CN110818904B - Tackifier, preparation method thereof and bi-component liquid silicone rubber adhesive containing tackifier - Google Patents

Tackifier, preparation method thereof and bi-component liquid silicone rubber adhesive containing tackifier Download PDF

Info

Publication number
CN110818904B
CN110818904B CN201911229810.3A CN201911229810A CN110818904B CN 110818904 B CN110818904 B CN 110818904B CN 201911229810 A CN201911229810 A CN 201911229810A CN 110818904 B CN110818904 B CN 110818904B
Authority
CN
China
Prior art keywords
parts
component
silicone rubber
tackifier
liquid silicone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911229810.3A
Other languages
Chinese (zh)
Other versions
CN110818904A (en
Inventor
李福中
庞文键
付子恩
刘润威
徐建明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou Baiyun Technology Co ltd
Original Assignee
Guangzhou Baiyun Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangzhou Baiyun Chemical Industry Co Ltd filed Critical Guangzhou Baiyun Chemical Industry Co Ltd
Priority to CN201911229810.3A priority Critical patent/CN110818904B/en
Publication of CN110818904A publication Critical patent/CN110818904A/en
Application granted granted Critical
Publication of CN110818904B publication Critical patent/CN110818904B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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 provides a tackifier, a preparation method thereof and a bi-component liquid silicone rubber adhesive containing the tackifier. The tackifier comprises the following preparation raw materials in parts by weight: 50-80 parts of 3-methacryloxypropyltrimethoxysilane, 30-60 parts of aminophenyltrimethoxysilane, 10-30 parts of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 5-20 parts of vinyl triethoxysilane, 5-15 parts of pH regulator, 30-50 parts of water and 70-90 parts of cosolvent. The adhesive comprises a component A and a component B; the component A comprises: base stock, hydrogen-containing silicone oil cross-linking agent, chain extender, tackifier and inhibitor as previously described; the component B comprises the following components in parts by weight: a binder and a catalyst. The adhesive disclosed by the invention has a good bonding effect on various base materials, the temperature resistance of the adhesive is further improved under the synergistic effect of the components, and the adhesive can be used in a high-temperature environment for a long time.

