CN116120892A - Surface gluing for bonding polyphosphazene rubber and metal, preparation method and application - Google Patents

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

Info

Publication number
CN116120892A
CN116120892A CN202211568908.3A CN202211568908A CN116120892A CN 116120892 A CN116120892 A CN 116120892A CN 202211568908 A CN202211568908 A CN 202211568908A CN 116120892 A CN116120892 A CN 116120892A
Authority
CN
China
Prior art keywords
rubber
percent
polyphosphazene
metal
accelerator
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.)
Pending
Application number
CN202211568908.3A
Other languages
Chinese (zh)
Inventor
肖啸
吕剑
涂东怀
马辉
谷玉杰
李春迎
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.)
Xian Modern Chemistry Research Institute
Original Assignee
Xian Modern Chemistry Research Institute
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 Xian Modern Chemistry Research Institute filed Critical Xian Modern Chemistry Research Institute
Priority to CN202211568908.3A priority Critical patent/CN116120892A/en
Publication of CN116120892A publication Critical patent/CN116120892A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2411/00—Characterised by the use of homopolymers or copolymers of chloroprene
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a surface gluing agent for bonding polyphosphazene rubber and metal, a preparation method and application thereof, wherein the surface gluing agent comprises the following components in percentage by mass: 5.27 to 5.84 percent of matrix rubber, 1.06 to 1.71 percent of chlorinated rubber, 4.79 to 6.53 percent of tackifying resin, 1.55 to 1.60 percent of reinforcing filler, 0.07 to 0.08 percent of vulcanizing agent, 0.12 to 0.13 percent of vulcanization accelerator, 0.25 to 0.26 percent of metal oxide, 0.51 to 0.52 percent of coupling agent and the balance of 83.46 to 85.60 percent of solvent; the double-coating adhesive is formed by the surface coating adhesive prepared by the invention and the commercially available kemlok primer adhesive chemlok@205, the bonding strength of the bonded metal and the polyphosphazene rubber is 2.0-2.3 MPa, and the technical requirement of the solid rocket engine on the bonding reliability of the shell/heat insulation layer interface can be met.

