CN116162440A - Bottom gluing for bonding polyphosphazene rubber and metal, preparation method and application - Google Patents

Bottom gluing for bonding polyphosphazene rubber and metal, preparation method and application Download PDF

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Publication number
CN116162440A
CN116162440A CN202211568896.4A CN202211568896A CN116162440A CN 116162440 A CN116162440 A CN 116162440A CN 202211568896 A CN202211568896 A CN 202211568896A CN 116162440 A CN116162440 A CN 116162440A
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rubber
polyphosphazene
metal
bonding
primer
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肖啸
吕剑
马辉
涂东怀
谷玉杰
毛伟
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Xian Modern Chemistry Research Institute
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Xian Modern Chemistry Research Institute
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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
    • C09J185/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Adhesives based on derivatives of such polymers
    • C09J185/02—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Adhesives based on derivatives of such polymers containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
    • C08J5/125—Adhesives in organic diluents
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C09J123/32—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur
    • C09J123/34—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur by chlorosulfonation
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2385/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
    • C08J2385/02—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2411/00—Characterised by the use of homopolymers or copolymers of chloroprene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2415/00—Characterised by the use of rubber derivatives
    • C08J2415/02—Rubber derivatives containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2423/32—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with phosphorus- or sulfur-containing compounds
    • C08J2423/34—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with phosphorus- or sulfur-containing compounds by chlorosulfonation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/02—Polyglycidyl ethers of bis-phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2485/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
    • C08J2485/02—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers containing phosphorus
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/166—Metal in the pretreated surface to be joined

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a bottom gluing agent for bonding polyphosphazene rubber and metal, a preparation method and application thereof, wherein the bottom gluing agent comprises the following components in percentage by mass: 5.11 to 6.50 percent of matrix rubber, 5.16 to 6.39 percent of chlorinated rubber, 3.30 to 5.80 percent of tackifying resin, 3.80 to 5.00 percent of reinforcing filler, 0.09 to 0.11 percent of cross-linking agent, 0.50 to 0.54 percent of metal oxide, 0.63 to 0.67 percent of coupling agent and the balance of solvent 75.75 to 80.56 percent.

Description

Bottom gluing for bonding polyphosphazene rubber and metal, preparation method and application
Technical Field
The invention relates to a heat vulcanization adhesive bottom gluing, in particular to a bottom gluing for bonding polyphosphazene rubber and metal, a preparation method and application thereof.
Background
The polyphosphazene rubber has excellent performances of high oxygen index, low heat conductivity, low smoke generation, ablation resistance, gas scouring resistance and the like, and the bonded composite part of the polyphosphazene rubber and metal is widely applied to the field of solid rocket engine charging. The metal and the polyphosphazene rubber form a vulcanized part in the rubber vulcanization process by adopting a hot vulcanization bonding process, so that the bonding strength between the metal and the polyphosphazene rubber can be effectively improved, and particularly, the complicated and difficult-to-mold part is improved. However, polyphosphazenes are inorganic/organic hybrid rubbers, which have low polar chemical group content in the molecular structure, poor surface activity, and poor adhesion to metals. At present, adhesive of foreign brands on the market, such as kemoloc, hangao, siban and the like, and special adhesive suitable for bonding polyphosphazene rubber and metal are not available in various domestic brands, and the existing adhesive products suitable for bonding systems of natural rubber/metal, ethylene propylene diene monomer rubber/metal, nitrile rubber/metal and the like are difficult to realize high-strength bonding of the polyphosphazene rubber and the metal, and cannot meet application requirements. Therefore, development of an adhesive suitable for bonding polyphosphazene rubber and metal is imperative.
From the perspective of rubber and metal bonding process analysis, the existing bonding process mainly comprises cold bonding and hot vulcanization bonding, and the main difference is whether the bonded rubber is vulcanized rubber or mixed rubber. The hot vulcanization bonding process is to bond unvulcanized rubber compound and metal through single-coating or double-coating adhesive under vulcanization conditions (temperature, pressure and time) so that rubber and metal produce certain bonding action in the vulcanization process to form a bonding piece. Cold bonding can be operated simply for some products with simple properties, saves resources, but is not suitable for products with complex shapes and higher requirements on bonding performance by using a cold bonding process, and can cause the problems of low bonding strength, short service life and the like of the products. Therefore, the heat vulcanization bonding technology is mainly adopted in the field of manufacturing the heat insulation layer of the solid rocket engine at present. However, there is a lack of an adhesive with reliable performance for the bonding of polyphosphazenes to metals, especially for the hot vulcanization bonding of polyphosphazenes to metals.