Description

Tackifier, preparation method thereof and bi-component liquid silicone rubber adhesive containing tackifier
Technical Field
The invention belongs to the field of adhesives, and particularly relates to a tackifier, a preparation method thereof and a bi-component liquid silicone rubber adhesive containing the tackifier.
Background
With the rapid development of industries such as electronic and electric products, automobile industry and the like, various electronic components and automobile accessories, particularly automobile engines, have higher and higher requirements on the heat resistance of the silicone rubber, and the environmental protection requirements on the silicone rubber are stricter and stricter. Silicone rubber adhesives are mainly classified into two main categories according to the vulcanization mechanism: one is a room temperature vulcanizing adhesive of a condensation type vulcanization mechanism, and the other is an addition type adhesive of a hydrosilylation type vulcanization mechanism. The condensed type adhesive has low vulcanization speed, limited vulcanization thickness and is influenced by the temperature and humidity of the environment, in addition, small molecular volatile matters are released in the vulcanization process, potential risks of swelling, corrosion and the like exist on certain specific materials, and the condensed type adhesive is limited in certain application fields, especially in the application fields with strict requirements on pursuit efficiency and occupational health; the addition type silicone rubber adhesive has no byproduct release in the vulcanization process, is neutral, nontoxic and noncorrosive, has high vulcanization efficiency, is more and more favored in the electronic and electrical industry, and relates to the use of the addition type silicone rubber adhesive, such as the adhesion of heating ceramic wafers of air conditioner heaters, the heat conduction adhesion fixation of heating components in the electronic industry and the like.
Most of traditional double-component addition type silicone rubber is heat-conducting pouring sealant and the like, and the traditional double-component addition type silicone rubber has no adhesion to a base material, or is easy to cause the breakage of internal chemical bonds after being used for a long time under a high-temperature condition (more than 250 ℃), so that the colloid falls off from the base material piece, the adhesion effect is lost, and components are damaged. The single-component addition type silicone rubber is difficult to be widely used due to the harsh storage conditions.
CN102627860A discloses a preparation method of flame-retardant, high-low temperature-resistant and high-thermal-conductivity addition type silicone rubber, which mainly explains the curing and molding of single-component addition type silicone rubber, and cerium oxide is added as a temperature-resistant material. The single-component addition type liquid silicone rubber is extremely harsh to store, and cerium oxide has certain toxicity, so that the addition type silicone rubber disclosed in the patent does not have the adhesive effect on a base material.
CN102532917A discloses a high temperature resistant liquid silicone rubber and a preparation method thereof. The liquid silicone rubber is prepared from a component A and a component B according to a mass ratio of 1: 10-10: 1; the component A is composed of base rubber and a platinum complex according to a certain proportion, the component B is composed of base rubber, hydrogen-containing polysiloxane and alkynol inhibitor according to a certain proportion, and the base rubber is composed of three vinyl-terminated organopolysiloxanes with different viscosities and vinyl contents, silicon dioxide and a high-temperature-resistant additive according to a certain proportion. However, when the hydrogen-containing polysiloxane is still used at high temperature for a long time, the hydrogen-containing polysiloxane is easy to break internal chemical bonds, so that the colloid falls off from the base material and loses the adhesive effect.
Therefore, the development of the high-temperature-resistant liquid silicone rubber has important significance and wide application value.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a tackifier, a preparation method thereof and a bi-component liquid silicone rubber adhesive containing the tackifier, wherein the adhesive has good adhesion and can be used for a long time under a high-temperature condition.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a tackifier, which comprises the following preparation raw materials in parts by weight: 50-80 parts of 3-methacryloxypropyltrimethoxysilane, 30-60 parts of aminophenyltrimethoxysilane, 10-30 parts of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 5-20 parts of vinyl triethoxysilane, 5-15 parts of pH regulator, 30-50 parts of water and 70-90 parts of cosolvent.
In the tackifier of the invention, the 3-methacryloxypropyltrimethoxysilane is 50 to 80 parts by weight, for example, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts and 80 parts.
In the tackifier of the invention, the amino phenyl trimethoxy silane is 30 to 60 parts by weight, for example, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts and 60 parts.
In the tackifier of the invention, the weight parts of the gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane are 10-30 parts, such as 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts and 30 parts.
In the tackifier of the present invention, the vinyl triethoxysilane may be 5 to 20 parts by weight, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, and 20 parts.
In the tackifier of the present invention, the pH adjuster may be 5 to 15 parts by weight, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, and 15 parts.
In the tackifier of the present invention, the water may be 30 to 50 parts by weight, for example, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 parts, 50 parts.
In the tackifier of the present invention, the weight part of the cosolvent is 70 to 90 parts, and may be, for example, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, 80 parts, 82 parts, 84 parts, 86 parts, 88 parts, or 90 parts.
The tackifier is 3-methacryloxypropyltrimethoxysilane, aminophenyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane and vinyl triethoxysilane, and the four silanes are matched with each other, so that the synergistic effect is achieved, the rheological property and the flexibility of the tackifier can be improved, and the toughness and the bonding property of the tackifier can be improved. The composite tackifier provides good fluidity and adhesiveness for the adhesive disclosed by the invention.
Preferably, the pH adjusting agent comprises any one of acetic acid, hydrochloric acid or carbonic acid or a combination of at least two thereof.
Preferably, the co-solvent comprises any one or a combination of at least two of ethanol, ethylene glycol, propylene glycol or glycerol, preferably ethanol and glycerol.
Preferably, the viscosifier has a pH of 6 to 8, which may be, for example, 6, 7, 8.
In a second aspect, the present invention provides a method for preparing the tackifier according to the first aspect, the method comprising the steps of:
(1) mixing and stirring 3-methacryloxypropyltrimethoxysilane, aminophenyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, vinyl triethoxysilane, water and a cosolvent according to the formula ratio, and reacting to obtain a hydrolysate;
(2) and (2) adding a pH regulator into the hydrolysate obtained in the step (1), and mixing and stirring to obtain the tackifier.
Preferably, the stirring temperature in step (1) is 100 ℃ and 120 ℃, for example, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃.
Preferably, the stirring time in step (1) is 120-150min, such as 120min, 122min, 124min, 126min, 128min, 130min, 132min, 134min, 136min, 138min, 140min, 142min, 144min, 146min, 148min, 150 min.
Preferably, the stirring temperature in step (2) is 20-30 deg.C, such as 20 deg.C, 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C, 25 deg.C, 26 deg.C, 27 deg.C, 28 deg.C, 29 deg.C, 30 deg.C.
Preferably, the stirring time in step (2) is 5-10min, such as 5min, 6min, 7min, 8min, 9min, 10 min.
In a third aspect, the invention provides a bi-component liquid silicone rubber adhesive, which comprises a component A and a component B;
the component A comprises the following components in parts by weight: 80-120 parts of base material, 1-20 parts of hydrogen-containing silicone oil cross-linking agent, 0.1-5 parts of chain extender, 0.1-5 parts of tackifier and 0.005-0.2 part of inhibitor according to the first aspect;
the component B comprises the following components in parts by weight: 80-120 parts of base material and 0.1-5 parts of catalyst.
In the component A of the adhesive, the weight parts of the base material are 80-120 parts, for example, 80 parts, 82 parts, 84 parts, 86 parts, 88 parts, 90 parts, 92 parts, 94 parts, 96 parts, 98 parts, 100 parts, 102 parts, 104 parts, 106 parts, 108 parts, 110 parts, 112 parts, 114 parts, 116 parts, 118 parts and 120 parts.