Description

Surface gluing for bonding polyphosphazene rubber and metal, preparation method and application
Technical Field
The invention relates to a hot vulcanization adhesive surface gluing, in particular to a surface 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 surface gluing method for bonding polyphosphazene rubber and metal, a preparation method and application. The double-coated adhesive is formed by the surface coating adhesive prepared by the invention and the commercially available kemlok primer adhesive chemlok@205, the bonding strength of the bonded metal and the polyphosphazene heat insulation layer is obviously higher than that of the double-coated adhesive formed by the kemlok primer adhesive chemlok@205 and the surface coating chemlok@220, and the technical requirement of the solid rocket engine on the bonding reliability of the shell/heat insulation layer interface can be met.
The technical scheme of the invention is as follows:
the surface coating adhesive for bonding the polyphosphazene rubber and the metal comprises the following components in percentage by mass:
5.27 to 5.84 percent of matrix rubber, 1.06 to 1.71 percent of chlorinated rubber, 4.79 to 6.53 percent of tackifying resin, 1.55 to 1.60 percent of reinforcing filler, 0.07 to 0.08 percent of vulcanizing agent, 0.12 to 0.13 percent of vulcanization accelerator, 0.25 to 0.26 percent of metal oxide, 0.51 to 0.52 percent of coupling agent and the balance of 83.46 to 85.60 percent of solvent;
optionally, the mass percentage composition is as follows: 5.32% of polyphosphazene rubber, 1.06% of chlorinated rubber, 5.09% of resol, 0.52% of E51 epoxy resin, 1.59% of fumed silica, 0.03% of dicumyl peroxide, 0.05% of sulfur, 0.11% of accelerator D, 0.02% of accelerator M, 0.26% of magnesium oxide, 0.51% of gamma-aminopropyl triethoxysilane, 68.35% of xylene and 17.09% of ethanol.
Optionally, the mass percentage composition is as follows: 5.29% of polyphosphazene rubber, 1.37% of chloropropane rubber, 5.11% of resol, 0.51% of E51 epoxy resin, 1.59% of fumed silica, 0.03% of dicumyl peroxide, 0.05% of sulfur, 0.1% of accelerator D, 0.03% of accelerator M, 0.26% of magnesium oxide, 0.51% of gamma-3-glycidoxypropyl trimethoxysilane, 68.12% of xylene and 17.03% of ethanol.
Optionally, the mass percentage composition is as follows: 5.28% of polyphosphazene rubber, 1.70% of neoprene, 5.11% of resol, 0.52% of E51 epoxy resin, 1.57% of fumed silica, 0.02% of dicumyl peroxide, 0.05% of sulfur, 0.1% of accelerator D, 0.03% of accelerator CZ, 0.26% of zinc oxide, 0.5% of gamma-aminopropyl triethoxysilane, 67.89% of xylene and 16.97% of methyl isobutyl ketone.
Optionally, the mass percentage composition is as follows: 5.28% of polyphosphazene rubber, 0.85% of neoprene, 0.85% of chlorosulfonated polyethylene, 5.11% of resol, 0.52% of E51 epoxy resin, 1.57% of fumed silica, 0.02% of dicumyl peroxide, 0.05% of sulfur, 0.1% of accelerator D, 0.03% of accelerator CZ, 0.26% of zinc oxide, 0.5% of gamma-methacryloxypropyl trimethoxysilane, 67.89% of dimethylbenzene and 16.97% of methyl isobutyl ketone.
Optionally, the mass percentage composition is as follows: 5.52% of polyphosphazene rubber, 0.84% of chlorinated natural rubber, 0.85% of chlorosulfonated polyethylene, 5.86% of resol, 0.67% of E51 epoxy resin, 1.56% of fumed silica, 0.02% of dicumyl peroxide, 0.05% of sulfur, 0.10% of accelerator D, 0.03% of accelerator CZ, 0.26% of zinc oxide, 0.5% of gamma-aminopropyl triethoxysilane, 66.99% of xylene and 16.75% of methyl isobutyl ketone.
Optionally, the mass percentage composition is as follows: 5.84% of polyphosphazene rubber, 1.68% of chlorinated natural rubber, 5.85% of resol, 0.67% of E51 epoxy resin, 1.55% of fumed silica, 0.02% of dicumyl peroxide, 0.05% of sulfur, 0.1% of accelerator D, 0.02% of accelerator CZ, 0.26% of zinc oxide, 0.5% of gamma-methacryloxypropyl trimethoxysilane, 66.77% of xylene and 16.69% of ethanol.
The invention relates to a preparation method of a surface gluing agent for bonding polyphosphazene rubber and metal, which comprises the following steps:
(1) Mixing the matrix rubber and the chlorinated rubber in proportion, and banburying for 60-80 min at 50-60 ℃;
(2) Taking out the banburying rubber mixture, and sequentially adding reinforcing filler, vulcanizing agent, vulcanization accelerator 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 to obtain the surface-coating glue solution.
The double-coated adhesive comprises a surface adhesive layer and a bottom adhesive layer, wherein the surface adhesive layer is any one of the surface adhesive layers for bonding the polyphosphazene rubber and the metal.
The double-coated adhesive is used for bonding polyphosphazene rubber and metal, and the preparation of the bonding of the polyphosphazene rubber and the metal comprises the following steps:
(1) Performing sand blasting treatment on the surface of the metal sheet, cleaning and airing;
(2) Coating a bottom coating on the dried metal surface, and baking at 40 ℃ for 40-50 min;