Disclosure of Invention
The invention aims to provide a primer adhesive for bonding polyphosphazene rubber and metal, a preparation method and application thereof, wherein the primer adhesive prepared by the invention and a commercially available kemlok top-coating adhesive chemlok@220 form a double-coating adhesive, the bonding strength of bonded metal and a polyphosphazene heat-insulating layer is obviously higher than that of the double-coating adhesive formed by the kemlok primer adhesive chemlok@205 and the surface-coating adhesive chemlok@220, and the technical requirement of a solid rocket engine on the bonding reliability of a shell/heat-insulating layer interface can be met.
The technical scheme of the invention is as follows:
the primer for bonding the polyphosphazene rubber and the metal comprises the following components in percentage by mass: 5.11 to 6.50 percent of matrix rubber, 5.16 to 6.39 percent of chlorinated rubber, 3.30 to 5.80 percent of tackifying resin, 3.80 to 5.00 percent of reinforcing filler, 0.09 to 0.11 percent of cross-linking agent, 0.50 to 0.54 percent of metal oxide, 0.63 to 0.67 percent of coupling agent and the balance of solvent 75.75 to 80.56 percent.
Optionally, the mass percentage composition is as follows: 6.32% of polyphosphazene rubber, 3.16% of chloroprene rubber, 3.16% of chlorosulfonated polyethylene, 5.05% of resol, 0.63% of E51 epoxy resin, 1.58% of gas-phase white carbon, 3.13% of N330 carbon black, 0.03% of dicumyl peroxide, 0.06% of sulfur, 0.3% of magnesium oxide, 0.2% of zinc oxide, 0.63% of gamma-aminopropyl triethoxysilane, 60.6% of xylene and 15.15% of methyl isobutyl ketone.
Optionally, the mass percentage composition is as follows: 5.12% of polyphosphazene rubber, 6.39% of chlorosulfonated polyethylene, 5.12% of resol, 0.65% of E51 epoxy resin, 1.59% of fumed silica, 3.17% of N330 carbon black, 0.03% of dicumyl peroxide, 0.06% of sulfur, 0.51% of magnesium oxide, 0.64% of gamma-aminopropyl triethoxysilane, 61.37% of xylene and 15.35% of methyl isobutyl ketone.
Optionally, the mass percentage composition is as follows: 5.32% of polyphosphazene rubber, 2.25% of chloropropion rubber, 3.27% of neoprene, 2.66% of resol, 0.66% of E51 epoxy resin, 1.66% of fumed silica, 3.29% of N330 carbon black, 0.03% of dicumyl peroxide, 0.06% of sulfur, 0.25% of magnesium oxide, 0.25% of zinc oxide, 0.66% of gamma-3-glycidyloxypropyl trimethoxysilane, 63.72% of xylene and 15.92% of ethanol.
Optionally, the mass percentage composition is as follows: 5.38% of polyphosphazene rubber, 2.68% of chloropropane rubber, 2.69% of chlorosulfonated polyethylene, 2.68% of resol, 0.67% of E51 epoxy resin, 2.68% of fumed silica, 1.35% of N330 carbon black, 0.03% of dicumyl peroxide, 0.06% of sulfur, 0.54% of zinc oxide, 0.67% of gamma-3-glycidoxypropyl trimethoxysilane, 64.45% of xylene and 16.12% of ethanol.
Optionally, the mass percentage composition is as follows: 6.47% of polyphosphazene rubber, 5.16% of chlorinated natural rubber, 5.16% of resol, 0.65% of E51 epoxy resin, 1.29% of fumed silica, 2.58% of N330 carbon black, 0.03% of dicumyl peroxide, 0.06% of sulfur, 0.52% of zinc oxide, 0.64% of gamma-aminopropyl triethoxysilane, 61.95% of xylene and 15.49% of ethanol.
Optionally, the mass percentage composition is as follows: 6.37% of polyphosphazene rubber, 2.12% of chlorinated natural rubber, 4.24% of chlorosulfonated polyethylene, 5.09% of resol, 0.65% of E51 epoxy resin, 1.27% of fumed silica, 2.55% of N330 carbon black, 0.03% of dicumyl peroxide, 0.06% of sulfur, 0.51% of magnesium oxide, 0.64% of gamma-methacryloxypropyl trimethoxysilane, 61.18% of xylene and 15.29% of ethanol.
