CN107722874B - Adhesive, preparation method and application thereof, and bonding method - Google Patents

Adhesive, preparation method and application thereof, and bonding method Download PDF

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Publication number
CN107722874B
CN107722874B CN201711082416.2A CN201711082416A CN107722874B CN 107722874 B CN107722874 B CN 107722874B CN 201711082416 A CN201711082416 A CN 201711082416A CN 107722874 B CN107722874 B CN 107722874B
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adhesive
rubber
parts
cross
solvent
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CN107722874A (en
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钟行
林华端
胡智枫
王林
邹婉艳
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Cproton Chemical Industry Co ltd
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Cproton Chemical Industry 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
    • C09J115/00—Adhesives based on rubber derivatives
    • C09J115/02—Rubber derivatives containing halogen
    • 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
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5455—Silicon-containing compounds containing nitrogen containing at least one group

Abstract

The invention relates toThe adhesive is prepared from at least rubber, a cross-linking agent and a solvent, wherein the cross-linking agent at least comprises an organic matter with isocyanate groups. The preparation method comprises the following steps: mixing the raw materials, and grinding. The bonding method of the adhesive comprises the following steps: coating the adhesive on the surface of a metal base material, baking at 165-175 ℃, attaching the natural rubber to the adhesive, and then placing the adhesive on a vulcanizing machine for heat vulcanization. The cross-linking agent can form a cross-linking structure with a rubber tissue at high temperature, and meanwhile, the rubber can also be vulcanized to form the cross-linking structure, the two cross-linking structures are mutually interpenetrated to form a very stable net structure, so that the adhesive has high bonding strength, and does not contain Pb3O4It is harmless to human body and has high adhesive strength.

Description

Adhesive, preparation method and application thereof, and bonding method
Technical Field
The invention relates to the field of materials, in particular to an adhesive, a preparation method and application thereof, and an adhesion method.
Background
Adhesive (adhesive): natural or synthetic, organic or inorganic substances, also called adhesives, are used to connect two or more parts or materials together by the actions of interfacial adhesion and cohesion, and are commonly called adhesives. In short, the adhesive is used for connecting the surfaces of homogeneous or heterogeneous objects together by the adhesive through the adhesion effect, and has the characteristics of continuous stress distribution, light weight, sealing, low process temperature and the like. The adhesive is suitable for connection of different materials, different thicknesses, ultrathin specifications and complex components.
The adhesive method is widely adopted for bonding rubber and metal, most of the adhesive systems on the market adopt aromatic nitroso compounds, and the aromatic nitroso compounds are generally mixed with Pb3O4In combination with Pb3O4The main functions are to oxidize the precursor of the aromatic nitroso compound into the aromatic nitroso compound and excite the aromatic nitroso compoundThe activity of the aromatic nitroso compound enables the aromatic nitroso compound to be combined with natural rubber and metal to form strong binding power.
However, the European Union promulgated Pb, which limited the lead content act, was toxic and had some carcinogenicity, on 7/1/20033O4The use of the product in the same industry in China has been forbidden for a long time. Therefore, there is a need for a Pb-free composition3O4And has an adhesive with strong adhesive property to rubber and metal.
Disclosure of Invention
The first object of the present invention is to provide an adhesive agent so that it does not contain Pb3O4It is harmless to human body, and has strong adhesive property to rubber and metal.
The second object of the present invention is to provide a method for preparing an adhesive agent to obtain Pb-free adhesive agent by a simple process3O4And the adhesive has strong adhesive property to rubber and metal.
The third objective of the present invention is to provide a bonding method of the adhesive, so that the adhesive can bond the natural rubber and the metal well, and a good bonding effect can be achieved.
The fourth purpose of the present invention is to provide an application of the adhesive in bonding natural rubber and metal, so as to achieve a good bonding effect between natural rubber and metal and to be harmless to human body.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The adhesive provided by the invention is prepared from at least the following raw materials: rubber, cross-linking agent and solvent; wherein the crosslinking agent comprises at least an organic substance having an isocyanate group.
