strength of the silicon rubber and the base material can be achieved by adding an adhesion promoter containing groups such as ester groups, carbon-carbon double bonds, hydrosilyl groups, hydroxyl groups, amino groups, alkoxy groups or epoxy groups into ALSR, and the reasons are that: during vulcanization, the adhesion promoter migrates to the surface of the adhesive layer and undergoes a physicochemical interaction with the surface of the substrate.
The acrylate-based adhesion promoter has good adhesion and high curing speed, is widely applied to modification of silicone rubber, but the glass transition temperature of polyacrylate is generally low, so that the movement of polyacrylate molecular chains is accelerated along with the rise of environmental temperature, a glue layer becomes soft and even flows, and the adhesion strength is greatly reduced. Further, when the humidity of the working environment during bonding is too high, the phenomenon of frosting and whitening is likely to occur, and therefore, the use requirement under severe conditions such as moist heat cannot be satisfied.
Disclosure of Invention
The invention aims to provide an organic silicon adhesion promoter and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
an organosilicon adhesion promoter is obtained by carrying out hydrosilylation reaction on polysiloxane containing phenolic hydroxyl and acrylate compounds; the polysiloxane containing phenolic hydroxyl is obtained by carrying out hydrosilylation reaction on a phenol compound containing carbon-carbon double bonds and hydrogen-containing polysiloxane.
Preferably, the number average molecular weight of the organosilicon adhesion promoter is 1000-15000.
Preferably, the viscosity of the silicone adhesion promoter is 10mPa · s to 5000mPa · s.
Preferably, the acrylate compound is at least one of dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate and diethylene glycol diacrylate.
Preferably, the phenol compound containing a carbon-carbon double bond is at least one of 4-vinylphenol, 2-allylphenol, 3', 5-di-2-propenyl-1, 1' -biphenyl-2, 4' -diol, eugenol and 2-methoxy- (1-propylene) phenol.
Preferably, the hydrogen-containing polysiloxane is at least one of hydrogen-containing silicone oil and hydrogen-containing MQ silicone resin.
Preferably, the hydrogen content of the hydrogenpolysiloxane is 0.5 wt% to 1.5 wt%.
Preferably, the number average molecular weight of the hydrogenpolysiloxane is 1000 to 20000.
Preferably, the molar ratio of the Si — H group in the phenolic hydroxyl group-containing polysiloxane to the C ═ C group in the acrylate compound is 0.25:1 to 3: 1.
Preferably, the molar ratio of the C ═ C group in the carbon-carbon double bond-containing phenol compound to the Si — H group in the hydrogenpolysiloxane is 1:1 to 1: 4.
The preparation method of the organic silicon adhesion promoter comprises the following steps:
1) dispersing a carbon-carbon double bond-containing phenolic compound and hydrogen-containing polysiloxane in a solvent, adding a platinum catalyst, and carrying out hydrosilylation reaction to obtain polysiloxane containing phenolic hydroxyl;
2) dispersing an acrylate compound and a platinum catalyst in a solvent, adding into the polysiloxane containing phenolic hydroxyl in the step 1), and carrying out hydrosilylation reaction to obtain the organic silicon adhesion promoter.
Preferably, the preparation method of the silicone adhesion promoter comprises the following steps:
1) dispersing a phenol compound containing carbon-carbon double bonds and hydrogen-containing polysiloxane in a solvent at 10-40 ℃, slowly adding a platinum catalyst, and heating to 50-100 ℃ after the platinum catalyst is added to react for 1-3 h to obtain polysiloxane containing phenolic hydroxyl;
2) dispersing an acrylate compound and a platinum catalyst in a solvent at the temperature of 20-40 ℃, heating to 60-120 ℃, slowly adding the mixture into the polysiloxane containing phenolic hydroxyl groups in the step 1), adding the mixture for 1-3 h, continuously reacting for 1-6 h after the addition, adding activated carbon for adsorbing for 2-10 h, filtering, and distilling under reduced pressure to obtain the organic silicon bonding promoter.
Preferably, the platinum catalyst is at least one of chloroplatinic acid and Karstedt platinum catalyst.
More preferably, the platinum catalyst is at least one of an isopropanol solution of chloroplatinic acid, a tetrahydrofuran solution of chloroplatinic acid and a Karstedt platinum catalyst, and the platinum concentration is 1000ppm to 4000 ppm.
Preferably, the solvent is at least one of toluene, xylene, tetrahydrofuran, methanol, ethanol, isopropanol, acetonitrile, cyclohexane, acetone, and 1, 4-dioxane.
Preferably, the amount of the platinum catalyst added in step 1) is 1ppm to 20 ppm.
Preferably, the amount of the platinum catalyst added in step 2) is 1ppm to 10 ppm.
A silicone rubber material is composed of the following components in parts by mass:
vinyl silicone oil: 90-120 parts;
white carbon black by a gas phase method: 30-50 parts;
hexamethyldisilazane: 5-15 parts;
high vinyl silicone oil: 1-5 parts;
hydrogen-containing silicone oil: 1-5 parts;
1-ethynyl-1-cyclohexanol: 0.003 to 0.06 portion;
the organic silicon adhesion promoter comprises: 1-5 parts;
karstedt platinum catalyst: 0.1 to 4 portions.
Preferably, the vinyl silicone oil has a vinyl group content of 0.1 mol% to 0.5 mol%.
Preferably, the vinyl content of the high vinyl silicone oil is 5 mol% to 10 mol%.
Preferably, the hydrogen content of the hydrogen-containing silicone oil is 0.6 wt% to 1.2 wt%.