The invention relates to a preparation method of a primer for bonding polyphosphazene rubber and metal, which comprises the following steps:
(1) Firstly, mixing matrix rubber and chlorinated rubber in proportion, and banburying at 50-60 ℃ for 60-80 min;
(2) Taking out the banburying rubber mixture, and sequentially adding reinforcing filler, cross-linking agent and metal oxide according to the mass percentage ratio to prepare a rubber compound;
(3) Adding tackifying resin, a coupling agent and a solvent into the prepared rubber compound according to a certain proportion, and stirring to obtain a mixed glue solution;
(4) Grinding the prepared mixed glue solution for 2-3 h to obtain the prime coating glue solution.
The double-coated adhesive comprises a surface adhesive layer and a bottom adhesive layer, wherein the bottom adhesive layer is any one of the bottom adhesive layers for bonding the polyphosphazene rubber and metal.
Optionally, the double-coated adhesive is used for bonding polyphosphazene rubber and metal, and the preparation of the polyphosphazene rubber and metal bonding comprises the following steps:
(1) Performing sand blasting treatment on the surface of the metal sheet, cleaning and airing;
(2) Coating the bottom glue on the dried metal surface, and baking at 40 ℃ for 40-50 min;
(3) Coating the surface of the metal surface coated with the primer in the step (2) with the primer, and baking at 40 ℃ for 40-50 min;
(4) And (3) attaching the metal sheet in the step (3) to the polyphosphazene compound rubber, then placing the compound rubber into a vulcanization mold, and performing hot vulcanization molding on the adhesive piece, wherein the vulcanization molding temperature is 150-165 ℃, the vulcanization pressure is 10-12 MPa, and the vulcanization time is 40-60 min.
Compared with the prior art, the invention has the following beneficial effects:
the primer adhesive prepared by the invention and the commercially available kemlok@220 surface coating adhesive form a double-coating adhesive, the bonding strength of bonded metal and polyphosphazene rubber is 2.3-2.6 MPa, and the bonding strength of bonded metal and polyphosphazene rubber formed by the double-coating adhesive consisting of the kemlok primer adhesive chemlok@205 and the surface coating adhesive chemlok@220 is 1.2-1.4 MPa. The primer prepared by the invention can meet the technical requirement of the solid rocket engine on the bonding reliability of the shell/heat insulation layer interface.
Detailed Description
The present invention will be further described in detail with reference to examples.
The invention relates to a double-coated adhesive bottom glue for thermal vulcanization bonding of polyphosphazene rubber and metal, which is prepared from the following raw materials in percentage by mass: 5.11 to 6.50 percent of matrix rubber, 5.16 to 6.39 percent of chlorinated rubber, 3.30 to 5.80 percent of tackifying resin, 3.80 to 5.00 percent of reinforcing filler, 0.09 to 0.11 percent of cross-linking agent, 0.50 to 0.54 percent of metal oxide, 0.63 to 0.67 percent of coupling agent, and the balance of solvent 75.75 to 80.56 percent, wherein the solid content of the bottom coating is controlled between 20 to 25 percent.
The matrix rubber is polyphosphazene which is mixed and substituted by phenoxy, p-ethylphenoxy and 2-allylphenoxy, the number average molecular weight is 50000-100000, and the structural formula is as follows:
Figure SMS_1
the chlorinated rubber is one or a mixture of more of chlorinated natural rubber, chloroprene rubber, chlorosulfonated polyethylene and chloropropion rubber, preferably chlorosulfonated polyethylene, chloroprene rubber and chloropropion rubber;
the tackifying resin is a mixture of epoxy resin and phenolic resin, preferably a mixture of bisphenol A type epoxy resin E51 and resole;
the reinforcing filler is one or a mixture of two of white carbon black and carbon black, preferably gas phase white carbon black and high reinforcing carbon black N330;
the cross-linking agent is peroxide, sulfur, preferably dicumyl peroxide or a mixture of benzoyl peroxide and sulfur;
the metal oxide is one or more of zinc oxide, magnesium oxide and titanium dioxide, preferably zinc oxide and magnesium oxide;
the coupling agent is one or a mixture of a plurality of gamma-aminopropyl triethoxysilane, gamma-3-glycidol ether oxygen propyl trimethoxysilane, gamma-methacryloxy propyl trimethoxysilane, 3-mercaptopropyl triethoxysilane and vinyl triethoxysilane;
the solvent is a mixed solution of at least two of xylene, ethanol and methyl isobutyl ketone.
