CN108570302B - Low-temperature impact resistant epoxy adhesive composition and preparation method thereof - Google Patents
Low-temperature impact resistant epoxy adhesive composition and preparation method thereof Download PDFInfo
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- CN108570302B CN108570302B CN201710137908.0A CN201710137908A CN108570302B CN 108570302 B CN108570302 B CN 108570302B CN 201710137908 A CN201710137908 A CN 201710137908A CN 108570302 B CN108570302 B CN 108570302B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a low-temperature impact resistant epoxy adhesive composition which is characterized by comprising the following components in parts by weight: at least two epoxy resins; at least one difunctional epoxy diluent; at least 3 toughening agents, wherein the toughening agents at least comprise a liquid rubber toughening agent with a core-shell structure, epoxy resin modified nitrile rubber and ketoxime terminated reaction type polyurethane elastic prepolymer; at least one inorganic filler; at least one water scavenger; at least one thixotropic agent; at least one heat-activated latent curing agent; at least one curing accelerator. The epoxy adhesive composition has good low-temperature impact resistance by taking two different epoxy resins as raw materials and adding a composite toughening agent at least comprising a liquid rubber toughening agent with a core-shell structure, epoxy resin modified nitrile rubber and ketoxime-terminated reaction type polyurethane elastic prepolymer.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a low-temperature impact resistant epoxy adhesive composition and a preparation method thereof.
Background
After the epoxy adhesive is cured, the epoxy adhesive is generally easy to crack under the action of external force because of poor toughness. In a general toughening method, the toughness of the material at normal temperature can be improved by adding a toughening agent, but the material with good toughness at normal temperature still becomes brittle at low temperature.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a low temperature impact resistant epoxy adhesive composition and a preparation method thereof.
The invention provides a low-temperature impact resistant epoxy adhesive composition which is characterized by comprising the following components in parts by weight:
at least two epoxy resins;
at least one difunctional epoxy diluent;
at least 3 toughening agents, wherein the toughening agents at least comprise a liquid rubber toughening agent with a core-shell structure, epoxy resin modified nitrile rubber and ketoxime terminated reaction type polyurethane elastic prepolymer;
at least one inorganic filler;
at least one water scavenger;
at least one thixotropic agent;
at least one heat-activated latent curing agent;
at least one curing accelerator.
Preferably, the method comprises the following steps:
12 wt% -18 wt% of epoxy resin, wherein the epoxy resin comprises liquid epoxy resin and solid epoxy resin;
34-46 wt% of liquid rubber toughening agent with a core-shell structure;
9-13 wt% of epoxy resin modified nitrile rubber;
12-16 wt% of ketoxime-terminated reaction type polyurethane elastic prepolymer;
1 to 3 weight percent of bifunctional epoxy diluent;
10 wt% -12 wt% of inorganic filler;
0.2 to 0.3 weight percent of water removing agent;
2.0 to 3.0 weight percent of thixotropic agent;
2 to 3 weight percent of heat activated latent curing agent;
0.2 to 0.4 weight percent of curing accelerator.
Preferably, the ketoxime-terminated reaction type polyurethane elastic prepolymer is a 100% ketoxime-terminated reaction type polyurethane elastic prepolymer, and the 100% ketoxime-terminated reaction type polyurethane elastic prepolymer is prepared according to the following method:
heating and polymerizing the dehydrated polyether polyol, trimethylolpropane and diphenylmethane diisocyanate under the protection of nitrogen and in the presence of a catalyst to obtain a prepolymer;
adding ketoxime compounds into the prepolymer to carry out end-capping reaction to obtain 100% ketoxime end-capped reactive polyurethane elastic prepolymer;
the molar ratio of ketoxime groups in the ketoxime compound to NCO groups in the prepolymer is 1.05: 1-1.1: 1.
Preferably, the liquid epoxy resin is liquid bisphenol a diglycidyl ether, the solid epoxy resin is solid bisphenol a diglycidyl ether, and the mass ratio of the solid epoxy resin to the liquid epoxy resin is 1: (3-4).
