CN108624002A - A kind of high temperature durability epoxy construction cementitious system and preparation method thereof - Google Patents
A kind of high temperature durability epoxy construction cementitious system and preparation method thereof Download PDFInfo
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- CN108624002A CN108624002A CN201810558575.3A CN201810558575A CN108624002A CN 108624002 A CN108624002 A CN 108624002A CN 201810558575 A CN201810558575 A CN 201810558575A CN 108624002 A CN108624002 A CN 108624002A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention belongs to field of adhesive technology, and in particular to a kind of high temperature durability epoxy construction cementitious system and preparation method thereof.Epoxy construction cementitious system of the present invention includes epoxy construction glued membrane and inhibits to corrode primer, with " special epoxy resin-arylamine solidified agent " for curing system, using Particular thermoplastic's resin and rubber elastomer as toughener, the temperature resistant grade of cementitious system is increased to 175 DEG C, glass transition temperature is increased to 190 DEG C；Heat ageing examines time lengthening to 3000h；High temperature durability epoxy construction cementitious system processing performance of the present invention is excellent, have the characteristics that high intensity, high tenacity, endurance, high temperature durability can be good, meet metal or composite material large area is glued moulding process, it solves aerospace flight vehicle and demand is glued to the high temperature durability of thermal structure part, be suitable for the splicing of aerospace field metal or composite material high-temperature-resistant structure part.
Description
Technical field
The invention belongs to field of adhesive technology, and in particular to a kind of high temperature durability epoxy construction cementitious system and its system
Preparation Method.
Background technology
Hot setting epoxy construction cementitious system is a kind of solidification temperature at 175-180 DEG C, and temperature in use is at 121 DEG C or more
Adhesive, generally by hot setting epoxy construction glued membrane and it is matched use inhibition corrosion primer constitute, have it is high-strength
The characteristics of being used for a long time under degree, high-durability and hot conditions is the manufacture of Aeronautics and Astronautics aircraft high temperature resistant load-carrying construction part
In important structural adhesive bonding material.
Domestic and international existing high-temp epoxy structural adhesive bonding system is mostly with " bisphenol type epoxy-dicyandiamide " for firming body
System is what is set up on the basis of toughener with " polysulfones and nitrile rubber ", and typically there are Hexcel companies in foreign countries
" Redux319 glued membranes/Redux119 primers " cementitious system, " FM300 glued membranes/BR127 primers " cementitious system of Cytec companies
Deng；Domestic " J-116 glued membranes/J-117 primers " cementitious system for typically having Institute of Petrochemistry, HLJ Academy of Science and
" SY-14 glued membranes and its mating SY-D4 primers " cementitious system of Beijing Research Inst. of Aeronautic Material of China Aviation engine group
Major advantage Deng, these above-mentioned cementitious systems be good toughness, it is latent have excellent performance, technical maturity it is high, aviation at home and abroad
Space industry has been widely used.However, being limited to the glass of " bisphenol type epoxy-dicyandiamide " curing system cured product
It is relatively low to change transition temperature, only 143 DEG C or so, and the long-term heat resistance of polysulfones and nitrile rubber toughener can be again poor, therefore
The said goods are used for a long time temperature and are no more than 135 DEG C, and the heat ageing examination time is only 1000 hours at such a temperature.
Invention content
To solve above-mentioned the deficiencies in the prior art, the present invention provides a kind of high temperature durability epoxy construction cementitious system and
Preparation method.
Technical solution of the present invention：
A kind of high temperature durability epoxy construction cementitious system, including epoxy construction glued membrane and inhibition corrosion primer, the ring
Oxide structure glued membrane is combined with carrier through hot pressing by following raw material with glued membrane manufacture：
75~100 parts of epoxy resin, 20~35 parts of arylamine solidified agent, 40~60 parts of thermoplastic resin, rubber elastomer 6~
15 parts, 3~9 parts of inorganic filler, 1~4 part of antioxidant；
The inhibition corrosion primer is made of following raw material：
75~100 parts of epoxy resin, 75~100 parts of thermoplastic resin, inhibits corrosive agent 3 at 20~30 parts of arylamine solidified agent
~9 parts, 3~9 parts of silane coupling agent, 1200~1600 parts of mixed solvent；
Epoxy resin in the epoxy construction glued membrane and inhibition corrosion primer is by bisphenol A type epoxy resin, xenol
Formaldehyde epoxy resin (BPNE), naphthalene novolac epoxy resin (BEBN) and carborane bisphenol diglycidyl (DGECB) are by certain
Weight ratio forms, and the chemical structural formula of wherein biphenyl novolac epoxy resin (BPNE) is as shown in Equation 1：
Formula 1：
The chemical structural formula of naphthalene novolac epoxy resin (BEBN) is as shown in Equation 2：
Formula 2：
Carborane bisphenol diglycidyl (DGECB) chemical structural formula is as shown in Equation 3：
Formula 3：
Compared with merely using bisphenol A type epoxy resin as matrix resin, the present invention is by introducing biphenyl epoxy novolac
Resin and naphthalene novolac epoxy resin improve the heat resistance and moisture-proof thermal characteristics of cementitious system, introduce carborane bis-phenol two and shrink
Glycerin ether makes epoxy knot provided by the invention because assigning cementitious system excellent antioxygenic property containing carborane structure in structure
Structure cementitious system has both heat resistance, humidity resistance and good processing performance.