The invention also relates to a preparation method of the adhesive, which comprises the following steps: mixing the raw materials, and grinding.
The invention also relates to a bonding method of the upper adhesive, which comprises the following steps: coating the adhesive on the surface of a metal base material, baking at 165-175 ℃, attaching the natural rubber to the adhesive, and then placing the adhesive on a vulcanizing machine for heat vulcanization.
The invention also relates to the application of the adhesive in bonding natural rubber and metal.
The cross-linking agent can form a cross-linking structure with a rubber tissue at high temperature, and meanwhile, the rubber can also be vulcanized to form the cross-linking structure, the two cross-linking structures are mutually interpenetrated to form a very stable net structure, so that the adhesive has high bonding strength, and does not contain Pb3O4It is harmless to human body and has high adhesive strength.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. Those whose specific conditions are not specified in the embodiment or examples are carried out according to the conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The adhesive of the embodiment of the invention, the preparation method and the application thereof, and the bonding method are specifically described below.
Some embodiments of the present invention provide an adhesive prepared from at least the following raw materials: rubber, cross-linking agent and solvent; wherein the crosslinking agent comprises at least an organic substance having an isocyanate group.
Some embodiments of the present invention provide an adhesive, which is prepared from at least the following raw materials in parts by weight: 10-15 parts of rubber, 10-15 parts of a cross-linking agent and 55-75 parts of a solvent, wherein the cross-linking agent at least comprises an organic matter containing isocyanate groups.
The invention further provides an adhesive, which is prepared from at least 10-15 parts of rubber, 10-15 parts of a cross-linking agent, 5-10 parts of a filler and 55-75 parts of a solvent by weight, wherein the cross-linking agent at least comprises an organic substance containing isocyanate groups.
Some embodiments of the invention also provide an adhesive, which is prepared from the following raw materials, by weight, 10-15 parts of rubber, 10-15 parts of a cross-linking agent, 5-10 parts of a filler and 55-75 parts of a solvent.
According to some embodiments, the rubber may be 10 to 15 parts, or 12 to 13 parts by weight; the cross-linking agent can be 10-15 parts, or 12-13 parts; the filler can be 5-10 parts, or 5-8 parts, or 6-8 parts; the solvent may be 55-75 parts, or 60-70 parts, or 65-70 parts.
According to some embodiments, the organic material having isocyanate groups includes one or more of isocyanatopropyltriethoxysilane, hexamethylene diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate, for example, the organic material having isocyanate groups is isocyanatopropyltriethoxysilane, and also toluene diisocyanate, and also a mixture of isocyanatopropyltriethoxysilane and hexamethylene diisocyanate, and preferably, the organic material having isocyanate groups is isocyanatopropyltriethoxysilane.
In the embodiment of the invention, because the organic matter with isocyanate groups is adopted, the use of lead tetraoxide with higher toxicity is avoided, and the isocyanate groups of the organic matter with isocyanate groups can react with metal and rubber to generate higher bonding strength. The isocyanate group of the organic matter with the isocyanate group can enter the rubber tissue and generate self-polymerization reaction at high temperature to form a cross-linking structure, and meanwhile, the rubber can also be vulcanized to form a cross-linking structure, and the two cross-linking structures are mutually interpenetrated to form a stable net structure. The isocyanate has extremely high activity at high temperature, can generate urea with moisture on the surface of metal, and the urea compound can be further chelated with metal hydride to form a firm hydrogen bond, so that the isopropyltriethoxysilane can react with metal and rubber to generate relatively high bonding strength. Particularly, when the organic matter having an isocyanate group is isocyanatopropyltriethoxysilane, the network structure formed by the organic matter having an isocyanate group is better and the adhesive strength is higher.
According to some embodiments, the rubber is a chlorinated rubber, preferably, the chlorinated rubber is a chlorinated natural rubber.