(3) Coating the surface glue on the metal surface coated with the bottom glue in the step (2), 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 surface coating adhesive prepared by the invention and the commercial kemlok primer adhesive chemlok@205 form a double-coating adhesive, the bonding strength of bonded metal and polyphosphazene rubber is 2.0-2.3 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 surface coating adhesive 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.
Accelerator D: diphenyl guanidine;
accelerator M: 2-mercaptobenzothiazole;
promoter CZ: n-cyclohexyl-2-benzothiazole sulfenamide;
the invention discloses a double-coated adhesive surface gluing method for thermal vulcanization bonding of polyphosphazene rubber and metal, which is prepared from the following raw materials in percentage by mass: 5.27 to 5.84 percent of matrix rubber, 1.06 to 1.71 percent of chlorinated rubber, 4.79 to 6.53 percent of tackifying resin, 1.55 to 1.60 percent of reinforcing filler, 0.07 to 0.08 percent of vulcanizing agent, 0.12 to 0.13 percent of vulcanization accelerator, 0.25 to 0.26 percent of metal oxide, 0.51 to 0.52 percent of coupling agent and 83.46 to 85.60 percent of solvent for the rest, wherein the solid content of the surface sizing is controlled between 15 percent and 16 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 fumed silica;
the vulcanizing agent is peroxide and sulfur, preferably dicumyl peroxide or a mixture of benzoyl peroxide and sulfur;
the vulcanization accelerator is one or more of aldehyde amine accelerator, guanidine accelerator, thiuram accelerator, thiazole accelerator and sulfenamide accelerator, preferably guanidine accelerator D, thiazole accelerator M and sulfenamide accelerator CZ;
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 surface gluing 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, vulcanizing agent, vulcanization accelerator 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) And grinding the prepared mixed glue solution for 2-3 hours by a ball mill to obtain a surface-coating glue solution, namely the double-coating adhesive surface 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 surface adhesive layer is the surface adhesive for bonding the polyphosphazene rubber and the metal. The primer may be any primer known in the art, such as the kemlok primer chemlok@205.
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 a kemlok primer adhesive chemlok@205 on the dried metal surface, and airing in an oven at 40 ℃ for 40-50 min;
(3) Coating the prepared surface coating adhesive on the metal surface coated with the bottom coating adhesive in the step (2), 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 glue formulation composition (mass-%):
component (A) Content/wt.%
Polyphosphazene rubber 5.32
Chlorosulfonated polyethylene 1.06
Resol phenolic resin 5.09
E51 epoxy resin 0.52
White carbon black by gas phase method 1.59
Dicumyl peroxide 0.03
Sulfur, sulfur and its preparation method 0.05
Accelerator D 0.11
Accelerator M 0.02
Magnesium oxide 0.26
Gamma-aminopropyl triethoxy silane 0.51
Xylene (P) 68.35
Ethanol 17.09
The adhesion strength of the polyphosphazene rubber to the metal (45 # steel) was 2.3MPa.
Example 2:
the present example is carried out with reference to the following glue formulation composition (mass-%):
Figure SMS_2
Figure SMS_3
the adhesion strength of the polyphosphazene rubber to the metal (45 # steel) was 2.0MPa.
Example 3:
the present example is carried out with reference to the following glue formulation composition (mass-%):
component (A) Content/wt.%
Polyphosphazene rubber 5.28
Neoprene rubber 1.70
Resol phenolic resin 5.11
E51 epoxy resin 0.52
White carbon black by gas phase method 1.57
Dicumyl peroxide 0.02
Sulfur, sulfur and its preparation method 0.05
Accelerator D 0.1
Promoter CZ 0.03
Zinc oxide 0.26
Gamma-aminopropyl triethoxy silane 0.5
Xylene (P) 67.89
Methyl isobutyl ketone 16.97
The adhesion strength of the polyphosphazene rubber to the metal (45 # steel) was 2.2MPa.
Example 4:
the present example is carried out with reference to the following glue formulation composition (mass-%):
Figure SMS_4
Figure SMS_5
the adhesion strength of the polyphosphazene rubber to the metal (45 # steel) was 2.3MPa.
Example 5:
the present example is carried out with reference to the following glue formulation composition (mass-%):
component (A) Content/wt.%
Polyphosphazene rubber 5.52
Chlorinated natural rubber 0.84
Chlorosulfonated polyethylene 0.85
Resol phenolic resin 5.86
E51 epoxy resin 0.67
White carbon black by gas phase method 1.56
Dicumyl peroxide 0.02
Sulfur, sulfur and its preparation method 0.05
Accelerator D 0.10
Promoter CZ 0.03
Zinc oxide 0.26
Gamma-aminopropyl triethoxy silane 0.5
Xylene (P) 66.99
Methyl isobutyl ketone 16.75
The adhesion strength of the polyphosphazene rubber to the metal (45 # steel) was 2.1MPa.
Example 6:
the present example is carried out with reference to the following glue formulation composition (mass-%):
component (A) Content/wt.%
Polyphosphazene rubber 5.84
Chlorinated natural rubber 1.68
Resol phenolic resin 5.85
E51 epoxy resin 0.67
White carbon black by gas phase method 1.55
Dicumyl peroxide 0.02
Sulfur, sulfur and its preparation method 0.05
Accelerator D 0.1
Promoter CZ 0.02
Zinc oxide 0.26
Gamma-methacryloxypropyl trimethoxysilane 0.5
Xylene (P) 66.77
Ethanol 16.69
The adhesion strength of the polyphosphazene rubber to the metal (45 # steel) was 2.2MPa.
