CN108570302A - A kind of low-temperature impact-resistant epoxy adhesive composition and preparation method thereof - Google Patents
A kind of low-temperature impact-resistant epoxy adhesive composition and preparation method thereof Download PDFInfo
- Publication number
- CN108570302A CN108570302A CN201710137908.0A CN201710137908A CN108570302A CN 108570302 A CN108570302 A CN 108570302A CN 201710137908 A CN201710137908 A CN 201710137908A CN 108570302 A CN108570302 A CN 108570302A
- Authority
- CN
- China
- Prior art keywords
- agent
- epoxy resin
- epoxy
- adhesive composition
- epoxy adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides a kind of low-temperature impact-resistant epoxy adhesive compositions, which is characterized in that including：At least two epoxy resin；At least one bifunctionality epoxide diluent；At least three kinds of toughener, the toughener include at least the reaction type polyurethane elastomeric prepolymer body of the nitrile rubber and ketoxime sealing end of the liquid rubber toughening agent, epoxy resin modification with nucleocapsid；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 is using two different epoxy resin as raw material, and it is added to the composite toughing agent of the reaction type polyurethane elastomeric prepolymer body of the nitrile rubber and ketoxime sealing end including at least liquid rubber toughening agent, epoxy resin modification with nucleocapsid, the epoxy adhesive composition obtained from has good low temperature impact performance.
Description
Technical field
The invention belongs to field of adhesive technology, and in particular to a kind of low-temperature impact-resistant epoxy adhesive composition and its system
Preparation Method.
Background technology
After epoxy adhesive curing, usually because poor toughness, is easy that embrittlement occurs under external force.General method for toughening is logical
The toughness of material under room temperature can be promoted by crossing addition toughener, but at low temperature, the material of room temperature good toughness can still become fragile.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide a kind of low-temperature impact-resistant epoxy adhesive composition
And preparation method thereof, low-temperature impact-resistant epoxy adhesive composition provided by the invention has good low temperature impact performance.
The present invention provides a kind of low-temperature impact-resistant epoxy adhesive compositions, which is characterized in that including：
At least two epoxy resin；
At least one bifunctionality epoxide diluent；
At least three kinds of toughener, the toughener include at least liquid rubber toughening agent, epoxy resin with nucleocapsid
The reaction type polyurethane elastomeric prepolymer body of modified nitrile rubber and ketoxime sealing end；
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.
Preferably, including：
The epoxy resin of 12wt%~18wt%, the epoxy resin include liquid epoxies and solid epoxy；
The liquid rubber toughening agent with nucleocapsid of 34wt%~46wt%；
The nitrile rubber of the epoxy resin modification of 9wt%~13wt%；
The reaction type polyurethane elastomeric prepolymer body of the ketoxime sealing end of 12wt%~16wt%；
The bifunctionality epoxide diluent of 1wt%~3wt%；
The inorganic filler of 10wt%~12wt%；
The deicer of 0.2wt%~0.3wt%；
The thixotropic agent of 2.0wt%~3.0wt%；
The latent curing agent of the thermal activation of 2wt%~3wt%；
The curing accelerator of 0.2wt%~0.4wt%.
Preferably, the reaction type polyurethane elastomeric prepolymer body of ketoxime sealing end is the reaction type polyurethane of 100% ketoxime sealing end
The reaction type polyurethane elastomeric prepolymer body of elastomeric prepolymer body, the 100% ketoxime sealing end is prepared as follows：
By dewatered polyether polyol, trimethylolpropane and methyl diphenylene diisocyanate in nitrogen protection, urge
Polymerisation is heated under agent existence condition, obtains prepolymer；
Oxime compound is added into the prepolymer, carries out end capping reaction, obtains the response type of 100% ketoxime sealing end
Elastic polyurethane performed polymer；
The molar ratio of ketoxime radical and NCO group in the prepolymer is 1.05 in the oxime compound:1~1.1:
1。
Preferably, the liquid epoxies is liquid bisphenol A type diglycidyl ether, and the solid epoxy is solid
The mass ratio of body bisphenol A-type diglycidyl ether, the solid epoxy and liquid epoxies is 1：(3~4).
Preferably, the nucleome material of the liquid rubber toughening agent with nucleocapsid is being 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.