The preparation method of the silicon rubber material comprises the following steps: adding a part of vinyl silicone oil, fumed silica and hexamethyldisilazane into a vacuum kneader, stirring for 3-5 h at 25-35 ℃, heating to 160-180 ℃, mixing for 1-2 h, vacuumizing, mixing for 1-4 h, cooling to 120-150 ℃, adding the rest of vinyl silicone oil and high vinyl silicone oil, continuing stirring for 1-2 h, cooling, grinding by using a three-roll grinder, adding hydrogen-containing silicone oil, 1-ethynyl-1-cyclohexanol, the organic silicon bonding accelerant and Karstedt platinum catalyst, defoaming for 10-30 min under the conditions of 25-35 ℃ and 0.01-0.1 MPa of vacuum degree, and curing for 1-3 h at 100-150 ℃ to obtain the silicon rubber material.
Preferably, the Karstedt platinum catalyst is added in an amount of 1ppm to 40 ppm.
Preferably, the molar ratio of the silicon-hydrogen bond to the carbon-carbon double bond in the raw material system of the silicon rubber material is 1: 1-1.7: 1.
The action mechanism of the organic silicon adhesion promoter of the invention is as follows: the organic silicon adhesion promoter is firmly adhered to the base material mainly through the interaction of hydrogen bonds, pi-pi conjugation and the like between polar groups on a molecular chain and the surface of the base material, meanwhile, because polysiloxane and ALSR have the same Si-O-Si main chain structure, the organic silicon adhesion promoter has good compatibility with the ALSR, and in addition, unreacted carbon-carbon double bonds in acrylic compounds or phenol compounds containing carbon-carbon double bonds and silicon hydrogen bonds on the polysiloxane can also participate in the ALSR vulcanization process to form a firm cross-linked network, so that the mechanical property of the ALSR is improved.
The invention has the beneficial effects that: the organic silicon adhesion promoter disclosed by the invention is simple to prepare, wide in raw material source, low in cost and easy to realize industrial production, can be used for remarkably improving the adhesion property and mechanical property of ALSR, can meet the use requirement in a damp and hot environment, and can be widely applied to the fields of electronic appliances, architectural decoration, transportation and the like.
Specifically, the method comprises the following steps:
1) the organic silicon adhesion promoter is added into ALSR, so that the adhesion strength of ALSR and base materials such as plastics and metals can be remarkably improved;
2) the Si-H or C ═ C group contained in the organic silicon adhesion promoter can participate in and promote the vulcanization process of ALSR, so that the vulcanization rate and the crosslinking density can be improved, the cohesive force of ALSR is enhanced, and the mechanical strength is improved;
3) the organic silicon adhesion promoter has the rigid structure of a benzene ring and the softness and the hydrophobicity of a fatty chain, and phenolic hydroxyl groups are easily oxidized into quinone groups and further crosslinked, so that the strength of an adhesive layer can be improved, and the use requirement in a damp and hot environment can be met.
Drawings
FIG. 1 is a Fourier infrared spectrum of hydrogen-containing silicone oil, eugenol, tripropylene glycol diacrylate, the phenolic hydroxyl group-containing polysiloxane of example 1, and the silicone adhesion promoter of example 1.
Fig. 2 is a gel permeation chromatogram of the silicone adhesion promoter of example 1.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
an organosilicon adhesion promoter, its preparation method includes the following steps:
1) adding 10g of isopropanol, 1.64g of eugenol (containing 0.01mol of C ═ C) and 3.78g of hydrogen-containing silicone oil (containing 0.03mol of Si-H) with the hydrogen content of 0.80 wt% into a 100mL reaction kettle at 25 ℃, stirring for 30min, slowly adding 0.01g of Karstedt platinum catalyst with the platinum concentration of 2000ppm into the reaction kettle, heating to 80 ℃ after the addition is finished, and reacting for 3H to obtain polysiloxane containing phenolic hydroxyl;
2) mixing and stirring 10g of isopropanol, 0.02g of Karstedt platinum catalyst with platinum concentration of 2000ppm and 3.01g of tripropylene glycol diacrylate (containing 0.02mol of C ═ C) at 20 ℃ for 20min to prepare a mixed solution, slowly dripping the mixed solution into the polysiloxane containing phenolic hydroxyl in the step 1) at 60 ℃, completing the addition for 1h, continuing to react for 3h, adding activated carbon for adsorption for 5h, filtering, and distilling under reduced pressure to obtain the organic silicon adhesion promoter.
Fourier transform infrared (FT-IR) spectra of hydrogen-containing silicone oil, eugenol, tripropylene glycol diacrylate, a polysiloxane containing phenolic hydroxyl groups and a silicone adhesion promoter are shown in FIG. 1, and Gel Permeation Chromatography (GPC) of the silicone adhesion promoter is shown in FIG. 2.
The test method comprises the following steps:
1) fourier infrared spectrum: directly dripping a liquid sample on a potassium bromide thin sheet by using a potassium bromide tabletting method, transmitting the sample by using infrared interference light and collecting an interference signal of the sample, wherein the wave number range is 4000cm-1～400cm-1Precision of 4cm-1The scanning times are 16 times;
2) gel permeation chromatography: dissolving a sample with Tetrahydrofuran (THF) to obtain a solution with a concentration of 0.5-1.0 wt%, and testing the molecular weight and distribution of the sample by using a gel permeation chromatograph, wherein monodisperse polystyrene is used as a standard sample.
