CN112251165B - Special prime coat-free platinum vulcanizing agent for combination of metal substrate and silica gel and preparation method thereof - Google Patents

Special prime coat-free platinum vulcanizing agent for combination of metal substrate and silica gel and preparation method thereof Download PDF

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CN112251165B
CN112251165B CN202011160402.XA CN202011160402A CN112251165B CN 112251165 B CN112251165 B CN 112251165B CN 202011160402 A CN202011160402 A CN 202011160402A CN 112251165 B CN112251165 B CN 112251165B
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agent
parts
silica gel
combination
vulcanizing agent
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CN112251165A (en
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段定敏
黄高元
段定超
梅永志
刘潜
李其悦
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Dongguan Zhongzhan Silicone Materials Co ltd
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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
    • C09J11/08—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
    • 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
    • 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
    • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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 relates to the field of platinum vulcanizing agents, and discloses a special primer-free platinum vulcanizing agent for combination of a metal substrate and silica gel and a preparation method thereof. The platinum vulcanizing agent comprises an agent A and an agent B, wherein the agent A comprises 50-60 parts by weight of methyl vinyl silicone rubber, 40-50 parts by weight of platinum catalyst and 5-15 parts by weight of hydrophobic white carbon black; the agent B comprises 65-75 parts of methyl vinyl silicone rubber, 45-55 parts of vinyl hydrogen-containing silicone oil, 40-50 parts of organic silicon modified acrylate metal adhesive, 5-15 parts of hydrophobic white carbon black and 0.5-3 parts of alkynol compound inhibitor. The platinum vulcanizing agent provided by the invention is added with the organic silicon modified acrylate metal adhesive, so that the platinum vulcanizing agent can be better suitable for the combination of a metal base material and silica gel, and the binding force of the metal base material and the silica gel is improved.

Description

Special prime coat-free platinum vulcanizing agent for combination of metal substrate and silica gel and preparation method thereof
Technical Field
The invention relates to a platinum vulcanizing agent, in particular to a special primer-free platinum vulcanizing agent for combination of a metal substrate and silica gel and preparation thereof, belonging to the technical field of polymers.
Background
The liquid silica gel has excellent transparency, tear strength, rebound resilience, yellowing resistance, heat stability, water resistance, good air permeability, heat aging resistance and weather resistance, moderate viscosity, convenient operation and high product transparency, can see whether the casting material in the mold has the defects of air bubbles and the like, has the linear shrinkage rate of less than or equal to 0.1 percent, and can reproduce the product with precise size. Particularly, the bi-component addition type vulcanized silicone rubber is a type of silicone rubber which is vigorously developed at home and abroad up to now.
In practical use, a metal substrate and silica gel are usually combined with each other. Because the metal base material is not suitable to be directly combined with the liquid silica gel and is easy to degum, and the like, in the specific operation, the metal base material and the silica gel are combined by brushing the treating agent firstly and then baking the base material, however, in the baking process, the volatilization of organic solvents such as toluene and the like in the traditional treating agent can seriously damage the body of staff and seriously pollute the environment. The conventional adhesive for silicon rubber and metal viscose generally comprises organic silicon polymer, defoaming agent, leveling agent and other auxiliary agents and curing agent. However, this silicone resin adhesive has a problem that the adhesive strength decreases after long-term use under high-temperature conditions.
The vulcanization mechanism of the two-component addition type vulcanized silicone rubber is completed based on the addition reaction of vinyl (or propenyl) on the crude rubber end group of the organosilicon methyl vinyl silicone rubber and hydrosilation on the molecule of a cross-linking agent. In the reaction process, the platinum vulcanizing agent is an important catalyst, and the principle is that under the condition that the catalyst Pt exists, the hydrogen-containing silicone oil and vinyl double bonds are subjected to hydrosilylation reaction, so that the aim of crosslinking vulcanization is fulfilled. Since the hydrosilylation reaction readily occurs in the presence of a Pt catalyst.