Preferably, 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 powder, carbon black
With it is one or more in glass microballoon；
The deicer is selected from calcium oxide；
The thixotropic agent is selected from hydrophobic type gas phase silica；
The latent curing agent of the thermal activation is one or more 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.
Preferably, further include the auxiliary agent of 0wt%~2wt%, the auxiliary agent is selected from plasticizer, tackifier, wetting agent, fire-retardant
It is one or more in agent, antiaging agent and pigment.
The present invention also provides a kind of preparation methods of above-mentioned epoxy adhesive composition, include the following steps：
A melting is heated after) mixing epoxy resin, obtains epoxy resin mixed liquor；
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.
Preferably, step A) in, the temperature for heating melting is 95~105 DEG C.
Compared with prior art, the present invention provides a kind of low-temperature impact-resistant epoxy adhesive compositions, which is characterized in that
Including：At least two epoxy resin；At least one bifunctionality epoxide diluent；At least three kinds of toughener, the toughener is at least
Include the poly- ammonia of response type of liquid rubber toughening agent with nucleocapsid, the nitrile rubber of epoxy resin modification and ketoxime sealing end
Ester elastomer performed polymer；At least one inorganic filler；At least one deicer；At least one thixotropic agent；At least one thermal activation
Latent curing agent；At least one curing accelerator.The present invention using two different epoxy resin as raw material, and be added to
Include having the response type of the liquid rubber toughening agent of nucleocapsid, the nitrile rubber of epoxy resin modification and ketoxime sealing end poly- less
The composite toughing agent of urethane elastomeric prepolymer body, the epoxy adhesive composition obtained from have good low-temperature impact resistance
Energy.
Specific implementation mode
The present invention provides a kind of low-temperature impact-resistant epoxy adhesive compositions, including：
At least two epoxy resin；
At least one bifunctionality epoxide diluent；
At least three kinds of toughener, the toughener include at least liquid rubber toughening agent, epoxy resin with nucleocapsid
The reaction type polyurethane elastomeric prepolymer body of modified nitrile rubber and ketoxime sealing end；
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.
Epoxy adhesive composition provided by the invention includes at least two epoxy resin, and the epoxy resin preferably divides
Containing there are two the epoxides of epoxy group, more preferably saturation polyepoxide, unsaturated polyepoxide, fat in minor structure
In fat adoption epoxides, alicyclic polyepoxide, aromatic polyepoxide and polyepoxide containing heterocycle at least
Two kinds, further 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 epoxy resin obtained of catalysis.
In certain specific embodiments of the invention, the epoxy adhesive composition includes two kinds of epoxy resin, institute
It states two kinds of epoxy resin and is selected from liquid epoxies (L_Epoxy) and solid epoxy (S_Epoxy), the liquid epoxy tree
It is the bisphenol A-type diglycidyl ether of liquid that fat, which is under room temperature, and the epoxide number of the liquid epoxies is 0.36~0.55, excellent
It is selected as 0.40~0.50, epoxide equivalent is 180~220, preferably 190~210.It is solid that the solid epoxy, which is under room temperature,
The bisphenol A-type diglycidyl ether of body, the epoxide number of the solid epoxy is 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
The epoxy resin of 12wt%~18wt%, preferably 13wt%~17wt%, more preferably 14wt%~16wt%.In asphalt mixtures modified by epoxy resin
In fat, the mass ratio of the solid epoxy and liquid epoxies is 1：(3~4), preferably 1：(3.2~3.6).
Epoxy adhesive composition provided by the invention includes at least one bifunctionality epoxide diluent, the difunctionality
Degree epoxide diluent is used to improve the viscosity and rheological attribute of adhesive, and it is anti-that the epoxy group in diluent participates in hot setting
It answers.In the present invention, the bifunctionality epoxide diluent is selected from the diglycidyl ether of representative examples of saturated aliphatic glycol, preferably full
With the diglycidyl ether of aliphatic C3-C5 glycol, it is remote that the bifunctionality epoxide diluent is preferably purchased from Anhui permanent (new)
The bis-epoxy base series of products of Chemical Co., Ltd., more preferably the bifunctionality epoxy of model XY205, XY207 and XY678
It is one or more in diluent.In the present invention, the epoxy adhesive composition includes double officials of 1wt%~3wt%
Energy degree epoxide diluent, preferably 1.5wt%~2.5wt%, more preferably 1.7wt%~2.2wt%.