As can be seen from fig. 1:
in curve A, 3518cm-1The broad peak at the position belongs to the stretching vibration peak of the phenolic hydroxyl group, 3070cm-1And 3006cm-1Where the term "CH ═ CH2Middle C-H stretching vibration peak of 1641cm-11608cm of a stretching vibration peak attributed to C ═ C-1And 1513cm-1A stretching vibration peak belonging to a benzene ring skeleton structure;
in curve B, 2968cm-1Is classified as-Si-CH3The antisymmetric stretching vibration peak of C-H in (2 cm)-11261cm from the stretching vibration peak belonging to-Si-H-1Is classified as-Si-CH3Characteristic absorption peak of (2), 1093cm-1And 1040cm-1A symmetric telescopic absorption peak belonging to-Si-O-Si;
in curve C, the peak at 2850cm in the phenolic hydroxyl group-containing polysiloxane was observed in addition to the above-mentioned characteristic peak-1Also appears to be attributed to-Si-CH2C-H symmetric stretching vibration peak in-and-Si-CH2The group is generated by hydrosilylation of a compound containing phenol having an activated carbon-carbon double bond with a hydrogenpolysiloxane, and is present at 3070cm-1And 3006cm-1Where the term "CH ═ CH2Middle C-H stretching vibration peak and 1641cm-1The stretching vibration peak attributed to C ═ C disappears, but because the dosage of the silicon-hydrogen bond is larger than that of the carbon-carbon double bond, a certain strength of-Si-H stretching vibration peak still exists, and the results show the successful synthesis of the polysiloxane containing the phenolic hydroxyl group;
in curve D, 1725cm-11203cm of a stretching vibration peak attributed to C ═ O-1A stretching vibration peak attributed to C-O-C;
in curve E, 3075cm in curve D-1And 3038cm-1Where the term "CH ═ CH2Middle C-H stretching vibration peak and 1628cm-1The stretching vibration peaks ascribed to C ═ C all disappeared, indicating that the silicone adhesion promoter had been successfully synthesized.
As can be seen from fig. 2: m of synthetic silicone adhesion promotersnIs 6100, Mw9200, a molecular weight distribution index PDI of 1.5, lower molecular weight and wider molecular weight distribution, which is beneficial to the movement of the addition type liquid silicone rubber, and further improves the tackifying effect.
A preparation method of the silicone rubber material comprises the following steps:
adding 80 parts by mass of vinyl silicone oil (with the vinyl content of 0.1 mol%), 40 parts by mass of fumed silica and 7 parts by mass of hexamethyldisilazane into a vacuum kneader, stirring for 4 hours at 30 ℃, heating to 170 ℃, mixing for 1 hour, vacuumizing and mixing for 2 hours, cooling to 130 ℃, adding 20 parts by mass of vinyl silicone oil (with the vinyl content of 0.25 mol%) and 2 parts by mass of high vinyl silicone oil (with the vinyl content of 5 mol%), continuing stirring for 1 hour, cooling, grinding by using a three-roll grinder, adding 2 parts by mass of hydrogen-containing silicone oil (with the hydrogen content of 0.75 wt%), 0.05 parts by mass of 1-ethynyl-1-cyclohexanol, 4 parts by mass of organosilicon adhesion promoter and 1.16 parts by mass of Karstedt platinum catalyst (with the platinum content of 2000ppm), stirring at 25 ℃, defoaming again at the vacuum degree of 0.01MPa for 10 minutes, curing for 1 hour at 120 ℃, thus obtaining the silicon rubber material.
Example 2:
an organosilicon adhesion promoter, its preparation method includes the following steps:
1) adding 10g of tetrahydrofuran, 1.34g of 2-allyl phenol (containing 0.01mol of C ═ C) and 1.34g of hydrogen-containing MQ silicon resin (containing 0.02mol of Si-H) with the hydrogen content of 1.5 wt% into a 100mL reaction kettle at 40 ℃, stirring for 40min, slowly adding 0.06g of tetrahydrofuran solution of chloroplatinic acid with the platinum concentration of 4000ppm into the reaction kettle, heating to 60 ℃ after the addition is finished, and reacting for 3H to obtain polysiloxane containing phenolic hydroxyl;
2) mixing and stirring 10g of tetrahydrofuran, 0.09g of tetrahydrofuran solution of chloroplatinic acid with platinum concentration of 4000ppm and 12.10g of tripropylene glycol diacrylate (containing 0.04mol of C ═ C) at 25 ℃ for 30min to prepare a mixed solution, slowly dripping the mixed solution into the polysiloxane containing phenolic hydroxyl groups in the step 1) at 60 ℃, completing the addition for 3h, continuing to react for 6h, adding activated carbon for adsorption for 10h, filtering, and distilling under reduced pressure to obtain the organic silicon adhesion promoter.
A preparation method of the silicone rubber material comprises the following steps:
adding 100 parts by mass of vinyl silicone oil (with the vinyl content of 0.5 mol%), 50 parts by mass of fumed silica and 15 parts by mass of hexamethyldisilazane into a vacuum kneader, stirring for 5h at 35 ℃, heating to 180 ℃, mixing for 2h, vacuumizing and mixing for 4h, cooling to 150 ℃, adding 20 parts by mass of vinyl silicone oil (with the vinyl content of 0.25 mol%) and 5 parts by mass of high vinyl silicone oil (with the vinyl content of 10 mol%), continuing stirring for 2h, cooling, grinding by using a three-roll grinder, adding 5 parts by mass of hydrogen-containing silicone oil (with the hydrogen content of 0.6 wt%), 0.06 part by mass of 1-ethynyl-1-cyclohexanol, 5 parts by mass of organosilicon adhesion promoter and 4 parts by mass of Karstedt platinum catalyst (with the platinum content of 2000ppm), stirring at 35 ℃, defoaming for 10min at the vacuum degree of 0.1MPa, and curing for 3h at 150 ℃, thus obtaining the silicon rubber material.