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. A surface coating adhesive for bonding polyphosphazene rubber and metal is characterized by comprising the following components in percentage by mass:
5.27 to 5.84 percent of matrix rubber, 1.06 to 1.71 percent of chlorinated rubber, 4.79 to 6.53 percent of tackifying resin, 1.55 to 1.60 percent of reinforcing filler, 0.07 to 0.08 percent of vulcanizing agent, 0.12 to 0.13 percent of vulcanization accelerator, 0.25 to 0.26 percent of metal oxide, 0.51 to 0.52 percent of coupling agent and the balance of 83.46 to 85.60 percent of solvent.
2. The topcoat for adhesion of polyphosphazene rubber to metal according to claim 1, wherein the topcoat comprises the following components in mass percent: 5.32% of polyphosphazene rubber, 1.06% of chlorinated rubber, 5.09% of resol, 0.52% of E51 epoxy resin, 1.59% of fumed silica, 0.03% of dicumyl peroxide, 0.05% of sulfur, 0.11% of accelerator D, 0.02% of accelerator M, 0.26% of magnesium oxide, 0.51% of gamma-aminopropyl triethoxysilane, 68.35% of xylene and 17.09% of ethanol.
3. The topcoat for adhesion of polyphosphazene rubber to metal according to claim 1, wherein the topcoat comprises the following components in mass percent: 5.29% of polyphosphazene rubber, 1.37% of chloropropane rubber, 5.11% of resol, 0.51% of E51 epoxy resin, 1.59% of fumed silica, 0.03% of dicumyl peroxide, 0.05% of sulfur, 0.1% of accelerator D, 0.03% of accelerator M, 0.26% of magnesium oxide, 0.51% of gamma-3-glycidoxypropyl trimethoxysilane, 68.12% of xylene and 17.03% of ethanol.
4. The topcoat for adhesion of polyphosphazene rubber to metal according to claim 1, wherein the topcoat comprises the following components in mass percent: 5.28% of polyphosphazene rubber, 1.70% of neoprene, 5.11% of resol, 0.52% of E51 epoxy resin, 1.57% of fumed silica, 0.02% of dicumyl peroxide, 0.05% of sulfur, 0.1% of accelerator D, 0.03% of accelerator CZ, 0.26% of zinc oxide, 0.5% of gamma-aminopropyl triethoxysilane, 67.89% of xylene and 16.97% of methyl isobutyl ketone.
5. The topcoat for adhesion of polyphosphazene rubber to metal according to claim 1, wherein the topcoat comprises the following components in mass percent: 5.28% of polyphosphazene rubber, 0.85% of neoprene, 0.85% of chlorosulfonated polyethylene, 5.11% of resol, 0.52% of E51 epoxy resin, 1.57% of fumed silica, 0.02% of dicumyl peroxide, 0.05% of sulfur, 0.1% of accelerator D, 0.03% of accelerator CZ, 0.26% of zinc oxide, 0.5% of gamma-methacryloxypropyl trimethoxysilane, 67.89% of dimethylbenzene and 16.97% of methyl isobutyl ketone.
6. The topcoat for adhesion of polyphosphazene rubber to metal according to claim 1, wherein the topcoat comprises the following components in mass percent: 5.52% of polyphosphazene rubber, 0.84% of chlorinated natural rubber, 0.85% of chlorosulfonated polyethylene, 5.86% of resol, 0.67% of E51 epoxy resin, 1.56% of fumed silica, 0.02% of dicumyl peroxide, 0.05% of sulfur, 0.10% of accelerator D, 0.03% of accelerator CZ, 0.26% of zinc oxide, 0.5% of gamma-aminopropyl triethoxysilane, 66.99% of xylene and 16.75% of methyl isobutyl ketone.
7. The topcoat for adhesion of polyphosphazene rubber to metal according to claim 1, wherein the topcoat comprises the following components in mass percent: 5.84% of polyphosphazene rubber, 1.68% of chlorinated natural rubber, 5.85% of resol, 0.67% of E51 epoxy resin, 1.55% of fumed silica, 0.02% of dicumyl peroxide, 0.05% of sulfur, 0.1% of accelerator D, 0.02% of accelerator CZ, 0.26% of zinc oxide, 0.5% of gamma-methacryloxypropyl trimethoxysilane, 66.77% of xylene and 16.69% of ethanol.
8. The method for preparing the surface sizing for bonding the polyphosphazene rubber and the metal according to any one of claims 1 to 7, which is characterized in that the preparation of the surface sizing comprises the following steps:
(1) Mixing the matrix rubber and the chlorinated rubber in proportion, and banburying for 60-80 min at 50-60 ℃;
(2) Taking out the banburying rubber mixture, and sequentially adding reinforcing filler, vulcanizing agent, vulcanization accelerator 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 to obtain the surface-coating glue solution.
9. A double-coated adhesive, which is characterized by comprising a surface adhesive layer and a bottom adhesive layer, wherein the surface adhesive layer is the surface adhesive for bonding the polyphosphazene rubber and the 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 a bottom coating on the dried metal surface, and baking at 40 ℃ for 40-50 min;
(3) Coating the surface glue on the metal surface coated with the bottom glue in the step (2), 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.
CN202211568908.3A 2022-12-08 2022-12-08 Surface gluing for bonding polyphosphazene rubber and metal, preparation method and application Pending CN116120892A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211568908.3A CN116120892A (en) 2022-12-08 2022-12-08 Surface gluing for bonding polyphosphazene rubber and metal, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211568908.3A CN116120892A (en) 2022-12-08 2022-12-08 Surface gluing for bonding polyphosphazene rubber and metal, preparation method and application