Epoxy adhesive composition provided by the invention further includes at least three kinds of toughener, and the toughener includes at least tool
There is the reaction type polyurethane elasticity of the liquid rubber toughening agent of nucleocapsid, the nitrile rubber of epoxy resin modification and ketoxime sealing end
Performed polymer.
Wherein, the liquid rubber toughening agent with nucleocapsid 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
Kind is a variety of, and 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 or acrylate of acrylic ester monomer and vi-ny l aromatic monomers
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 nucleocapsid is less than 400nm, preferably 100~300nm.
The present invention can be city there is no specifically limited to the source of the liquid rubber toughening agent with nucleocapsid
Sell product, can also voluntarily prepare, preparation method can with application reference number for EP1632533 European patent, application No. is
The United States Patent (USP) of US4778851 and US6111015, above patent document are incorporated by reference herein.Tool of the present invention
There is the liquid rubber toughening agent of nucleocapsid that can also be purchased from trade name " ACE MX " series of Kaneka Corporation
Product, the more preferably liquid rubber toughening agent with nucleocapsid of model MX153 or MX154.The rubber grain exists
Mass percentage in rubber toughening agent is preferably 33.3%~40%.
In the present invention, the epoxy adhesive composition includes the liquid with nucleocapsid of 34wt%~46wt%
Body rubber toughener, preferably 38wt%~44wt%, more preferably 40wt%~42wt%.
In the nitrile rubber of the epoxy resin modification, the nitrile rubber is preferably liquid nitrile rubber, solid for epoxy
Common one kind toughener in change system, by modification, active reactive group such as carboxyl or amido etc., with epoxy molecule
A large amount of existing epoxy reactions form soft segment in structure, are precipitated, physically form from the matrix of three-dimensional system after solidification
The two phase structure of thermosetting phase and rubber phase can greatly improve toughness.The molecular backbone of liquid nitrile rubber 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 liquid butyronitrile of carboxyl
Rubber, acrylonitrile monomer content is 15wt%~30wt% ranges in molecular structure, the liquid nitrile rubber can with it is excessive
Epichlorohydrin reaction forms the liquid nitrile rubber that end group is epoxy group, can also under the action of catalyst be given birth to epoxy resin
At epoxy resin addition product.Above two reactive mode can promote compatibility of the rubber with epoxy resin-base.
The present invention can be voluntarily to make there is no specifically limited to the source of the nitrile rubber of the epoxy resin modification
It is standby, or commercial product.The preparation method can refer to Publication No. US2003/0196753, US2005-0070634
With the patent of US6776860, the present invention will introduce the preparation method of the nitrile rubber of epoxy resin modification in above-mentioned patent
Herein as reference.Wherein, the nitrile rubber of the epoxy resin modification of commercialization can be purchased from U.S. CVC Thermoset
The addition product of the CTBN1300x8 or 1300x13 and epoxy resin of the trade name Hypro of Specialties companies
Hypro861340。
In the present invention, the epoxy adhesive composition includes the fourth of the epoxy resin modification of 9wt%~13wt%
Nitrile rubber, preferably 10wt%~12wt%, more preferably 10.5wt%~11.5wt%.
The reaction type polyurethane elastomeric prepolymer body of the ketoxime sealing end is the reaction type polyurethane elasticity of 100% ketoxime sealing end
The reaction type polyurethane elastomeric prepolymer body of performed polymer, the 100% ketoxime sealing end is prepared as follows：
By dewatered polyether polyol, trimethylolpropane and methyl diphenylene diisocyanate in nitrogen protection, urge
Polymerisation is heated under agent existence condition, obtains prepolymer；
Oxime compound is added into the prepolymer, carries out end capping reaction, obtains the response type of 100% ketoxime sealing end
Elastic polyurethane performed polymer；
In the oxime compound in ketoxime radical and the prepolymer-molar ratio of NCO group is 1.05:1~
1.1:1。
Specifically, polyether polyols dehydration of alcohols is obtained dewatered polyether polyol by the present invention first, then, three hydroxyls are added
Methylpropane and catalyst mixing, under conditions of nitrogen protection, add methyl diphenylene diisocyanate (MDI), carry out
Heating reaction, obtains prepolymer.
Wherein, the number-average molecular weight of the polyether polyol 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 reaction is 2 hours.In detection prepolymer-NCO group contains
Amount, which is 3.3% (mass percent), can stop reacting.