In the component A of the adhesive, the hydrogen-containing silicone oil crosslinking agent is 1-20 parts by weight, and can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts and 20 parts, for example.
In the component A of the adhesive, the weight part of the chain extender is 0.1-5 parts, for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 2 parts, 3 parts, 4 parts and 5 parts.
In the component a of the adhesive of the present invention, the tackifier according to the first aspect may be 0.1 to 5 parts by weight, for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 2 parts, 3 parts, 4 parts, and 5 parts.
In the component A of the adhesive, the weight part of the inhibitor is 0.005-0.2 part, and can be, for example, 0.005 part, 0.006 part, 0.007 part, 0.008 part, 0.009 part, 0.01 part, 0.02 part, 0.04 part, 0.06 part, 0.08 part, 0.1 part, 0.12 part, 0.14 part, 0.16 part, 0.18 part and 0.2 part.
In the component B of the adhesive, the weight parts of the base material are 80-120 parts, for example, 80 parts, 82 parts, 84 parts, 86 parts, 88 parts, 90 parts, 92 parts, 94 parts, 96 parts, 98 parts, 100 parts, 102 parts, 104 parts, 106 parts, 108 parts, 110 parts, 112 parts, 114 parts, 116 parts, 118 parts and 120 parts.
In the component B of the adhesive, the weight part of the catalyst is 0.1-5 parts, such as 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 2 parts, 3 parts, 4 parts and 5 parts.
Preferably, the mass ratio of the A component and the B component is (0.8-1.2):1, and may be, for example, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, preferably 1: 1.
Preferably, the base materials of the component A and the component B comprise the following components in parts by weight: 80-120 parts of alpha, omega-divinyl polydimethylsiloxane, 80-120 parts of ferric oxide and 1-15 parts of fumed silica.
In the base material of the component A and the component B, the weight portion of the alpha, omega-divinyl polydimethylsiloxane is 80-120 parts, for example, 80 parts, 82 parts, 84 parts, 86 parts, 88 parts, 90 parts, 92 parts, 94 parts, 96 parts, 98 parts, 100 parts, 102 parts, 104 parts, 106 parts, 108 parts, 110 parts, 112 parts, 114 parts, 116 parts, 118 parts and 120 parts.
In the base material of the component A and the component B, the weight portion of the ferric oxide is 80-120, for example, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, 100, 102, 104, 106, 108, 110, 112, 114, 116, 118, 120.
In the base material of the component A and the component B, the fumed silica is 1 to 15 parts by weight, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts and 15 parts.
According to the invention, the problem of harsh storage conditions of single-component addition type is solved in a double-component mode, the temperature resistance of the single-component addition type liquid silicone rubber adhesive is mainly increased by adding the ferric oxide filler, the synergistic effect of the mutual matching of the four silanes in the self-made tackifier is realized, the surfaces of the fumed silica and the ferric oxide simultaneously contain a large number of active group Si-H groups, all the components are connected through chemical bonds, and the particles are more tightly combined, so that the heat resistance of the single-component addition type liquid silicone rubber adhesive is further improved, the single-component addition type liquid silicone rubber adhesive can be used in an environment with the temperature of more than 250 ℃ for a long time, and the addition type liquid silicone rubber adhesive can. Has good bonding effect on base materials such as aluminum, stainless steel, glass, ceramics and the like. In addition, the fumed silica plays a reinforcing role in the liquid silicone rubber binder disclosed by the invention, and the requirements of white or semitransparent products are met. The fumed silica has super strong adhesion, tear resistance, heat resistance and ageing resistance.
Preferably, the viscosity of the α, ω -divinylpolydimethylsiloxane is 1000-20000mpa.s, and may be, for example, 1000mpa.s, 2000mpa.s, 3000mpa.s, 4000mpa.s, 5000mpa.s, 6000mpa.s, 7000mpa.s, 8000mpa.s, 9000mpa.s, 10000mpa.s, 12000mpa.s, 14000mpa.s, 15000mpa.s, 16000mpa.s, 18000mpa.s, 20000 mpa.s.
Preferably, the α, ω -divinylpolydimethylsiloxane has a vinyl content of 0.1 to 0.4%, and may be, for example, 0.1%, 0.12%, 0.14%, 0.16%, 0.18%, 0.2%, 0.22%, 0.24%, 0.26%, 0.28%, 0.3%, 0.32%, 0.34%, 0.36%, 0.38%, 0.4%.
Preferably, the particle size of the iron sesquioxide is 5 to 15 μm, and may be, for example, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, or 15 μm.
Preferably, the specific surface area of the fumed silica is 100-380m2G, may be, for example, 100m2/g、110m2/g、120m2/g、130m2/g、140m2/g、150m2/g、160m2/g、170m2/g、180m2/g、190m2/g、200m2/g、220m2/g、240m2/g、260m2/g、280m2/g、300m2/g、320m2/g、340m2/g、360m2/g、380m2/g。
Preferably, the hydrogen-containing silicone oil cross-linking agent is branched-chain hydrogen-containing silicone oil. The adhesive is beneficial to obtaining higher strength and toughness. The branched chain type hydrogen-containing silicone oil branched chain hydrogen-containing polysiloxane is hydrogen-containing silicone oil containing partial T chain links, and the T chain links form a branched chain structure by molecules formed by hydrolysis of raw materials possibly containing a small amount of methyltrichlorosilane and silicon trichloride. The position and the number of the silicon-hydrogen bonds on the molecular chain have direct influence on the performance of the addition type liquid silicone rubber, and when the branched chain type hydrogen-containing silicone oil is used, the molecular chain is increased by crosslinking polysiloxane molecules, so that the mechanical strength of the silicone rubber can be greatly increased. When the content of the silicon-hydrogen bonds in the molecular chain is higher, the hardness of the vulcanized rubber is generally higher, and when the content of the silicon-hydrogen bonds is lower, the elongation at break is higher.
Preferably, the branched hydrogen-containing silicone oil has a hydrogen content of 0.36 to 0.56 wt%, and may be, for example, 0.36%, 0.38%, 0.4%, 0.42%, 0.44%, 0.46%, 0.48%, 0.5%, 0.52%, 0.54%, 0.56%.
Preferably, the chain extender is hydrogen-terminated silicone oil. The adhesive is beneficial to obtaining higher strength and toughness. The hydrogen-terminated group has larger reactivity, so that the reaction rate is accelerated, the tear strength of the vulcanized rubber is improved, and meanwhile, the hydrogen-terminated group is crosslinked with polysiloxane molecules to increase molecular chains, so that the mechanical strength of the silicone rubber is greatly improved.
The terminal hydrogen-containing silicone oil is polysiloxane which introduces a silicon-hydrogen bond at the tail end of the terminal by utilizing a Si-H bond on the terminal group of the hydrogen-containing silicone oil through hydrosilation reaction.
Preferably, the hydrogen content of the hydrogen-terminated silicone oil is 0.05% -0.1%;
preferably, the inhibitor comprises any one or a combination of at least two of 1-ethynyl-cyclohexanol, 2-methyl-3-butyn-2-ol, 2-methyl-1-hexyn-3-ol, 3, 5-dimethyl-1-ethynyl-3-ol or 3,7, 11-trimethyl-1-dodecayn-3-ol.
Preferably, the catalyst is a platinum catalyst.
Preferably, the platinum content in the platinum catalyst is 1000-5000ppm, and may be, for example, 1000ppm, 1500ppm, 2000ppm, 2500ppm, 3000ppm, 3500ppm, 4000ppm, 4500ppm, 5000 ppm.
Preferably, the platinum catalyst comprises any one or a combination of at least two of platinum vinylsiloxane, platinum-alkyne chelate, or chloroplatinic acid.
Preferably, the platinumvinyl siloxane comprises any one of or a combination of at least two of a tetramethyltetravinylcyclotetrasiloxane chloroplatinate complex, a tetramethyldivinyldisiloxane chloroplatinate complex or a diphenyldivinyltetrachlorodisiloxane complex chloroplatinate;
preferably, the platinum-alkynylsulphate chelate comprises any one of or a combination of at least two of bis (alkynylbis (triphenylphosphine) platinum chelate or bis (alkynylbis) (cyclodialkenyl) chelate.
In a fourth aspect, the invention provides a preparation method of the two-component liquid silicone rubber adhesive in the third aspect, wherein the preparation method comprises the following steps:
(1) mixing and stirring the base material, the hydrogen-containing silicone oil cross-linking agent, the chain extender, the tackifier and the inhibitor in the first aspect according to the formula amount to prepare a component A; mixing and stirring the base material and the catalyst according to the formula amount to prepare a component B;
(2) and (2) mixing the component A and the component B obtained in the step (1) to obtain the bi-component liquid silicone rubber adhesive.