Example 3:
an organosilicon adhesion promoter, its preparation method includes the following steps:
1) adding 10g of ethanol, 1.33g of 3', 5-di-2-propenyl-1, 1' -biphenyl-2, 4' -diol (containing 0.01mol of C ═ C) and 3.03g of hydrogen-containing silicone oil (containing 0.03mol of Si-H) with the hydrogen content of 1.0 wt% into a 100mL reaction kettle at 10 ℃, stirring for 30min, slowly adding 0.05g of Karstedt platinum catalyst with the platinum concentration of 3000ppm into the reaction kettle, heating to 50 ℃ after the addition is finished, and reacting for 2H to obtain polysiloxane containing phenolic hydroxyl;
2) mixing and stirring 10g of ethanol, 0.04g of Karstedt platinum catalyst with platinum concentration of 3000ppm and 2.26g of 1, 6-hexanediol diacrylate (containing 0.02mol of C ═ C) at 40 ℃ for 40min to prepare a mixed solution, slowly dropwise adding the mixed solution into the polysiloxane containing phenolic hydroxyl groups in the step 1) at 75 ℃ for 2h, continuing to react for 3h, adding activated carbon for adsorbing for 6h, filtering, and distilling under reduced pressure to obtain the organic silicon adhesion promoter.
A preparation method of the silicone rubber material comprises the following steps:
adding 90 parts by mass of vinyl silicone oil (with the vinyl content of 0.25mol percent), 40 parts by mass of fumed silica and 10 parts by mass of hexamethyldisilazane into a vacuum kneader, stirring for 4 hours at 30 ℃, heating to 170 ℃, mixing for 1.5 hours, vacuumizing and mixing for 2 hours, cooling to 130 ℃, adding 20 parts by mass of vinyl silicone oil (with the vinyl content of 0.25mol percent) and 3 parts by mass of high vinyl silicone oil (with the vinyl content of 7.5mol percent), continuing stirring for 1 hour, cooling, grinding by using a three-roll grinder, adding 3 parts by mass of hydrogen-containing silicone oil (with the hydrogen content of 0.8wt percent), 0.01 part by mass of 1-ethynyl-1-cyclohexanol, 3 parts by mass of organic silicon adhesion promoter and 0.5 part by mass of Karstedt platinum catalyst (with the platinum content of 2000ppm), stirring at 25 ℃, defoaming for 10 minutes under the vacuum degree of 0.01MPa, and curing for 2 hours at 125 ℃, thus obtaining the silicon rubber material.
Example 4:
an organosilicon adhesion promoter, its preparation method includes the following steps:
1) adding 10g of acetone, 1.64g of 2-methoxy- (1-propylene) phenol (containing 0.01mol of C ═ C) and 1.89g of hydrogen-containing MQ silicon resin (containing 0.015mol of Si-H) with the hydrogen content of 0.80 wt% into a 100mL reaction kettle at 30 ℃, stirring for 30min, slowly adding 0.03g of Karstedt platinum catalyst with the platinum concentration of 2000ppm into the reaction kettle, heating to 50 ℃ after the addition is finished, and reacting for 2H to obtain polysiloxane containing phenolic hydroxyl;
2) mixing and stirring 10g of acetone, 0.04g of Karstedt platinum catalyst with platinum concentration of 2000ppm and 1.06g of neopentyl glycol diacrylate (containing 0.01mol of C ═ C) at 25 ℃ for 20min to prepare a mixed solution, slowly dropwise adding the mixed solution into the polysiloxane containing phenolic hydroxyl groups in the step 1) at 60 ℃ for 2h, continuing to react for 4h, adding activated carbon for adsorption for 5h, filtering, and distilling under reduced pressure to obtain the organic silicon adhesion promoter.
A preparation method of the silicone rubber material comprises the following steps:
adding 90 parts by mass of vinyl silicone oil (with the vinyl content of 0.5mol percent), 35 parts by mass of fumed silica and 12 parts by mass of hexamethyldisilazane into a vacuum kneader, stirring for 4 hours at 30 ℃, heating to 170 ℃, mixing for 1.5 hours, vacuumizing and mixing for 2 hours, cooling to 140 ℃, adding 15 parts by mass of vinyl silicone oil (with the vinyl content of 0.25mol percent) and 3 parts by mass of high vinyl silicone oil (with the vinyl content of 8.5mol percent), continuing stirring for 2 hours, cooling, grinding by using a three-roll grinder, adding 3 parts by mass of hydrogen-containing silicone oil (with the hydrogen content of 1wt percent), 0.04 part by mass of 1-ethynyl-1-cyclohexanol, 4 parts by mass of organosilicon adhesion promoter and 1.07 part by mass of Karstedt platinum catalyst (with the platinum content of 2000ppm), stirring at 25 ℃, defoaming for 10 minutes under the vacuum degree of 0.01MPa, and curing for 2 hours at 130 ℃, thus obtaining the silicon rubber material.
Example 5:
an organosilicon adhesion promoter, its preparation method includes the following steps:
1) adding 10g of isopropanol, 1.64g of eugenol (containing 0.01mol of C ═ C) and 3.78g of hydrogen-containing silicone oil (containing 0.03mol of Si-H) with the hydrogen content of 0.80 wt% into a 100mL reaction kettle at 25 ℃, stirring for 30min, slowly adding 0.03g of Karstedt platinum catalyst with the platinum concentration of 2000ppm into the reaction kettle, heating to 80 ℃ after the addition is finished, and reacting for 2H to obtain polysiloxane containing phenolic hydroxyl;
2) mixing 10g of isopropanol, 0.03g of Karstedt platinum catalyst with platinum concentration of 2000ppm and 1.07g of diethylene glycol diacrylate (containing 0.01mol of C ═ C) at 25 ℃ and stirring for 30min to prepare a mixed solution, slowly dropwise adding the mixed solution into the polysiloxane containing phenolic hydroxyl groups in the step 1) at 60 ℃ for 1h, continuing to react for 4h, adding activated carbon for adsorption for 5h, filtering, and distilling under reduced pressure to obtain the organic silicon adhesion promoter.