The invention also provides a preparation method of the double-coated adhesive primer for thermal vulcanization adhesion of the polyphosphazene rubber and metal, which comprises the following steps:
(1) Firstly, mixing matrix rubber and chlorinated rubber in proportion, banburying at 50-60 ℃ for 60-80 min so as to uniformly mix the matrix rubber and the chlorinated rubber;
(2) Taking out the banburying rubber mixture, and sequentially adding reinforcing filler, cross-linking agent and metal oxide on an open mill according to the mass percentage ratio to prepare a rubber compound;
(3) Cutting the prepared rubber compound into small blocks, adding tackifying resin, coupling agent and solvent according to a certain proportion, and stirring for 30min to obtain mixed glue solution;
(4) Grinding the prepared mixed glue solution for 2-3 hours by a ball mill to obtain a base-coated glue solution, namely the double-coated adhesive base-coated glue for thermal vulcanization bonding of polyphosphazene rubber and metal.
The double-coated adhesive comprises a surface adhesive layer and a bottom adhesive layer, wherein the bottom adhesive layer is the bottom adhesive layer for bonding the polyphosphazene rubber and the metal; the face coating is any face coating in the prior art, such as a kemlok face coating chemlok@220.
The preparation of the polyphosphazene rubber and metal bonding piece comprises the following steps:
(1) Performing sand blasting treatment on the surface of the metal sheet, cleaning the metal sheet with acetone, and airing the metal sheet at room temperature;
(2) Coating the prepared bottom glue on the dried metal surface, and airing in an oven at 40 ℃ for 40-50 min;
(3) Coating the metal surface coated with the primer in the step (2) with a kemlok top coating adhesive chemlok@220, and airing in an oven at 40 ℃ for 40-50 min;
(4) And (3) attaching the metal sheet in the step (3) to the polyphosphazene compound rubber, then placing the compound rubber into a vulcanization mold, and performing hot vulcanization molding on the adhesive piece, wherein the vulcanization molding temperature is 150-165 ℃, the vulcanization pressure is 10-12 MPa, and the vulcanization time is 40-60 min.
Further, the metal sheet used in the step (1) is aluminum sheet, 45# steel sheet, high manganese steel or cold rolled steel; and (3) preheating a vulcanization mold for more than 20 minutes before vulcanization in the step (4).
The prepared adhesive piece is used for testing the tensile shear adhesive strength of polyphosphazene rubber and metal according to GB/T13936-2014 method for measuring tensile shear strength of adhesive of vulcanized rubber and metal.
The following examples are given as preferred examples, and are mainly used for understanding the present invention, but the present invention is not limited to these examples.
Comparative example 1:
the comparative example adopts a double-coating adhesive consisting of a kemlok primer adhesive chemlok@205 and a surface adhesive chemlok@220, and the bonding strength of the bonded polyphosphazene rubber and metal (45 # steel) is 1.2-1.4 MPa.
Example 1:
the present example is carried out with reference to the following primer formulation composition (mass%):
Figure SMS_2
/>
Figure SMS_3
the adhesion strength of the polyphosphazene rubber to the metal (45 # steel) was 2.6MPa.
Example 2:
the present example is carried out with reference to the following primer formulation composition (mass%):
component (A) Content/wt.%
Polyphosphazene rubber 5.12
Chlorosulfonated polyethylene 6.39
Resol phenolic resin 5.12
E51 epoxy resin 0.65
White carbon black by gas phase method 1.59
N330 carbon black 3.17
Dicumyl peroxide 0.03
Sulfur, sulfur and its preparation method 0.06
Magnesium oxide 0.51
Gamma-aminopropyl triethoxy silane 0.64
Xylene (P) 61.37
Methyl isobutyl ketone 15.35
The adhesion strength of the polyphosphazene rubber to the metal (45 # steel) was 2.3MPa.