Preferably, in step (1), the stirring time for preparing the component A and the component B is 30-40min, such as 30min, 32min, 34min, 36min, 38min and 40 min.
Preferably, in step (1), the stirring temperature for preparing both the A-component and the B-component is 20-30 deg.C, and may be, for example, 20 deg.C, 22 deg.C, 24 deg.C, 26 deg.C, 28 deg.C, 30 deg.C.
Preferably, the mixing time in step (2) is 5-10min, such as 5min, 6min, 7min, 8min, 9min, 10 min.
Preferably, the mixing temperature in step (2) is 20-30 deg.C, such as 20 deg.C, 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C, 25 deg.C, 26 deg.C, 27 deg.C, 28 deg.C, 29 deg.C, 30 deg.C.
In a fifth aspect, the present invention provides the use of the two-component liquid silicone rubber adhesive of the fourth aspect for bonding aluminum substrates, stainless steel substrates, glass substrates or ceramic substrates.
Compared with the prior art, the invention has the following beneficial effects:
(1) the bi-component liquid silicone rubber adhesive provided by the invention solves the problem of harsh single-component addition type storage conditions in a bi-component mode, the temperature resistance and mechanical properties of the bi-component liquid silicone rubber adhesive are improved mainly by adding ferric oxide and fumed silica filler, and the silane in the self-made tackifier is matched with each other for synergistic interaction, so that the temperature resistance of the bi-component liquid silicone rubber adhesive is further improved, the addition type liquid silicone rubber adhesive has adhesive property, and the addition type liquid silicone rubber adhesive can be used for a long time under a high-temperature condition.
(2) After the high-temperature aging treatment, the shear strength of the bonded aluminum sheet of the bi-component liquid silicone rubber adhesive is still more than 1MPa, the shear strength of the bonded stainless steel is more than 0.85MPa, the shear strength of the bonded glass is more than 1MPa, and the shear strength of the bonded ceramic is more than 0.87 MPa.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a tackifier and a double-component liquid silicone rubber adhesive comprising the tackifier:
the tackifier of this embodiment comprises in parts by weight: 55 parts of 3-methacryloxypropyltrimethoxysilane, 35 parts of aminophenyltrimethoxysilane, 10 parts of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 8 parts of vinyltriethoxysilane, 10 parts of acetic acid, 40 parts of water and 80 parts of ethanol.
The preparation method of the tackifier comprises the following steps:
(1) mixing and stirring 3-methacryloxypropyltrimethoxysilane, aminophenyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, vinyl triethoxysilane, water and ethanol according to the formula ratio, and reacting to obtain a hydrolysate;
(2) and (2) adding acetic acid into the hydrolysate obtained in the step (1), mixing and stirring, and adjusting the pH value to 7 to obtain the tackifier.
The bi-component liquid silicone rubber adhesive comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 100 parts of base material, 8 parts of branched chain type hydrogen-containing silicone oil (Runza KH536) with the hydrogen content of 0.36 percent, 1 part of terminal hydrogen-containing silicone oil (Runza KH501) with the hydrogen content of 0.05 percent, 1 part of tackifier provided by the embodiment and 0.05 part of 1-ethynyl-cyclohexanol; the component B comprises the following components in parts by weight: 100 portions of base material and 0.5 portion of bis (alkynyl) (cyclodialkenyl) platinum chelate compound with platinum content of 3000 ppm; the mass ratio of the component A to the component B is 1: 1.
The base materials of the component A and the component B comprise the following components in parts by weight: alpha, omega-divinylpolydimethylsiloxane (viscosity 1000mpa.s, vinyl content 0.3%) 100 part of ferric oxide (the particle size is 5 mu m)100 parts and fumed silica (the specific surface area is 150 m)2Per g)5 parts.
The preparation method of the bi-component liquid silicone rubber adhesive comprises the following steps:
(1) mixing and stirring the base materials (alpha, omega-divinyl polydimethylsiloxane, ferric oxide and fumed silica), the hydrogen-containing silicone oil cross-linking agent (lubricating KH536), the chain extender (lubricating KH501), the tackifier and the inhibitor (1-ethynyl-cyclohexanol) provided by the embodiment at 30 ℃ for 30min according to the formula ratio to obtain a component A; mixing and stirring the base materials (alpha, omega-divinyl polydimethylsiloxane, ferric oxide and fumed silica) and the catalyst (bis (alkynyl) (cyclodialkenyl) platinum chelate) for 30min at the temperature of 30 ℃ according to the formula amount to prepare a component B;
(2) and (2) mixing the component A and the component B obtained in the step (1) in a mass ratio of 1:1 to obtain the bi-component liquid silicone rubber adhesive.
Example 2
The embodiment provides a tackifier and a double-component liquid silicone rubber adhesive comprising the tackifier:
the tackifier of this embodiment comprises in parts by weight: 70 parts of 3-methacryloxypropyltrimethoxysilane, 40 parts of aminophenyltrimethoxysilane, 15 parts of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 10 parts of vinyltriethoxysilane, 10 parts of acetic acid, 40 parts of water and 80 parts of ethanol.
The preparation method of the tackifier comprises the following steps:
(1) mixing and stirring 3-methacryloxypropyltrimethoxysilane, aminophenyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, vinyl triethoxysilane, water and ethanol according to the formula ratio, and reacting to obtain a hydrolysate;
(2) and (2) adding acetic acid into the hydrolysate obtained in the step (1), mixing and stirring, and adjusting the pH value to 8 to obtain the tackifier.
The bi-component liquid silicone rubber adhesive comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 100 parts of base material, 8 parts of branched chain type hydrogen-containing silicone oil (Runza KH536) with the hydrogen content of 0.36 percent, 1 part of terminal hydrogen-containing silicone oil (Runza KH501) with the hydrogen content of 0.05 percent, 1 part of tackifier provided by the embodiment and 0.05 part of 1-ethynyl-cyclohexanol; the component B comprises the following components in parts by weight: 100 portions of base material and 0.5 portion of bis (alkynyl) (cyclodialkenyl) platinum chelate compound with platinum content of 3000 ppm; the mass ratio of the component A to the component B is 1: 1.
The base materials of the component A and the component B comprise the following components in parts by weight: 100 parts of alpha, omega-divinyl polydimethylsiloxane (with the viscosity of 1500mpa.s and the vinyl content of 0.4 percent), 100 parts of ferric oxide (with the particle size of 10 mu m), and fumed silica (with the specific surface area of 200 m)2Per g)5 parts.
The preparation method of the bi-component liquid silicone rubber adhesive comprises the following steps:
(1) mixing and stirring the base materials (alpha, omega-divinyl polydimethylsiloxane, ferric oxide and fumed silica), the hydrogen-containing silicone oil cross-linking agent (lubricating KH536), the chain extender (lubricating KH501), the tackifier and the inhibitor (1-ethynyl-cyclohexanol) provided by the embodiment at 30 ℃ for 30min according to the formula ratio to obtain a component A; mixing and stirring the base materials (alpha, omega-divinyl polydimethylsiloxane, ferric oxide and fumed silica) and the catalyst (bis (alkynyl) (cyclodialkenyl) platinum chelate) for 30min at the temperature of 30 ℃ according to the formula amount to prepare a component B;
(2) and (2) mixing the component A and the component B obtained in the step (1) in a mass ratio of 1:1 to obtain the bi-component liquid silicone rubber adhesive.
Example 3
The embodiment provides a tackifier and a double-component liquid silicone rubber adhesive comprising the tackifier:
the tackifier of this embodiment comprises in parts by weight: 80 parts of 3-methacryloxypropyltrimethoxysilane, 60 parts of aminophenyltrimethoxysilane, 20 parts of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 20 parts of vinyltriethoxysilane, 10 parts of hydrochloric acid, 40 parts of water and 80 parts of glycerol.
The preparation method of the tackifier comprises the following steps:
(1) mixing and stirring 3-methacryloxypropyltrimethoxysilane, aminophenyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, vinyl triethoxysilane, water and glycerol according to the formula ratio, and reacting to obtain a hydrolysate;
(2) and (2) adding hydrochloric acid into the hydrolysate obtained in the step (1), mixing and stirring, and adjusting the pH value to 8 to obtain the tackifier.