Preferably, the core body material of the liquid rubber toughening agent with the core-shell structure is a copolymer of alkadiene and monoolefine, the shell material is an epoxy functionalized alkyl (meth) acrylate homopolymer or copolymer, and the average particle size of the liquid rubber toughening agent with the core-shell structure is less than 400 nm.
Preferably, the difunctional epoxy diluent is selected from the group consisting of diglycidyl ethers of saturated aliphatic diols;
the inorganic filler is selected from one or more of calcium carbonate, talcum powder, mica, quartz powder, bentonite, wollastonite, metal powder, carbon black and glass beads;
the water removing agent is selected from calcium oxide;
the thixotropic agent is selected from hydrophobic fumed silica;
the heat-activated latent curing agent is selected from one or more of guanidine and derivatives thereof, urea and derivatives thereof;
the curing accelerator is selected from catalytically active substituted ureas containing phenyl and dimethyl groups.
Preferably, the paint also comprises 0 wt% -2 wt% of auxiliary agents, wherein the auxiliary agents are selected from one or more of plasticizers, tackifiers, wetting agents, flame retardants, anti-aging agents and pigments.
The invention also provides a preparation method of the epoxy adhesive composition, which comprises the following steps:
A) mixing epoxy resin, heating and melting to obtain epoxy resin mixed solution;
B) adding a bifunctional epoxy diluent, a toughening agent, an inorganic filler, a water removing agent, a thixotropic agent, a thermally activated latent curing agent and a curing accelerator into the epoxy resin mixed solution, mixing and stirring, and defoaming in vacuum to obtain the epoxy adhesive composition.
Preferably, in the step A), the heating and melting temperature is 95-105 ℃.
Compared with the prior art, the invention provides a low-temperature impact resistant epoxy adhesive composition which is characterized by comprising the following components in parts by weight: at least two epoxy resins; at least one difunctional epoxy diluent; at least 3 toughening agents, wherein the toughening agents at least comprise a liquid rubber toughening agent with a core-shell structure, epoxy resin modified nitrile rubber and ketoxime terminated reaction type polyurethane elastic prepolymer; at least one inorganic filler; at least one water scavenger; at least one thixotropic agent; at least one heat-activated latent curing agent; at least one curing accelerator. The epoxy adhesive composition has good low-temperature impact resistance by taking two different epoxy resins as raw materials and adding a composite toughening agent at least comprising a liquid rubber toughening agent with a core-shell structure, epoxy resin modified nitrile rubber and ketoxime-terminated reaction type polyurethane elastic prepolymer.
Detailed Description
The invention provides a low-temperature impact resistant epoxy adhesive composition, which comprises the following components in part by weight:
at least two epoxy resins;
at least one difunctional epoxy diluent;
at least 3 toughening agents, wherein the toughening agents at least comprise a liquid rubber toughening agent with a core-shell structure, epoxy resin modified nitrile rubber and ketoxime terminated reaction type polyurethane elastic prepolymer;
at least one inorganic filler;
at least one water scavenger;
at least one thixotropic agent;
at least one heat-activated latent curing agent;
at least one curing accelerator.
The epoxy adhesive composition provided by the invention comprises at least two epoxy resins, wherein the epoxy resins are preferably at least two of epoxides containing two epoxy groups in the molecular structure, more preferably at least two of saturated polyepoxides, unsaturated polyepoxides, aliphatic polyepoxides, alicyclic polyepoxides, aromatic polyepoxides and polyepoxides containing heterocyclic rings, and further preferably polyglycidyl ethers and derivatives thereof, wherein the polyglycidyl ethers are selected from glycidyl ethers of polyhydric alcohol poly, polyglycidyl ethers of diamines or polyglycidyl ethers of polycarboxylic acids, and most preferably epoxy resins prepared by reacting bisphenol A and epichlorohydrin under the catalysis of alkali.
In some embodiments of the present invention, the Epoxy adhesive composition includes two Epoxy resins selected from a liquid Epoxy resin (L _ Epoxy) and a solid Epoxy resin (S _ Epoxy), the liquid Epoxy resin is a bisphenol a type diglycidyl ether which is liquid at normal temperature, the liquid Epoxy resin has an Epoxy value of 0.36 to 0.55, preferably 0.40 to 0.50, and an Epoxy equivalent of 180 to 220, preferably 190 to 210. The solid epoxy resin is bisphenol A type diglycidyl ether which is solid at normal temperature, the epoxy value of the solid epoxy resin is 0.16-0.24, preferably 0.18-0.22, and the epoxy equivalent is 400-600, preferably 450-550. In the present invention, the epoxy adhesive composition comprises 12 wt% to 18 wt% of epoxy resin, preferably 13 wt% to 17 wt%, and more preferably 14 wt% to 16 wt%. In the epoxy resin, the mass ratio of the solid epoxy resin to the liquid epoxy resin is 1: (3-4), preferably 1: (3.2-3.6).
The epoxy adhesive composition provided by the invention comprises at least one bifunctional epoxy diluent, wherein the bifunctional epoxy diluent is used for improving the viscosity and rheological property of the adhesive, and an epoxy group in the diluent participates in a high-temperature curing reaction. In the present invention, the difunctional epoxy diluent is selected from the diglycidyl ethers of saturated aliphatic diols, preferably the diglycidyl ethers of saturated aliphatic C3-C5 diols, preferably the difunctional epoxy diluents are products of the diepoxy series available from anhui constant (new) telechemicals ltd, more preferably one or more of the difunctional epoxy diluents of type XY205, XY207 and XY 678. In the present invention, the epoxy adhesive composition comprises 1 wt% to 3 wt% of a bifunctional epoxy diluent, preferably 1.5 wt% to 2.5 wt%, and more preferably 1.7 wt% to 2.2 wt%.
The epoxy adhesive composition provided by the invention also comprises at least 3 toughening agents, wherein the toughening agents at least comprise a liquid rubber toughening agent with a core-shell structure, epoxy resin modified nitrile rubber and ketoxime terminated reaction type polyurethane elastic prepolymer.
The liquid rubber toughening agent with the core-shell structure comprises rubber particles, wherein the rubber particles comprise a core body material and a shell material coated on the surface of the core body material. In the present invention, the core body material is comprised of an elastomeric polymer, preferably one or more of a homopolymer of a diene monomer, a copolymer of a diene monomer and a mono-olefin, preferably one or more of a vinyl aromatic monomer, a nitrile based monomer, and an acrylate based monomer. The core material has a glass transition temperature of less than-40 ℃.
The shell material is selected from a polymerization product of an acrylate monomer and a vinyl aromatic monomer or a polymerization product of an acrylate monomer and an unsaturated halogenated olefin monomer, more preferably an epoxy-functionalized alkyl (meth) acrylate homopolymer or an epoxy-functionalized alkyl (meth) acrylate copolymer with a vinyl monomer, and has a glass transition temperature of more than 50 ℃.
The average particle size of the liquid rubber toughening agent with the core-shell structure is less than 400nm, and preferably 100-300 nm.
The source of the liquid rubber toughening agent with the core-shell structure is not particularly limited in the invention, and the liquid rubber toughening agent can be a commercial product or can be prepared by self, and the preparation method can refer to European patent with application number EP1632533, US patents with application numbers US4778851 and US6111015, which are all incorporated by reference herein. The liquid rubber toughening agent with the core-shell structure can also be purchased from Kaneka Corporation under the trade name of ACE MX series, and is more preferably the liquid rubber toughening agent with the core-shell structure with the model of MX153 or MX 154. The mass percentage content of the rubber particles in the rubber toughening agent is preferably 33.3-40%.
In the invention, the epoxy adhesive composition comprises 34 wt% -46 wt% of the liquid rubber toughening agent with the core-shell structure, preferably 38 wt% -44 wt%, and more preferably 40 wt% -42 wt%.
In the epoxy resin modified nitrile rubber, the nitrile rubber is preferably liquid nitrile rubber, is a common toughening agent in an epoxy curing system, reacts with a large amount of epoxy groups in an epoxy resin molecular structure through modification and active reaction groups such as carboxyl or amino and the like to form soft blocks, is separated out from a matrix of a three-dimensional system after curing, and physically forms a two-phase structure of a thermosetting phase and a rubber phase, so that the toughness can be greatly improved. The molecular main chain of the liquid nitrile rubber is a copolymer of butadiene monomer and acrylonitrile monomer. The liquid nitrile rubber with the number average molecular weight of 3000-10000 and the terminal group of carboxyl is preferably selected, the content of acrylonitrile monomer in the molecular structure is 15-30 wt%, the liquid nitrile rubber can react with excessive epichlorohydrin to form the liquid nitrile rubber with the terminal group of epoxy, and the liquid nitrile rubber can also react with epoxy resin to generate epoxy resin addition compound under the action of a catalyst. Both of the two reaction modes can improve the compatibility of the rubber and the epoxy resin matrix.
The source of the epoxy resin modified nitrile rubber is not particularly limited, and the nitrile rubber can be prepared by self or can be a commercially available product. Reference may be made to the patents published under the numbers US2003/0196753, US2005-0070634 and US6776860, the present invention incorporating therein by reference the processes for the preparation of epoxy modified nitrile rubbers. Among them, commercial epoxy resin-modified nitrile rubbers are available as the adduct Hypro861340 of Hypro to epoxy resin, CTBN1300x8 or 1300x13 available from CVC thermosettes specialties, usa.
In the invention, the epoxy resin modified nitrile rubber is contained in the epoxy adhesive composition by 9-13 wt%, preferably 10-12 wt%, and more preferably 10.5-11.5 wt%.
The ketoxime-terminated reaction type polyurethane elastic prepolymer is a 100% ketoxime-terminated reaction type polyurethane elastic prepolymer, and the 100% ketoxime-terminated reaction type polyurethane elastic prepolymer is prepared according to the following method:
heating and polymerizing the dehydrated polyether polyol, trimethylolpropane and diphenylmethane diisocyanate under the protection of nitrogen and in the presence of a catalyst to obtain a prepolymer;
adding ketoxime compounds into the prepolymer to carry out end-capping reaction to obtain 100% ketoxime end-capped reactive polyurethane elastic prepolymer;
the molar ratio of ketoxime groups in the ketoxime compound to-NCO groups in the prepolymer is 1.05: 1-1.1: 1.
Specifically, the method comprises the steps of firstly dehydrating polyether polyol to obtain dehydrated polyether polyol, then adding trimethylolpropane and a catalyst for mixing, adding diphenylmethane diisocyanate (MDI) under the protection of nitrogen, and carrying out heating reaction to obtain a prepolymer.
Wherein the number average molecular weight of the polyether polyol is 1000D-5000D, preferably 2000D-4000D; the catalyst is preferably an organic tin catalyst, more preferably, the organic tin catalyst is selected from dibutyltin dilaurate, the heating reaction temperature is preferably 85-90 ℃, and the heating reaction time is 2 hours. The reaction was stopped by detecting the content of-NCO groups in the prepolymer at 3.3% (mass%).
After the prepolymer is obtained, adding a ketoxime compound into the prepolymer to carry out end-capping reaction to obtain a 100% ketoxime end-capped reactive polyurethane elastic prepolymer;
in the present invention, the ketoxime is not particularly limited in kind, and any ketoxime compound known to those skilled in the art may be used for blocking, and is preferably butanone oxime or cyclohexanone oxime. The molar ratio of ketoxime groups in the ketoxime compound to-NCO groups in the prepolymer is 1.05: 1-1.1: 1, the blocking reaction temperature is preferably 85-90 ℃, and the blocking reaction time is preferably 1-1.5 hours.
And (3) determining the content of-NCO groups in the reaction product after the end-capping reaction to be 0, namely determining that the reaction is finished, and obtaining the 100% ketoxime end-capped reactive polyurethane elastic prepolymer after vacuum defoaming.
The number average molecular weight of the finally obtained 100% ketoxime-terminated reaction type polyurethane elastic prepolymer is 4000-12000, and is preferably 4000-10000.
The epoxy adhesive composition also comprises at least one inorganic filler, wherein the inorganic filler is selected from one or more of calcium carbonate, talcum powder, mica, quartz powder, bentonite, wollastonite, metal powder, carbon black and glass beads. The filler can mainly play roles in improving rheological property, reducing cost, absorbing moisture, promoting bonding and the like in the adhesive. The epoxy adhesive composition comprises 10 wt% to 12 wt% of an inorganic filler, preferably 10.5 wt% to 11.5 wt%, and more preferably 10.8 wt% to 11.2 wt%.
The epoxy adhesive composition also comprises at least one water scavenger, wherein the water scavenger is selected from calcium oxide, and the epoxy adhesive composition comprises 0.2-0.3 wt% of water scavenger, preferably 0.22-0.28 wt%, and more preferably 0.24-0.26 wt%.
The epoxy adhesive composition of the present invention further comprises at least one thixotropic agent selected from the group consisting of hydrophobic fumed silica. The invention preferably adopts R202 type fumed silica purchased from the winning creative moralisia company, can obviously improve the high-temperature thixotropy and prevent the occurrence of high-temperature sagging. The epoxy adhesive composition comprises 2.0 wt% to 3.0 wt% of thixotropic agent, preferably 2.2 wt% to 2.8 wt%, more preferably 2.4 wt% to 2.6 wt%.
The epoxy adhesive composition also comprises at least one latent curing agent activated by heat, and the high-temperature epoxy curing agent is selected and activated by heating, wherein the curing temperature is over 140 ℃. The heat-activated latent curing agent is selected from one or more of guanidine and derivatives thereof, urea and derivatives thereof. In some embodiments of the invention, it is preferred to use dicyandiamide (cyanoguanidine) curing agents in powder form, the particle size of the powder particles being less than or equal to 10 μm, to enhance the dispersing effect and to improve the storage stability of the adhesive. The epoxy adhesive composition comprises 2 to 3 weight percent of heat-activated latent curing agent, preferably 2.2 to 2.8 weight percent, and more preferably 2.4 to 2.6 weight percent.
The epoxy adhesive composition also comprises at least one curing accelerator, wherein the curing accelerator is selected from catalytically active substituted urea containing phenyl and dimethyl, and the curing accelerator can remarkably prolong the storage life of a product besides playing a catalytic role. In the present invention, a dimethylurea-based curing accelerator having a low catalytic activity is preferably used, and p-chlorophenyl-N, N-dimethylurea, 3-phenyl-1, 1-dimethylurea, 3, 4-dichlorophenyl-N, N-dimethylurea are more preferable. In the present invention, the dimethylurea curing accelerator is preferably available from DYHARD UR series products of Alzchem, and is preferably a dimethylurea curing accelerator having a model number of UR200, UR300, UE400, UR500, UR700 or UR 800. The epoxy adhesive composition comprises 0.2 wt% -0.4 wt% of curing accelerator, preferably 0.25 wt% -0.35 wt%, more preferably 0.27 wt% -0.32 wt%.
Preferably, the epoxy adhesive composition of the present invention further comprises an auxiliary agent selected from one or more of a plasticizer, a tackifier, a wetting agent, a flame retardant, an anti-aging agent and a pigment. The present invention is not particularly limited with respect to the specific kinds of the plasticizer, the tackifier, the wetting agent, the flame retardant, the antioxidant and the pigment, and the kinds of the auxiliaries known to those skilled in the art may be used. In the present invention, the epoxy adhesive composition comprises 0 wt% to 2 wt% of an auxiliary agent, preferably 0.2 wt% to 1 wt%, and more preferably 0.4 wt% to 0.6 wt%.
The invention also provides a preparation method of the epoxy adhesive composition, which comprises the following steps:
A) mixing epoxy resin, heating and melting to obtain epoxy resin mixed solution;
B) adding a bifunctional epoxy diluent, a toughening agent, an inorganic filler, a water removing agent, a thixotropic agent, a thermally activated latent curing agent and a curing accelerator into the epoxy resin mixed solution, mixing and stirring, and defoaming in vacuum to obtain the epoxy adhesive composition.
The invention firstly mixes the epoxy resin and heats and melts the epoxy resin to obtain the epoxy resin mixed solution.
Specifically, heating liquid epoxy resin to 95-105 ℃, adding solid epoxy resin, mixing and stirring until the solid epoxy resin is molten to obtain epoxy resin mixed liquid;
and then adding a bifunctional epoxy diluent, a toughening agent, an inorganic filler, a water removing agent, a thixotropic agent, a heat-activated latent curing agent and a curing accelerator into the epoxy resin mixed solution, mixing and stirring, and defoaming in vacuum to obtain the epoxy adhesive composition.
Adding a bifunctional epoxy diluent and a toughening agent into the epoxy resin mixed solution, uniformly dispersing, adding an inorganic filler, a water removing agent, a thixotropic agent, a thermally activated latent curing agent and a curing accelerator, mixing and stirring, and defoaming in vacuum to obtain the epoxy adhesive composition.
Wherein the toughening agent at least comprises a liquid rubber toughening agent with a core-shell structure, epoxy resin modified nitrile rubber and ketoxime terminated reaction type polyurethane elastic prepolymer
The epoxy adhesive composition has good low-temperature impact resistance by taking two different epoxy resins as raw materials and adding a composite toughening agent at least comprising a liquid rubber toughening agent with a core-shell structure, epoxy resin modified nitrile rubber and ketoxime-terminated reaction type polyurethane elastic prepolymer.
The invention selects at least three composite toughening agents, wherein the use of the ketoxime-terminated reaction type polyurethane elastic prepolymer can reduce the use amount of expensive liquid rubber toughening agent with a core-shell structure and epoxy resin modified nitrile rubber, thereby reducing the cost; in addition, the preparation method of the ketoxime-terminated reaction type polyurethane elastic prepolymer provided by the invention is simpler and safer, and has low cost and stable storage.
For further understanding of the present invention, the low temperature impact resistant epoxy adhesive composition and the preparation method thereof provided by the present invention are illustrated below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
EXAMPLE 1 preparation of toughener A
100 parts of polyether polyol (DL-2000D) with the molecular weight of 2000D is added into a reactor, dehydration is carried out for 30 minutes at the temperature of 105 ℃, then 0.6 part of trimethylolpropane and 0.1 part of organic tin catalyst are added and evenly mixed, 26.5 parts of MDI is added under the protection of nitrogen, the temperature is regulated to 85-90 ℃, the reaction is carried out for 2.0 hours under the condition, a prepolymer is obtained, and the mass percentage content of-NCO groups of the prepolymer is detected to be 3.3%. 10.1 parts of butanone oxime is added according to the molar ratio of the ketoxime group to the-NCO group of 1.1:1, blocking reaction is carried out for 1.5 hours at 85-90 ℃, the content of the-NCO group in the product is detected to be zero, and the toughening agent A is obtained.
The number average molecular weight of toughening agent A was determined to be 4500, the weight average molecular weight was 11000, and the dispersion index was 2.4.