According to some embodiments, the crosslinking agent includes one or more of p-dinitrosobenzene, p-benzoquinone dioxime, and dicumyl peroxide, and an organic substance having an isocyanate group, for example, the crosslinking agent is an organic substance having an isocyanate group and p-dinitrosobenzene, or an organic substance having an isocyanate group and p-benzoquinone dioxime, or an organic substance having an isocyanate group and dicumyl peroxide, or an organic substance having an isocyanate group, p-dinitrosobenzene, p-benzoquinone dioxime, and the like.
Preferably, the crosslinking agent includes one or both of p-benzoquinone dioxime and dicumyl peroxide, and organic matter having an isocyanate group and p-dinitrosobenzene, for example, the crosslinking agent includes organic matter having an isocyanate group, p-dinitrosobenzene, p-benzoquinone dioxime and dicumyl peroxide, wherein the mass ratio of the p-dinitrosobenzene in the crosslinking agent is 70-90%.
The dinitrosobenzene can be used as a tackifier, dicumyl peroxide is decomposed at high temperature to form a free active radical, and the free active radical can excite the activity of the dinitrosobenzene, so that the dinitrosobenzene and rubber generate a crosslinking effect, and the binding power of an adhesive product is further improved.
According to some embodiments, the solvent comprises one or more of xylene, toluene and tetrachloroethylene, preferably the solvent comprises one or both of toluene and tetrachloroethylene and xylene, for example the solvent comprises xylene and toluene, or xylene and tetrachloroethylene, or xylene, toluene and tetrachloroethylene. Further preferably, the mass ratio of xylene to the solvent is 60% or more. Among them, tetrachloroethylene is preferable because tetrachloroethylene is easily decomposed at high temperature to generate toxic corrosive fumes.
According to some embodiments, the filler includes one or more of carbon black, silica, and zinc oxide, for example, the filler may be carbon black, silica, or zinc oxide, and may also be carbon black, silica, or the like. Preferably, the filler comprises carbon black and one or more of white carbon black, silica and zinc oxide, and the proportion of the carbon black in the filler is not less than 80%. Carbon black, as a reinforcing filler in rubber vulcanization, has a significant impact on the rubber's physical mechanical process.
Some embodiments of the present invention also relate to a method of preparing the above adhesive, comprising: mixing various raw materials, grinding, preferably, the grinding fineness is 5-10 mu m, and preferably, the solid content of the adhesive is controlled to be 20-30%.
When the raw materials include rubber, a solvent, dinitrosobenzene, p-benzoquinone dioxime, a filler, and an organic matter having an isocyanate group, some embodiments of the present invention also relate to a method for preparing the above adhesive, which includes: firstly, dissolving rubber in a solvent to form a rubber solution, mixing and grinding part of the rubber solution, dinitrosobenzene, p-benzoquinone dioxime and a filler, and then adding the rest of the rubber solution and an organic matter with an isocyanate group; wherein the rubber solution for grinding can account for 40-60% of the rubber solution. By adopting the mode, various substances can be mixed with each other to form a system with uniform phase, and better bonding strength can be achieved when bonding is carried out conveniently.
Some embodiments of the invention also relate to a method of preparing an adhesive: dissolving chlorinated natural rubber and mixed xylene in proportion, taking a certain amount of rubber solution, adding p-dinitrosobenzene, p-benzoquinone dioxime, a filler and a mixed xylene solvent in proportion, placing the mixture in a sand mill for grinding, controlling the fineness to be 5-10 mu m, after grinding, adding the rest rubber solution and isocyanatopropyl triethoxysilane to obtain an adhesive product, and controlling the solid content of the adhesive to be 20-30%, wherein the mixed xylene solvent is a mixed solvent jointly composed of other solvents such as toluene and the like besides xylene, and the ground rubber solution can account for 40-60% of the rubber solution.
Some embodiments of the present invention also relate to a method for bonding the above adhesive, which comprises the following steps: coating an adhesive on the surface of a metal base material, baking at 165-175 ℃, attaching natural rubber to the adhesive, and then placing the adhesive on a vulcanizing machine for heat vulcanization; preferably, the baking time is 4-6 min; preferably, the vulcanizing temperature is 165-175 ℃, and the vulcanizing time is 4-6 min. Wherein the baking can be performed in an oven.