The bi-component liquid silicone rubber adhesive comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 100 parts of base material, 8 parts of branched chain type hydrogen-containing silicone oil (Runza KH536) with the hydrogen content of 0.36 percent, 1 part of terminal hydrogen-containing silicone oil (Runza KH501) with the hydrogen content of 0.05 percent, 1 part of tackifier provided by the embodiment and 0.05 part of 1-ethynyl-cyclohexanol; the component B comprises the following components in parts by weight: 100 portions of base material and 0.5 portion of bis (alkynyl) (cyclodialkenyl) platinum chelate compound with platinum content of 3000 ppm; the mass ratio of the component A to the component B is 1: 1.
The base materials of the component A and the component B comprise the following components in parts by weight: 100 parts of alpha, omega-divinyl polydimethylsiloxane (viscosity of 1000mpa.s, vinyl content of 0.3%), 100 parts of ferric oxide (particle size of 5 mu m), and fumed silica (specific surface area of 300 m)2Per g)5 parts.
The preparation method of the bi-component liquid silicone rubber adhesive comprises the following steps:
(1) mixing and stirring the base materials (alpha, omega-divinyl polydimethylsiloxane, ferric oxide and fumed silica), the hydrogen-containing silicone oil cross-linking agent (lubricating KH536), the chain extender (lubricating KH501), the tackifier and the inhibitor (1-ethynyl-cyclohexanol) provided by the embodiment at 30 ℃ for 30min according to the formula ratio to obtain a component A; mixing and stirring the base materials (alpha, omega-divinyl polydimethylsiloxane, ferric oxide and fumed silica) and the catalyst (bis (alkynyl) (cyclodialkenyl) platinum chelate) for 30min at the temperature of 30 ℃ according to the formula amount to prepare a component B;
(2) and (2) mixing the component A and the component B obtained in the step (1) in a mass ratio of 1:1 to obtain the bi-component liquid silicone rubber adhesive.
Example 4
The embodiment provides a tackifier and a double-component liquid silicone rubber adhesive comprising the tackifier:
the tackifier of this embodiment comprises in parts by weight: 60 parts of 3-methacryloxypropyltrimethoxysilane, 60 parts of aminophenyltrimethoxysilane, 30 parts of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 10 parts of vinyltriethoxysilane, 10 parts of hydrochloric acid, 40 parts of water and 80 parts of glycerol.
The preparation method of the tackifier comprises the following steps:
(1) mixing and stirring 3-methacryloxypropyltrimethoxysilane, aminophenyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, vinyl triethoxysilane, water and glycerol according to the formula ratio, and reacting to obtain a hydrolysate;
(2) and (2) adding hydrochloric acid into the hydrolysate obtained in the step (1), mixing and stirring, and adjusting the pH value to 8 to obtain the tackifier.
The bi-component liquid silicone rubber adhesive comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 100 parts of base material, 8 parts of branched hydrogen-containing silicone oil (Runzao KH536) with the hydrogen content of 0.36 percent, 1 part of hydrogen-terminated silicone oil (Runzao KH501) with the hydrogen content of 0.05 percent, 1 part of tackifier provided in the example and 0.05 part of 3, 5-dimethyl-1-ethynyl-3-alcohol; the component B comprises the following components in parts by weight: 100 parts of base material, 1 part of chloroplatinic acid tetramethyl divinyl disiloxane complex with platinum content of 3500 ppm; the mass ratio of the component A to the component B is 1: 1.
The base materials of the component A and the component B comprise the following components in parts by weight: 100 parts of alpha, omega-divinyl polydimethylsiloxane (viscosity of 1000mpa.s, vinyl content of 0.3%), 100 parts of ferric oxide (particle size of 5 mu m), and fumed silica (specific surface area of 300 m)2Per g)5 parts.
The preparation method of the bi-component liquid silicone rubber adhesive comprises the following steps:
(1) mixing and stirring the base materials (alpha, omega-divinyl polydimethylsiloxane, ferric oxide and fumed silica), the hydrogen-containing silicone oil cross-linking agent (Runzhe KH536), the chain extender (Runzhe KH501), the tackifier and the inhibitor (3, 5-dimethyl-1-ethynyl-3-ol) provided by the embodiment at the temperature of 30 ℃ for 30min according to the formula amount to obtain a component A; mixing and stirring the base material (alpha, omega-divinyl polydimethylsiloxane, ferric oxide and fumed silica) and the catalyst (tetramethyldivinyl disiloxane chloroplatinate complex) at 30 ℃ for 30min according to the formula amount to prepare a component B;
(2) and (2) mixing the component A and the component B obtained in the step (1) in a mass ratio of 1:1 to obtain the bi-component liquid silicone rubber adhesive.
Example 5
The embodiment provides a tackifier and a double-component liquid silicone rubber adhesive comprising the tackifier:
the tackifier of this embodiment comprises in parts by weight: 50 parts of 3-methacryloxypropyltrimethoxysilane, 30 parts of aminophenyltrimethoxysilane, 30 parts of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 20 parts of vinyltriethoxysilane, 10 parts of acetic acid, 40 parts of water and 80 parts of ethanol.
The preparation method of the tackifier comprises the following steps:
(1) mixing and stirring 3-methacryloxypropyltrimethoxysilane, aminophenyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, vinyl triethoxysilane, water and ethanol according to the formula ratio, and reacting to obtain a hydrolysate;
(2) and (2) adding acetic acid into the hydrolysate obtained in the step (1), mixing and stirring, and adjusting the pH value to 7 to obtain the tackifier.
The composition and preparation method of the bi-component liquid silicone rubber adhesive in this embodiment are the same as those in embodiment 1, except that the tackifier prepared in this embodiment is added to the tackifier.
Example 6
The embodiment provides a tackifier and a double-component liquid silicone rubber adhesive comprising the tackifier:
the tackifier of this embodiment comprises in parts by weight: 80 parts of 3-methacryloxypropyltrimethoxysilane, 30 parts of aminophenyltrimethoxysilane, 10 parts of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 5 parts of vinyltriethoxysilane, 10 parts of acetic acid, 40 parts of water and 80 parts of ethanol.
The preparation method of the tackifier comprises the following steps:
(1) mixing and stirring 3-methacryloxypropyltrimethoxysilane, aminophenyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, vinyl triethoxysilane, water and ethanol according to the formula ratio, and reacting to obtain a hydrolysate;
(2) and (2) adding acetic acid into the hydrolysate obtained in the step (1), mixing and stirring, and adjusting the pH value to 7 to obtain the tackifier.
The composition and preparation method of the bi-component liquid silicone rubber adhesive in this embodiment are the same as those in embodiment 1, except that the tackifier prepared in this embodiment is added to the tackifier.
Example 7
The content and the preparation method of each component of the tackifier and the two-component liquid silicone rubber adhesive containing the tackifier are the same as those of the embodiment 1, and the difference is only that the mass ratio of the component A to the component B is 0.8.
Example 8
The embodiment provides a tackifier and a two-component liquid silicone rubber adhesive containing the tackifier, the content of each component of the tackifier and the two-component liquid silicone rubber adhesive containing the tackifier and the preparation method of the tackifier are the same as those of the embodiment 1, and the difference is only that the mass ratio of the component A to the component B is 1.2.
Example 9
The content and the preparation method of each component of the tackifier and the two-component liquid silicone rubber adhesive containing the tackifier are the same as those of the embodiment 1, and the difference is only that the mass ratio of the component A to the component B is 0.5.
Example 10
The embodiment provides a tackifier and a two-component liquid silicone rubber adhesive containing the tackifier, the content of each component of the tackifier and the two-component liquid silicone rubber adhesive containing the tackifier and the preparation method of the tackifier are the same as those of the embodiment 1, and the difference is only that the mass ratio of the component A to the component B is 2.
Comparative example 1
The comparative example provides a tackifier and a two-component liquid silicone rubber adhesive containing the same:
the tackifier of the comparative example comprises the following components in parts by weight: 65 parts of 3-methacryloxypropyltrimethoxysilane, 25 parts of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 18 parts of vinyl triethoxysilane, 10 parts of acetic acid, 40 parts of water and 80 parts of ethanol.
The contents of other components and the preparation method of the two-component liquid silicone rubber adhesive in the comparative example are the same as those in example 1, and the difference is only that the tackifier prepared in the comparative example is added into the tackifier.