Publications (1)

Publication Number Publication Date
CN116120892A true CN116120892A (en) 2023-05-16

Family

ID=86296413

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211568908.3A Pending CN116120892A (en) 2022-12-08 2022-12-08 Surface gluing for bonding polyphosphazene rubber and metal, preparation method and application

Country Status (1)

Country Link
CN (1) CN116120892A (en)

Citations (2)

* 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
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 (2)

* 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
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李爱元等: "聚磷腈高分子材料在航空航天领域中的应用", 《胶体与聚合物》, vol. 25, no. 4, pages 43 *

Similar Documents

Publication Publication Date Title
CN101875830B (en) Phenolic resin/phosphate hybrid adhesive and preparation method thereof
CN112877010B (en) Natural rubber and metal hot vulcanization adhesive as well as preparation method and application thereof
CN105419180A (en) High-performance fluorine rubber composite material
CN101497773B (en) Undercoat adhesive for bonding hot vulcanization and preparation thereof
CN107189339B (en) A kind of superfine silicon carbide high silica fiber enhancing phenolic aldehyde heat-resisting composite and preparation method thereof
CN108727830A (en) A kind of high tenacity flame-retarded heat-conducting silica gel piece and preparation method thereof
CN108424656A (en) A kind of high fire-retardance resistance oil silicone rubber composite material
CN115820166B (en) Adhesive for bonding polyphosphazene rubber and metal, preparation method and application
CN116120892A (en) Surface gluing for bonding polyphosphazene rubber and metal, preparation method and application
CN116162440A (en) Bottom gluing for bonding polyphosphazene rubber and metal, preparation method and application
CN111114039B (en) Environment-friendly composite damping plate for vibration and noise reduction and preparation method thereof
CN107674372A (en) A kind of phenolic aldehyde foam thermal insulation material and preparation method thereof
US4243774A (en) Rubber composition
CN105820448A (en) Cellulose resin rubber material
CN103980850B (en) The preparation method of phthalonitrile modified phenolic resin adhesive
CN116463080A (en) Neoprene adhesive and preparation method thereof
CN114989703A (en) Steel structure surface heat-insulating anticorrosive paint and preparation method thereof
CN102952478B (en) Filter adhesive film prepared by mixing neoprene and ethylene propylene diene monomer (EPDM)
CN103670798B (en) A kind of improve NEPE propelling agent and the method for lining interfacial adhesion
CN110272587B (en) Cold-resistant high-temperature-resistant flame-retardant composite material and preparation method thereof
CN102952484B (en) Filter film adhesive compounded by neoprene and chlorosulfonated polyethylene rubber
CN106700102A (en) Polyphenylene sulfide reinforced composite material and preparing method thereof
CN102952468B (en) Filter adhesive film prepared by mixing neoprene and brominated butyl rubber
CN105602119A (en) High-temperature-resistant rubber guide wheel for centerless grinding machine
CN105542328A (en) Improved butyl rubber and preparation method 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