CN107142054A - A kind of Impact-resistant epoxy adhesive adhesive composition and preparation method thereof - Google Patents
A kind of Impact-resistant epoxy adhesive adhesive composition and preparation method thereof Download PDFInfo
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- CN107142054A CN107142054A CN201710515265.9A CN201710515265A CN107142054A CN 107142054 A CN107142054 A CN 107142054A CN 201710515265 A CN201710515265 A CN 201710515265A CN 107142054 A CN107142054 A CN 107142054A
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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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/286—Oximes
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/48—Polyethers
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K2003/2241—Titanium dioxide
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- 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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Abstract
The invention provides a kind of Impact-resistant epoxy adhesive adhesive composition, the present invention is using two kinds of different epoxy resin as raw material, and it with the addition of the composite toughing agent for the polysulfide rubber toughener formation at least including the liquid rubber toughening agent with core shell structure, the nitrile rubber of epoxy resin modification, the reaction type polyurethane elastomeric prepolymer body of ketoxime end-blocking and epoxy resin modification, epoxy adhesive composition all has good impact resistance under normal temperature and cryogenic conditions obtained from, and steel steel tensile shear strength is also obviously improved.
Description
Technical field
The invention belongs to field of adhesive technology, and in particular to a kind of Impact-resistant epoxy adhesive adhesive composition and its preparation side
Method.
Background technology
After epoxy adhesive curing, usually because poor toughness, easily occurs embrittlement under external force.Industry is tough in order to evaluate its
Property generally using impact strength this index, its method of testing uses ISO 11343：2003 standards.General method for toughening can
To lift the toughness of material under normal temperature, but at low temperature, the material of normal temperature good toughness can still become fragile.Another aspect low temperature is tough
Toughness under the good material of property, normal temperature is possible to die down.
The content of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of Impact-resistant epoxy adhesive adhesive composition and its
Preparation method, the Impact-resistant epoxy adhesive adhesive composition that the present invention is provided all has good resistance to punching under normal temperature and cryogenic conditions
Performance is hit, and steel-steel tensile shear strength is also obviously improved.
The invention provides a kind of Impact-resistant epoxy adhesive adhesive composition, including：
At least two epoxy resin；
At least one bifunctionality epoxide diluent；
At least four kinds of toughener, the toughener at least includes liquid rubber toughening agent, epoxy resin with core shell structure
The polysulfide rubber toughness reinforcing of modified nitrile rubber, the reaction type polyurethane elastomeric prepolymer body of ketoxime end-blocking and epoxy resin modification
Agent；
At least one inorganic filler；
At least one deicer；
At least one thixotropic agent；
The latent curing agent of at least one thermal activation；
At least one curing accelerator.
It is preferred that, including：
16wt%~18wt% epoxy resin, the epoxy resin includes liquid epoxies and solid epoxy；
30wt%~36wt% the liquid rubber toughening agent with core shell structure；
The nitrile rubber of 9wt%~13wt% epoxy resin modification；
The reaction type polyurethane elastomeric prepolymer body of 10wt%~12wt% ketoximes end-blocking；
The polysulfide rubber toughener of 6wt%~8wt% epoxy resin modifications；
1wt%~2wt% bifunctionality epoxide diluent；
10wt%~12wt% inorganic filler；
0.2wt%~0.3wt% deicer；
2.0wt%~3.0wt% thixotropic agent；
The latent curing agent of 2wt%~3wt% thermal activation；
0.2wt%-0.4wt% curing accelerator.
It is preferred that, the polysulfide rubber toughener of the epoxy resin modification is prepared as follows：
By the polysulfide rubber with Formulas I structure and bisphenol A epoxide resin according to thiol group than epoxide group mol ratio 1:
(2.2~2.5) mix, heating response is carried out under conditions of 90 DEG C ± 5 DEG C 3 hours, obtain the polysulfide rubber of epoxy resin modification
Glue toughener；
In Formulas I ,-R- is-(CH2)2-O-CH2-O-(CH2)2-, 12≤a+b+c≤28.
It is preferred that, the reaction type polyurethane elastomeric prepolymer body of the ketoxime end-blocking gathers for the response type that 100% ketoxime is blocked
Urethane elastomeric prepolymer body, the reaction type polyurethane elastomeric prepolymer body of the 100% ketoxime end-blocking is prepared as follows：
By the PPG after dehydration, trimethylolpropane and methyl diphenylene diisocyanate nitrogen protection, urge
Heating carries out polymerisation under agent existence condition, obtains prepolymer；
Oxime compound is added into the prepolymer, end capping reaction is carried out, the response type of 100% ketoxime end-blocking is obtained
Elastic polyurethane performed polymer；
The mol ratio of ketoxime radical and NCO group in the prepolymer is 1.05 in the oxime compound:1~1.1:
1。
It is preferred that, the liquid epoxies is liquid bisphenol A type diglycidyl ether, and the solid epoxy is solid
Body bisphenol A-type diglycidyl ether, the mass ratio of the solid epoxy and liquid epoxies is 1：(3~4).
It is preferred that, the nucleome material of the liquid rubber toughening agent with core shell structure is total to for alkadienes and monoolefine
Polymers, case material be Epoxy functionalized (methyl) acrylate homopolymer or copolymer, it is described have nucleocapsid knot
The average grain diameter of the liquid rubber toughening agent of structure is less than 400nm.