After obtaining above-mentioned prepolymer, oxime compound is added into the prepolymer, carries out end capping reaction, obtains
The reaction type polyurethane elastomeric prepolymer body of 100% ketoxime sealing end；
In the present invention, to the type of the ketoxime there is no specifically limited, 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-molar 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.
Measure in the reaction product after the end capping reaction-content of NCO group is 0, you can judgement reaction terminates, vacuum
After deaeration, the reaction type polyurethane elastomeric prepolymer body of 100% ketoxime sealing end is obtained.
The number-average molecular weight of the reaction type polyurethane elastomeric prepolymer body of finally obtained 100% ketoxime sealing end is 4000~
12000, preferably 4000~10000.
Epoxy adhesive composition of the present invention further includes at least one inorganic filler, and the inorganic filler is selected from carbon
It is one or more in sour calcium, talcum powder, mica, silica flour, bentonite, wollastonite, metal powder, carbon black and glass microballoon.
The filler can mainly play in adhesive to be improved rheological attribute, reduces cost, absorb moisture, promote the effects that bonding.Institute
The inorganic filler that epoxy adhesive composition includes 10wt%~12wt% is stated, preferably 10.5wt%~11.5wt% is more excellent
It is selected as 10.8wt%~11.2wt%.
Epoxy adhesive composition of the present invention further includes at least one deicer, and the deicer is selected from oxidation
Calcium, the epoxy adhesive composition include the deicer of 0.2wt%~0.3wt%, preferably 0.22wt%~0.28wt%,
More preferably 0.24wt%~0.26wt%.
Epoxy adhesive composition of the present invention further 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., can significantly improve
High temperature thixotropy prevents high temperature sagging.The epoxy adhesive composition includes the thixotropic agent of 2.0wt%~3.0wt%,
Preferably 2.2wt%~2.8wt%, more preferably 2.4wt%~2.6wt%.
Epoxy adhesive composition of the present invention further 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 at 140 DEG C or more.The latent curing of the thermal activation
Agent is one or more 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 grain size is less than or equal to 10 μm, to improve dispersion effect
With the storage stability for improving adhesive.The epoxy adhesive composition includes the latent of the thermal activation of 2wt%~3wt%
Property curing agent, preferably 2.2wt%~2.8wt%, more preferably 2.4wt%~2.6wt%.
Epoxy adhesive composition of the present invention further 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 be shown in addition to playing catalytic action
It writes and extends product shelf life.In the present invention, it is preferred to using the lower 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.The Wear Characteristics of Epoxy Adhesive
Agent composition includes the curing accelerator of 0.2wt%~0.4wt%, preferably 0.25wt%~0.35wt%, more preferably
0.27wt%~0.32wt%.
Preferably, epoxy adhesive composition of the present invention further includes auxiliary agent, and the auxiliary agent is selected from plasticizer, thickening
It is 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 type there is no specifically limited, well known to a person skilled in the art auxiliary agent types
.In the present invention, the epoxy adhesive composition includes the auxiliary agent of 0wt%~2wt%, and preferably 0.2wt%~
1wt%, more preferably 0.4wt%~0.6wt%.
The present invention also provides a kind of preparation methods of above-mentioned epoxy adhesive composition, include the following steps：
A melting is heated after) mixing epoxy resin, obtains epoxy resin mixed liquor；
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 first mixing epoxy resin, obtains epoxy resin mixed liquor.
Specifically, liquid epoxies is heated to 95~105 DEG C, solid epoxy is added, is mixed until solid
Body epoxy resin melts, and obtains epoxy resin mixed liquor；
Then, bifunctionality epoxide diluent is added into the epoxy resin mixed liquor, toughener, inorganic filler, removes
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 bifunctionality epoxide diluent, toughener is added into the epoxy resin mixed liquor,
It adds inorganic filler, deicer, thixotropic agent, the latent curing agent of thermal activation and curing accelerator to be mixed, vacuum
Deaeration obtains epoxy adhesive composition.
Wherein, the toughener includes at least the fourth of the liquid rubber toughening agent, epoxy resin modification with nucleocapsid
The reaction type polyurethane elastomeric prepolymer body of nitrile rubber and ketoxime sealing end
The present invention is added to using two different epoxy resin as raw material including at least the liquid with nucleocapsid
The composite toughening of the reaction type polyurethane elastomeric prepolymer body of rubber toughening agent, the nitrile rubber of epoxy resin modification and ketoxime sealing end
Agent, the epoxy adhesive composition obtained from have good low temperature impact performance.