Comparative example 2
The comparative example provides a tackifier and a two-component liquid silicone rubber adhesive containing the same:
the tackifier of the comparative example comprises the following components in parts by weight: 35 parts of aminophenyl trimethoxy silane, 65 parts of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 8 parts of vinyl triethoxy silane, 10 parts of acetic acid, 40 parts of water and 80 parts of ethanol.
The contents of other components and the preparation method of the two-component liquid silicone rubber adhesive in the comparative example are the same as those in example 1, and the difference is only that the tackifier prepared in the comparative example is added into the tackifier.
Comparative example 3
The comparative example provides a tackifier and a two-component liquid silicone rubber adhesive containing the same:
the tackifier of the comparative example comprises the following components in parts by weight: 55 parts of 3-methacryloxypropyltrimethoxysilane, 35 parts of aminophenyltrimethoxysilane, 18 parts of vinyltriethoxysilane, 10 parts of acetic acid, 40 parts of water and 80 parts of ethanol.
The contents of other components and the preparation method of the two-component liquid silicone rubber adhesive in the comparative example are the same as those in example 1, and the difference is only that the tackifier prepared in the comparative example is added into the tackifier.
Comparative example 4
The comparative example provides a tackifier and a two-component liquid silicone rubber adhesive containing the same:
the tackifier of the comparative example comprises the following components in parts by weight: 55 parts of 3-methacryloxypropyltrimethoxysilane, 35 parts of aminophenyltrimethoxysilane, 18 parts of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 10 parts of acetic acid, 40 parts of water and 80 parts of ethanol.
The contents of other components and the preparation method of the two-component liquid silicone rubber adhesive in the comparative example are the same as those in example 1, and the difference is only that the tackifier prepared in the comparative example is added into the tackifier.
Comparative example 5
The content and the preparation method of each component of the two-component liquid silicone rubber adhesive are the same as those in example 1, and the difference is only that no tackifier is added to the two-component liquid silicone rubber adhesive provided by the comparative example.
Comparative example 6
The comparative example provides a two-component liquid silicone rubber adhesive, and the content of each component of the two-component liquid silicone rubber adhesive and the preparation method are the same as those in example 1, except that the two-component liquid silicone rubber adhesive provided by the comparative example does not contain ferric oxide.
Comparative example 7
The comparative example provides a tackifier and a two-component liquid silicone rubber adhesive containing the same:
the tackifier of the comparative example comprises the following components in parts by weight: 60 parts of 3-methacryloxypropyltrimethoxysilane, 25 parts of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 10 parts of vinyl triethoxysilane, 10 parts of acetic acid, 40 parts of water and 80 parts of ethanol.
The preparation method of the tackifier comprises the following steps:
(1) mixing and stirring 3-methacryloxypropyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, vinyl triethoxysilane, water and a cosolvent according to the formula ratio, and reacting to obtain a hydrolysate;
(2) and (2) adding acetic acid into the hydrolysate obtained in the step (1), mixing and stirring, and adjusting the pH value to 7 to obtain the tackifier.
The double-component liquid silicone rubber adhesive comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 100 parts of base material, 8 parts of branched chain type hydrogen-containing silicone oil with the hydrogen content of 0.36 percent, 1 part of terminal hydrogen-containing silicone oil with the hydrogen content of 0.05 percent, 1 part of tackifier and 0.05 part of 1-ethynyl-cyclohexanol, wherein the hydrogen content of the branched chain type hydrogen-containing silicone oil is 0.05 percent; the component B comprises the following components in parts by weight: 100 parts of base material and 0.5 part of platinum-alkyne-based chelate with platinum content of 3000 ppm; the mass ratio of the component A to the component B is 1: 1.
The base materials of the component A and the component B comprise the following components in parts by weight: 100 parts of alpha, omega-divinyl polydimethylsiloxane (with the viscosity of 1000mpa.s and the vinyl content of 0.3%) and fumed silica (with the specific surface area of 150 m)2Per g)5 parts.
The preparation method of the bi-component liquid silicone rubber adhesive comprises the following steps:
(1) mixing and stirring the base material (alpha, omega-divinyl polydimethylsiloxane, fumed silica), the hydrogen-containing silicone oil cross-linking agent (branched hydrogen-containing silicone oil with the hydrogen content of 0.36%), the chain extender (terminal hydrogen-containing silicone oil with the hydrogen content of 0.05%), the tackifier and the inhibitor (1-ethynyl-cyclohexanol) provided by the embodiment at 30 ℃ for 30min according to the formula amount to obtain a component A; mixing and stirring the base material (alpha, omega-divinyl polydimethylsiloxane, fumed silica) and the catalyst (platinum-alkyne chelate with platinum content of 3000 ppm) at 30 ℃ for 30min according to the formula amount to prepare a component B;
(2) and (2) mixing the component A and the component B obtained in the step (1) in a mass ratio of 1:1 to obtain the bi-component liquid silicone rubber adhesive.
The two-component liquid silicone rubber adhesives prepared in the above examples 1 to 10 and the two-component liquid silicone rubber adhesives prepared in the comparative examples 1 to 7 were debubbled under vacuum conditions, and were respectively coated on the surfaces of aluminum sheets, stainless steel, glass, and ceramics, and vulcanized at 70 ℃ for 30 minutes to prepare samples, and the adhesive shear strength of each sample after aging at room temperature and 250 ℃ for 7 days was tested according to the test method of the national standard GB7124-1986, and the specific test results are shown in table 1.
TABLE 1
Figure BDA0002303225600000201
From the above test results, it can be seen that the shear strength of the bonded aluminum sheets of the two-component liquid silicone rubber adhesive prepared in examples 1-10 is still above 1Mpa, the shear strength of the bonded stainless steel is above 0.85Mpa, the shear strength of the bonded glass is above 1Mpa, and the shear strength of the bonded ceramic is above 0.87Mpa after high-temperature aging treatment. The silicon rubber adhesive prepared by the invention has good adhesion to aluminum sheets, stainless steel, glass and ceramics, and the adhesion strength is kept within a good range after being baked for 7 days at a high temperature of 250 ℃, so that the heat resistance of the silicon rubber adhesive is proved to be excellent.
In the comparative example 1, the tackifier does not use aminophenyltrimethoxysilane, but an iron oxide filler is added, the bonding performance of the tackifier is slightly worse than that of the two-component liquid silicone rubber adhesive prepared in examples 1-10 under the normal temperature condition, and the bonding shear strength of the tackifier is reduced by a larger extent after aging for 7 days than that of the tackifier added with aminophenyltrimethoxysilane and iron oxide. Comparative example 5, in which no tackifier was added, the shear strength was low both at normal temperature and after baking at high temperature, indicating that the adhesiveness of the addition type silicone rubber was greatly affected by the absence of tackifier; comparative example 6 no iron oxide filler was added, and after high temperature baking, the shear strength decreased very significantly, almost in a non-stick state; comparative example 7, in which neither aminophenyltrimethoxysilane nor iron oxide was added, showed slightly poorer adhesive strength than examples 1 to 7 under normal temperature conditions, but the magnitude of the decrease in adhesive strength after aging for 7 days was the largest in all comparative examples. Therefore, the iron oxide filler and the aminophenyl trimethoxy silane are used together to play a synergistic effect, so that the temperature resistance of the invention is further improved, and the bonding performance is good.
The applicant states that the tackifier, the preparation method thereof and the two-component liquid silicone rubber adhesive containing the tackifier are illustrated by the above examples, but the invention is not limited by the above examples, i.e. the invention is not meant to be implemented only by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (26)