It is preferred that, the bifunctionality epoxide diluent is selected from the diglycidyl ether of representative examples of saturated aliphatic glycol；
The inorganic filler is selected from calcium carbonate, talcum powder, mica, silica flour, bentonite, wollastonite, metal dust, carbon black
With the one or more in glass microballoon；
The deicer is selected from calcium oxide；
The thixotropic agent is selected from hydrophobic type gas phase silica；
One or more of the latent curing agent of the thermal activation in guanidine and its derivative, urea and its derivative；
The curing accelerator is selected from the substituted urea containing phenyl and dimethyl for having catalytic activity.
It is preferred that, include 0wt%~2wt% auxiliary agent, the auxiliary agent is selected from plasticizer, tackifier, wetting agent, fire-retardant
One or more in agent, antiaging agent and pigment.
Present invention also offers a kind of preparation method of above-mentioned Impact-resistant epoxy adhesive adhesive composition, comprise the following steps：
A melting is heated after) epoxy resin is mixed, epoxy resin mixed liquor is obtained；
B bifunctionality epoxide diluent, toughener, inorganic filler, water removal) are added into the epoxy resin mixed liquor
Agent, thixotropic agent, the latent curing agent of thermal activation and curing accelerator are mixed, and vacuum defoamation obtains epoxy adhesive
Composition.
It is preferred that, step A) in, the temperature of heating melting is 95~105 DEG C.
Compared with prior art, the invention provides a kind of Impact-resistant epoxy adhesive adhesive composition, including：At least two rings
Oxygen tree fat；At least one bifunctionality epoxide diluent；At least four kinds of toughener, the toughener at least includes having nucleocapsid knot
The liquid rubber toughening agent of structure, the nitrile rubber of epoxy resin modification, ketoxime end-blocking reaction type polyurethane elastomeric prepolymer body and
The polysulfide rubber toughener of epoxy resin modification；At least one inorganic filler；At least one deicer；At least one thixotropic agent；
The latent curing agent of at least one thermal activation；At least one curing accelerator.The present invention using two kinds of different epoxy resin as
Raw material, and with the addition of liquid rubber toughening agent, the nitrile rubber of epoxy resin modification, the ketone at least including there is core shell structure
The composite toughing agent of the polysulfide rubber toughener formation of the reaction type polyurethane elastomeric prepolymer body and epoxy resin modification of oxime end-blocking,
The epoxy adhesive composition obtained from all has good impact resistance, and steel-steel under normal temperature and cryogenic conditions
Tensile shear strength is also obviously improved.
Embodiment
A kind of Impact-resistant epoxy adhesive adhesive composition, including：
At least two epoxy resin；
At least one bifunctionality epoxide diluent；
At least four kinds of toughener, the toughener at least includes liquid rubber toughening agent, epoxy resin with core shell structure
The polysulfide rubber toughness reinforcing of modified nitrile rubber, the reaction type polyurethane elastomeric prepolymer body of ketoxime end-blocking and epoxy resin modification
Agent；
At least one inorganic filler；
At least one deicer；
At least one thixotropic agent；
The latent curing agent of at least one thermal activation；
At least one curing accelerator.
The epoxy adhesive composition that the present invention is provided includes at least two epoxy resin, and the epoxy resin is preferably point
Epoxides containing two epoxide groups in minor structure, more preferably saturation polyepoxide, unsaturated polyepoxide, fat
In fat adoption epoxides, alicyclic polyepoxide, aromatic polyepoxide and polyepoxide containing heterocycle at least
Two kinds, more preferably polyglycidyl ether and its derivative, it is sweet that the polyglycidyl ether is selected from the shrink that polyalcohol gathers
The polyglycidyl ether of oily ether, the polyglycidyl ether of diamines or polybasic carboxylic acid, most preferably bisphenol-A are with epoxychloropropane in alkali
The lower obtained epoxy resin of catalysis.
In certain specific embodiments of the invention, the epoxy adhesive composition includes two kinds of epoxy resin, institute
State two kinds of epoxy resin and be selected from liquid epoxies (L_Epoxy) and solid epoxy (S_Epoxy), the Breakup of Liquid Ring oxygen tree
Fat is is the bisphenol A-type diglycidyl ether of liquid under normal temperature, and the epoxide number of the liquid epoxies is 0.36~0.55, excellent
Elect 0.40~0.50 as, epoxide equivalent is 180~220, preferably 190~210.It under normal temperature is solid that the solid epoxy, which is,
The bisphenol A-type diglycidyl ether of body, the epoxide number of the solid epoxy for 0.16~0.24, preferably 0.18~
0.22, epoxide equivalent is 400~600, preferably 450~550.In the present invention, the epoxy adhesive composition includes
16wt%~18wt% epoxy resin, preferably 16.5wt%~17.5wt%.In the epoxy, the solid ring oxygen tree
The mass ratio of fat and liquid epoxies is 1：(3~4), preferably 1：(3.2~3.6).
The epoxy adhesive composition that the present invention is provided includes at least one bifunctionality epoxide diluent, the difunctionality
It is anti-that the epoxide group that degree epoxide diluent is used to improve in the viscosity and rheological attribute of adhesive, diluent participates in hot setting
Should.In the present invention, the bifunctionality epoxide diluent is selected from the diglycidyl ether of representative examples of saturated aliphatic glycol, preferably satisfies
With the diglycidyl ether of aliphatic C3-C5 glycol, the bifunctionality epoxide diluent is preferably remote purchased from Anhui permanent (new)
The bis-epoxy base series of products of Chemical Co., Ltd., more preferably model XY205, XY207 and XY678 bifunctionality epoxy
One or more in diluent.In the present invention, the epoxy adhesive composition includes 1wt%~2wt% double officials
Energy degree epoxide diluent, more preferably preferably 1.2wt%~1.8wt%, 1.4wt%~1.6wt%.
The epoxy adhesive composition that the present invention is provided also includes at least four kinds of toughener, and the toughener at least includes tool
There is the reaction type polyurethane elasticity of liquid rubber toughening agent, the nitrile rubber of epoxy resin modification, the ketoxime end-blocking of core shell structure
The polysulfide rubber toughener of performed polymer and epoxy resin modification.
Wherein, the liquid rubber toughening agent with core shell structure includes rubber grain, and the rubber grain includes core
Body material and the case material for being coated on nucleome material surface.In the present invention, the nucleome material is by elastomer polymer
Composition, the elastomer polymer is preferably one in the copolymer of diolefinic monomer homopolymer, diolefinic monomer and monoolefine
Plant or a variety of, the monoolefine is preferably one kind in vi-ny l aromatic monomers, acrylonitrile monomer and acrylic ester monomer
Or it is a variety of.The glass transition temperature of the nucleome material is less than -40 DEG C.
The case material is selected from the polymerizate of acrylic ester monomer and vi-ny l aromatic monomers, or acrylate
The polymerizate of class monomer and unsaturated alkenyl halide monomer, more preferably Epoxy functionalized (methyl) alkyl acrylate
The copolymer of homopolymer or Epoxy functionalized (methyl) alkyl acrylate and vinyl monomer, the glass of the case material
Glass transition temperature is more than 50 DEG C.
The average grain diameter of the liquid rubber toughening agent with core shell structure is less than 400nm, preferably 100~300nm.
The present invention is not specifically limited to the source of the liquid rubber toughening agent with core shell structure, can be city
Product is sold, can also voluntarily be prepared, its preparation method may be referred to Application No. EP1632533 European patent, Application No.
US4778851 and US6111015 United States Patent (USP), above-mentioned patent document is incorporated by reference herein.Tool of the present invention
The liquid rubber toughening agent for having core shell structure can also be purchased from Kaneka Corporation trade name " ACE MX " series
The liquid rubber toughening agent with core shell structure of product, more preferably model MX153 or MX154.The rubber grain exists
Weight/mass percentage composition in rubber toughening agent is preferably 33.3%~40%.
In the present invention, the epoxy adhesive composition includes the 30wt%~36wt% liquid with core shell structure
Body rubber toughener, preferably 32wt%~34wt%, more preferably 32.5wt%~33.5wt%.
In the nitrile rubber of the epoxy resin modification, the nitrile rubber is preferably LNBR, is that epoxy is consolidated
The class toughener commonly used in change system, passes through modification, active reactive group such as carboxyl or amido etc., with epoxy molecule
The epoxy reaction formation soft segment largely existed in structure, separates out from the matrix of three-dimensional system after solidification, physically forms
The two phase structure of thermosetting phase and rubber phase, can greatly improve toughness.The molecular backbone of LNBR is divinylic monomer
With the copolymer of acrylonitrile monemer.The end group that preferred number average molecular weight of the present invention is 3000~10000 is the nitrile (HTBN) of carboxyl
Acrylonitrile monomer content is 15wt%~30wt% scopes in rubber, molecular structure, and the LNBR can be with excess
Epichlorohydrin reaction formation end group is the LNBR of epoxy radicals, can also the life under catalyst action with epoxy resin
Into epoxy resin addition product.Above two reactive mode can lift compatibility of the rubber with epoxy resin-base.
The present invention is not specifically limited to the source of the nitrile rubber of the epoxy resin modification, can be voluntarily to make
It is standby, or commercially available prod.The preparation method may be referred to Publication No. US2003/0196753, US2005-0070634
With US6776860 patent, the present invention introduces the preparation method of the nitrile rubber in above-mentioned patent for epoxy resin modification
Herein as reference.Wherein, the nitrile rubber of the epoxy resin modification of commercialization can be purchased from U.S. CVC Thermoset
The trade name Hypro of Specialties companies CTBN1300x8 or 1300x13 and the addition product of epoxy resin
Hypro861340。
In the present invention, the epoxy adhesive composition includes the fourth of 9wt%~13wt% epoxy resin modification
Nitrile rubber, preferably 10wt%~12wt%, more preferably 10.5wt%~11.5wt%.
The reaction type polyurethane elasticity that the reaction type polyurethane elastomeric prepolymer body of the ketoxime end-blocking blocks for 100% ketoxime
Performed polymer, the reaction type polyurethane elastomeric prepolymer body of the 100% ketoxime end-blocking is prepared as follows：
By the PPG after dehydration, trimethylolpropane and methyl diphenylene diisocyanate nitrogen protection, urge
Polymerisation is heated under agent existence condition, prepolymer is obtained；
Oxime compound is added into the prepolymer, end capping reaction is carried out, the response type of 100% ketoxime end-blocking is obtained
Elastic polyurethane performed polymer；
In the oxime compound in ketoxime radical and the prepolymer-mol ratio of NCO group is 1.05:1~
1.1:1。
Specifically, the present invention polyether polyols dehydration of alcohols be dehydrated first after PPG, then, addition three hydroxyls
Methylpropane and catalyst mixing, under conditions of nitrogen protection, add methyl diphenylene diisocyanate (MDI), carry out
Heating response, obtains prepolymer.
Wherein, the number-average molecular weight of the PPG is 1000D~5000D, preferably 2000D~4000D；It is described
Catalyst is preferably organotin catalysts, it is furthermore preferred that the organotin catalysts are selected from dibutyl tin laurate, it is described to add
The temperature of thermal response is preferably 85~90 DEG C, and the time of the heating response is 2 hours.In detection prepolymer-NCO group contains
Reaction can be stopped for 3.3% (mass percent) by measuring.
Obtain after above-mentioned prepolymer, oxime compound is added into the prepolymer, carry out end capping reaction, obtain
The reaction type polyurethane elastomeric prepolymer body of 100% ketoxime end-blocking；
In the present invention, the species to the ketoxime is not specifically limited, and well known to a person skilled in the art for sealing
The oxime compound at end, preferably diacetylmonoxime or cyclohexanone oxime.In the oxime compound ketoxime radical with it is described
In prepolymer-mol ratio of NCO group is 1.05:1~1.1:1, the temperature of the end capping reaction is preferably 85~90 DEG C, described
The time of end capping reaction is preferably 1~1.5 hour.
Determine in the reaction product after the end capping reaction-content of NCO group is 0, you can judge that reaction terminates, vacuum
After deaeration, the reaction type polyurethane elastomeric prepolymer body of 100% ketoxime end-blocking is obtained.
The number-average molecular weight of the reaction type polyurethane elastomeric prepolymer body of the 100% ketoxime end-blocking finally given for 4000~
12000, preferably 4000~10000.
In the present invention, the epoxy adhesive composition include 10wt%~12wt% ketoximes end-blocking response type gather
Urethane elastomeric prepolymer body, more preferably preferably 10.5wt%~11.5wt%, 10.8wt%~11.2wt%.
In the present invention, the polysulfide rubber toughener of the epoxy resin modification is preferably prepared as follows：
By the polysulfide rubber with Formulas I structure and bisphenol A epoxide resin according to thiol group than epoxide group mol ratio 1:
(2.2~2.5) mix, heating response is carried out under conditions of 90 DEG C ± 5 DEG C 3 hours, obtain the polysulfide rubber of epoxy resin modification
Glue toughener；
Wherein, the polysulfide rubber is the liquid polysulfide rubber that end group is mercapto functional group, it is preferred to use model G10's
In the polysulfide rubber of polysulfide rubber or model G21, the polysulfide rubber of the model G10 sulfhydryl content be 1.4wt%~
1.5wt%, number-average molecular weight is 4400~4700；In the polysulfide rubber of the model G21 sulfhydryl content be 2.5wt%~
3.1wt%, number-average molecular weight is 2100~2700.The present invention is not particularly limited to the source of the polysulfide rubber, general city
Sell.It is preferred that being purchased from Akzo Nobel Co., Ltd.
In Formulas I ,-R- is-(CH2)2-O-CH2-O-(CH2)2-, a, b and c are the degree of polymerization, 12≤a+b+c≤28.
The epoxide equivalent of bisphenol A epoxide resin is preferably 182~192, in the present invention, it is preferred to using model BE199-
90 bisphenol A epoxide resin.The present invention is not specifically limited to the source of the epoxy resin, general commercially available.It is preferred that
It is purchased from Changchun chemical industry (Jiangsu) Co., Ltd.
Epoxy adhesive composition of the present invention also includes at least one inorganic filler, and the inorganic filler is selected from carbon
One or more in sour calcium, talcum powder, mica, silica flour, bentonite, wollastonite, metal dust, carbon black and glass microballoon.
The filler can mainly play improvement rheological attribute in adhesive, reduce cost, absorb moisture, promote the effect such as bonding.Institute
Stating epoxy adhesive composition includes 10wt%~12wt% inorganic filler, preferably 10.5wt%~11.5wt%, more excellent
Elect 10.8wt%~11.2wt% as.
Epoxy adhesive composition of the present invention also includes at least one deicer, and the deicer is selected from oxidation
Calcium, the epoxy adhesive composition includes 0.2wt%~0.3wt% deicer, preferably 0.22wt%~0.28wt%,
More preferably 0.24wt%~0.26wt%.
Epoxy adhesive composition of the present invention also includes at least one thixotropic agent, and the thixotropic agent is selected from hydrophobic type
Aerosil.Present invention preferably employs the R202 type aerosils purchased from Evonik Degussa Corp., it can significantly improve
High temperature thixotropy, prevents high temperature sagging.The epoxy adhesive composition includes 2.0wt%~3.0wt% thixotropic agent,
Preferably 2.2wt%~2.8wt%, more preferably 2.4wt%~2.6wt%.
Epoxy adhesive composition of the present invention also includes the latent curing agent of at least one thermal activation, the present invention
High-temp epoxy curing agent is selected, is activated by heating, solidification temperature is more than 140 DEG C.The latent curing of the thermal activation
One or more of the agent in guanidine and its derivative, urea and its derivative.It is excellent in some specific embodiments of the present invention
Choosing uses powdered dicyandiamide (cyanoguanidines) curing agent, and powder particle particle diameter is less than or equal to 10 μm, to improve dispersion effect
With the storage stability of improvement adhesive.Described epoxy adhesive composition includes the latent of 2wt%~3wt% thermal activation
Property curing agent, preferably 2.2wt%~2.8wt%, more preferably 2.4wt%~2.6wt%.
Epoxy adhesive composition of the present invention also includes at least one curing accelerator, the curing accelerator choosing
The substituted urea containing phenyl and dimethyl of own catalytic activity, the curing accelerator can also show except playing catalytic action
Write extension product shelf life.In the present invention, it is preferred to using the relatively low dimethyl ureas curing accelerator of catalytic activity, more preferably
For rubigan-N, N- dimethyl ureas, 3- phenyl -1,1- dimethyl urea, 3,4- dichlorophenyls-N, N- dimethyl urea.In this hair
In bright, the dimethyl ureas curing accelerator is preferably purchased from the DYHARD UR series of products of Alzchem companies, preferably type
Number be UR200, UR300, UE400, UR500, UR700 or UR800 dimethyl ureas curing accelerator.Described Wear Characteristics of Epoxy Adhesive
Agent composition includes 0.2wt%~0.4wt% curing accelerator, preferably 0.25wt%~0.35wt%, more preferably
0.27wt%~0.32wt%.
It is preferred that, epoxy adhesive composition of the present invention also includes auxiliary agent, and the auxiliary agent is selected from plasticizer, thickening
One or more in agent, wetting agent, fire retardant, antiaging agent and pigment.The present invention is to the plasticizer, tackifier, wetting
Agent, fire retardant, antiaging agent and pigment specific species it is not specifically limited, well known to a person skilled in the art auxiliary agent species
.In the present invention, the epoxy adhesive composition includes 0wt%~2wt% auxiliary agent, and preferably 0.2wt%~
1wt%, more preferably 0.4wt%~0.6wt%.
Present invention also offers a kind of preparation method of above-mentioned epoxy adhesive composition, comprise the following steps：
A melting is heated after) epoxy resin is mixed, epoxy resin mixed liquor is obtained；
B bifunctionality epoxide diluent, toughener, inorganic filler, water removal) are added into the epoxy resin mixed liquor
Agent, thixotropic agent, the latent curing agent of thermal activation and curing accelerator are mixed, and vacuum defoamation obtains epoxy adhesive
Composition.
The present invention heats melting after epoxy resin is mixed first, obtains epoxy resin mixed liquor.
Specifically, liquid epoxies is heated into 95~105 DEG C, solid epoxy is added, is mixed until solid
Body epoxy resin is melted, and obtains epoxy resin mixed liquor；
Then, bifunctionality epoxide diluent, toughener are added into the epoxy resin mixed liquor, inorganic filler, is removed
Aqua, thixotropic agent, the latent curing agent of thermal activation and curing accelerator are mixed, and vacuum defoamation obtains Wear Characteristics of Epoxy Adhesive
Agent composition.
Specifically, be uniformly dispersed after adding bifunctionality epoxide diluent, toughener into the epoxy resin mixed liquor,
Add inorganic filler, deicer, thixotropic agent, the latent curing agent of thermal activation and curing accelerator to mix, vacuum
Deaeration, obtains epoxy adhesive composition.
Wherein, the toughener at least includes the liquid rubber toughening agent with core shell structure, the fourth of epoxy resin modification
The polysulfide rubber toughener of nitrile rubber, the reaction type polyurethane elastomeric prepolymer body of ketoxime end-blocking and epoxy resin modification.
The present invention with the addition of the liquid at least including having core shell structure using two kinds of different epoxy resin as raw material
Rubber toughening agent, the nitrile rubber of epoxy resin modification, the reaction type polyurethane elastomeric prepolymer body and epoxy resin of ketoxime end-blocking
The composite toughing agent of modified polysulfide rubber toughener formation, epoxy adhesive composition is in normal temperature and low temperature bar obtained from
All there is good impact resistance under part, and steel-steel tensile shear strength is also obviously improved.
For a further understanding of the present invention, the Impact-resistant epoxy adhesive stick that the present invention is provided is combined with reference to embodiment
Thing and preparation method thereof is illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1 (epoxy resin modification polysulfide toughener D1)
Polysulfide virgin rubber G10 (being purchased from Akzo Nobel Co., Ltd) meters 164g is weighed to be added in reactor, then
Bisphenol A epoxide resin (BE188-90, epoxide equivalent 182~192 are purchased from Changchun chemical industry (Jiangsu) Co., Ltd) 36g is added, is mixed
After closing uniformly, room temperature is cooled to after the lower 90 DEG C of reactions 3.5h of stirring condition, obtained thick liquid product toughener D1.
It is 5200~5700 to determine its number-average molecular weight.
Embodiment 2 (epoxy resin modification polysulfide toughener D2)
Polysulfide virgin rubber G21 (being purchased from Akzo Nobel Co., Ltd) meters 138g is weighed to be added in reactor, then
Bisphenol A epoxide resin (BE188-90, epoxide equivalent 182~192 are purchased from Changchun chemical industry (Jiangsu) Co., Ltd) 62g is added, is mixed
After closing uniformly, room temperature is cooled to after the lower 90 DEG C of reactions 3h of stirring condition, obtained thick liquid product toughener D2.
It is 3000~3600 to determine its number-average molecular weight.
The toughening agent C 1 of embodiment 3
Number-average molecular weight is added in reactor to be dehydrated at 2000D 100 parts, 105 DEG C of PPG (DL-2000D)
30 minutes, rear 0.6 part of the trimethylolpropane that adds was well mixed for 0.1 part with organotin catalysts, is added under nitrogen protection
MDI26.5 parts, regulating and controlling temperature is to 85~90 DEG C, and reaction 2.0 hours, obtains prepolymer under the conditions of this, detects-the NCO of prepolymer
The weight/mass percentage composition of group is 3.3%.Mol ratio 1.1 according to ketoxime radical compared to-NCO group:1 adds diacetylmonoxime 10.1
Part, end capping reaction is done 1.5 hours at 85~90 DEG C, in detection product-content of NCO group is zero, obtains toughening agent C 1.
The number-average molecular weight for determining toughening agent C 1 is 4500, and weight average molecular weight is 11000, and dispersion index is 2.4.
The preparation of the toughening agent C 2 of embodiment 4
200 parts of the PPG (DL 4000D) that number-average molecular weight is 4000D is added in reactor, is dehydrated at 105 DEG C
30 minutes, rear 1.0 parts of the trimethylolpropane that adds was well mixed for 0.2 part with organotin catalysts, is added under nitrogen protection
MDI28 parts, regulating and controlling temperature is to 85~90 DEG C, and reaction 2.5 hours, obtains prepolymer under the conditions of this, detects-NCO the bases of prepolymer
The content of group is 1.9%.Mol ratio 1.1 according to ketoxime radical compared to-NCO group:1 adds 13 parts of cyclohexanone oxime, 85~90
End capping reaction is done at DEG C 1.5 hours, in detection product-content of NCO group is zero, obtains toughening agent C 2.
The number-average molecular weight for determining toughening agent C 2 is 8600, and weight average molecular weight is 22000, and dispersion index is 2.6.
Embodiment 5~10
According to the material quality number of table 1, liquid epoxies is heated to 95~105 DEG C, solid epoxy is added, mixed
Stirring is closed until solid epoxy melting, obtains epoxy resin mixed liquor；
It is uniformly dispersed, adds after adding bifunctionality epoxide diluent, toughener into the epoxy resin mixed liquor
Inorganic filler, deicer, thixotropic agent, the latent curing agent of thermal activation and curing accelerator are mixed, and vacuum defoamation is obtained
To epoxy adhesive composition.
Carry out the test of steel/steel tensile shear strength to epoxy adhesive composition obtained above, specific method for making sample and
The measure (rigid material is to rigid material) of test reference standard GBT 7124-2008 adhesive tensile shear strengths, is as a result shown in
Table 1：
Impact strength test is carried out to epoxy adhesive composition obtained above, specific method is：
Impact strength test is tried with reference to ISO11343 standards using the drop impacts of Instron companies of U.S. CEAST 9350
Test machine.Drop impact speed is 2m/s, and the environmental cabinet that test environment temperature is attached troops to a unit by equipment is provided.Test block use thickness for
Dried after removing degreasing before 0.6mm cold rolling steel disc, bonding with acetone, bonding plane is 30x20mm.Using 0.2mm glass steel balls
Bondline thickness is controlled, adhesive curing condition is 180 DEG C/45min, and as a result every group of 5 test blocks take arithmetic average (reference
US20110297317A1), it the results are shown in Table 1.
The raw material composition and the performance measurement result of product of the embodiment 5~10 of table 1
Particularly point out：
Hard resin used in embodiment 5/7/9 is D.E.R.671 epoxy resin (DOW Chemical Co., Ltd)
Hard resin BE501H epoxy resin used in embodiment 6/8/10, Changchun chemical industry (Jiangsu) Co., Ltd
Toughening agent C 1:Ketoxime blocked polyurethane (using the PPG of number-average molecular weight 2000~3000) preparation method
See embodiment 3)
Toughening agent C 2：Ketoxime blocked polyurethane (using the PPG of number-average molecular weight 4000~5000) preparation method is shown in
Embodiment 4)
Epoxy resin modification polysulfide toughener D1 (embodiment 5/7/9, preparation method is shown in embodiment 1)
Epoxy resin modification polysulfide toughener D2 (embodiment 6/8/10, preparation method is shown in embodiment 2)
In addition to unspecified, the component that embodiment 5~10 is used is following raw material：
Liquid epoxies is BE188-90 Changchun chemical industry (Jiangsu) Co., Ltd；
Core shell rubbers are MX154 Core-shell rubber particles/epoxy resin (wherein core-shell particles mass fraction is 40%) Japan
Kaneka companies；
Modified butadiene acrylonitrile rubber is the LNBR of Hypro-861340 epoxy resin modifications, U.S. CVC
Thermoset Specialties (wherein core-shell particles mass fraction is 40%)；
Reactive diluent is：XY678 bifunctionality epoxide diluents, the remote Chemical Co., Ltd. of Anhui perseverance (new)；
Curing agent is Dyhard 100S dicy-curing agents, AlzChem A Ziken Chemical Co., Ltd.s；
Curing accelerator is UR300, AlzChem A Ziken Chemical Co., Ltd.s；
Tackifier are Adeka Resin EP-49-10N (Adeka Corporation, Japanese rising sun electrochemical industry strain formula meeting
Society).
Water absorbing agent is CaO, Shanghai Fan Hua inorganic chemical industries Co., Ltd；
Filler is calcium carbonate (fine particle calcium carbonate) S-CCR-100, Jiande Shuangchao Calcium Industry Co., Ltd.；
Thixotropic agent：Gas-phase silica, AEROSILR202, Ying Chuan Specialty Chemicals Co., Ltd.
Pigment is TiO2, model 218, Shanghai Hei Hu Chemical Industry Science Co., Ltd；
Glass microballoon is 140 mesh Shanghai Li Cai new materials Co., Ltds.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of Impact-resistant epoxy adhesive adhesive composition, it is characterised in that including：
At least two epoxy resin；
At least one bifunctionality epoxide diluent；
At least four kinds of toughener, the toughener at least includes liquid rubber toughening agent, epoxy resin modification with core shell structure
Nitrile rubber, ketoxime end-blocking reaction type polyurethane elastomeric prepolymer body and epoxy resin modification polysulfide rubber toughener；
At least one inorganic filler；
At least one deicer；
At least one thixotropic agent；
The latent curing agent of at least one thermal activation；
At least one curing accelerator.
2. Impact-resistant epoxy adhesive adhesive composition according to claim 1, it is characterised in that including：
16wt%~18wt% epoxy resin, the epoxy resin includes liquid epoxies and solid epoxy；
30wt%~36wt% the liquid rubber toughening agent with core shell structure；
The nitrile rubber of 9wt%~13wt% epoxy resin modification；
The reaction type polyurethane elastomeric prepolymer body of 10wt%~12wt% ketoximes end-blocking；
The polysulfide rubber toughener of 6wt%~8wt% epoxy resin modifications；
1wt%~2wt% bifunctionality epoxide diluent；
10wt%~12wt% inorganic filler；
0.2wt%~0.3wt% deicer；
2.0wt%~3.0wt% thixotropic agent；
The latent curing agent of 2wt%~3wt% thermal activation；
0.2wt%-0.4wt% curing accelerator.
3. Impact-resistant epoxy adhesive adhesive composition according to claim 1, it is characterised in that the epoxy resin modification
Polysulfide rubber toughener is prepared as follows：
By the polysulfide rubber with Formulas I structure and bisphenol A epoxide resin according to thiol group and epoxide group mol ratio 1：(2.2
~2.5) mix, heating response is carried out under conditions of 90 DEG C ± 5 DEG C 3~3.5 hours, obtain the polysulfide rubber of epoxy resin modification
Glue toughener；
In Formulas I ,-R- is-(CH2)2-O-CH2-O-(CH2)2-, 12≤a+b+c≤28.
4. Impact-resistant epoxy adhesive adhesive composition according to claim 1, it is characterised in that the reaction of the ketoxime end-blocking
Type polyurethane elastomeric prepolymer body is the reaction type polyurethane elastomeric prepolymer body that 100% ketoxime is blocked, the 100% ketoxime end-blocking
Reaction type polyurethane elastomeric prepolymer body is prepared as follows：
By the PPG after dehydration, trimethylolpropane and methyl diphenylene diisocyanate in nitrogen protection, catalyst
Heating carries out polymerisation under existence condition, obtains prepolymer；
Oxime compound is added into the prepolymer, end capping reaction is carried out, the poly- ammonia of response type of 100% ketoxime end-blocking is obtained
Ester elastomer performed polymer；
The mol ratio of ketoxime radical and NCO group in the prepolymer is 1.05 in the oxime compound:1~1.1:1.
5. Impact-resistant epoxy adhesive adhesive composition according to claim 2, it is characterised in that the liquid epoxies is
Liquid bisphenol A type diglycidyl ether, the solid epoxy is solid bisphenol A type diglycidyl ethers, the solid ring
The mass ratio of oxygen tree fat and liquid epoxies is 1：(3~4).
6. Impact-resistant epoxy adhesive adhesive composition according to claim 1, it is characterised in that described with core shell structure
The nucleome material of liquid rubber toughening agent is the copolymer of alkadienes and monoolefine, and case material is Epoxy functionalized (first
Base) acrylate homopolymer or copolymer, the average grain diameter of the liquid rubber toughening agent with core shell structure is less than
400nm。
7. Impact-resistant epoxy adhesive adhesive composition according to claim 1, it is characterised in that the bifunctionality epoxy is dilute
Release the diglycidyl ether that agent is selected from representative examples of saturated aliphatic glycol；
The inorganic filler is selected from calcium carbonate, talcum powder, mica, silica flour, bentonite, wollastonite, metal dust, carbon black and glass
One or more in glass microballon；
The deicer is selected from calcium oxide；
The thixotropic agent is selected from hydrophobic type gas phase silica；
One or more of the latent curing agent of the thermal activation in guanidine and its derivative, urea and its derivative；
The curing accelerator is selected from the substituted urea containing phenyl and dimethyl for having catalytic activity.
8. Impact-resistant epoxy adhesive adhesive composition according to claim 1, it is characterised in that also including 0wt%~2wt%
Auxiliary agent, one or more of the auxiliary agent in plasticizer, tackifier, wetting agent, fire retardant, antiaging agent and pigment.
9. a kind of preparation method of Impact-resistant epoxy adhesive adhesive composition as described in claim 1~8 any one, its feature
It is, comprises the following steps：
A melting is heated after) epoxy resin is mixed, epoxy resin mixed liquor is obtained；
B bifunctionality epoxide diluent, toughener) are added into the epoxy resin mixed liquor, inorganic filler, deicer, is touched
Become agent, the latent curing agent of thermal activation and curing accelerator to mix, vacuum defoamation, obtain epoxy adhesive combination
Thing.
10. preparation method according to claim 9, it is characterised in that step A) in, the temperature of heating melting for 95~
105℃。
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651977A (en) * | 2018-12-25 | 2019-04-19 | 杭州之江新材料有限公司 | A kind of epoxy one-component structure glue and preparation method thereof |
| CN110003421A (en) * | 2019-04-22 | 2019-07-12 | 黑龙江省科学院石油化学研究院 | A kind of ultralow temperature toughening material and modified cyanic acid ester resin and its preparation method and application |
| CN111139009A (en) * | 2020-01-09 | 2020-05-12 | 湖北回天新材料股份有限公司 | Vehicle body structure adhesive with excellent low-temperature oil surface wettability and preparation method thereof |
| CN113817289A (en) * | 2021-09-28 | 2021-12-21 | 江苏泰特尔新材料科技股份有限公司 | High-toughness transparent alicyclic epoxy resin composition |
| CN114656911A (en) * | 2022-04-08 | 2022-06-24 | 韦尔通(厦门)科技股份有限公司 | Low-viscosity conductive adhesive composition |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046546A (en) * | 1990-05-28 | 1990-10-31 | 中国科学院化学研究所 | Single component, the tough epoxy tackiness agent that does not trickle |
| CN102648262A (en) * | 2009-11-05 | 2012-08-22 | 陶氏环球技术有限责任公司 | Structural epoxy resin adhasives containing elastomeric tougheners capped with ketoximes |
| CN104497941A (en) * | 2014-12-26 | 2015-04-08 | 上海大学 | Two-component toughened anti-shock epoxy structural adhesive and preparation method thereof |
-
2017
- 2017-06-29 CN CN201710515265.9A patent/CN107142054B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046546A (en) * | 1990-05-28 | 1990-10-31 | 中国科学院化学研究所 | Single component, the tough epoxy tackiness agent that does not trickle |
| CN102648262A (en) * | 2009-11-05 | 2012-08-22 | 陶氏环球技术有限责任公司 | Structural epoxy resin adhasives containing elastomeric tougheners capped with ketoximes |
| CN104497941A (en) * | 2014-12-26 | 2015-04-08 | 上海大学 | Two-component toughened anti-shock epoxy structural adhesive and preparation method thereof |
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| CN109651977A (en) * | 2018-12-25 | 2019-04-19 | 杭州之江新材料有限公司 | A kind of epoxy one-component structure glue and preparation method thereof |
| CN110003421A (en) * | 2019-04-22 | 2019-07-12 | 黑龙江省科学院石油化学研究院 | A kind of ultralow temperature toughening material and modified cyanic acid ester resin and its preparation method and application |
| CN110003421B (en) * | 2019-04-22 | 2020-11-10 | 黑龙江省科学院石油化学研究院 | Ultralow-temperature toughening material and modified cyanate ester resin as well as preparation method and application thereof |
| US11437162B2 (en) | 2019-12-31 | 2022-09-06 | Industrial Technology Research Institute | Conductive material composition and conductive material prepared therefrom |
| CN111139009A (en) * | 2020-01-09 | 2020-05-12 | 湖北回天新材料股份有限公司 | Vehicle body structure adhesive with excellent low-temperature oil surface wettability and preparation method thereof |
| CN111139009B (en) * | 2020-01-09 | 2022-01-11 | 湖北回天新材料股份有限公司 | Vehicle body structure adhesive with excellent low-temperature oil surface wettability and preparation method thereof |
| CN113817289A (en) * | 2021-09-28 | 2021-12-21 | 江苏泰特尔新材料科技股份有限公司 | High-toughness transparent alicyclic epoxy resin composition |
| CN114656911A (en) * | 2022-04-08 | 2022-06-24 | 韦尔通(厦门)科技股份有限公司 | Low-viscosity conductive adhesive composition |
| CN115820082A (en) * | 2022-11-24 | 2023-03-21 | 国网浙江省电力有限公司超高压分公司 | Thermosensitive color-changing temperature-indicating coating and preparation method thereof |
| CN115820082B (en) * | 2022-11-24 | 2023-09-08 | 国网浙江省电力有限公司超高压分公司 | Thermochromic temperature-indicating paint and preparation method thereof |
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