The present invention selects at least three kinds of composite toughing agents, wherein the reaction type polyurethane elastomeric prepolymer body of ketoxime sealing end
Using the dosage for the nitrile rubber that can reduce the expensive liquid rubber toughening agent and epoxy resin modification with nucleocapsid,
To reduce cost；In addition, the preparation method of the reaction type polyurethane elastomeric prepolymer body of ketoxime sealing end provided by the invention is simpler
It is single, safer, at low cost and stable storing.
For a further understanding of the present invention, with reference to embodiment to low-temperature impact-resistant epoxy adhesive provided by the invention
Composition and preparation method thereof illustrates, and protection scope of the present invention is not limited by the following examples.
The preparation of 1 toughener A of embodiment
It is added in reactor at 100 parts, 105 DEG C of the polyether polyol (DL-2000D) that molecular weight is 2000D and is dehydrated 30 points
Clock, rear 0.6 part of the trimethylolpropane that is added are uniformly mixed for 0.1 part with organotin catalysts, and MDI26.5 is added under nitrogen protection
Part, regulating and controlling temperature reacts 2.0 hours to 85~90 DEG C, under the conditions of this, obtains prepolymer, detect prepolymer-matter of NCO group
It is 3.3% to measure percentage composition.Molar ratio 1.1 according to ketoxime radical compared to-NCO group:1 10.1 parts of diacetylmonoxime of addition, 85~
End capping reaction is done at 90 DEG C 1.5 hours, detect in product-content of NCO group is zero, obtain toughener A.
The number-average molecular weight for measuring toughener A is 4500, weight average molecular weight 11000, dispersion index 2.4.
The preparation of 2 toughener B of embodiment
200 parts of the polyether polyol (DL 4000D) that molecular weight is 4000D is added in reactor, 30 points are dehydrated at 105 DEG C
Clock, rear 1.0 parts of the trimethylolpropane that is added are uniformly mixed for 0.2 part with organotin catalysts, and MDI28 is added under nitrogen protection
Part, regulating and controlling temperature reacts 2.5 hours to 85~90 DEG C, under the conditions of this, obtain prepolymer, detect prepolymer-NCO group contains
Amount is 1.9%.Molar ratio 1.1 according to ketoxime radical compared to-NCO group:It is done at 1 13 parts, 85~90 DEG C of cyclohexanone oxime of addition
End capping reaction 1.5 hours, detect in product-content of NCO group is zero, obtain toughener B.
The number-average molecular weight for measuring toughener B is 8600, weight average molecular weight 22000, dispersion index 2.6.
Embodiment 3~8
According to 1 material quality number of table, liquid epoxies is heated to 95~105 DEG C, solid epoxy is added, is mixed
Stirring is closed until solid epoxy melting, obtains epoxy resin mixed liquor；
It is uniformly dispersed, adds after bifunctionality epoxide diluent, toughener is added 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 obtains
To epoxy adhesive composition.
The test of steel/steel tensile shear strength carried out to epoxy adhesive composition obtained above, specific method for making sample and
The measurement (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 9350 drop impacts of Instron companies of U.S. CEAST
Test machine.Drop impact speed is 2m/s, and test environment temperature is provided by the environmental cabinet that equipment is attached.Test block use thickness for
The cold rolling steel disc of 0.6mm is dried after removing degreasing before being bonded with acetone, bonding plane 30x20mm.Using 0.2mm glass steel balls
Bondline thickness is controlled, adhesive curing condition is 180 DEG C/45min, 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 of 1 embodiment 3~4 of table forms and the performance measurement result of product
It particularly points out：
Hard resin used in embodiment 3~5 is D.E.R.671 epoxy resin (DOW Chemical Co., Ltd)
Hard resin BE501H epoxy resin used in embodiment 6~8, Changchun chemical industry (Jiangsu) Co., Ltd.