Example 3:
the present example is carried out with reference to the following primer formulation composition (mass%):
component (A) Content/wt.%
Polyphosphazene rubber 5.32
Chloropropyl rubber 2.25
Neoprene rubber 3.27
Resol phenolic resin 2.66
E51 epoxy resin 0.66
White carbon black by gas phase method 1.66
N330 carbon black 3.29
Dicumyl peroxide 0.03
Sulfur, sulfur and its preparation method 0.06
Magnesium oxide 0.25
Zinc oxide 0.25
Gamma-3-glycidoxypropyl trimethoxysilane 0.66
Xylene (P) 63.72
Ethanol 15.92
The adhesion strength of the polyphosphazene rubber to the metal (45 # steel) was 2.4MPa.
Example 4:
the present example is carried out with reference to the following primer formulation composition (mass%):
Figure SMS_4
Figure SMS_5
the adhesion strength of the polyphosphazene rubber to the metal (45 # steel) was 2.5MPa.
Example 5:
the present example is carried out with reference to the following primer formulation composition (mass%):
component (A) Content/wt.%
Polyphosphazene rubber 6.47
Chlorinated natural rubber 5.16
Resol phenolic resin 5.16
E51 epoxy resin 0.65
White carbon black by gas phase method 1.29
N330 carbon black 2.58
Dicumyl peroxide 0.03
Sulfur, sulfur and its preparation method 0.06
Zinc oxide 0.52
Gamma-aminopropyl triethoxy silane 0.64
Xylene (P) 61.95
Ethanol 15.49
The adhesion strength of the polyphosphazene rubber to the metal (45 # steel) was 2.4MPa.
Example 6:
the present example is carried out with reference to the following primer formulation composition (mass%):
Figure SMS_6
Figure SMS_7
the adhesion strength of the polyphosphazene rubber to the metal (45 # steel) was 2.3MPa.
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.

Claims (10)

1. The primer for bonding the polyphosphazene rubber and the metal is characterized by comprising the following components in percentage by mass: 5.11 to 6.50 percent of matrix rubber, 5.16 to 6.39 percent of chlorinated rubber, 3.30 to 5.80 percent of tackifying resin, 3.80 to 5.00 percent of reinforcing filler, 0.09 to 0.11 percent of cross-linking agent, 0.50 to 0.54 percent of metal oxide, 0.63 to 0.67 percent of coupling agent and the balance of solvent 75.75 to 80.56 percent.
2. The primer for bonding a polyphosphazene rubber and a metal according to claim 1, wherein the primer comprises the following components in percentage by mass: 6.32% of polyphosphazene rubber, 3.16% of chloroprene rubber, 3.16% of chlorosulfonated polyethylene, 5.05% of resol, 0.63% of E51 epoxy resin, 1.58% of gas-phase white carbon, 3.13% of N330 carbon black, 0.03% of dicumyl peroxide, 0.06% of sulfur, 0.3% of magnesium oxide, 0.2% of zinc oxide, 0.63% of gamma-aminopropyl triethoxysilane, 60.6% of xylene and 15.15% of methyl isobutyl ketone.
3. The primer for bonding a polyphosphazene rubber and a metal according to claim 1, wherein the primer comprises the following components in percentage by mass: 5.12% of polyphosphazene rubber, 6.39% of chlorosulfonated polyethylene, 5.12% of resol, 0.65% of E51 epoxy resin, 1.59% of fumed silica, 3.17% of N330 carbon black, 0.03% of dicumyl peroxide, 0.06% of sulfur, 0.51% of magnesium oxide, 0.64% of gamma-aminopropyl triethoxysilane, 61.37% of xylene and 15.35% of methyl isobutyl ketone.
4. The primer for bonding a polyphosphazene rubber and a metal according to claim 1, wherein the primer comprises the following components in percentage by mass: 5.32% of polyphosphazene rubber, 2.25% of chloropropion rubber, 3.27% of neoprene, 2.66% of resol, 0.66% of E51 epoxy resin, 1.66% of fumed silica, 3.29% of N330 carbon black, 0.03% of dicumyl peroxide, 0.06% of sulfur, 0.25% of magnesium oxide, 0.25% of zinc oxide, 0.66% of gamma-3-glycidyloxypropyl trimethoxysilane, 63.72% of xylene and 15.92% of ethanol.
5. The primer for bonding a polyphosphazene rubber and a metal according to claim 1, wherein the primer comprises the following components in percentage by mass: 5.38% of polyphosphazene rubber, 2.68% of chloropropane rubber, 2.69% of chlorosulfonated polyethylene, 2.68% of resol, 0.67% of E51 epoxy resin, 2.68% of fumed silica, 1.35% of N330 carbon black, 0.03% of dicumyl peroxide, 0.06% of sulfur, 0.54% of zinc oxide, 0.67% of gamma-3-glycidoxypropyl trimethoxysilane, 64.45% of xylene and 16.12% of ethanol.
6. The primer for bonding a polyphosphazene rubber and a metal according to claim 1, wherein the primer comprises the following components in percentage by mass: 6.47% of polyphosphazene rubber, 5.16% of chlorinated natural rubber, 5.16% of resol, 0.65% of E51 epoxy resin, 1.29% of fumed silica, 2.58% of N330 carbon black, 0.03% of dicumyl peroxide, 0.06% of sulfur, 0.52% of zinc oxide, 0.64% of gamma-aminopropyl triethoxysilane, 61.95% of xylene and 15.49% of ethanol.
7. The primer for bonding a polyphosphazene rubber and a metal according to claim 1, wherein the primer comprises the following components in percentage by mass: 6.37% of polyphosphazene rubber, 2.12% of chlorinated natural rubber, 4.24% of chlorosulfonated polyethylene, 5.09% of resol, 0.65% of E51 epoxy resin, 1.27% of fumed silica, 2.55% of N330 carbon black, 0.03% of dicumyl peroxide, 0.06% of sulfur, 0.51% of magnesium oxide, 0.64% of gamma-methacryloxypropyl trimethoxysilane, 61.18% of xylene and 15.29% of ethanol.
8. A process for preparing a primer for bonding a polyphosphazene rubber to a metal as defined in any one of claims 1 to 7, comprising the steps of:
(1) Firstly, mixing matrix rubber and chlorinated rubber in proportion, and banburying at 50-60 ℃ for 60-80 min;
(2) Taking out the banburying rubber mixture, and sequentially adding reinforcing filler, cross-linking agent and metal oxide according to the mass percentage ratio to prepare a rubber compound;
(3) Adding tackifying resin, a coupling agent and a solvent into the prepared rubber compound according to a certain proportion, and stirring to obtain a mixed glue solution;
(4) Grinding the prepared mixed glue solution for 2-3 h to obtain the prime coating glue solution.
9. A double-coated adhesive, comprising a surface adhesive layer and a bottom adhesive layer, wherein the bottom adhesive layer is the bottom adhesive layer for bonding the polyphosphazene rubber and metal according to any one of claims 1-7.
10. Use of the double-coated adhesive of claim 9 for bonding polyphosphazene rubber to metal, the preparation of the polyphosphazene rubber to metal bond comprising the steps of:
(1) Performing sand blasting treatment on the surface of the metal sheet, cleaning and airing;
(2) Coating the bottom glue on the dried metal surface, and baking at 40 ℃ for 40-50 min;
(3) Coating the surface of the metal surface coated with the primer in the step (2) with the primer, and baking at 40 ℃ for 40-50 min;
(4) And (3) attaching the metal sheet in the step (3) to the polyphosphazene compound rubber, then placing the compound rubber into a vulcanization mold, and performing hot vulcanization molding on the adhesive piece, wherein the vulcanization molding temperature is 150-165 ℃, the vulcanization pressure is 10-12 MPa, and the vulcanization time is 40-60 min.
CN202211568896.4A 2022-12-08 2022-12-08 Bottom gluing for bonding polyphosphazene rubber and metal, preparation method and application Pending CN116162440A (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
US4535095A (en) * 1984-12-10 1985-08-13 Ethyl Corporation Polyphosphazene compounding process
US4870113A (en) * 1988-12-23 1989-09-26 Ethyl Corporation Rigid polyphosphazene foam and process for making same
CN112877010A (en) * 2021-01-15 2021-06-01 中北大学 Natural rubber and metal hot vulcanization adhesive as well as preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4535095A (en) * 1984-12-10 1985-08-13 Ethyl Corporation Polyphosphazene compounding process
US4870113A (en) * 1988-12-23 1989-09-26 Ethyl Corporation Rigid polyphosphazene foam and process for making same
CN112877010A (en) * 2021-01-15 2021-06-01 中北大学 Natural rubber and metal hot vulcanization adhesive as well as preparation method and application thereof

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Title
李爱元等: "聚磷腈高分子材料在航空航天领域中的应", 《胶体与聚合物》, vol. 25, no. 4, pages 40 *

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