A preparation method of the silicone rubber material comprises the following steps:
adding 80 parts by mass of vinyl silicone oil (the vinyl content is 0.3 mol%), 40 parts by mass of fumed silica and 8 parts by mass of hexamethyldisilazane into a vacuum kneader, stirring for 4 hours at 30 ℃, heating to 170 ℃, mixing for 2 hours, vacuumizing and mixing for 2 hours, cooling to 130 ℃, adding 20 parts by mass of vinyl silicone oil (the vinyl content is 0.25 mol%) and 2 parts by mass of high vinyl silicone oil (the vinyl content is 9 mol%), continuing stirring for 1.5 hours, cooling, grinding by using a three-roll grinder, adding 3 parts by mass of hydrogen-containing silicone oil (the hydrogen content is 1.2 wt%), 0.04 parts by mass of 1-ethynyl-1-cyclohexanol, 4 parts by mass of organosilicon adhesion promoter and 0.81 part by mass of Karstedt platinum catalyst (the platinum content is 2000ppm), stirring at 25 ℃, defoaming for 10 minutes under the vacuum degree of 0.01MPa, and curing for 1 hour at 120 ℃, thus obtaining the silicon rubber material.
Example 6:
an organosilicon adhesion promoter, its preparation method includes the following steps:
1) adding 10g of xylene, 1.20g of 4-vinylphenol (containing 0.01mol of C ═ C) and 8.06g of hydrogen-containing silicone oil (containing 0.04mol of Si-H) with the hydrogen content of 0.5 wt% into a 100mL reaction kettle at 10 ℃, stirring for 20min, slowly adding 0.02g of an isopropanol solution of chloroplatinic acid with the platinum concentration of 1000ppm into the reaction kettle, heating to 100 ℃ after the addition is finished, and reacting for 1H to obtain polysiloxane containing phenolic hydroxyl groups;
2) 10g of toluene, 0.01g of Karstedt platinum catalyst with platinum concentration of 1000ppm and 1.21g of dipropylene glycol diacrylate (containing 0.01mol of C ═ C) are mixed and stirred for 30min at 25 ℃ to prepare a mixed solution, the mixed solution is slowly and dropwise added into the polysiloxane containing phenolic hydroxyl groups in the step 1) at 120 ℃ for 1h, the reaction is continued for 1h, then activated carbon is added for adsorption for 2h, and the mixture is filtered and distilled under reduced pressure to obtain the organic silicon adhesion promoter.
A preparation method of the silicone rubber material comprises the following steps:
adding 80 parts by mass of vinyl silicone oil (with the vinyl content of 0.25 mol%), 30 parts by mass of fumed silica and 5 parts by mass of hexamethyldisilazane into a vacuum kneader, stirring for 3 hours at 25 ℃, heating to 160 ℃, mixing for 1 hour, vacuumizing and mixing for 1 hour, cooling to 120 ℃, adding 10 parts by mass of vinyl silicone oil (with the vinyl content of 0.25 mol%) and 1 part by mass of high vinyl silicone oil (with the vinyl content of 6 mol%), continuing stirring for 1 hour, cooling, grinding by using a three-roll grinder, adding 1 part by mass of hydrogen-containing silicone oil (with the hydrogen content of 0.75 wt%), 0.003 part by mass of 1-ethynyl-1-cyclohexanol, 1 part by mass of organosilicon adhesion promoter and 0.1 part by mass of Karstedt platinum catalyst (with the platinum content of 2000ppm), stirring at 25 ℃, defoaming again at the vacuum degree of 0.01MPa for 10 minutes, curing for 1 hour at 100 ℃, thus obtaining the silicon rubber material.
Example 7:
an organosilicon adhesion promoter, its preparation method includes the following steps:
1) adding 10g of isopropanol, 1.64g of eugenol (containing 0.01mol of C ═ C) and 3.78g of hydrogen-containing silicone oil (containing 0.03mol of Si-H) with the hydrogen content of 0.80 wt% into a 100mL reaction kettle at 25 ℃, stirring for 30min, slowly adding 0.01g of Karstedt platinum catalyst with the platinum concentration of 2000ppm into the reaction kettle, heating to 80 ℃ after the addition is finished, and reacting for 3H to obtain polysiloxane containing phenolic hydroxyl;
2) 10g of isopropanol, 0.02g of Karstedt platinum catalyst with platinum concentration of 2000ppm and 3.01g of tripropylene glycol diacrylate (containing 0.02mol of C ═ C) are mixed and stirred for 40min at 25 ℃ to prepare a mixed solution, the mixed solution is slowly dripped into the polysiloxane containing phenolic hydroxyl groups in the step 1) at 60 ℃ for 1h, the reaction is continued for 3h, activated carbon is added for adsorption for 5h, and the mixture is filtered and distilled under reduced pressure to obtain the organic silicon adhesion promoter.
A preparation method of the silicone rubber material comprises the following steps:
adding 80 parts by mass of vinyl silicone oil (with the vinyl content of 0.25 mol%), 40 parts by mass of fumed silica and 6 parts by mass of hexamethyldisilazane into a vacuum kneader, stirring for 4 hours at 30 ℃, heating to 170 ℃, mixing for 1 hour, vacuumizing and mixing for 2 hours, cooling to 130 ℃, adding 20 parts by mass of vinyl silicone oil (with the vinyl content of 0.25 mol%) and 2 parts by mass of high vinyl silicone oil (with the vinyl content of 8.7 mol%), continuing to stir for 1 hour, cooling, grinding by using a three-roll grinder, adding 1 part by mass of hydrogen-containing silicone oil (with the hydrogen content of 0.75 wt%), 0.04 part by mass of 1-ethynyl-1-cyclohexanol, 4 parts by mass of organosilicon adhesion promoter and 1.14 parts by mass of Karstedt platinum catalyst (with the platinum content of 2000ppm), stirring at 25 ℃, defoaming at the vacuum degree of 0.01MPa for 20 minutes, and curing for 1 hour at 120 ℃, thus obtaining the silicon rubber material.