1. The tackifier is characterized by comprising the following raw materials in parts by weight: 50-80 parts of 3-methacryloxypropyltrimethoxysilane, 30-60 parts of aminophenyltrimethoxysilane, 10-30 parts of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, 5-20 parts of vinyl triethoxysilane, 5-15 parts of pH regulator, 30-50 parts of water and 70-90 parts of cosolvent;
the tackifier is prepared by the preparation method:
(1) mixing and stirring 3-methacryloxypropyltrimethoxysilane, aminophenyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, vinyl triethoxysilane, water and a cosolvent according to the formula ratio, and reacting to obtain a hydrolysate;
(2) and (2) adding a pH regulator into the hydrolysate obtained in the step (1), and mixing and stirring to obtain the tackifier.
2. The adhesion promotion agent of claim 1 wherein the pH adjustment agent comprises any one or a combination of at least two of acetic acid, hydrochloric acid, or carbonic acid.
3. The viscosifying agent of claim 1, wherein the co-solvent comprises any one of ethanol, ethylene glycol, propylene glycol, or glycerol, or a combination of at least two thereof.
4. The viscosifying agent of claim 3, wherein the co-solvents are ethanol and glycerol.
5. The viscosifying agent of claim 1, characterized in that the viscosifying agent has a pH of 6-8.
6. The method for preparing the tackifier according to any one of claims 1 to 5, wherein the method comprises the steps of:
(1) mixing and stirring 3-methacryloxypropyltrimethoxysilane, aminophenyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, vinyl triethoxysilane, water and a cosolvent according to the formula ratio, and reacting to obtain a hydrolysate;
(2) and (2) adding a pH regulator into the hydrolysate obtained in the step (1), and mixing and stirring to obtain the tackifier.
7. The method as claimed in claim 6, wherein the stirring temperature in step (1) is 100-120 ℃, and the stirring time is 120-150 min.
8. The method according to claim 6, wherein the stirring temperature in the step (2) is 20 to 30 ℃ and the stirring time is 5 to 10 min.
9. The bi-component liquid silicone rubber adhesive is characterized by comprising a component A and a component B;
the component A comprises the following components in parts by weight: 80-120 parts of base stock, 1-20 parts of hydrogen-containing silicone oil cross-linking agent, 0.1-5 parts of chain extender, 0.1-5 parts of tackifier as defined in any one of claims 1-5 and 0.005-0.2 parts of inhibitor;
the component B comprises the following components in parts by weight: 80-120 parts of base material and 0.1-5 parts of catalyst;
the base materials of the component A and the component B comprise the following components in parts by weight: 80-120 parts of alpha, omega-divinyl polydimethylsiloxane, 80-120 parts of ferric oxide and 1-15 parts of fumed silica.
10. The two-component liquid silicone rubber adhesive according to claim 9, wherein the mass ratio of the component A to the component B is (0.8-1.2): 1.
11. The two-part liquid silicone rubber adhesive according to claim 9, wherein the viscosity of the α, ω -divinylpolydimethylsiloxane is 1000-.
12. The two-part liquid silicone rubber adhesive of claim 9, wherein the α, ω -divinylpolydimethylsiloxane has a vinyl content of 0.1 to 0.4%.
13. The two-part liquid silicone rubber adhesive of claim 9, wherein the particle size of the ferric oxide is 5-15 μm.
14. The two-component liquid silicone rubber adhesive as claimed in claim 9, wherein the fumed silica has a specific surface area of 100-380m2/g。
15. The two-component liquid silicone rubber adhesive according to claim 9, wherein the hydrogen-containing silicone oil cross-linking agent is a branched-chain type hydrogen-containing silicone oil, and the hydrogen content of the branched-chain type hydrogen-containing silicone oil is 0.36-0.56 wt%.
16. The two-component liquid silicone rubber adhesive according to claim 9, wherein the chain extender is hydrogen-terminated silicone oil, and the hydrogen content of the hydrogen-terminated silicone oil is 0.05% -0.1%.
17. The two-part liquid silicone rubber adhesive of claim 9, wherein the inhibitor comprises any one of 1-ethynyl-cyclohexanol, 2-methyl-3-butyn-2-ol, 2-methyl-1-hexyn-3-ol, 3, 5-dimethyl-1-ethynyl-3-ol, or 3,7, 11-trimethyl-1-dodecayn-3-ol, or a combination of at least two thereof.
18. The two-part liquid silicone rubber adhesive of claim 9, wherein the catalyst is a platinum catalyst.
19. The two-component liquid silicone rubber adhesive of claim 18, wherein the platinum content in the platinum catalyst is 1000-5000 ppm.
20. The two-part liquid silicone rubber adhesive of claim 18, wherein the platinum catalyst comprises any one of or a combination of at least two of platinum vinyl siloxane, platinum-alkyne chelate, or chloroplatinic acid.
21. The two-part liquid silicone rubber adhesive of claim 20, wherein the platinum vinyl siloxane comprises any one of or a combination of at least two of a tetramethyltetravinylcyclotetrasiloxane chloroplatinate complex, a tetramethyldivinyldisiloxane chloroplatinate complex, or a diphenyldivinyltetrachlorodisiloxane complex chloroplatinate.
22. The two-part liquid silicone rubber adhesive of claim 20, wherein the platinum-alkyne-based chelate includes any one of bis (alkynyl) bis (triphenylphosphine) platinum chelate or bis (alkynyl) (cyclodialkenyl) chelate or a combination of at least two thereof.
23. The method of preparing the two-part liquid silicone rubber adhesive according to any one of claims 9-22, wherein the method of preparing comprises the steps of:
(1) mixing and stirring the base material, the hydrogen-containing silicone oil cross-linking agent, the chain extender, the tackifier and the inhibitor according to any one of claims 1 to 5 according to the formula amount to prepare a component A; mixing and stirring the base material and the catalyst according to the formula amount to prepare a component B;
(2) and (2) mixing the component A and the component B obtained in the step (1) to obtain the bi-component liquid silicone rubber adhesive.
24. The method for preparing the two-component liquid silicone rubber adhesive according to claim 23, wherein in step (1), the stirring time for preparing the component A and the component B is 30-40min, and the stirring temperature for preparing the component A and the component B is 20-30 ℃.
25. The method for preparing the two-component liquid silicone rubber adhesive according to claim 23, wherein the mixing time in step (2) is 5-10min, and the mixing temperature is 20-30 ℃.
26. Use of the two-part liquid silicone rubber adhesive according to any one of claims 9 to 22 in bonding aluminum substrates, stainless steel substrates, glass substrates or ceramic substrates.
CN201911229810.3A 2019-12-04 2019-12-04 Tackifier, preparation method thereof and bi-component liquid silicone rubber adhesive containing tackifier Active CN110818904B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911229810.3A CN110818904B (en) 2019-12-04 2019-12-04 Tackifier, preparation method thereof and bi-component liquid silicone rubber adhesive containing tackifier