Make toughener by oneself：Toughener A (embodiment 3/6/7)；Toughener B (embodiment 4/5/8)
In addition to unspecified, the group that embodiment 3~8 uses is divided into following raw material：
Liquid epoxies is the Changchun BE188-90 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 liquid nitrile rubber 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.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of low-temperature impact-resistant epoxy adhesive composition, which is characterized in that including：
At least two epoxy resin；
At least one bifunctionality epoxide diluent；
At least three kinds of toughener, the toughener include at least liquid rubber toughening agent, epoxy resin modification with nucleocapsid
Nitrile rubber and ketoxime sealing end reaction type polyurethane elastomeric prepolymer body；
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. low-temperature impact-resistant epoxy adhesive composition according to claim 1, which is characterized in that including：
The epoxy resin of 12wt%~18wt%, the epoxy resin include liquid epoxies and solid epoxy；
The liquid rubber toughening agent with nucleocapsid of 34wt%~46wt%；
The nitrile rubber of the epoxy resin modification of 9wt%~13wt%；
The reaction type polyurethane elastomeric prepolymer body of the ketoxime sealing end of 12wt%~16wt%；
The bifunctionality epoxide diluent of 1wt%~3wt%；
The inorganic filler of 10wt%~12wt%；
The deicer of 0.2wt%~0.3wt%；
The thixotropic agent of 2.0wt%~3.0wt%；
The latent curing agent of the thermal activation of 2wt%~3wt%；
The curing accelerator of 0.2wt%~0.4wt%.
3. low-temperature impact-resistant epoxy adhesive composition according to claim 1, which is characterized in that the reaction of ketoxime sealing end
Type polyurethane elastomeric prepolymer body is the reaction type polyurethane elastomeric prepolymer body of 100% ketoxime sealing end, the 100% ketoxime sealing end
Reaction type polyurethane elastomeric prepolymer body is prepared as follows：
By dewatered polyether polyol, 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, carries out end capping reaction, obtains the poly- ammonia of response type of 100% ketoxime sealing end
Ester elastomer performed polymer；
The molar ratio of ketoxime radical and NCO group in the prepolymer is 1.05 in the oxime compound:1~1.1:1.
4. epoxy adhesive composition according to claim 2, which is characterized in that the liquid epoxies is that liquid is double
Phenol A type diglycidyl ethers, the solid epoxy are solid bisphenol A type diglycidyl ethers, the solid epoxy
Mass ratio with liquid epoxies is 1：(3~4).
5. epoxy adhesive composition according to claim 2, which is characterized in that the liquid rubber with nucleocapsid
The nucleome material of glue toughener is the copolymer of alkadienes and monoolefine, and case material is Epoxy functionalized (methyl) propylene
The average grain diameter of acid alkyl ester homopolymer or copolymer, the liquid rubber toughening agent with nucleocapsid is less than 400nm.
6. epoxy adhesive composition according to claim 2, which is characterized in that the bifunctionality epoxide diluent choosing
The diglycidyl ether of self-saturation aliphatic diol；
The inorganic filler is selected from calcium carbonate, talcum powder, mica, silica flour, bentonite, wollastonite, metal powder, carbon black and glass
It is one or more in glass microballon；
The deicer is selected from calcium oxide；
The thixotropic agent is selected from hydrophobic type gas phase silica；
The latent curing agent of the thermal activation is one or more 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.
7. epoxy adhesive composition according to claim 2, which is characterized in that further include helping for 0wt%~2wt%
Agent, the auxiliary agent are one or more in plasticizer, tackifier, wetting agent, fire retardant, antiaging agent and pigment.
8. a kind of preparation method of epoxy adhesive composition as described in claim 1~7 any one, which is characterized in that
Include the following steps：
A melting is heated after) mixing epoxy resin, obtains epoxy resin mixed liquor；
B bifunctionality epoxide diluent) is added into the epoxy resin mixed liquor, toughener, inorganic filler, deicer, touches
Become agent, the latent curing agent of thermal activation and curing accelerator to be mixed, vacuum defoamation obtains epoxy adhesive combination
Object.