Further, the epoxy construction glued membrane by following raw material and glued membrane manufacture carrier through the compound system of hot pressing
At：
80~90 parts of epoxy resin, 25~30 parts of arylamine solidified agent, 45~55 parts of thermoplastic resin, rubber elastomer 9~
12 parts, 5~7 parts of inorganic filler, 2~3 parts of antioxidant；
The inhibition corrosion primer is made of following raw material：
80~90 parts of epoxy resin, 80~90 parts of thermoplastic resin, inhibits corrosive agent 5~7 at 22~28 parts of arylamine solidified agent
Part, 5~7 parts of silane coupling agent, 1400~1500 parts of mixed solvent.
Further, the bisphenol A type epoxy resin, biphenyl novolac epoxy resin, naphthalene novolac epoxy resin and carbon boron
The weight ratio of alkane bisphenol diglycidyl is (1~4):(1~3):(1~2):1.
Further, the bisphenol A type epoxy resin is in the bisphenol A type epoxy resin of E-51, E-55 or E-44 model
One kind.
Further, the arylamine solidified agent in the epoxy construction glued membrane and inhibition corrosion primer is by 4,4 '-diamino
Diphenyl sulphone (DPS) (DDS), 4,4 '-di-2-ethylhexylphosphine oxides (the chloro- 2,6- diethylanilines of 3-), benzene is by weight for 1,3,5- triamidos (4- phenoxy groups)
Than (1~4):(1~3):1 composition；
Relative to the dicy-curing agent that existing high-temp epoxy structural adhesive bonding system uses, the arylamine that the present invention uses cures
Agent has a clear superiority in high temperature resistant and thermostabilization, wherein 1,3,5- triamido (4- phenoxy groups) benzene is three branched structures, it can
To improve the crosslink density of cementitious system, the halogen atom contained in 4,4 '-di-2-ethylhexylphosphine oxides (3- chloro-2,6-diethyl anilines) is assigned
Give the certain flame-retarding characteristic of cementitious system.
Further, the thermoplastic resin in the epoxy construction glued membrane and inhibition corrosion primer is by phenolphthalein base polyarylether
Sulfone (PES-C), cardo polyetherketone (PEK-C), epoxy-terminated phthalazone polyether sulphone (E-PPES), epoxy-terminated two
One or more of azepine naphthalenone poly(aryl ether ketone) (E-PPEK) forms.
Relative to the polysulfones toughener that existing high-temp epoxy structural adhesive bonding system uses, thermoplastic resin of the present invention is as increasing
The polyethersulfone with cardo and cardo polyetherketone temperature resistant grade higher of tough dose of use, thermal stability is more preferable, and epoxy-terminated two
Azepine naphthalenone polyether sulphone and epoxy-terminated phthalazone poly(aryl ether ketone) are then because epoxy-terminated presence can be with arylamine solidified agent
Chemical crosslinking is formed, to resist the sliding of strand under hot conditions, improves mechanical system performance and heat resistance；
Further, the rubber elastomer in the epoxy construction glued membrane is by epoxy terminated nitrile rubber, end carboxyl butyronitrile
One or more of rubber or Core-shell rubber particles form；
Relative to the nitrile rubber that existing high-temp epoxy sqtructural adhesive uses, rubber elastomer of the present invention is as toughener
The epoxy group nitrile rubber and carboxy nitrile rubber of use are chemically crosslinked because epoxy-terminated presence can be formed with arylamine solidified agent,
So as to resist the sliding of strand under hot conditions, mechanical system performance and heat resistance are improved, Core-shell rubber particles cure because of it
It is not influenced in the process by curing reaction Kinetics, cures front and back its form, size, ingredient and any change does not occur, to reduce
It is on the modulus of cementitious system and durothermic influence.
Further, the inorganic filler in the epoxy construction glued membrane is by aluminium powder, flake asbestos, titanium dioxide or alumina powder
One or more of compositions；Antioxidant in the epoxy construction glued membrane is by 6- di-tert-butyl-4-methy phenols, hydroquinone
Or one or more of tert-butyl hydroquinone composition, effectively increase the thermal-oxidative aging property of adhesive.
Further, the inhibition corrosive agent inhibited in corrosion primer is strontium chromate；In the inhibition corrosion primer
Silane coupling agent by methyl tri-tert peroxy-silane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane or
One or more of γ-glycidyl ether oxygen propyl trimethoxy silicane forms；It is described to inhibit the mixing in corrosion primer molten
Agent is by chloroform and cyclohexanone by weight 1:1 is formulated.
Further, the glued membrane manufacture with carrier be nylon gauze, polyester gauze, non-woven fabrics, glass fiber woven cloth,
One kind in silica fibrage cloth or carbon fiber woven cloth.
Steps are as follows for a kind of preparation method of high temperature durability epoxy construction cementitious system of the present invention：
A, epoxy construction glue film manufacturing process：
A1, divide by weight weigh epoxy resin, arylamine solidified agent, thermoplastic resin, rubber elastomer, inorganic filler and
Antioxidant；
A2, the epoxy resin for weighing step A1 are added in reaction kettle, are heated to 220~230 DEG C, under stirring
Thermoplastic resin is added at one time, 60min is kept the temperature at 190~200 DEG C, homogeneous blending resin is made；
A3, using mechanical blending method by homogeneous blending resin and arylamine solidified agent, rubber elastomer, nothing made from step A2
Machine filler and antioxidant are uniformly mixed, and sizing material is made；
A4, glued membrane manufacture with carrier assist membrance casting condition under, by sizing material made from step A3 and glued membrane manufacture carrier
Epoxy construction glued membrane is made in hot pressing composite membrane-forming；
B, inhibit corrosion primer preparation method：
B1, it weighs epoxy resin respectively by weight, arylamine solidified agent, thermoplastic resin, inhibits corrosive agent, is silane coupled
Agent and mixed solvent；
B2, a quarter for taking the epoxy resin that step B1 weighs will inhibit corrosive agent to be dispersed in institute by grinding
It states in a quarter epoxy resin, the dispersion for inhibiting corrosive agent and epoxy resin is made；
Under B3, room temperature thermoplastic resin is dissolved in the mixed solvent under stirring, will pressed down made from step B2 respectively
The dispersion of corrosive agent and epoxy resin processed, remaining 3/4ths epoxy resin, arylamine solidified agent and silane coupling agent uniformly divide
It dissipates and is dissolved in the mixed solvent, be made and inhibit corrosion primer.
Further, hot pressing film-forming temperature described in step A4 is 90~100 DEG C.
Advantageous effect of the present invention：
High temperature durability epoxy construction cementitious system of the present invention is from Molecular Design angle, with " specific epoxy tree
Fat-arylamine solidified agent " is curing system, and a kind of high temperature is prepared for as toughener using Particular thermoplastic's resin and rubber elastomer
The temperature resistant grade of hot setting epoxy construction cementitious system is increased to 175 DEG C, vitrifying by durability epoxy construction cementitious system
Transition temperature is increased to 190 DEG C；The heat aging performance examination of high temperature durability epoxy construction cementitious system of the present invention extends to
3000h improves structural member reliability and service life to extend structural member maintenance cycle；High temperature durability of the present invention
Epoxy construction cementitious system processing performance is excellent, temperature resistant grade is high, thermal-oxidative aging property and wet-hot aging performance protrude, and has high-strength
The features such as degree, high tenacity, endurance, meets metal or composite material large area is glued moulding process, solves aerospace and fly
Row device is glued demand to the high temperature durability of thermal structure part, is suitable for aerospace field metal or composite material high temperature resistant knot
The splicing of component.
Specific implementation mode
With reference to embodiment, the following further describes the technical solution of the present invention, and however, it is not limited to this, every right
Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit of the technical scheme of the invention and range, should all be contained
It covers in protection scope of the present invention.
Embodiment 1
A kind of high temperature durability epoxy construction cementitious system, including epoxy construction glued membrane and inhibition corrosion primer, the ring
Oxide structure glued membrane is combined with carrier through hot pressing by following raw material with glued membrane manufacture：
75~100 parts of epoxy resin, 20~35 parts of arylamine solidified agent, 40~60 parts of thermoplastic resin, rubber elastomer 6~
15 parts, 3~9 parts of inorganic filler, antioxidant 1~4；
The inhibition corrosion primer is made of following raw material：
75~100 parts of epoxy resin, 75~100 parts of thermoplastic resin, inhibits corrosive agent 3 at 20~30 parts of arylamine solidified agent
~9 parts, 3~9 parts of silane coupling agent, 1200~1600 parts of mixed solvent；
Epoxy resin in the epoxy construction glued membrane and inhibition corrosion primer is by bisphenol A type epoxy resin, xenol
Formaldehyde epoxy resin, naphthalene novolac epoxy resin and carborane bisphenol diglycidyl are formed by certain weight ratio.
Steps are as follows for the preparation method of the present embodiment high temperature durability epoxy construction cementitious system：
A, epoxy construction glue film manufacturing process：
A1, divide by weight weigh epoxy resin, arylamine solidified agent, thermoplastic resin, rubber elastomer, inorganic filler and
Antioxidant；
A2, the epoxy resin for weighing step A1 are added in reaction kettle, are heated to 220~230 DEG C, under stirring
Thermoplastic resin is added at one time, 60min is kept the temperature at 190~200 DEG C, homogeneous blending resin is made；
A3, using mechanical blending method by homogeneous blending resin and arylamine solidified agent, rubber elastomer, nothing made from step A2
Machine filler and antioxidant are uniformly mixed, and sizing material is made；
A4, glued membrane manufacture with carrier assist membrance casting condition under, by sizing material made from step A3 and glued membrane manufacture carrier
Epoxy construction glued membrane is made in hot pressing composite membrane-forming at a temperature of 90~100 DEG C；
B, inhibit corrosion primer preparation method：
B1, it weighs epoxy resin respectively by weight, arylamine solidified agent, thermoplastic resin, inhibits corrosive agent, is silane coupled
Agent and mixed solvent；
B2, a quarter for taking the epoxy resin that step B1 weighs will inhibit corrosive agent grinding to be dispersed in described four
In/mono- epoxy resin, the dispersion for inhibiting corrosive agent and epoxy resin is made；
Under B3, room temperature thermoplastic resin is dissolved in the mixed solvent under stirring, will pressed down made from step B2 respectively
The dispersion of corrosive agent and epoxy resin processed, remaining 3/4ths epoxy resin, arylamine solidified agent and silane coupling agent uniformly divide
It dissipates and is dissolved in the mixed solvent, be made and inhibit corrosion primer.
Embodiment 2
A kind of high temperature durability epoxy construction cementitious system, including epoxy construction glued membrane and inhibition corrosion primer, the ring
Oxide structure glued membrane is combined with carrier through hot pressing by following raw material with glued membrane manufacture：
75~100 parts of epoxy resin, 20~35 parts of arylamine solidified agent, 40~60 parts of thermoplastic resin, rubber elastomer 6~
15 parts, 3~9 parts of inorganic filler, 1~4 part of antioxidant；
The inhibition corrosion primer is made of following raw material：
75~100 parts of epoxy resin, 75~100 parts of thermoplastic resin, inhibits corrosive agent 3 at 20~30 parts of arylamine solidified agent
~9 parts, 3~9 parts of silane coupling agent, 1200~1600 parts of mixed solvent；
Epoxy resin in the epoxy construction glued membrane and inhibition corrosion primer is by bisphenol A type epoxy resin, xenol
Formaldehyde epoxy resin, naphthalene novolac epoxy resin and carborane bisphenol diglycidyl are by weight (1~4):(1~3):(1~
2):1 composition, wherein bisphenol A type epoxy resin are one kind in the bisphenol A type epoxy resin of E-51, E-55 or E-44 model.
The epoxy construction glued membrane and inhibit the arylamine solidified agent in corrosion primer by 4,4 '-diaminodiphenylsulfones, 4,
4 '-di-2-ethylhexylphosphine oxides (the chloro- 2,6- diethylanilines of 3-), 1,3,5- triamidos (4- phenoxy groups) benzene are by weight (1~4):(1~
3):1 composition；Thermoplastic resin in the epoxy construction glued membrane and inhibition corrosion primer is by polyethersulfone with cardo, phenolphthalein
One kind or several in base poly(aryl ether ketone), epoxy-terminated phthalazone polyether sulphone, epoxy-terminated phthalazone poly(aryl ether ketone)
Kind composition.
Rubber elastomer in the epoxy construction glued membrane is by epoxy terminated nitrile rubber, nbr carboxyl terminal or nucleocapsid
One or more of rubber particles form；Inorganic filler in the epoxy construction glued membrane by aluminium powder, flake asbestos, titanium dioxide or
One or more of alumina powder forms；Antioxidant in the epoxy construction glued membrane is by 6- di-t-butyl -4- methylbenzenes
One or more of phenol, hydroquinone or tert-butyl hydroquinone form.
The inhibition corrosive agent inhibited in corrosion primer is strontium chromate；The silane coupling agent inhibited in corrosion primer
By methyl tri-tert peroxy-silane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane or γ-glycidol
One or more of ether oxygen propyl trimethoxy silicane forms；The mixed solvent inhibited in corrosion primer is by chloroform
With cyclohexanone by weight 1:1 is formulated.
Embodiment 3
The present embodiment high temperature durability epoxy construction cementitious system the difference from example 2 is that, the present embodiment epoxy knot
Structure glued membrane is combined with carrier through hot pressing by following raw material with glued membrane manufacture：
80~90 parts of epoxy resin, 25~30 parts of arylamine solidified agent, 45~55 parts of thermoplastic resin, rubber elastomer 9~
12 parts, 5~7 parts of inorganic filler, 2~3 parts of antioxidant；
The inhibition corrosion primer is made of following raw material：
80~90 parts of epoxy resin, 80~90 parts of thermoplastic resin, inhibits corrosive agent 5~7 at 22~28 parts of arylamine solidified agent
Part, 5~7 parts of silane coupling agent, 1400~1500 parts of mixed solvent.
Embodiment 4
The present embodiment high temperature durability epoxy construction cementitious system the difference from example 2 is that, the present embodiment epoxy knot
Structure glued membrane is combined with carrier through hot pressing by following raw material with glued membrane manufacture：
100 parts of epoxy resin, 35 parts of arylamine solidified agent, 60 parts of thermoplastic resin, 15 parts of rubber elastomer, inorganic filler 9
Part, 4 parts of antioxidant；
The present embodiment inhibits corrosion primer to be made of following raw material：
100 parts of epoxy resin, 100 parts of thermoplastic resin, inhibits 9 parts of corrosive agent, silane coupling agent at 30 parts of arylamine solidified agent
9 parts, 1600 parts of mixed solvent；
Bisphenol-A type ring of the epoxy resin in primer by E-51 models is corroded in the present embodiment epoxy construction glued membrane and inhibition
Oxygen resin, biphenyl novolac epoxy resin, naphthalene novolac epoxy resin and bisphenol fluorene epoxy are by weight 4:3:2:1, i.e. E-51 types
Number 40 parts of bisphenol A type epoxy resin, 30 parts of biphenyl novolac epoxy resin, 20 parts of naphthalene novolac epoxy resin, carborane bis-phenol
10 parts of diglycidyl ether；
Arylamine solidified agent in the present embodiment epoxy construction glued membrane and inhibition corrosion primer is by 4,4 '-diamino hexichol
Sulfone, 4,4 '-di-2-ethylhexylphosphine oxides (the chloro- 2,6- diethylanilines of 3-), 1,3,5- triamidos (4- phenoxy groups) benzene are by weight 4:3:1 group
At；
The present embodiment epoxy construction glued membrane and inhibit the thermoplastic resin in corrosion primer by polyethersulfone with cardo and
Epoxy-terminated phthalazone polyether sulphone is by weight 1:1 composition；Rubber elastomer is by epoxy terminated nitrile rubber and nucleocapsid
Rubber particles are by weight 1:1 composition；
Inorganic filler in the present embodiment epoxy construction glued membrane is aluminium powder, and antioxidant is 6- di-t-butyl -4- methylbenzenes
Phenol；
It is strontium chromate that the present embodiment, which inhibits the inhibition corrosive agent in corrosion primer, and silane coupling agent is methyl tri-tert mistake
Oxosilane；Mixed solvent is by chloroform and cyclohexanone by weight 1:1 is formulated.
The manufacture of the present embodiment glued membrane is nylon gauze with carrier, and specification is 80 mesh, surface density 25g/m2。
Steps are as follows for the preparation method of the present embodiment high temperature durability epoxy construction cementitious system：
A, epoxy construction glue film manufacturing process：
A1, the bisphenol A type epoxy resin for weighing 40 parts of E-51 models respectively, 30 parts of biphenyl novolac epoxy resins, 20 parts of naphthalenes
Base novolac epoxy resin, 10 parts of carborane bisphenol diglycidyls, 14 part of 4,4 '-diaminodiphenylsulfone, 10.5 part of 4,4 '-Asia
Methyl bis- (the chloro- 2,6- diethylanilines of 3-), 3.5 parts of 1,3,5- triamidos (4- phenoxy groups) benzene, 30 parts of polyethersulfone with cardo,
30 parts of epoxy-terminated phthalazone polyether sulphones, 7.5 parts of epoxy terminated nitrile rubbers, 7.5 parts of Core-shell rubber particles, 9 parts of aluminium
Powder and 4 parts of 6- di-tert-butyl-4-methy phenols；
A2, bisphenol A type epoxy resin, biphenyl novolac epoxy resin, naphthalene phenolic aldehyde by the step A1 E-51 models weighed
Epoxy resin and carborane bisphenol diglycidyl are added in reaction kettle, are heated to 220~230 DEG C, under stirring
Polyethersulfone with cardo and epoxy-terminated phthalazone polyether sulphone are added at one time, kept the temperature at 190~200 DEG C
Homogeneous blending resin is made in 60min；
A3, using double roll mill or kneader, with mechanical blending method by homogeneous blending resin and 4 made from step A2,
4 '-diaminodiphenylsulfones, 4,4 '-di-2-ethylhexylphosphine oxides (the chloro- 2,6- diethylanilines of 3-), 3,5- triamidos (4- phenoxy groups) benzene, end
Epoxy group nitrile rubber, Core-shell rubber particles, aluminium powder and 6- di-tert-butyl-4-methy phenols are uniformly mixed, and sizing material is made；
A4, glued membrane manufacture with carrier assist membrance casting condition under, will be made from step A3 using double roller hot calender film-making machine
Sizing material and nylon gauze hot pressing composite membrane-forming at a temperature of 90~100 DEG C, are made epoxy construction glued membrane, the face of epoxy construction glued membrane
Density is respectively 166~196g/m2With 360~390g/m2；
B, inhibit corrosion primer preparation method：
B1, the bisphenol A type epoxy resin for weighing 40 parts of E-51 models respectively, 30 parts of biphenyl novolac epoxy resins, 20 parts of naphthalenes
Base novolac epoxy resin, 10 parts of carborane bisphenol diglycidyls, 12 part of 4,4 '-diaminodiphenylsulfone, 9 part of 4,4 '-methylene
Base bis- (the chloro- 2,6- diethylanilines of 3-), 3 parts of 1,3,5- triamidos (4- phenoxy groups) benzene, 50 parts of polyethersulfone with cardo, 50 parts
Epoxy-terminated phthalazone polyether sulphone, 9 parts of strontium chromates, 9 parts of methyl tri-tert peroxy-silanes, 800 parts of chloroforms and
800 parts of cyclohexanone；
B2, bisphenol A type epoxy resin, biphenyl novolac epoxy resin, the naphthalene phenolic aldehyde for taking the E-51 models that step B1 weighs
The a quarter of the epoxy resin of epoxy resin and carborane bisphenol diglycidyl composition, strontium chromate is ground by three rollers
Machine is ground, it is made to be dispersed in a quarter epoxy resin, grinds three times to five times until being uniformly dispersed, system
It must inhibit the dispersion of corrosive agent and epoxy resin；
Thermoplastic resin is dissolved under stirring to 800 parts of chloroforms and 800 parts of cyclohexanone compositions under B3, room temperature
In the mixed solvent, respectively by the dispersion for inhibiting corrosive agent and epoxy resin made from step B2, remaining 3/4ths asphalt mixtures modified by epoxy resin
Fat, 4,4 '-diaminodiphenylsulfones, 4,4 '-di-2-ethylhexylphosphine oxides (the chloro- 2,6- diethylanilines of 3-), 1,3,5- triamidos (4- benzene oxygen
Base) benzene and methyl tri-tert peroxy-silane is evenly dispersed is dissolved in the mixed solvent, it is made and inhibits corrosion primer.
The present embodiment high temperature durability epoxy structural rubber junctor line aluminium alloy is glued test specimen the performance test results：
The present embodiment high temperature durability structural adhesive bonding -55 DEG C of down cut intensity of system are 31.2MPa, and room temperature shear strength can
To reach 32.4MPa, 175 DEG C of shear strengths can reach 28.6MPa, and glass transition temperature reaches 192.5 DEG C, 5% heat
Weightless temperature reaches 395.8 DEG C, embodies high intensity and high-temperature resistant grade characteristic；The present embodiment high temperature durability structure glue junctor
Be 90 ° of peel strengths of board-to-board reached 4.2kN/m (glued membrane surface density be 166~196g/m2), the stripping of honeycomb sandwich construction roller
Having reached 145.0N.m/m from intensity, (glued membrane surface density is 360~390g/m2), honeycomb sandwich construction planar stretch intensity reaches
(glued membrane surface density is 390g/m to 6.1MPa2), embody cementitious system high tenacity feature；The present embodiment high temperature durability structure
Cementitious system excelling in fatigue property passes through 10.0MPa × 10 under room temperature experiment condition7Fatigue behaviour is examined；The present embodiment high temperature
Durable construction cementitious system still maintains its higher mechanical property after the examination of 175 DEG C × 3000h heat aging performances,
Room temperature and 175 DEG C of down cut intensity still reach the high value of 27.8MPa and 25.6MPa, room temperature and 175 DEG C of honeycomb planar stretches
Intensity still reaches 5.4MPa and 4.3MPa.Illustrate that the present embodiment high temperature durability structural adhesive bonding system can meet aluminium alloy structure
The splicing of part is molded, and with high intensity, high tenacity, high-temperature stability.
The present embodiment high temperature durability epoxy construction cementitious system epoxy base carbon fiber composite material co-curing Adhesive Test
Part the performance test results：
The present embodiment high temperature durability structural adhesive bonding -55 DEG C of down cut intensity of system are 30.5MPa, and room temperature shear strength reaches
32.1MPa is arrived, 175 DEG C of shear strengths can reach 27.8MPa, and be that composite material interlayer destroys；The present embodiment high temperature
Durable construction cementitious system composite honeycomb sandwich structures planar stretch intensity has reached 3.1MPa, and (glued membrane surface density is
360-390g/m2), failure mode destroys for aramid fiber paper honeycomb core material.The test result illustrates the embodiment high temperature durability knot
Structure cementitious system there is preferable co-curing to be glued adaptability epoxy base carbon fiber composite material.
Embodiment 5
The present embodiment high temperature durability epoxy construction cementitious system the difference from example 2 is that, the present embodiment epoxy knot
Structure glued membrane is combined with carrier through hot pressing by following raw material with glued membrane manufacture：
90 parts of epoxy resin, 30 parts of arylamine solidified agent, 50 parts of thermoplastic resin, 12 parts of rubber elastomer, inorganic filler 7
Part, 3 parts of antioxidant；
The present embodiment inhibits corrosion primer to be made of following raw material：
90 parts of epoxy resin, 90 parts of thermoplastic resin, inhibits 7 parts of corrosive agent, silane coupling agent 7 at 28 parts of arylamine solidified agent
Part, 1500 parts of mixed solvent；
Bisphenol-A type ring of the epoxy resin in primer by E-51 models is corroded in the present embodiment epoxy construction glued membrane and inhibition
Oxygen resin, biphenyl novolac epoxy resin, naphthalene novolac epoxy resin and carborane bisphenol diglycidyl are by weight 3:2:
1:1；
Arylamine solidified agent in the present embodiment epoxy construction glued membrane and inhibition corrosion primer is by 4,4 '-diamino hexichol
Sulfone, 4,4 '-di-2-ethylhexylphosphine oxides (the chloro- 2,6- diethylanilines of 3-) and 1,3,5- triamidos (4- phenoxy groups) benzene are by weight 3:2:1
Composition；
The present embodiment epoxy construction glued membrane and inhibit the thermoplastic resin in corrosion primer by cardo polyetherketone and
Epoxy-terminated phthalazone poly(aryl ether ketone) is by weight 1:1 composition；Rubber elastomer in the present embodiment epoxy construction glued membrane
By nbr carboxyl terminal and Core-shell rubber particles by weight 1:1 composition；
Inorganic filler in the present embodiment epoxy construction glued membrane is flake asbestos, and antioxidant is hydroquinone；The present embodiment
It is strontium chromate to inhibit the inhibition corrosive agent in corrosion primer, and silane coupling agent is gamma-amino propyl trimethoxy silicane；It mixes molten
Agent is by chloroform and cyclohexanone by weight 1:1 is formulated；The manufacture of the present embodiment glued membrane is polyester gauze with carrier.
Embodiment 6
The present embodiment high temperature durability epoxy construction cementitious system the difference from example 2 is that, the present embodiment epoxy knot
Structure glued membrane is combined with carrier through hot pressing by following raw material with glued membrane manufacture：
80 parts of epoxy resin, 25 parts of arylamine solidified agent, 45 parts of thermoplastic resin, 9 parts of rubber elastomer, 5 parts of inorganic filler,
2 parts of antioxidant；
The present embodiment inhibits corrosion primer to be made of following raw material：
80 parts of epoxy resin, 80 parts of thermoplastic resin, inhibits 5 parts of corrosive agent, silane coupling agent 5 at 25 parts of arylamine solidified agent
Part, 1400 parts of mixed solvent；
Bisphenol-A type ring of the epoxy resin in primer by E-55 models is corroded in the present embodiment epoxy construction glued membrane and inhibition
Oxygen resin, biphenyl novolac epoxy resin, naphthalene novolac epoxy resin and carborane bisphenol diglycidyl are by weight 2:1:
1:1；
Arylamine solidified agent in the present embodiment epoxy construction glued membrane and inhibition corrosion primer is by 4,4 '-diamino hexichol
Sulfone, 4,4 '-di-2-ethylhexylphosphine oxides (the chloro- 2,6- diethylanilines of 3-) and 1,3,5- triamidos (4- phenoxy groups) benzene are by weight 2:1:1
Composition；
The present embodiment epoxy construction glued membrane and inhibit the thermoplastic resin in corrosion primer by polyethersulfone with cardo and
Epoxy-terminated phthalazone poly(aryl ether ketone) is by weight 1:1 composition；Rubber elastomer in the present embodiment epoxy construction glued membrane
For epoxy terminated nitrile rubber；
Inorganic filler in the present embodiment epoxy construction glued membrane is titanium dioxide, and antioxidant is tert-butyl hydroquinone；This
It is strontium chromate that embodiment, which inhibits the inhibition corrosive agent in corrosion primer, and silane coupling agent is vinyl trimethylsilane；It mixes molten
Agent is by chloroform and cyclohexanone by weight 1:1 is formulated；The manufacture of the present embodiment glued membrane is non-woven fabrics with carrier.
Embodiment 7
The present embodiment high temperature durability epoxy construction cementitious system the difference from example 2 is that, the present embodiment epoxy knot
Structure glued membrane is combined with carrier through hot pressing by following raw material with glued membrane manufacture：
75 parts of epoxy resin, 20 parts of arylamine solidified agent, 40 parts of thermoplastic resin, 6 parts of rubber elastomer, 3 parts of inorganic filler,
1 part of antioxidant；
The present embodiment inhibits corrosion primer to be made of following raw material：
75 parts of epoxy resin, 75 parts of thermoplastic resin, inhibits 3 parts of corrosive agent, silane coupling agent 3 at 22 parts of arylamine solidified agent
Part, 1200 parts of mixed solvent；
Bisphenol-A type ring of the epoxy resin in primer by E-44 models is corroded in the present embodiment epoxy construction glued membrane and inhibition
Oxygen resin, biphenyl novolac epoxy resin, naphthalene novolac epoxy resin and carborane bisphenol diglycidyl are by weight 1:1:
1:1；
Arylamine solidified agent in the present embodiment epoxy construction glued membrane and inhibition corrosion primer is by 4,4 '-diamino hexichol
Sulfone, 4,4 '-di-2-ethylhexylphosphine oxides (the chloro- 2,6- diethylanilines of 3-) and 1,3,5- triamidos (4- phenoxy groups) benzene are by weight 1:1:1
Composition；
The present embodiment epoxy construction glued membrane and inhibit the thermoplastic resin in corrosion primer by cardo polyetherketone and
Epoxy-terminated phthalazone polyether sulphone is by weight 1:1 composition；Rubber elastomer in the present embodiment epoxy construction glued membrane
For Core-shell rubber particles；
Inorganic filler in the present embodiment epoxy construction glued membrane is alumina powder, and antioxidant is 6- di-t-butyl -4- first
Base phenol；It is strontium chromate that the present embodiment, which inhibits the inhibition corrosive agent in corrosion primer, and silane coupling agent is γ-glycidyl ether oxygen
Propyl trimethoxy silicane；Mixed solvent is by chloroform and cyclohexanone by weight 1:1 is formulated；The present embodiment glued membrane system
It is glass fiber woven cloth to make with carrier.
Claims (10)
1. a kind of high temperature durability epoxy construction cementitious system, including epoxy construction glued membrane and inhibition corrosion primer, feature exist
It is combined through hot pressing with carrier with glued membrane manufacture by following raw material in the epoxy construction glued membrane：
75~100 parts of epoxy resin, 20~35 parts of arylamine solidified agent, 40~60 parts of thermoplastic resin, rubber elastomer 6~15
Part, 3~9 parts of inorganic filler, 1~4 part of antioxidant；
The inhibition corrosion primer is made of following raw material：
75~100 parts of epoxy resin, 75~100 parts of thermoplastic resin, inhibits corrosive agent 3~9 at 20~30 parts of arylamine solidified agent
Part, 3~9 parts of silane coupling agent, 1200~1600 parts of mixed solvent；
Epoxy resin in the epoxy construction glued membrane and inhibition corrosion primer is by bisphenol A type epoxy resin, biphenyl phenolic aldehyde ring
Oxygen resin, naphthalene novolac epoxy resin and carborane bisphenol diglycidyl are formed by certain weight ratio.
2. a kind of high temperature durability epoxy construction cementitious system according to claim 1, it is characterised in that the epoxy construction
Glued membrane is combined with carrier through hot pressing by following raw material with glued membrane manufacture：
80~90 parts of epoxy resin, 25~30 parts of arylamine solidified agent, 45~55 parts of thermoplastic resin, 9~12 parts of rubber elastomer,
5~7 parts of inorganic filler, 2~3 parts of antioxidant；
The inhibition corrosion primer is made of following raw material：
80~90 parts of epoxy resin, 22~28 parts of arylamine solidified agent, 80~90 parts of thermoplastic resin, inhibit 5~7 parts of corrosive agent,
5~7 parts of silane coupling agent, 1400~1500 parts of mixed solvent.
3. a kind of high temperature durability epoxy construction cementitious system according to claim 1 or claim 2, it is characterised in that the bisphenol-A
The weight ratio of type epoxy resin, biphenyl novolac epoxy resin, naphthalene novolac epoxy resin and carborane bisphenol diglycidyl
For (1~4):(1~3):(1~2):1.
4. a kind of high temperature durability epoxy construction cementitious system according to claim 3, it is characterised in that the bisphenol-A type ring
Oxygen resin is one kind in the bisphenol A type epoxy resin of E-51, E-55 or E-44 model.
5. a kind of high temperature durability epoxy construction cementitious system according to claim 4, it is characterised in that the epoxy construction
Arylamine solidified agent in glued membrane and inhibition corrosion primer is by 4,4 '-diaminodiphenylsulfones, 4,4 '-di-2-ethylhexylphosphine oxides (the chloro- 2,6- of 3-
Diethylaniline), 1,3,5- triamidos (4- phenoxy groups) benzene is by weight (1~4):(1~3):1 composition；The epoxy construction
Thermoplastic resin in glued membrane and inhibition corrosion primer is by polyethersulfone with cardo, cardo polyetherketone, epoxy-terminated two
One or more of azepine naphthalenone polyether sulphone, epoxy-terminated phthalazone poly(aryl ether ketone) form.
6. a kind of high temperature durability epoxy construction cementitious system according to claim 5, it is characterised in that the epoxy construction
Rubber elastomer in glued membrane is by one kind in epoxy terminated nitrile rubber, nbr carboxyl terminal or Core-shell rubber particles or several
Kind composition；Inorganic filler in the epoxy construction glued membrane is by one kind in aluminium powder, flake asbestos, titanium dioxide or alumina powder or several
Kind composition；Antioxidant in the epoxy construction glued membrane is by 6- di-tert-butyl-4-methy phenols, hydroquinone or tertiary butyl pair
One or more of benzenediol forms.
7. a kind of high temperature durability epoxy construction cementitious system according to claim 6, it is characterised in that the inhibition corrosion
Inhibition corrosive agent in primer is strontium chromate；The silane coupling agent inhibited in corrosion primer is by methyl tri-tert peroxide silicon
Alkane, gamma-amino propyl trimethoxy silicane, vinyl trimethylsilane or γ-glycidyl ether oxygen propyl trimethoxy silicane
One or more of composition；The mixed solvent inhibited in corrosion primer is by chloroform and cyclohexanone by weight 1:1
It is formulated.
8. a kind of high temperature durability epoxy construction cementitious system according to claim 7, it is characterised in that the glued membrane manufacture
It is nylon gauze, polyester gauze, non-woven fabrics, glass fiber woven cloth, silica fibrage cloth or carbon fiber woven cloth with carrier
In one kind.
9. a kind of preparation method of the high temperature durability epoxy construction cementitious system as described in claim 1-8 is any, feature exist
In the preparation method, steps are as follows：
A, epoxy construction glue film manufacturing process：
A1, divide weigh epoxy resin, arylamine solidified agent, thermoplastic resin, rubber elastomer, inorganic filler and antioxygen by weight
Agent；
A2, the epoxy resin for weighing step A1 are added in reaction kettle, are heated to 220~230 DEG C, will be hot under stirring
Plastic resin is added at one time, and 60min is kept the temperature at 190~200 DEG C, and homogeneous blending resin is made；
A3, using mechanical blending method by homogeneous blending resin made from step A2 and arylamine solidified agent, rubber elastomer, inorganic fill out
Material and antioxidant are uniformly mixed, and sizing material is made；
A4, glued membrane manufacture with carrier assist membrance casting condition under, by sizing material made from step A3 and glued membrane manufacture carrier hot pressing
Epoxy construction glued membrane is made in composite membrane-forming；
B, inhibit corrosion primer preparation method：
B1, weigh respectively by weight epoxy resin, arylamine solidified agent, thermoplastic resin, inhibit corrosive agent, silane coupling agent and
Mixed solvent；
B2, a quarter for taking the epoxy resin that step B1 weighs will inhibit corrosive agent to be dispersed in described four by grinding
In/mono- epoxy resin, the dispersion for inhibiting corrosive agent and epoxy resin is made；
Under B3, room temperature thermoplastic resin is dissolved in the mixed solvent under stirring, will inhibit rotten made from step B2 respectively
Dispersion, remaining 3/4ths epoxy resin, arylamine solidified agent and the silane coupling agent for losing agent and epoxy resin are evenly dispersed molten
In the mixed solvent, it is made and inhibits corrosion primer.
10. a kind of preparation method of high temperature durability epoxy construction cementitious system according to claim 9, it is characterised in that step
Hot pressing film-forming temperature described in rapid A4 is 90~100 DEG C.
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| CN113201302A (en) * | 2021-05-06 | 2021-08-03 | 黑龙江省科学院石油化学研究院 | Diamino bisphthalonitrile modified epoxy resin adhesive and preparation method thereof |
| CN113201302B (en) * | 2021-05-06 | 2023-03-03 | 黑龙江省科学院石油化学研究院 | Diamino bisphthalonitrile modified epoxy resin adhesive and preparation method thereof |
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