EXAMPLE 2 preparation of toughener B
200 parts of polyether polyol (DL 4000D) with the molecular weight of 4000D are added into a reactor, dehydration is carried out for 30 minutes at 105 ℃, then 1.0 part of trimethylolpropane and 0.2 part of organic tin catalyst are added and mixed uniformly, 28 parts of MDI is added under the protection of nitrogen, the temperature is regulated to 85-90 ℃, the reaction is carried out for 2.5 hours under the condition, a prepolymer is obtained, and the content of-NCO groups of the prepolymer is detected to be 1.9%. Adding 13 parts of cyclohexanone oxime according to the molar ratio of the ketoxime group to the-NCO group of 1.1:1, carrying out end-capping reaction for 1.5 hours at 85-90 ℃, and detecting that the content of the-NCO group in the product is zero to obtain the toughening agent B.
The number average molecular weight of the toughening agent B was measured to be 8600, the weight average molecular weight was measured to be 22000, and the dispersion index was measured to be 2.6.
Examples 3 to 8
Heating liquid epoxy resin to 95-105 ℃ according to the mass parts of the raw materials in the table 1, adding solid epoxy resin, mixing and stirring until the solid epoxy resin is molten to obtain epoxy resin mixed solution;
adding a bifunctional epoxy diluent and a toughening agent into the epoxy resin mixed solution, uniformly dispersing, adding an inorganic filler, a water removing agent, a thixotropic agent, a thermally activated latent curing agent and a curing accelerator, mixing and stirring, and defoaming in vacuum to obtain the epoxy adhesive composition.
The epoxy adhesive composition obtained above was subjected to steel/steel tensile shear strength test, specific sample preparation method and test reference standard GBT 7124-:
the obtained epoxy adhesive composition is subjected to an impact strength test, and the specific method comprises the following steps:
the impact strength was measured according to ISO11343 standard using a CEAST 9350 drop hammer impact tester from Instron, USA. The impact speed of the drop hammer is 2m/s, and the test environment temperature is provided by an environment box which is attached to the equipment. The test piece is made of a cold-rolled steel sheet with the thickness of 0.6mm, oil stain is removed before bonding, and then the steel sheet is wiped dry by acetone, and the bonding surface is 30x20 mm. The thickness of the glue layer was controlled using 0.2mm glass beads, the glue curing conditions were 180 ℃/45min, 5 test pieces per group, and the results were arithmetically averaged (see US20110297317a1), and are shown in table 1.
TABLE 1 measurement results of raw material compositions and products of examples 3 to 4
In particular, it is pointed out that:
the solid resin used in examples 3 to 5 was D.E.R.671 epoxy resin (Dow chemical Co., Ltd.)
The solid resin BE501H epoxy resin used in examples 6 to 8, Changchun chemical engineering (Jiangsu) Co., Ltd.
Self-made toughening agent: toughener a (example 3/6/7); toughening agent B (example 4/5/8)
Examples 3 to 8 used the following raw materials, unless otherwise specified:
the liquid epoxy resin is BE188-90 Changchun chemical engineering (Jiangsu) Co.Ltd;
the core-shell rubber is MX154 core-shell rubber particles/epoxy resin (wherein the mass fraction of the core-shell particles is 40 percent);
the modified nitrile rubber is Hypro-861340 epoxy resin modified liquid nitrile rubber, American CVCThermoset Specialties (wherein the mass fraction of the core-shell particles is 40%);
the active diluents are: XY678 bifunctional epoxy Diluent, Anhui Heng (New) remote chemical Co., Ltd;
the curing agent is Dyhard 100S dicyandiamide curing agent, Alzchem Azken chemical Co., Ltd;
the curing accelerator was UR300, Alzchem Azken chemical Co., Ltd;
the tackifier is Adeka Resin EP-49-10N (Adeka Corporation, Asahi Denka Co., Ltd., Japan).
The water absorbent is CaO, and is obtained by Shanghai Van Waals inorganic chemical Co Ltd;
the filler is calcium carbonate (light calcium) S-CCR-100, double super calcium industry Co., Ltd, Jiande city;
thixotropic agent: fumed silica, AEROSILR202, Windage specialty Chemicals, Inc.