Through the baking and hot vulcanization processes, the isocyanate groups of the organic matters with the isocyanate groups can enter the rubber tissues, the self-polymerization reaction is carried out at high temperature to form a cross-linking structure, meanwhile, the rubber can also be vulcanized to form the cross-linking structure, and the two cross-linking structures are mutually interpenetrated to form a very stable net structure. The isocyanate has extremely high activity at high temperature, can generate urea with moisture on the surface of metal, and the urea compound can be further chelated with metal hydride to form a firm hydrogen bond, so that the isopropyltriethoxysilane can react with metal and rubber to generate relatively high bonding strength.
In addition, dicumyl peroxide is decomposed at high temperature to form free activating groups, and the free activating groups can excite the activity of dinitrosobenzene, so that the dinitrosobenzene and rubber generate a crosslinking effect, and the binding power of an adhesive product is further improved.
Some embodiments of the invention also relate to the use of adhesives to bond natural rubber to metal.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The adhesive provided in this embodiment is prepared from the following raw materials in parts by weight: 15 parts of rubber, 15 parts of a cross-linking agent, 10 parts of a filler and 75 parts of a solvent.
Wherein the rubber is chlorinated natural rubber. The cross-linking agent is a mixture of dinitrosobenzene, dicumyl peroxide and isocyanatopropyltriethoxysilane, wherein the dinitrosobenzene accounts for 70% of the mass ratio of the cross-linking agent, the dicumyl peroxide accounts for 10% of the mass ratio of the dinitrosobenzene, and the isocyanatopropyltriethoxysilane accounts for 20% of the mass ratio of the dinitrosobenzene. The solvent is a mixture of xylene and toluene, and the mass ratio of the xylene in the solvent is 65%. The filler is a mixture of carbon black and white carbon black, and the carbon black accounts for 85% of the filler.
The preparation method of the adhesive of the embodiment comprises the following steps: dissolving chlorinated natural rubber and a solvent in proportion, adding 40% of rubber solution into dinitrosobenzene and a filler in proportion, placing the mixture into a sand mill for grinding, controlling the fineness to be 6 mu m, and after grinding is finished, adding the rest of rubber solution and isocyanatopropyltriethoxysilane to obtain an adhesive product, wherein the solid content of the adhesive is controlled to be 25%.
Coating the adhesive on the surface of a metal base material, baking for 4min at 165 ℃, then adhering natural rubber to the adhesive, and then placing the adhesive on a vulcanizing machine for heat vulcanization at the vulcanization temperature of 170 ℃ for 4 min. Wherein the baking is performed in an oven.
Example 2
The adhesive provided in this embodiment is prepared from the following raw materials in parts by weight: 10 parts of rubber, 10 parts of a cross-linking agent, 5 parts of a filler and 60 parts of a solvent.
Wherein the rubber is chlorinated natural rubber. The cross-linking agent is a mixture of dinitrosobenzene, dicumyl peroxide and isocyanatopropyltriethoxysilane, wherein the dinitrosobenzene accounts for 80% of the mass ratio of the cross-linking agent, the dicumyl peroxide accounts for 5% of the mass ratio of the cross-linking agent, and the isocyanatopropyltriethoxysilane accounts for 15% of the mass ratio of the dinitrosobenzene. The solvent is a mixture of xylene and toluene, and the mass ratio of the xylene in the solvent is 70%. The filler is a mixture of carbon black and white carbon black, and the proportion of the carbon black in the filler is 90%.
The preparation method of the adhesive of the embodiment comprises the following steps: dissolving chlorinated natural rubber and a solvent in proportion, adding 50% of rubber solution into dinitrosobenzene and a filler in proportion, placing the mixture into a sand mill for grinding, controlling the fineness to be 9 mu m, and after grinding is finished, adding the rest of rubber solution and isocyanatopropyltriethoxysilane to obtain an adhesive product, wherein the solid content of the adhesive is controlled to be 29%.
Coating the adhesive on the surface of a metal base material, baking at 175 ℃ for 4min, then adhering natural rubber to the adhesive, and then placing the adhesive on a vulcanizing machine for heat vulcanization at the vulcanization temperature of 165 ℃ for 6 min. Wherein the baking is performed in an oven.
Example 3
The adhesive provided in this embodiment is prepared from the following raw materials in parts by weight: 12 parts of rubber, 13 parts of a cross-linking agent, 7 parts of a filler and 70 parts of a solvent.
Wherein the rubber is chlorinated natural rubber. The cross-linking agent is a mixture of dinitrosobenzene, dicumyl peroxide and isocyanatopropyltriethoxysilane, wherein the dinitrosobenzene accounts for 85% of the mass ratio of the cross-linking agent, the dicumyl peroxide accounts for 5% of the mass ratio of the cross-linking agent, and the isocyanatopropyltriethoxysilane accounts for 10% of the mass ratio of the dinitrosobenzene. The solvent is a mixture of xylene and toluene, and the mass ratio of the xylene in the solvent is 75%. The filler is a mixture of carbon black and white carbon black, and the carbon black accounts for 95% of the filler.
The preparation method of the adhesive of the embodiment comprises the following steps: dissolving chlorinated natural rubber and a solvent in proportion, adding p-dinitrosobenzene and a filler into 55% of rubber solution in proportion, grinding the mixture in a sand grinder with the fineness controlled at 7 mu m, and adding the rest rubber solution and isocyanatopropyltriethoxysilane into the mixture after grinding to obtain an adhesive product, wherein the solid content of the adhesive is controlled at 27%.
Coating the adhesive on the surface of a metal base material, baking for 5min at 170 ℃, then adhering the natural rubber to the adhesive, and then placing the adhesive on a vulcanizing machine for heat vulcanization at the vulcanization temperature of 170 ℃ for 5 min. Wherein the baking is performed in an oven.
Example 4
The adhesive provided in this embodiment is prepared from the following raw materials in parts by weight: 13 parts of rubber, 12 parts of a cross-linking agent, 8 parts of a filler and 65 parts of a solvent.
Wherein the rubber is chlorinated natural rubber. The cross-linking agent is a mixture of dinitrosobenzene, dicumyl peroxide and isocyanatopropyltriethoxysilane, wherein the dinitrosobenzene accounts for 85% of the mass ratio of the cross-linking agent, the dicumyl peroxide accounts for 5% of the mass ratio of the cross-linking agent, and the isocyanatopropyltriethoxysilane accounts for 10% of the mass ratio of the dinitrosobenzene. The solvent is a mixture of xylene and toluene, and the mass ratio of the xylene in the solvent is 75%. The filler is a mixture of carbon black and white carbon black, and the carbon black accounts for 95% of the filler.
The preparation method of the adhesive of the embodiment comprises the following steps: dissolving chlorinated natural rubber and a solvent in proportion, adding p-dinitrosobenzene and a filler into 55% of rubber solution in proportion, grinding the mixture in a sand grinder with the fineness controlled at 7 mu m, and adding the rest rubber solution and isocyanatopropyltriethoxysilane into the mixture after grinding to obtain an adhesive product, wherein the solid content of the adhesive is controlled at 27%.
Coating the adhesive on the surface of a metal base material, baking for 5min at 170 ℃, then adhering the natural rubber to the adhesive, and then placing the adhesive on a vulcanizing machine for heat vulcanization at the vulcanization temperature of 170 ℃ for 5 min. Wherein the baking is performed in an oven.
Example 5
The adhesive provided in this embodiment is prepared from the following raw materials in parts by weight: 12 parts of rubber, 11 parts of a cross-linking agent, 6 parts of a filler and 59 parts of a solvent.
Wherein the rubber is chlorinated natural rubber. The cross-linking agent is a mixture of dinitrosobenzene, dicumyl peroxide and isocyanatopropyltriethoxysilane, wherein the dinitrosobenzene accounts for 85% of the mass ratio of the cross-linking agent, the dicumyl peroxide accounts for 5% of the mass ratio of the cross-linking agent, and the isocyanatopropyltriethoxysilane accounts for 10% of the mass ratio of the dinitrosobenzene. The solvent is a mixture of xylene and toluene, and the mass ratio of the xylene in the solvent is 75%. The filler is a mixture of carbon black and white carbon black, and the carbon black accounts for 95% of the filler.
The preparation method of the adhesive of the embodiment comprises the following steps: dissolving chlorinated natural rubber and a solvent in proportion, adding p-dinitrosobenzene and a filler into 55% of rubber solution in proportion, grinding the mixture in a sand grinder with the fineness controlled at 7 mu m, and adding the rest rubber solution and isocyanatopropyltriethoxysilane into the mixture after grinding to obtain an adhesive product, wherein the solid content of the adhesive is controlled at 27%.
Coating the adhesive on the surface of a metal base material, baking for 5min at 170 ℃, then adhering the natural rubber to the adhesive, and then placing the adhesive on a vulcanizing machine for heat vulcanization at the vulcanization temperature of 170 ℃ for 5 min. Wherein the baking is performed in an oven.
Example 6
The adhesive provided in this embodiment is prepared from the following raw materials in parts by weight: 13 parts of rubber, 12 parts of a cross-linking agent, 8 parts of a filler and 65 parts of a solvent.
Wherein, the organic matter of the isocyanate group is isocyanic acid propyl triethoxy silane, and the rubber is chlorinated natural rubber. The cross-linking agent is a mixture of dinitrosobenzene, p-benzoquinone dioxime, dicumyl peroxide and isocyanatopropyltriethoxysilane, wherein the mass ratio of the dinitrosobenzene to the cross-linking agent is 70%, the mass ratio of the dicumyl peroxide to the cross-linking agent is 5%, the mass ratio of the p-benzoquinone dioxime to the isocyanatopropyltriethoxysilane is 20%. The solvent is xylene and the filler is carbon black.
The preparation method of the adhesive of the embodiment comprises the following steps: dissolving chlorinated natural rubber and a solvent in proportion, taking 55% of rubber solution, adding p-dinitrosobenzene, p-benzoquinone dioxime and a filler in proportion, placing the mixture in a sand mill for grinding, controlling the fineness to be 7 mu m (changing to be mu m), and after grinding, adding the rest of rubber solution and isocyanatopropyltriethoxysilane to obtain an adhesive product, wherein the solid content of the adhesive is controlled to be 27%.
Coating the adhesive on the surface of a metal base material, baking for 5min at 170 ℃, then adhering the natural rubber to the adhesive, and then placing the adhesive on a vulcanizing machine for heat vulcanization at the vulcanization temperature of 170 ℃ for 5 min. Wherein the baking is performed in an oven.
Examples 7 to 9
This example differs from example 3 only in that the isopropyltriethoxysilane isocyanate is replaced with hexamethylene diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate in that order.
The bonded products obtained in examples 1 to 9 were examined for the adhesion strength between the vulcanized rubber and the hard plate in GB/T7760-2003, and the retention ratio of the rubber remaining in the bonded area was recorded. The results are shown in Table I.
Watch 1
Detecting items 90 degree peel adhesion Strength after vulcanization (KN/m)
Example 1 10.8
Example 2 11.2
Example 3 11.0
Example 4 10.5
Example 5 11.3
Example 6 11.4
Example 7 10.8
Example 8 10.6
Example 9 10.3
As can be seen from the table I, the adhesive provided by the embodiment of the invention has good bonding strength to bonding between natural rubber and metal.
In conclusion, the cross-linking agent can form a cross-linking structure with a rubber tissue at high temperature, and simultaneously, the rubber can be vulcanized to form the cross-linking structure, the two cross-linking structures are mutually interpenetrated to form a very stable net structure, so that the adhesive has high bonding strength, and the adhesive does not contain Pb3O4It is harmless to human body and has high adhesive strength.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (16)

1. An adhesive, characterized in that it is prepared from at least the following raw materials: rubber, cross-linking agent and solvent; the raw materials comprise the following components in parts by weight: 10-15 parts of rubber, 10-15 parts of a cross-linking agent and 55-75 parts of a solvent, wherein the cross-linking agent at least comprises an organic matter with an isocyanate group, the organic matter with the isocyanate group is isocyanatopropyltriethoxysilane, and the solvent comprises xylene and one or two of toluene and tetrachloroethylene;
the cross-linking agent also comprises p-dinitrosobenzene and dicumyl peroxide, wherein the mass ratio of the p-dinitrosobenzene in the cross-linking agent is 70-90%.
2. The adhesive of claim 1 wherein the rubber is a chlorinated rubber in parts by weight.
3. The adhesive of claim 2 wherein the chlorinated rubber is chlorinated natural rubber.
4. The adhesive according to claim 1, wherein the mass ratio of the xylene to the solvent is greater than or equal to 60%.
5. The adhesive according to any one of claims 1 to 4, characterized in that the raw materials further comprise a filler.
6. The adhesive of claim 5 wherein the filler comprises one or more of carbon black, silica and zinc oxide.
7. The adhesive of claim 5 wherein the filler comprises carbon black and one or more of silica and zinc oxide.
8. The adhesive according to claim 5, characterized in that the raw materials comprise, in parts by weight: 10-15 parts of rubber, 10-15 parts of a cross-linking agent, 5-10 parts of a filler and 55-75 parts of a solvent.
9. The method for preparing the adhesive according to any one of claims 1 to 8, wherein the method comprises the following steps: mixing the raw materials and grinding.
10. The preparation method of the adhesive according to claim 9, wherein the grinding fineness is 5-10 μm.
11. The method for preparing the adhesive according to claim 9, wherein the solid content of the adhesive is controlled to be 20-30%.
12. The method of claim 9, wherein when the raw materials include the rubber, the solvent, p-dinitrosobenzene, filler and the organic matter having isocyanate groups, the rubber is dissolved in the solvent to form a rubber solution, a part of the rubber solution is mixed with the p-dinitrosobenzene and the filler and ground, and the rest of the rubber solution and the organic matter having isocyanate groups are added.
13. The method for bonding adhesives according to any one of claims 1 to 8, comprising the steps of: after the adhesive is coated on the surface of a metal base material, baking is carried out at 165-175 ℃, then natural rubber is attached to the adhesive, and then the adhesive is placed on a vulcanizing machine for heat vulcanization.
14. The method for bonding adhesives according to claim 13, wherein the baking time is 4-6 min.
15. The method for bonding adhesives according to claim 13, wherein the vulcanization temperature is 165-175 ℃ and the vulcanization time is 4-6 min.
16. Use of the adhesive according to any one of claims 1 to 8 for bonding natural rubber and metal.
CN201711082416.2A 2017-11-07 2017-11-07 Adhesive, preparation method and application thereof, and bonding method Active CN107722874B (en)

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CN112812711B (en) * 2021-01-25 2023-07-18 安徽普力通新材料科技有限公司 High-reactivity metal-rubber hot vulcanization adhesive and application method thereof
CN115366431A (en) * 2022-07-01 2022-11-22 宁波永灵航空科技有限公司 Method for fixing silicon rubber and metal parts for processing parts of aero-engine

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CN102807832B (en) * 2012-07-12 2013-12-04 同济大学 Environment-friendly adhesive for bonding metal and elastomer
CN103627345A (en) * 2013-11-07 2014-03-12 贾梦虹 Silane coupling agent and preparation method thereof as well as metal adhesive containing silane coupling agent
CN105349064A (en) * 2015-12-15 2016-02-24 上海橡胶制品研究所有限公司 Adhesive for carrying out heat vulcanization adhesion on EPDM (Ethylene-Propylene-Diene Monomer) and metal
CN105670548B (en) * 2016-03-01 2018-10-26 沈阳化工大学 A kind of natural rubber/styrene-butadiene rubber metal fever vulcanizing adhesive

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