In this reaction, no by-products are evolved. Because low molecular substances are not released in the crosslinking process, the addition type room temperature vulcanized silicone rubber does not shrink in the vulcanization process. The vulcanized rubber has the advantages of no toxicity, high mechanical strength, excellent hydrolytic stability, good low compression deformation, low combustibility, deep vulcanization, excellent electrical property and chemical stability, water resistance, ozone resistance, weather aging resistance, simple usage and strong process applicability, thus being widely used as encapsulating and molding materials. After various electronic and electric elements are coated and encapsulated with room temperature vulcanized silicone rubber, the coating can play a role in protection such as moisture prevention, corrosion prevention, shock prevention and the like.
At present, there are few reports of platinum vulcanizing agents for silica gel in combination with other materials. Patent CN104927363A discloses a novel platinum vulcanizing agent and a preparation process thereof. The platinum vulcanizing agent comprises a component A and a component B which are respectively added in use, wherein the component A is a mixture of methyl vinyl silicone rubber and a tetramethyl divinyl disiloxane platinum complex; the component B is a mixture of methyl hydrogen polysiloxane, fumed silica and an inhibitor. Although the platinum vulcanizing agent can achieve the purpose of crosslinking vulcanization, the problems that a metal base material is not suitable to be directly combined with liquid silica gel and is easy to degum and the like cannot be solved; namely, the surface of the joint is still required to be pretreated by brushing the treating agent so as to improve the bonding strength of the metal base material and the silica gel.
Disclosure of Invention
Aiming at the defects of the prior art, the invention mainly aims to provide a special bottom-coating-free platinum vulcanizing agent for combining a metal base material and silica gel.
The invention also aims to provide a preparation method of the primer-free special platinum vulcanizing agent for combining the metal base material and the silica gel.
The purpose of the invention is realized by the following technical scheme:
a platinum vulcanizing agent special for primer-free combination of a metal base material and silica gel comprises an agent A and an agent B, and each dosage form comprises the following components in parts by weight:
an agent A: 50-60 parts of methyl vinyl silicone rubber (crude rubber), 40-50 parts of platinum catalyst and 5-15 parts of hydrophobic white carbon black;
and (2) agent B: 65-75 parts of methyl vinyl silicone rubber (crude rubber), 45-55 parts of vinyl hydrogen-containing silicone oil, 40-50 parts of organic silicon modified acrylate metal adhesive, 5-15 parts of hydrophobic white carbon black and 0.5-3 parts of alkynol compound inhibitor;
the organic silicon modified acrylate metal adhesive is prepared by the following method:
mixing double-end hydroxypropyl silicone oil and a polyisocyanate compound, heating to 80-120 ℃, stirring for reaction, then cooling to 50-70 ℃, adding hydroxyethyl methacrylate, and continuing to react to obtain an organic silicon modified acrylate prepolymer; then carrying out polymerization reaction on the acrylate monomer and an acrylate monomer under the condition of a photoinitiator to obtain the organic silicon modified acrylate metal adhesive.
In the invention, the molecular weight of the methyl vinyl silicone rubber in the agent A and the agent B is preferably 50-180 ten thousand.
Preferably, the platinum catalyst in the agent A is selected from 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) (Karstedt's catalyst) or chloroplatinic acid, more preferably 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0).
Preferably, the specific surface area of the hydrophobic white carbon black in the agent A and the agent B is 250-400m2/g。
Preferably, the vinyl hydrogen-containing silicone oil in the agent B has a vinyl content of 0.1-10% and a hydrogen content of 0.15-1.6%. Vinyl content and hydrogen content are generally referred to in the art as mass fractions.
Preferably, the viscosity of the double-end hydroxypropyl silicone oil is 20-200 cst, and the molecular weight is 500-10000. Too high a molecular weight or viscosity is detrimental to the formation of the silicone modified acrylate prepolymer.
Preferably, the polyisocyanate compound is one or a combination of two or more selected from the group consisting of diphenylmethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.
Preferably, the acrylate monomer is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, 2-methyl methacrylate, and 2-ethyl methacrylate.
Preferably, the weight ratio of the hydroxypropyl silicone oil at the two ends to the polyisocyanate compound to the hydroxyethyl methacrylate is 5-10:2-5: 1-3; the mass ratio of the organosilicon modified acrylate prepolymer to the acrylate monomer in the polymerization reaction is 0.8-2: 1.
Preferably, the alkynol compound inhibitor in the agent B is selected from silanized alkynol or ethynyl cyclohexanol.
The preparation method of the primer-free special platinum vulcanizing agent for the combination of the metal base material and the silica gel comprises the following preparation steps:
(1) mixing to prepare an agent A: uniformly mixing 50-60 parts of methyl vinyl silicone rubber, 40-50 parts of platinum catalyst and 5-15 parts of hydrophobic white carbon black by an extruder to obtain an agent A;
(2) mixing to prepare an agent B: mixing 65-75 parts of methyl vinyl silicone rubber, 45-55 parts of vinyl hydrogen-containing silicone oil, 40-50 parts of organic silicon modified acrylate metal adhesive, 5-15 parts of hydrophobic white carbon black and 0.5-3 parts of alkynol compound inhibitor uniformly by an extruder to obtain an agent B;
(3) the resulting agent A and agent B were stored separately.
Compared with the prior art, the technical scheme provided by the invention has the following technical advantages:
1. the platinum vulcanizing agent provided by the invention is a solvent-free product, has no baking process, no volatilization of harmful substances, no harm to the body of staff and no pollution to the environment.
2. Compared with the prior art that vinyl hydrogen-containing silicone oil is adopted, the vinyl hydrogen-containing silicone oil is adopted as a cross-linking agent, so that higher cross-linking density can be achieved, and the bonding strength is higher.
3. The platinum vulcanizing agent provided by the invention is added with the organic silicon modified acrylate metal adhesive, so that the platinum vulcanizing agent can be better suitable for the combination of a metal base material and silica gel, and the binding force of the metal base material and the silica gel is improved.
Detailed Description
The invention is described in detail below with reference to specific examples, but is not to be construed as limited thereto, and any limited number of modifications made by anyone within the scope of the claims are still within the scope of the invention.
Example 1
The primer-free special platinum vulcanizing agent for the combination of the metal base material and the silica gel comprises an agent A and an agent B, and each dosage form comprises the following components in parts by weight:
an agent A: 60 parts of methyl vinyl silicone rubber (crude rubber, Dongjue organic silicon, molecular weight is 50-70 ten thousand), 50 parts of platinum catalyst (1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) and-Pt 5000ppm solution), and hydrophobic white carbon black (Kabet TS720, specific surface area is 250-400 m)2Per g)15 parts;
and (2) agent B: 65 parts of methyl vinyl silicone rubber (crude rubber, Dongjue organic silicon with the molecular weight of 50-70 ten thousand), 45 parts of vinyl hydrogen-containing silicone oil (XB-714, the vinyl content is 5 percent, and the hydrogen content is 0.15 percent), 40 parts of organic silicon modified acrylate metal adhesive, and hydrophobic white carbon black (Kabot TS720, the specific surface area is 250-25 parts/g) of alkynol compound inhibitor (ethynl cyclohexanol) 1 part.
The organic silicon modified acrylate metal adhesive is prepared by the following method: mixing double-end hydroxypropyl silicone oil (with the viscosity of 20cst and the average molecular weight of 600) and hexamethylene diisocyanate, heating to 100-120 ℃, stirring for reaction, then cooling to 50-70 ℃, adding hydroxyethyl methacrylate for continuous reaction, wherein the mass ratio of the double-end hydroxypropyl silicone oil to the hexamethylene diisocyanate to the hydroxyethyl methacrylate is 4:2:1, and obtaining an organic silicon modified acrylate prepolymer; then carrying out polymerization reaction on the prepolymer and acrylate monomers, namely methyl acrylate and 2-ethyl methacrylate, under the condition of a photoinitiator, wherein the mass ratio of the polymerization reaction of the organic silicon modified acrylate prepolymer and the acrylate monomers is 1: 1. Obtaining the organic silicon modified acrylate metal adhesive.
The metal base material and silica gel combined primer-free special platinum vulcanizing agent is prepared by the following method:
(1) mixing to prepare an agent A: uniformly mixing methyl vinyl silicone rubber, a platinum catalyst and hydrophobic white carbon black at the temperature of 120-150 ℃ under a vacuum condition through an extruder to obtain an agent A;
(2) mixing to prepare an agent B: uniformly mixing methyl vinyl silicone rubber, vinyl hydrogen-containing silicone oil, organic silicon modified acrylate metal adhesive, hydrophobic white carbon black and alkynol compound inhibitor by an extruder at the temperature of 120-150 ℃ under a vacuum condition to obtain an agent B;
(3) and (4) storing the obtained agent A and the agent B separately to obtain the primer-free special platinum vulcanizing agent for combining the metal base material and the silica gel.
Example 2
The primer-free special platinum vulcanizing agent for the combination of the metal base material and the silica gel comprises an agent A and an agent B, and each dosage form comprises the following components in parts by weight:
an agent A: 50 parts of methyl vinyl silicone rubber (crude rubber, Dongjue organic silicon, molecular weight is 160-180 ten thousand), 40 parts of platinum catalyst (1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) and-Pt 5000ppm solution), and hydrophobic white carbon black (Kabet TS720, specific surface area is 250-400 m)2Per g)5 parts;
and (2) agent B: 75 parts of methyl vinyl silicone rubber (crude rubber, Dongjue organic silicon with the molecular weight of 160-180 ten thousand) and vinyl hydrogen-containing silicone oil (XB-714, ethylene)55 portions of base content of 0.25 percent and hydrogen content of 1.0 percent, 50 portions of organic silicon modified acrylate metal adhesive, and hydrophobic white carbon black (Kabot TS720, specific surface area of 250-215 parts/g) of alkynol compound inhibitor (silanized alkynol) 2 parts.
The organic silicon modified acrylate metal adhesive is prepared by the following method: mixing double-end hydroxypropyl silicone oil (with the viscosity of 160cst and the average molecular weight of 10000) and isophorone diisocyanate, heating to 80-100 ℃, stirring for reaction, then cooling to 50-70 ℃, adding hydroxyethyl methacrylate for continuous reaction, wherein the mass ratio of the double-end hydroxypropyl silicone oil to the isophorone diisocyanate to the hydroxyethyl methacrylate is 10:3:1, and obtaining an organic silicon modified acrylate prepolymer; then carrying out polymerization reaction on the prepolymer and acrylate monomers, namely methyl acrylate and 2-ethyl methacrylate, under the condition of a photoinitiator, wherein the mass ratio of the polymerization reaction of the organic silicon modified acrylate prepolymer and the acrylate monomers is 1.5: 1. Obtaining the organic silicon modified acrylate metal adhesive.
The metal base material and silica gel combined primer-free special platinum vulcanizing agent is prepared by the following method:
(1) mixing to prepare an agent A: uniformly mixing methyl vinyl silicone rubber, a platinum catalyst and hydrophobic white carbon black at the temperature of 120-150 ℃ under a vacuum condition through an extruder to obtain an agent A;
(2) mixing to prepare an agent B: uniformly mixing methyl vinyl silicone rubber, vinyl hydrogen-containing silicone oil, organic silicon modified acrylate metal adhesive, hydrophobic white carbon black and alkynol compound inhibitor by an extruder at the temperature of 120-150 ℃ under a vacuum condition to obtain an agent B;
(3) and (4) storing the obtained agent A and the agent B separately to obtain the primer-free special platinum vulcanizing agent for combining the metal base material and the silica gel.
Comparative example 1
The platinum vulcanizing agent of the comparative example comprises an agent A and an agent B, and each dosage form comprises the following components in parts by weight:
an agent A: 60 parts of methyl vinyl silicone rubber (crude rubber, Dongjue organic silicon, molecular weight is 50-70 ten thousand), and platinum50 portions of catalyst (1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0), -Pt 5000ppm solution), hydrophobic white carbon black (Kabot TS720, specific surface area of 250-2Per g)15 parts;
and (2) agent B: 65 parts of methyl vinyl silicone rubber (crude rubber, Dongjue organic silicon, molecular weight is 50-70 ten thousand), 45 parts of vinyl hydrogen-containing silicone oil (XB-714, the vinyl content is 5 percent, and the hydrogen content is 0.15 percent), and hydrophobic white carbon black (Kabet TS720, the specific surface area is 250-25 parts/g) of alkynol compound inhibitor (ethynl cyclohexanol) 1 part.
The platinum vulcanizing agent is prepared by the following method:
(1) mixing to prepare an agent A: uniformly mixing methyl vinyl silicone rubber, a platinum catalyst and hydrophobic white carbon black at the temperature of 120-150 ℃ under a vacuum condition through an extruder to obtain an agent A;
(2) mixing to prepare an agent B: uniformly mixing methyl vinyl silicone rubber, vinyl hydrogen-containing silicone oil, hydrophobic white carbon black and an alkynol compound inhibitor by an extruder at the temperature of 120-150 ℃ under a vacuum condition to obtain an agent B;
(3) and (4) storing the obtained agent A and the agent B separately to obtain the platinum vulcanizing agent.
Comparative example 2
The platinum vulcanizing agent of the comparative example comprises an agent A and an agent B, and each dosage form comprises the following components in parts by weight:
an agent A: 50 parts of methyl vinyl silicone rubber (crude rubber, Dongjue organic silicon, molecular weight is 160-180 ten thousand), 40 parts of platinum catalyst (1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) and-Pt 5000ppm solution), and hydrophobic white carbon black (Kabet TS720, specific surface area is 250-400 m)2Per g)5 parts;
and (2) agent B: 75 parts of methyl vinyl silicone rubber (crude rubber, Dongjue organic silicon, molecular weight is 160-180 ten thousand), 55 parts of vinyl hydrogen-containing silicone oil (XB-714, the vinyl content is 0.25 percent, and the hydrogen content is 1.0 percent), and hydrophobic white carbon black (Kabet TS720, the specific surface area is 250-215 parts/g) of alkynol compound inhibitor (silanized alkynol) 2 parts.
The platinum vulcanizing agent is prepared by the following method:
(1) mixing to prepare an agent A: uniformly mixing methyl vinyl silicone rubber, a platinum catalyst and hydrophobic white carbon black at the temperature of 120-150 ℃ under a vacuum condition through an extruder to obtain an agent A;
(2) mixing to prepare an agent B: uniformly mixing methyl vinyl silicone rubber, vinyl hydrogen-containing silicone oil, hydrophobic white carbon black and an alkynol compound inhibitor by an extruder at the temperature of 120-150 ℃ under a vacuum condition to obtain an agent B;
(3) and (4) storing the obtained agent A and the agent B separately to obtain the platinum vulcanizing agent.
Comparative example 3
The platinum vulcanizing agent of the comparative example comprises an agent A and an agent B, and each dosage form comprises the following components in parts by weight:
an agent A: 60 parts of methyl vinyl silicone rubber (crude rubber, Dongjue organic silicon, molecular weight is 50-70 ten thousand), 50 parts of platinum catalyst (1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) and-Pt 5000ppm solution), and hydrophobic white carbon black (Kabet TS720, specific surface area is 250-400 m)2Per g)15 parts;
and (2) agent B: 65 parts of methyl vinyl silicone rubber (crude rubber, Dongjue organic silicon, molecular weight is 60-80 ten thousand), 45 parts of vinyl hydrogen-containing silicone oil (XB-714, the vinyl content is 5 percent, and the hydrogen content is 0.15 percent), 40 parts of common metal adhesive (alpha-cyanoacrylate adhesive), and hydrophobic white carbon black (Kabet TS720, the specific surface area is 250-400 m)25 parts/g) of alkynol compound inhibitor (ethynl cyclohexanol) 1 part.