Example 8:
an organosilicon adhesion promoter, its preparation method includes the following steps:
1) adding 10g of isopropanol, 1.64g of eugenol (containing 0.01mol of C ═ C) and 3.78g of hydrogen-containing silicone oil (containing 0.03mol of Si-H) with the hydrogen content of 0.80 wt% into a 100mL reaction kettle at 25 ℃, stirring for 30min, slowly adding 0.01g of Karstedt platinum catalyst with the platinum concentration of 2000ppm into the reaction kettle, heating to 70 ℃ after the addition is finished, and reacting for 3H to obtain polysiloxane containing phenolic hydroxyl;
2) mixing and stirring 10g of isopropanol, 0.02g of Karstedt platinum catalyst with platinum concentration of 2000ppm and 3.01g of tripropylene glycol diacrylate (containing 0.02mol of C ═ C) at 20 ℃ for 20min to prepare a mixed solution, slowly dropwise adding the mixed solution into the polysiloxane containing phenolic hydroxyl groups in the step 1) at 70 ℃ for 1h, continuing to react for 6h, adding activated carbon for adsorption for 10h, filtering, and distilling under reduced pressure to obtain the organic silicon adhesion promoter.
A preparation method of the silicone rubber material comprises the following steps:
adding 80 parts by mass of vinyl silicone oil (with the vinyl content of 0.4 mol%), 40 parts by mass of fumed silica and 6 parts by mass of hexamethyldisilazane into a vacuum kneader, stirring for 4 hours at 30 ℃, heating to 170 ℃, mixing for 1 hour, vacuumizing and mixing for 2 hours, cooling to 130 ℃, adding 20 parts by mass of vinyl silicone oil (with the vinyl content of 0.25 mol%) and 2 parts by mass of high vinyl silicone oil (with the vinyl content of 9 mol%), continuing stirring for 1 hour, cooling, grinding by using a three-roll grinder, adding 1 part by mass of hydrogen-containing silicone oil (with the hydrogen content of 0.75 wt%), 0.04 part by mass of 1-ethynyl-1-cyclohexanol, 2 parts by mass of organosilicon adhesion promoter and 3.02 parts by mass of Karstedt platinum catalyst (with the platinum content of 2000ppm), stirring at 25 ℃, defoaming again at 20min under the vacuum degree of 0.01MPa, curing for 1 hour at 120 ℃, thus obtaining the silicon rubber material.
Comparative example 1:
a preparation method of the silicone rubber material comprises the following steps:
adding 80 parts by mass of vinyl silicone oil (the vinyl content is 0.25mol percent), 40 parts by mass of fumed silica and 6 parts by mass of hexamethyldisilazane into a vacuum kneader, stirring for 4h at 30 ℃, heating to 170 ℃, mixing for 1h, vacuumizing and mixing for 2h, cooling to 130 ℃, adding 20 parts by mass of vinyl silicone oil (the vinyl content is 0.25 mol%) and 2 parts by mass of high vinyl silicone oil (the vinyl content is 8.7 mol%), continuing stirring for 1h, cooling, grinding by using a three-roll grinder, adding 1 part by mass of hydrogen-containing silicone oil (the hydrogen content is 0.75 wt%), 0.04 part by mass of 1-ethynyl-1-cyclohexanol and 1.12 parts by mass of Karstedt platinum catalyst (the platinum content is 2000ppm), stirring at 25 ℃, defoaming for 20min under the vacuum degree of 0.01MPa, and curing for 1h at 120 ℃ to obtain the silicone rubber material.
Comparative example 2:
the preparation method of the organic silicon adhesion promoter containing phenolic hydroxyl comprises the following steps:
adding 10g of isopropanol, 1.64g of eugenol (containing 0.01mol of C ═ C) and 3.78g of hydrogen-containing silicone oil (containing 0.03mol of Si-H) with the hydrogen content of 0.80 wt% into a 100mL reaction kettle at 25 ℃, stirring for 10min, slowly adding 0.02g of an isopropanol solution of chloroplatinic acid with the platinum concentration of 2000ppm into the reaction kettle, heating to 80 ℃ after adding, reacting for 3H, adding activated carbon for adsorption for 5H, filtering, and distilling under reduced pressure to obtain the organic silicon adhesion promoter containing phenolic hydroxyl groups.
A preparation method of the silicone rubber material comprises the following steps:
adding 80 parts by mass of vinyl silicone oil (with the vinyl content of 0.25 mol%), 40 parts by mass of fumed silica and 6 parts by mass of hexamethyldisilazane into a vacuum kneader, stirring for 4 hours at 30 ℃, heating to 170 ℃, mixing for 1 hour, vacuumizing and mixing for 2 hours, cooling to 130 ℃, adding 20 parts by mass of vinyl silicone oil (with the vinyl content of 0.25 mol%) and 2 parts by mass of high vinyl silicone oil (with the vinyl content of 8.7 mol%), continuing to stir for 1 hour, cooling, grinding by using a three-roll grinder, adding 1 part by mass of hydrogen-containing silicone oil (with the hydrogen content of 0.75 wt%), 0.04 part by mass of 1-ethynyl-1-cyclohexanol, 4 parts by mass of phenolic hydroxyl-containing silicone adhesion promoter and 0.8 part by mass of Karstedt platinum catalyst (with the platinum content of 2000ppm), stirring at 25 ℃, defoaming for 20 minutes under the vacuum degree of 0.01MPa, and curing for 1h at 120 ℃ to obtain the silicon rubber material.
Comparative example 3:
an organosilicon adhesion promoter containing acrylate group is prepared by the following steps:
adding 10g of isopropanol, 1.51g of tripropylene glycol diacrylate (containing 0.01mol of C ═ C) and 0.95g of hydrogen-containing silicone oil (containing 0.0075mol of Si-H) with the hydrogen content of 0.80 wt% into a 100mL reaction kettle at 50 ℃, stirring for 30min, slowly adding 0.01g of an isopropanol solution of chloroplatinic acid with the platinum concentration of 2000ppm into the reaction kettle, heating to 80 ℃ after the addition is finished, reacting for 3H, adding activated carbon for adsorption for 5H, filtering, and distilling under reduced pressure to obtain the organic silicon bonding accelerator containing acrylate groups.
A preparation method of the silicone rubber material comprises the following steps:
adding 80 parts by mass of vinyl silicone oil (with the vinyl content of 0.25 mol%), 40 parts by mass of fumed silica and 6 parts by mass of hexamethyldisilazane into a vacuum kneader, stirring for 4 hours at 30 ℃, heating to 170 ℃, mixing for 1 hour, vacuumizing and mixing for 2 hours, cooling to 130 ℃, adding 20 parts by mass of vinyl silicone oil (with the vinyl content of 0.25 mol%) and 2 parts by mass of high vinyl silicone oil (with the vinyl content of 8.7 mol%), continuing to stir for 1 hour, cooling, grinding by using a three-roll grinder, adding 2 parts by mass of hydrogen-containing silicone oil (with the hydrogen content of 0.75 wt%), 0.04 parts by mass of 1-ethynyl-1-cyclohexanol, 4 parts by mass of acrylate-group-containing silicone adhesion promoter and 0.8 part by mass of Karstedt platinum catalyst (with the platinum content of 2000ppm), stirring at 25 ℃, defoaming for 20 minutes under the vacuum degree of 0.01MPa, and curing for 1h at 120 ℃ to obtain the silicon rubber material.
And (3) performance testing:
1) the results of the adhesion performance test of the silicone rubber materials of examples 1 to 8 and comparative examples 1 to 3 with different base materials are shown in the following table:
TABLE 1 test results of adhesion Properties of Silicone rubber materials to various substrates
Figure BDA0002936126410000111
Figure BDA0002936126410000121
As can be seen from Table 1: the silicone rubber material without the addition of the adhesion promoter (comparative example 1) has poor adhesion performance, while the silicone rubber materials of examples 1-8 and 5 base materials have excellent adhesion strength, i.e., the silicone adhesion promoter of the present invention can significantly improve the adhesion performance of addition type liquid silicone rubber and base materials such as PC, PA, etc., and the adhesion performance is superior to the prior art, for example: the adhesive strength to the PC substrate in example 8 reached 3.5MPa, which is 600% higher than that of comparative example 1, because: the phenol compound containing carbon-carbon double bonds and the acrylate compound are successfully grafted to the hydrogen-containing polysiloxane through hydrosilylation reaction, the hydrogen-containing polysiloxane and the liquid silicone rubber both contain Si-O-Si main chains, unreacted carbon-carbon double bonds or silicon hydrogen bonds of the hydrogen-containing polysiloxane in the raw materials can also participate in the vulcanization process of ALSR to form a cross-linked network, so that the adhesion promoter has good compatibility with the silicone rubber, polar groups such as acrylate groups and phenolic hydroxyl groups in the molecules of the adhesion promoter can form mutual effects such as hydrogen bonds with the surface of a base material, and a benzene ring structure in the adhesion promoter can also perform pi-pi conjugation with the surface of the base material, so that the adhesion promoter is like a bridge to connect the silicone rubber and the base material, and has an adhesion effect.
2) The results of the adhesion performance test (heat resistance test) of the silicone rubber materials of examples 1 to 8 and comparative examples 1 to 3 with the PC base material at different environmental temperatures are shown in the following table:
TABLE 2 test results of adhesion properties of silicone rubber materials and PC base materials at different environmental temperatures
Figure BDA0002936126410000122
Figure BDA0002936126410000131
As can be seen from Table 2: comparative example 1 the ALSR without addition of the adhesion promoter has poor adhesion property, the adhesion strength with the PC substrate rapidly decreases with increasing temperature, the adhesion strength is lost after 75 ℃, the adhesion strength of the ALSR in examples 1 to 8 decreases more slowly, and the adhesion strength of example 8 to the PC substrate at 75 ℃ is 2.1MPa and even 0.7MPa at 150 ℃, i.e. the ALSR of the present invention can be used under high temperature conditions, because: on one hand, the silicon-hydrogen bond in the organic silicon bonding promoter can generate silicon-hydrogen addition reaction with the carbon-carbon double bond of the ALSR, and the silicon-hydrogen bond is used as a chemical crosslinking point to promote further crosslinking of the ALSR, so that cohesive energy of a bonding glue layer is improved; on the other hand, phenolic hydroxyl in the organosilicon adhesion promoter is easily oxidized into quinonyl at high temperature, and the quinonyl can perform Michael addition reaction and Schiff base reaction with various nucleophiles (such as amide, amino, mercaptan and the like), so that the bond energy of the formed chemical covalent bond is stronger than that of a hydrogen bond and other weak interaction, the interface state between the adhesive layer and the bonded substrate can be improved, and the adhesive layer still has good adhesion performance when being heated.
3) The results of the adhesion performance test (moisture resistance test) of the silicone rubber materials of examples 1 to 8 and comparative examples 1 to 3 with the PC base material at different soaking times are shown in the following table:
TABLE 3 bonding Performance test results of silicone rubber materials and PC base materials under different soaking times
Figure BDA0002936126410000132
Figure BDA0002936126410000141
As can be seen from Table 3: the organosilicon adhesion promoter can endow ALSR with good water resistance. The ALSR and the PC substrate in the comparative example 1 have low tensile shear strength and small interaction force, water molecules are easily adsorbed to the surface of the substrate and permeate into the bonding interface of the substrate and cause obvious reduction of the bonding strength, and after the organosilicon adhesion promoter disclosed by the invention is added, the interaction force of the ALSR and the PC substrate is strong, the bonding adsorption force is improved, and the water molecules are more difficult to permeate into the bonding interface of the substrate and the PC substrate, so that the bonding strength of a sample is only slightly reduced or unchanged after the sample is soaked in water for 8 hours, and the sample has excellent humidity resistance.