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911229810.3A CN110818904B (en) 2019-12-04 2019-12-04 Tackifier, preparation method thereof and bi-component liquid silicone rubber adhesive containing tackifier

Publications (2)

Publication Number Publication Date
CN110818904A CN110818904A (en) 2020-02-21
CN110818904B true CN110818904B (en) 2021-06-29

Family

ID=69544008

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911229810.3A Active CN110818904B (en) 2019-12-04 2019-12-04 Tackifier, preparation method thereof and bi-component liquid silicone rubber adhesive containing tackifier

Country Status (1)

Country Link
CN (1) CN110818904B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112094413A (en) * 2020-09-15 2020-12-18 湖北大学 Self-repairing type siloxane polymer for bonding lithium battery electrode and preparation method thereof
CN112680180B (en) * 2020-12-28 2022-04-15 广州市白云化工实业有限公司 Addition type silicone rubber with high bonding strength and preparation method thereof
CN113801626A (en) * 2021-09-24 2021-12-17 广州集泰化工股份有限公司 Single-component addition type adhesive and preparation method thereof
CN114321122A (en) * 2021-12-03 2022-04-12 武汉航空仪表有限责任公司 Forming method of bi-component fireproof flame-retardant organic silicon sealant
CN116836392A (en) * 2023-08-01 2023-10-03 深圳市晨日科技股份有限公司 Organosilicon tackifier and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104177837A (en) * 2014-08-06 2014-12-03 绵阳惠利电子材料有限公司 Tackifier and preparation method thereof as well as addition-type organic silicon rubber and preparation method thereof
CN104892945A (en) * 2015-06-06 2015-09-09 深圳市富达瑞有机硅材料有限公司 Organic silicon rubber composite tackifier and preparation method thereof
CN109897182A (en) * 2019-03-02 2019-06-18 江西省龙海化工有限公司 A kind of aqueous macromolecular amount silane coupling agent and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8261833B2 (en) * 2009-02-25 2012-09-11 Halliburton Energy Services, Inc. Methods and compositions for consolidating particulate matter in a subterranean formation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104177837A (en) * 2014-08-06 2014-12-03 绵阳惠利电子材料有限公司 Tackifier and preparation method thereof as well as addition-type organic silicon rubber and preparation method thereof
CN104892945A (en) * 2015-06-06 2015-09-09 深圳市富达瑞有机硅材料有限公司 Organic silicon rubber composite tackifier and preparation method thereof
CN109897182A (en) * 2019-03-02 2019-06-18 江西省龙海化工有限公司 A kind of aqueous macromolecular amount silane coupling agent and preparation method thereof

Also Published As

Publication number Publication date
CN110818904A (en) 2020-02-21

Similar Documents

Publication Publication Date Title
CN110818904B (en) Tackifier, preparation method thereof and bi-component liquid silicone rubber adhesive containing tackifier
KR101293184B1 (en) Pt-CATALYZED, ADDITION-CROSSLINKING SILICONE COMPOSITIONS SELF-ADHESIVE AT ROOM TEMPERATURE
CN100485008C (en) Primer for heat curing polysiloxanes elastomer
WO2018043270A1 (en) Curable organopolysiloxane composition, and protection agent or adhesive composition for electrical/electronic components
TW201609978A (en) Curable organopolysiloxane composition and encapsulant or adhesive composition for electrical/electronic devices
CA2061974A1 (en) Addition-curable silicone adhesive compositions
US5468805A (en) Room-temperature-curable organopolysiloxane composition method for its preparation
CN111394052B (en) Dealcoholized condensed type double-component room temperature vulcanized silicone rubber and preparation method thereof
TWI417343B (en) Room temperature hardened organopolysiloxane composition
TWI415901B (en) Room temperature hardened organopolysiloxane compositions and planar panel display devices
CN114262550A (en) Silane modified acrylic resin, synthetic method and primer for silicone rubber
TW201542741A (en) Adhesion promoter, curable organopolysiloxane composition comprising thereof
CN113583626B (en) Organic silicon gel and preparation method thereof
TWI404764B (en) Room temperature hardening polyorganosiloxane composition
TWI462970B (en) Room-temperature curable organopolysiloxane composition
CN112210341B (en) Double-vulcanization system building sealant and preparation method thereof
EP2060597B1 (en) Method for bonding polyamide resin and fluoroelastomer
KR20150013174A (en) Curable resin composition and primer composition
US11795274B2 (en) Crosslinkable compositions based on organopolysiloxanes having organyloxy groups
KR20090122510A (en) Silicone composition for dielectrically encapsulating electronic device
CN113698911A (en) Organic silicon gel and preparation method thereof
CN113667310B (en) Liquid silicone rubber and preparation method and application thereof
KR101325890B1 (en) Self-adhesive hardener composition
JP2015199851A (en) Protectant or adhesive composition for electric and electronic component
JP7353026B2 (en) Room temperature curable polyorganosiloxane composition and cured product thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP01 Change in the name or title of a patent holder
CP01 Change in the name or title of a patent holder

Address after: Guangzhou private science and Technology Park Yunan road Baiyun District of Guangzhou City, Guangdong Province, No. 1 510540

Patentee after: Guangzhou Baiyun Technology Co.,Ltd.

Address before: Guangzhou private science and Technology Park Yunan road Baiyun District of Guangzhou City, Guangdong Province, No. 1 510540

Patentee before: GUANGZHOU BAIYUN CHEMICAL INDUSTRY Co.,Ltd.