The platinum vulcanizing agent is prepared by the following method:
(1) mixing to prepare an agent A: uniformly mixing methyl vinyl silicone rubber, a platinum catalyst and hydrophobic white carbon black at the temperature of 120-150 ℃ under a vacuum condition through an extruder to obtain an agent A;
(2) mixing to prepare an agent B: uniformly mixing methyl vinyl silicone rubber, vinyl hydrogen-containing silicone oil, alpha-cyanoacrylate adhesive, hydrophobic white carbon black and alkynol compound inhibitor by an extruder at the temperature of 120-150 ℃ under a vacuum condition to obtain an agent B;
(3) and (4) storing the obtained agent A and the agent B separately to obtain the platinum vulcanizing agent.
Comparative example 4
The platinum vulcanizing agent of the comparative example comprises an agent A and an agent B, and each dosage form comprises the following components in parts by weight:
an agent A: 50 parts of methyl vinyl silicone rubber (crude rubber, Dongjue organic silicon, molecular weight is 160-180 ten thousand), 40 parts of platinum catalyst (1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) and-Pt 5000ppm solution), and hydrophobic white carbon black (Kabet TS720, specific surface area is 250-400 m)2Per g)5 parts;
and (2) agent B: 75 parts of methyl vinyl silicone rubber (crude rubber, Dongjue organic silicon, the molecular weight is 160-180 ten thousand), 55 parts of vinyl hydrogen-containing silicone oil (XB-714, the vinyl content is 0.25 percent, and the hydrogen content is 1.0 percent), 50 parts of common metal adhesive (alpha-cyanoacrylate adhesive), and hydrophobic white carbon black (Kabet TS720, the specific surface area is 250-400 m)215 parts/g) of alkynol compound inhibitor (silanized alkynol) 2 parts.
The platinum vulcanizing agent is prepared by the following method:
(1) mixing to prepare an agent A: uniformly mixing methyl vinyl silicone rubber, a platinum catalyst and hydrophobic white carbon black at the temperature of 120-150 ℃ under a vacuum condition through an extruder to obtain an agent A;
(2) mixing to prepare an agent B: uniformly mixing methyl vinyl silicone rubber, vinyl hydrogen-containing silicone oil, alpha-cyanoacrylate adhesive, hydrophobic white carbon black and alkynol compound inhibitor by an extruder at the temperature of 120-150 ℃ under a vacuum condition to obtain an agent B;
(3) and (4) storing the obtained agent A and the agent B separately to obtain the platinum vulcanizing agent.
And (3) performance testing:
the platinum vulcanizing agents obtained in the above examples and comparative examples were applied to vulcanization of silicone rubber and bonded to a metal base material (stainless steel sheet), the metal base material was simply cleaned before bonding without applying a pretreatment agent by brush and baking to the base material, and then the base material was directly coated with a silica gel base material mixed with the platinum vulcanizing agent (Pt concentration was controlled to 6ppm), and bonding strength was tested after heating vulcanization, according to the method of GB/T2791-1995 "test method for peel strength of adhesive T versus flexible material". The test results are shown in table 1 below.
TABLE 1 comparison of Peel Strength Properties
Figure BDA0002744116890000111
The results in table 1 show that the bonding force between the vulcanized silicone rubber and the metal substrate can be significantly improved by adding the organic silicon modified acrylate metal adhesive into the platinum vulcanizing agent without brushing a pretreatment agent and baking the substrate. Compared with the method without adding the adhesive and adding the common acrylate metal adhesive, the bonding strength is obviously improved. The organosilicon modified acrylate metal adhesive has better compatibility with a silicone rubber main body, and can better realize the bonding effect of the silicone rubber and a metal base material.
While the preferred embodiments of the present invention have been illustrated and described in detail, it should be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings without inventive faculty. Therefore, any technical solutions that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the prior art according to the present inventive concept should be within the scope of protection defined by the present claims.

Claims (8)

1. A special platinum vulcanizing agent for the combination of a metal substrate and silica gel without prime coat is characterized in that: the primer-free special platinum vulcanizing agent for the combination of the metal base material and the silica gel comprises an agent A and an agent B, and each dosage form comprises the following components in parts by weight:
an agent A: 50-60 parts of methyl vinyl silicone rubber, 40-50 parts of platinum catalyst and 5-15 parts of hydrophobic white carbon black;
and (2) agent B: 65-75 parts of methyl vinyl silicone rubber, 45-55 parts of vinyl hydrogen-containing silicone oil, 40-50 parts of organic silicon modified acrylate metal adhesive, 5-15 parts of hydrophobic white carbon black and 0.5-3 parts of alkynol compound inhibitor; the vinyl hydrogen-containing silicone oil has a vinyl content of 0.1-10% and a hydrogen content of 0.15-1.6%;
the organic silicon modified acrylate metal adhesive is prepared by the following method:
mixing double-end hydroxypropyl silicone oil and a polyisocyanate compound, heating to 80-120 ℃, stirring for reaction, then cooling to 50-70 ℃, adding hydroxyethyl methacrylate, and continuing to react to obtain an organic silicon modified acrylate prepolymer; then carrying out polymerization reaction on the acrylate monomer and an acrylate monomer under the condition of a photoinitiator to obtain an organic silicon modified acrylate metal adhesive; the mass ratio of the double-end hydroxypropyl silicone oil to the polyisocyanate compound to the hydroxyethyl methacrylate is 5-10:2-5: 1-3; the mass ratio of the organosilicon modified acrylate prepolymer to the acrylate monomer in the polymerization reaction is 0.8-2: 1.
2. The primer-free special platinum vulcanizing agent for the combination of the metal base material and the silica gel according to claim 1, which is characterized in that: the molecular weight of the methyl vinyl silicone rubber in the agent A and the agent B is 50-180 ten thousand.
3. The primer-free special platinum vulcanizing agent for the combination of the metal base material and the silica gel according to claim 1, which is characterized in that: the platinum catalyst in the agent A is selected from 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) or chloroplatinic acid.
4. The primer-free special platinum vulcanizing agent for the combination of the metal base material and the silica gel according to claim 1, which is characterized in that: the specific surface area of the hydrophobic white carbon black in the agent A and the agent B is 250-400m2/g。
5. The primer-free special platinum vulcanizing agent for the combination of the metal base material and the silica gel according to claim 1, which is characterized in that: the viscosity of the double-end hydroxypropyl silicone oil is 20-200 cst, and the molecular weight of the double-end hydroxypropyl silicone oil is 500-10000.
6. The primer-free special platinum vulcanizing agent for the combination of the metal base material and the silica gel according to claim 1, which is characterized in that: the polyisocyanate compound is one or the combination of more than two of diphenyl methylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate and dicyclohexyl methane diisocyanate; the acrylate monomer is at least one selected from methyl acrylate, ethyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate.
7. The primer-free special platinum vulcanizing agent for the combination of the metal base material and the silica gel according to claim 1, which is characterized in that: the alkynol compound inhibitor in the agent B is selected from silanized alkynol or ethynl cyclohexanol.
8. The preparation method of the primer-free special platinum vulcanizing agent for the combination of the metal base material and the silica gel according to any one of claims 1 to 7, which is characterized by comprising the following preparation steps:
(1) mixing to prepare an agent A: uniformly mixing 50-60 parts of methyl vinyl silicone rubber, 40-50 parts of platinum catalyst and 5-15 parts of hydrophobic white carbon black by an extruder to obtain an agent A;
(2) mixing to prepare an agent B: mixing 65-75 parts of methyl vinyl silicone rubber, 45-55 parts of vinyl hydrogen-containing silicone oil, 40-50 parts of organic silicon modified acrylate metal adhesive, 5-15 parts of hydrophobic white carbon black and 0.5-3 parts of alkynol compound inhibitor uniformly by an extruder to obtain an agent B;
(3) the resulting agent A and agent B were stored separately.
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