4) The mechanical property test results of the silicone rubber materials of examples 1 to 8 and comparative examples 1 to 3 are shown in the following table:
TABLE 4 mechanical Properties of Silicone rubber materials
Figure BDA0002936126410000142
As can be seen from Table 4: the organic silicon adhesion promoter of the invention also improves the mechanical property of ALSR to a certain extent, because: on one hand, carbon-carbon double bonds or silicon-hydrogen bonds contained in the adhesion promoter can participate in the vulcanization process of the ALSR to form a crosslinking network, so that the crosslinking density is improved; on the other hand, the adhesion promoter contains rich phenolic hydroxyl groups, can perform condensation reaction with active hydroxyl groups on the surface of the filler fumed silica or silanol groups of a silicone rubber molecular chain, and can also form hydrogen bond action with oxygen atoms in a silicone rubber molecular chain Si-O-Si main chain, so that the interaction between fillers such as fumed silica and the like and ALSR is enhanced, and the mechanical property of the ALSR is improved.
The test method comprises the following steps:
1) adhesion performance (adhesive tensile shear strength) test: according to the test of GB/T13936-2014 standard, the length of the adhesive is (12.5 +/-0.5) mm, the width is (25.0 +/-0.2) mm, the thickness is (2.0 +/-0.1) mm, the length of the bonded substrate is (100.0 +/-0.2) mm, the width is (25.0 +/-0.2) mm, and the thickness is (2.0 +/-0.1) mm;
2) and (3) testing heat resistance: taking a PC substrate as an example, placing a standard sample for bonding performance test in a WD-10kET microcomputer control electronic type universal tester produced by Guangzhou wide material testing instrument limited, keeping the temperature for 15min under different temperature conditions, and performing tensile test according to the GB/T13936-;
3) moisture resistance test: taking a PC substrate as an example, placing a standard sample for bonding performance test in distilled water at 25 ℃ for soaking for different times, wiping water on the surface of the sample with filter paper, and then placing for 24 hours at room temperature to perform bonding performance test;
4) and (3) testing mechanical properties: respectively testing the tensile strength, the elongation at break and the tearing strength of the silicon rubber sample on a tensile testing machine according to GB/T528-; and (4) according to the GB/T531.1-2008 standard, a Shore A type durometer is adopted to carry out hardness test on the silicon rubber sample.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (9)

1. An organosilicon adhesion promoter, characterized in that: the organic silicon adhesion promoter is obtained by carrying out hydrosilylation reaction on polysiloxane containing phenolic hydroxyl and acrylate compounds; the polysiloxane containing phenolic hydroxyl is obtained by carrying out hydrosilylation reaction on a phenol compound containing carbon-carbon double bonds and hydrogen-containing polysiloxane; the acrylate compound is at least one of dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate and diethylene glycol diacrylate.
2. The silicone adhesion promoter according to claim 1, wherein: the phenol compound containing carbon-carbon double bonds is at least one of 4-vinylphenol, 2-allylphenol, 3', 5-di-2-propenyl-1, 1' -biphenyl-2, 4' -diphenol, eugenol and 2-methoxy- (1-propylene) phenol.
3. The silicone adhesion promoter according to claim 1, wherein: the hydrogen-containing polysiloxane is at least one of hydrogen-containing silicone oil and hydrogen-containing MQ silicone resin.
4. The silicone adhesion promoter according to claim 1, wherein: the molar ratio of the Si-H group in the polysiloxane containing the phenolic hydroxyl group to the C-C group in the acrylate compound is 0.25: 1-3: 1.
5. The silicone adhesion promoter according to claim 1, wherein: the molar ratio of the C ═ C groups in the carbon-carbon double bond-containing phenol compound to the Si-H groups in the hydrogenpolysiloxane is 1:1 to 1: 4.
6. The method for preparing the silicone adhesion promoter according to any one of claims 1 to 5, characterized by comprising the steps of:
1) dispersing a carbon-carbon double bond-containing phenolic compound and hydrogen-containing polysiloxane in a solvent, adding a platinum catalyst, and carrying out hydrosilylation reaction to obtain polysiloxane containing phenolic hydroxyl;
2) dispersing an acrylate compound and a platinum catalyst in a solvent, adding into the polysiloxane containing phenolic hydroxyl in the step 1), and carrying out hydrosilylation reaction to obtain the organic silicon adhesion promoter.
7. The method for producing the silicone adhesion promoter according to claim 6, characterized in that: the platinum catalyst is at least one of chloroplatinic acid and Karstedt platinum catalyst.
8. The method for producing the silicone adhesion promoter according to claim 6 or 7, characterized in that: the solvent is at least one of toluene, xylene, tetrahydrofuran, methanol, ethanol, isopropanol, acetonitrile, cyclohexane, acetone and 1, 4-dioxane.
9. Use of the silicone adhesion promoter of claim 1 in addition to liquid silicone rubber.
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CN103351467A (en) * 2013-07-18 2013-10-16 东莞市贝特利新材料有限公司 Addition type liquid silicone rubber bonding accelerant and preparation method and application thereof
CN106715528A (en) * 2014-09-05 2017-05-24 赢创德固赛有限公司 Process for the preparation of eugenol polyethers that can be hydrosilylated and eugenol polyethersiloxanes and use thereof

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