The pigment being TiO2Model 218, Shanghai black tiger chemical technology, Inc.;
the glass beads are 140-mesh Shanghai color new material company Limited.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A low temperature impact resistant epoxy adhesive composition comprising:
12 wt% -18 wt% of epoxy resin, wherein the epoxy resin comprises liquid epoxy resin and solid epoxy resin;
34-46 wt% of liquid rubber toughening agent with a core-shell structure;
9-13 wt% of epoxy resin modified nitrile rubber;
12-16 wt% of ketoxime-terminated reaction type polyurethane elastic prepolymer; the ketoxime-terminated reaction type polyurethane elastic prepolymer is a 100% ketoxime-terminated reaction type polyurethane elastic prepolymer, and the 100% ketoxime-terminated reaction type polyurethane elastic prepolymer is prepared according to the following method:
heating the dehydrated polyether polyol, trimethylolpropane and diphenylmethane diisocyanate under the protection of nitrogen and in the presence of a catalyst to perform polymerization reaction to obtain a prepolymer;
adding ketoxime compounds into the prepolymer to carry out end-capping reaction to obtain 100% ketoxime end-capped reactive polyurethane elastic prepolymer;
the molar ratio of ketoxime groups in the ketoxime compound to NCO groups in the prepolymer is 1.05: 1-1.1: 1;
1 to 3 weight percent of bifunctional epoxy diluent;
10 wt% -12 wt% of inorganic filler;
0.2 to 0.3 weight percent of water removing agent;
2.0 to 3.0 weight percent of thixotropic agent;
2 to 3 weight percent of heat activated latent curing agent;
0.2 to 0.4 weight percent of curing accelerator.
2. The epoxy adhesive composition according to claim 1, wherein the liquid epoxy resin is a liquid bisphenol a diglycidyl ether, the solid epoxy resin is a solid bisphenol a diglycidyl ether, and the mass ratio of the solid epoxy resin to the liquid epoxy resin is 1: (3-4).
3. The epoxy adhesive composition of claim 1, wherein the core material of the liquid rubber toughening agent with the core-shell structure is a copolymer of alkadiene and monoolefin, the shell material is epoxy functionalized alkyl (meth) acrylate homopolymer or copolymer, and the average particle size of the liquid rubber toughening agent with the core-shell structure is less than 400 nm.
4. The epoxy adhesive composition of claim 1, wherein the difunctional epoxy diluent is selected from the group consisting of diglycidyl ethers of saturated aliphatic diols;
the inorganic filler is selected from one or more of calcium carbonate, talcum powder, mica, quartz powder, bentonite, wollastonite, metal powder, carbon black and glass beads;
the water removing agent is selected from calcium oxide;
the thixotropic agent is selected from hydrophobic fumed silica;
the heat-activated latent curing agent is selected from one or more of guanidine and derivatives thereof, urea and derivatives thereof;
the curing accelerator is selected from catalytically active substituted ureas containing phenyl and dimethyl groups.
5. The epoxy adhesive composition of claim 1, further comprising 0 wt% to 2 wt% of an auxiliary agent selected from one or more of a plasticizer, a tackifier, a wetting agent, a flame retardant, an anti-aging agent, and a pigment.
6. A method for preparing the epoxy adhesive composition according to any one of claims 1 to 5, comprising the steps of:
A) mixing epoxy resin, heating and melting to obtain epoxy resin mixed solution;
B) adding a bifunctional epoxy diluent, a toughening agent, an inorganic filler, a water removing agent, a thixotropic agent, a thermally activated latent curing agent and a curing accelerator into the epoxy resin mixed solution, mixing and stirring, and defoaming in vacuum to obtain the epoxy adhesive composition.
7. The method according to claim 6, wherein the temperature for melting by heating in step A) is 95 to 105 ℃.
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| CN109651977B (en) * | 2018-12-25 | 2020-04-14 | 杭州之江新材料有限公司 | Epoxy single-component structural adhesive 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 |
| 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 |
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| 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 |
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| 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 |
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