9. preparation method according to claim 8, which is characterized in that step A) in, the temperature for heating melting is 95~105
℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710137908.0A CN108570302B (en) | 2017-03-09 | 2017-03-09 | Low-temperature impact resistant epoxy adhesive composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710137908.0A CN108570302B (en) | 2017-03-09 | 2017-03-09 | Low-temperature impact resistant epoxy adhesive composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108570302A true CN108570302A (en) | 2018-09-25 |
| CN108570302B CN108570302B (en) | 2020-05-01 |
Family
ID=63577892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710137908.0A Active CN108570302B (en) | 2017-03-09 | 2017-03-09 | Low-temperature impact resistant epoxy adhesive composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108570302B (en) |
Cited By (4)
| 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 |
| 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 |
| CN111139010A (en) * | 2020-01-09 | 2020-05-12 | 湖北回天新材料股份有限公司 | Structural adhesive with excellent low-temperature impact peel strength and preparation method thereof |
| CN113278395A (en) * | 2021-04-12 | 2021-08-20 | 广东博汇新材料科技股份有限公司 | Pre-forming glue spraying composition and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102037050A (en) * | 2008-05-28 | 2011-04-27 | Sika技术股份公司 | Heat-curing epoxy resin composition comprising an accelerator having heteroatoms |
| 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 |
-
2017
- 2017-03-09 CN CN201710137908.0A patent/CN108570302B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102037050A (en) * | 2008-05-28 | 2011-04-27 | Sika技术股份公司 | Heat-curing epoxy resin composition comprising an accelerator having heteroatoms |
| 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 |
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 |
| 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 |
| CN111139010A (en) * | 2020-01-09 | 2020-05-12 | 湖北回天新材料股份有限公司 | Structural adhesive with excellent low-temperature impact peel strength 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 |
| CN111139010B (en) * | 2020-01-09 | 2022-01-11 | 湖北回天新材料股份有限公司 | Structural adhesive with excellent low-temperature impact peel strength and preparation method thereof |
| CN113278395A (en) * | 2021-04-12 | 2021-08-20 | 广东博汇新材料科技股份有限公司 | Pre-forming glue spraying composition and preparation method thereof |
| CN113278395B (en) * | 2021-04-12 | 2022-03-18 | 广东博汇新材料科技股份有限公司 | Pre-forming glue spraying composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108570302B (en) | 2020-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107142054B (en) | A kind of Impact-resistant epoxy adhesive adhesive composition and preparation method thereof | |
| CN108300389B (en) | A kind of epoxy adhesive composition and preparation method thereof and application | |
| CN109651977A (en) | A kind of epoxy one-component structure glue and preparation method thereof | |
| CN108570302A (en) | A kind of low-temperature impact-resistant epoxy adhesive composition and preparation method thereof | |
| CA2568290C (en) | Adhesive of epoxy resin, diene copolymer-modified epoxy resin, phenolic-terminated elastomeric toughener and polyester segment polymer | |
| CN101528797B (en) | Derivatized solid epoxy resin and uses thereof | |
| EP2655516B1 (en) | Structural epoxy resin adhesives containing chain-extended elastomeric tougheners capped with phenol, polyphenol or aminophenol compounds | |
| CN101528802B (en) | Heat-curable epoxy resin composition containing one blocked and one epoxide-terminated polyurethane prepolymer | |
| KR102626996B1 (en) | Blocked polyurethane toughener for epoxy adhesives | |
| EP2566922B1 (en) | 1c epoxy resin composition with reduced toxicity | |
| US20210371717A1 (en) | Blocked polyurethane tougheners for epoxy adhesives | |
| CN109593323A (en) | A kind of adduct of polyethers amine-epoxy and preparation method thereof and the good single-component epoxy composition and preparation method thereof of storage | |
| US10023774B2 (en) | Adhesive composition and uses thereof | |
| JP2010536953A (en) | Two-component impact-resistant epoxy adhesive | |
| JP2018530643A (en) | Highly elastic toughened one-part epoxy structural adhesive with high aspect ratio filler | |
| KR101994355B1 (en) | Structural epoxy adhesives composition | |
| JP6739921B2 (en) | Urethane-modified epoxy resin composition and cured product thereof | |
| EP2491088A2 (en) | Impact resistant two-component epoxy-based substance curing at room temperature | |
| JP4883264B2 (en) | Heat-curing one-part resin composition | |
| JP2003055534A (en) | Resin composition for composite material, intermediate material for composite material, and composite material | |
| CN101885956A (en) | Composite cloth adhesive bridging agent and preparation method thereof | |
| JP2000007889A (en) | Epoxy resin composition | |
| JP3400881B2 (en) | Epoxy resin composition | |
| CN117362586A (en) | Polyurethane toughening agent and adhesive composition prepared from same | |
| WO2023091662A1 (en) | Polycarbonate as a chemical blowing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |