CN114539957A - Dual-curing flexible epoxy adhesive and preparation method thereof - Google Patents

Dual-curing flexible epoxy adhesive and preparation method thereof Download PDF

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Publication number
CN114539957A
CN114539957A CN202110381344.1A CN202110381344A CN114539957A CN 114539957 A CN114539957 A CN 114539957A CN 202110381344 A CN202110381344 A CN 202110381344A CN 114539957 A CN114539957 A CN 114539957A
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parts
antioxidant
epoxy resin
curing
dual
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陈林志
王诚
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Ai Shuo New Materials Shanghai Co ltd
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Ai Shuo New Materials Shanghai Co ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen

Abstract

The invention discloses a dual-curing flexible epoxy adhesive which comprises, by weight, 80-120 parts of toughened epoxy resin, 1-30 parts of diluent, 20-55 parts of composite curing agent, 5-15 parts of curing accelerator, 1-3 parts of filler and 0.5-2 parts of antioxidant, wherein the toughened epoxy resin is polyether modified epoxy resin. In the technical scheme, the polyether modified epoxy resin is used as the resin main body, so that the bonding performance of the epoxy resin is kept, the flexibility of the whole material is improved, and the epoxy adhesive has better usability in application. The inventor realizes the curability at room temperature by using the composite curing agent and the curing accelerator, improves the curing rate of the whole material, saves the curing time and improves the working efficiency when the epoxy adhesive is used.

Description

Dual-curing flexible epoxy adhesive and preparation method thereof
Technical Field
The application belongs to the technical field of adhesives, and particularly relates to a dual-curing flexible epoxy adhesive and a preparation method thereof.
Background
Epoxy resin is also called epoxy glue, and is a high molecular polymer, and the molecule of the epoxy resin contains more than two epoxy groups. It is a polycondensation product of epichlorohydrin and bisphenol A or a polyol. Because of the chemical activity of the epoxy group, the epoxy group can be opened by a plurality of compounds containing active hydrogen, and the epoxy group is cured and crosslinked to form a network structure, so that the epoxy group is a thermosetting resin. The epoxy adhesive has excellent electrical insulation performance and bonding performance with various materials, so that the epoxy adhesive is widely applied to various fields. However, the existing epoxy glue can be cured at a higher temperature, the curing time is longer, the working efficiency is often reduced, the flexibility of the existing epoxy glue is generally poor, and the cured product of the epoxy glue is prone to stress cracking, and particularly when the epoxy glue is applied to some special fields, such as the communication and aerospace fields, the poor flexibility of the epoxy glue can seriously affect the use performance of devices.
Patent application No. 201611264523.2 discloses an epoxy resin composition and a preparation method thereof, wherein the epoxy resin composition in the technical scheme mainly comprises bisphenol a type liquid epoxy resin, bisphenol a type solid epoxy resin, novolac epoxy resin, dicyandiamide curing agent and organic urea accelerator, and the epoxy resin in the technical scheme has good adhesive property, but needs poor high-temperature curing and flexibility, and cannot meet the requirements of the existing market on rapid curing and excellent flexibility of the epoxy resin.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a dual-curing flexible epoxy adhesive which comprises, by weight, 80-120 parts of toughened epoxy resin, 1-30 parts of a diluent, 20-55 parts of a composite curing agent, 5-15 parts of a curing accelerator, 1-3 parts of a filler and 0.5-2 parts of an antioxidant, wherein the toughened epoxy resin is polyether modified epoxy resin.
Preferably, the epoxy equivalent of the polyether modified epoxy resin is 300-400 g/eq.
Preferably, the diluent is an ether solvent.
Preferably, the ether solvent is at least one selected from the group consisting of diglycidyl ether, polyglycidyl ether, propylene oxide butyl ether, propylene oxide phenyl ether, diepoxide ethyl ether, and trimethylolpropane tri-propyl ether.
Preferably, the composite curing agent is at least one selected from the group consisting of aliphatic amines, alicyclic amines, and aromatic amines.
Preferably, the aliphatic amine is at least one selected from the group consisting of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, and polyetheramine.
Preferably, the curing accelerator contains an imidazole group in a molecule.
Preferably, the particle size of the filler is 300-400 meshes.
Preferably, the antioxidant is selected from the group consisting of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 1024, antioxidant 697, antioxidant 565, antioxidant DSTDP, antioxidant DLTDP, antioxidant 618, antioxidant 168, and antioxidant 626.
The second aspect of the invention provides a preparation method of the dual-curing flexible epoxy glue, which at least comprises the following steps:
(1) mixing 80-120 parts of toughened epoxy resin, 1-30 parts of diluent, 1-3 parts of filler and 0.5-2 parts of antioxidant into a stirring tank A, and stirring to obtain a component A;
(2) mixing 20-55 parts of composite curing agent and 5-15 parts of curing accelerator into a stirring tank B, and stirring to obtain a component B;
(3) mixing the component A and the component B at room temperature to obtain the final product
Has the advantages that: in the technical scheme, the polyether modified epoxy resin is used as the resin main body, so that the bonding performance of the epoxy resin is kept, the flexibility of the whole material is improved, and the epoxy adhesive has better usability in application. The inventor realizes the curability at room temperature by using the composite curing agent and the curing accelerator, improves the curing rate of the whole material, saves the curing time and improves the working efficiency when the epoxy adhesive is used.
Detailed Description
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.
In order to solve the technical problems, the first aspect of the invention provides a dual-curing flexible epoxy adhesive which comprises, by weight, 80-120 parts of toughened epoxy resin, 1-30 parts of a diluent, 20-55 parts of a composite curing agent, 5-15 parts of a curing accelerator, 1-3 parts of a filler and 0.5-2 parts of an antioxidant, wherein the toughened epoxy resin is polyether modified epoxy resin.
Polyether modified epoxy resin
As a preferable technical scheme, the epoxy equivalent of the polyether modified epoxy resin is 300-400 g/eq.
As a preferable technical scheme, the epoxy equivalent of the polyether modified epoxy resin is 320 g/eq.
Since the epoxy resin has few flexible chain segments in the molecule, the cured product of the epoxy resin is easy to generate stress cracking phenomenon in the using process. In the technical scheme, the polyether modified epoxy resin is used, and the flexibility of the epoxy resin is improved through the flexibility of the polyether chain segment by introducing the polyether chain segment into the epoxy resin. When the cured epoxy resin is subjected to external stress, the polyether chain segment can well absorb a part of impact force to prevent the cured epoxy resin from cracking due to stress. However, due to the introduction of the polyether segment, the content of the epoxy group is diluted, so that the crosslinking density is reduced during curing, and the bonding performance of the epoxy resin is influenced to a certain extent. The epoxy equivalent is the grams of epoxy resin containing one equivalent of epoxy groups. However, the inventors found that the curing rate is slower when the polyether-modified epoxy resin is used, and the inventors considered that the possible reason is that the introduction of the polyether segment increases the steric hindrance of the curing reaction, and the curing rate becomes slower.
As a preferred technical solution, the diluent is an ether solvent.
As a preferable embodiment, the ether solvent is at least one selected from diglycidyl ether, polyglycidyl ether, propylene oxide butyl ether, propylene oxide phenyl ether, propylene oxide ethyl ether, and propylene oxide propyl ether.
Composite curing agent
As a preferable technical solution, the composite curing agent is selected from aliphatic amines, alicyclic amines and aromatic amines.
In a preferred embodiment, the aliphatic amine is at least one selected from the group consisting of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, and polyetheramine.
As a preferable technical scheme, the composite curing agent is a mixture of hexamethylene diamine and polyether amine, and the mass ratio of the hexamethylene diamine to the polyether amine is (1-3): 1.
as a preferred embodiment, the polyetheramine is at least one selected from the group consisting of polyetheramine D220, polyetheramine D400, and polyetheramine D2000.
Both hexamethylene diamine and polyether amine curing agents can well cure epoxy resin at room temperature. The inventor finds that the polyether modified epoxy resin is cured by compounding a certain amount of hexamethylenediamine and a polyether amine curing agent, so that the polyether modified epoxy resin has a high curing rate, the heat resistance and the impact toughness of the whole material can be improved, and the epoxy adhesive can be rapidly cured at room temperature.
Curing accelerator
In a preferred embodiment, the curing accelerator contains an imidazole group in a molecule.
As a preferred technical scheme, the curing accelerator is 2-methylimidazole and/or 2-ethyl-4-methylimidazole.
The inventor can reduce the curing temperature of the polyether modified epoxy resin by adding a certain amount of curing accelerator, so that the polyether modified epoxy resin can be well cured at room temperature, and the curing rate can be further improved. However, when epoxy is used in solid devices, it also needs to have good wear resistance.
Filler
As a preferable technical scheme, the particle size of the filler is 300-400 meshes.
As a preferable technical scheme, the filler is mica powder, and the particle size of the mica powder is 325 meshes.
By adding the filler into the epoxy resin, the wear resistance of the epoxy resin can be improved, so that the epoxy resin has better applicability. The inventor unexpectedly finds that when mica powder is added into the polyether modified epoxy resin, the wear resistance and heat resistance of the whole material can be improved, the toughness and ageing resistance of the material can be improved, and the mica powder has better compatibility with the polyether modified epoxy resin when the mesh number of the mica powder is controlled. However, poor compatibility occurs when the particle size of the mica powder is too large, and agglomeration occurs when the particle size of the mica powder is too small, which both reduce the performance of the material body.
As a preferable technical scheme, the antioxidant is selected from 1010, 1076, 1098, 1024, 697, 565, DSTDP, DLTDP, 618, 168 and 626.
The second aspect of the invention provides a preparation method of the dual-curing flexible epoxy adhesive, which at least comprises the following steps:
(1) mixing 80-120 parts of toughened epoxy resin, 1-30 parts of diluent, 1-3 parts of filler and 0.5-2 parts of antioxidant into a stirring tank A, and stirring to obtain a component A;
(2) mixing 20-55 parts of composite curing agent and 5-15 parts of curing accelerator into a stirring tank B, and stirring to obtain a component B;
(3) mixing the component A and the component B at room temperature to obtain the product.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
The dual-curing flexible epoxy adhesive comprises, by weight, 100 parts of toughened epoxy resin, 15 parts of diluent, 45 parts of composite curing agent, 10 parts of curing accelerator, 2 parts of filler and 0.5 part of antioxidant, wherein the toughened epoxy resin is polyether modified epoxy resin which is purchased from complex advanced materials (Shanghai) Limited company under the brand number: japanese ADEKA, epoxy equivalent 320 g/eq. The diluent is an ether solvent, the ether solvent is diglycidyl ether, the composite curing agent is a mixture of hexamethylene diamine and polyether amine, and the mass ratio of the hexamethylene diamine to the polyether amine is 1: 1. the polyether amine curing agent is polyether amine D220, and the polyether amine D220 is purchased from the special industrial product business of Weijia in the Nanshan region of Shenzhen. The curing accelerator is 2-ethyl-4-methylimidazole, and the 2-ethyl-4-methylimidazole is purchased from Jinchuan chemical Co., Ltd, Jinan, and has a CAS number of 931-36-2. The filler is mica powder, the particle size of the mica powder is 325 meshes, and the mica powder is purchased from a processing plant of Shengtai mineral products in Lingshou county and has the brand number of 325 meshes. The antioxidant is selected from antioxidant 1010, and the antioxidant 1010 is purchased from Gaozogalping Co., Ltd.
A second aspect of the present invention provides a method for preparing a dual-curing flexible epoxy glue, comprising the following steps:
(1) mixing 100 parts of toughened epoxy resin, 15 parts of diluent, 2 parts of filler and 0.5 part of antioxidant into a stirring tank A, and stirring for 30min under the condition of 500r/min to obtain a component A;
(2) mixing 45 parts of composite curing agent and 10 parts of curing accelerator into a stirring tank B, and stirring for 30min under the condition of 500r/min to obtain a component B;
(3) mixing the component A and the component B at room temperature to obtain the product.
Example 2
The dual-curing flexible epoxy adhesive comprises, by weight, 100 parts of toughened epoxy resin, 15 parts of diluent, 45 parts of composite curing agent, 10 parts of curing accelerator, 2 parts of filler and 0.5 part of antioxidant, wherein the toughened epoxy resin is polyether modified epoxy resin which is purchased from complex advanced materials (Shanghai) Limited company under the brand number: japanese ADEKA, epoxy equivalent 320 g/eq. The diluent is an ether solvent, the ether solvent is diglycidyl ether, the composite curing agent is a mixture of hexamethylene diamine and polyether amine, and the mass ratio of the hexamethylene diamine to the polyether amine is 3: 1. the polyether amine curing agent is polyether amine D220, and the polyether amine D220 is purchased from the special industrial product business of Weijia in the Nanshan region of Shenzhen. The curing accelerator is 2-ethyl-4-methylimidazole, and the 2-ethyl-4-methylimidazole is purchased from Jinchuan chemical Co., Ltd, Jinan, and has a CAS number of 931-36-2. The filler is mica powder, the particle size of the mica powder is 325 meshes, and the mica powder is purchased from a processing plant of Shengtai mineral products in Lingshou county and has the brand number of 325 meshes. The antioxidant is selected from antioxidant 1010, and the antioxidant 1010 is purchased from Gaozogalping Co., Ltd.
A second aspect of the present invention provides a method for preparing a dual-curing flexible epoxy glue, comprising the following steps:
(1) mixing 100 parts of toughened epoxy resin, 15 parts of diluent, 2 parts of filler and 0.5 part of antioxidant into a stirring tank A, and stirring for 30min under the condition of 500r/min to obtain a component A;
(2) mixing 45 parts of composite curing agent and 10 parts of curing accelerator into a stirring tank B, and stirring for 30min under the condition of 500r/min to obtain a component B;
(3) mixing the component A and the component B at room temperature to obtain the product.
Comparative example 1
The dual-curing flexible epoxy glue comprises, by weight, 100 parts of epoxy resin, 15 parts of diluent, 45 parts of composite curing agent, 10 parts of curing accelerator, 2 parts of filler and 0.5 part of antioxidant, wherein the epoxy resin is purchased from the fields of China and broadcasters and has the brand number: e-44. The diluent is an ether solvent, the ether solvent is diglycidyl ether, the composite curing agent is a mixture of hexamethylene diamine and polyether amine, and the mass ratio of the hexamethylene diamine to the polyether amine is 1: 1. the polyether amine curing agent is polyether amine D220, and the polyether amine D220 is purchased from the special industrial product business of Weijia in the Nanshan region of Shenzhen. The curing accelerator is 2-ethyl-4-methylimidazole, and the 2-ethyl-4-methylimidazole is purchased from Jinchuan chemical Co., Ltd, Jinan, and has a CAS number of 931-36-2. The filler is mica powder, the particle size of the mica powder is 325 meshes, and the mica powder is purchased from a processing plant of Shengtai mineral products in Lingshou county and has the brand number of 325 meshes. The antioxidant is selected from antioxidant 1010, and the antioxidant 1010 is purchased from Gaozogalping Co., Ltd.
A second aspect of the present invention provides a method for preparing a dual-curing flexible epoxy glue, comprising the following steps:
(1) mixing 100 parts of epoxy resin, 15 parts of diluent, 2 parts of filler and 0.5 part of antioxidant into a stirring tank A, and stirring for 30min under the condition of 500r/min to obtain a component A;
(2) mixing 45 parts of composite curing agent and 10 parts of curing accelerator into a stirring tank B, and stirring for 30min under the condition of 500r/min to obtain a component B;
(3) mixing the component A and the component B at room temperature to obtain the product.
Comparative example 2
The dual-curing flexible epoxy adhesive comprises, by weight, 100 parts of toughened epoxy resin, 15 parts of diluent, 45 parts of curing agent, 10 parts of curing accelerator, 2 parts of filler and 0.5 part of antioxidant, wherein the toughened epoxy resin is polyether modified epoxy resin which is purchased from complex advanced materials (Shanghai) Limited company under the brand number: japanese ADEKA, epoxy equivalent 320 g/eq. The diluent is an ether solvent, the ether solvent is diglycidyl ether, the curing agent is aliphatic amine, and the aliphatic amine curing agent is hexamethylene diamine. The curing accelerator is 2-ethyl-4-methylimidazole, and the 2-ethyl-4-methylimidazole is purchased from Jinchuan chemical Co., Ltd, Jinan, and has a CAS number of 931-36-2. The filler is mica powder, the particle size of the mica powder is 325 meshes, and the mica powder is purchased from a processing plant of Shengtai mineral products in Lingshou county and has the brand number of 325 meshes. The antioxidant is selected from antioxidant 1010, and the antioxidant 1010 is purchased from Gaozogalping Co., Ltd.
A second aspect of the present invention provides a method for preparing a dual-curing flexible epoxy glue, comprising the following steps:
(1) mixing 100 parts of toughened epoxy resin, 15 parts of diluent, 2 parts of filler and 0.5 part of antioxidant into a stirring tank A, and stirring for 30min under the condition of 500r/min to obtain a component A;
(2) mixing 45 parts of curing agent and 10 parts of curing accelerator into a stirring tank B, and stirring for 30min under the condition of 500r/min to obtain a component B;
(3) mixing the component A and the component B at room temperature to obtain the product.
Comparative example 3
The dual-curing flexible epoxy adhesive comprises, by weight, 100 parts of toughened epoxy resin, 15 parts of diluent, 45 parts of curing agent, 10 parts of curing accelerator, 2 parts of filler and 0.5 part of antioxidant, wherein the toughened epoxy resin is polyether modified epoxy resin which is purchased from complex advanced materials (Shanghai) Limited company under the brand number: japanese ADEKA, epoxy equivalent is 320 g/eq. The diluent is an ether solvent, the ether solvent is diglycidyl ether, the curing agent is polyetheramine D220, and the polyetheramine D220 is purchased from the trade company of Weijia special chemicals in the Nanshan region of Shenzhen. The curing accelerator is 2-ethyl-4-methylimidazole, and the 2-ethyl-4-methylimidazole is purchased from Jinchuan chemical Co., Ltd, Jinan, and has a CAS number of 931-36-2. The filler is mica powder, the particle size of the mica powder is 325 meshes, and the mica powder is purchased from a processing plant of Shengtai mineral products in Lingshou county and has the brand number of 325 meshes. The antioxidant is selected from antioxidant 1010, and the antioxidant 1010 is purchased from Gaozogalping Co., Ltd.
The second aspect of this embodiment provides a method for preparing the dual-curing flexible epoxy glue, including the following steps:
(1) mixing 100 parts of toughened epoxy resin, 15 parts of diluent, 2 parts of filler and 0.5 part of antioxidant into a stirring tank A, and stirring for 30min at the speed of 500r/min to obtain a component A;
(2) mixing 45 parts of curing agent and 10 parts of curing accelerator into a stirring tank B, and stirring for 30min under the condition of 500r/min to obtain a component B;
(3) mixing the component A and the component B at room temperature to obtain the product.
Comparative example 4
The dual-curing flexible epoxy adhesive comprises, by weight, 100 parts of toughened epoxy resin, 15 parts of diluent, 45 parts of composite curing agent, 10 parts of curing accelerator, 2 parts of filler and 0.5 part of antioxidant, wherein the toughened epoxy resin is polyether modified epoxy resin which is purchased from complex advanced materials (Shanghai) Limited company under the brand number: japanese ADEKA, epoxy equivalent 320 g/eq. The diluent is an ether solvent, the ether solvent is diglycidyl ether, the composite curing agent is a mixture of hexamethylene diamine and polyether amine, and the mass ratio of the hexamethylene diamine to the polyether amine is 1: 1. the polyether amine curing agent is polyether amine D220, and the polyether amine D220 is purchased from the special industrial product business of Weijia in the Nanshan region of Shenzhen. The curing accelerator is 2-ethyl-4-methylimidazole, and the 2-ethyl-4-methylimidazole is purchased from Jinchuan chemical Co., Ltd, Jinan, and has a CAS number of 931-36-2. The filler is mica powder, the particle size of the mica powder is 200 meshes, and the mica powder is purchased from a Gantai mineral product processing factory in Lingshou county and is 200 meshes in mark. The antioxidant is selected from antioxidant 1010, and the antioxidant 1010 is purchased from Gaozogalping Co., Ltd.
A second aspect of the present invention provides a method for preparing a dual-curing flexible epoxy glue, comprising the following steps:
(1) mixing 100 parts of toughened epoxy resin, 15 parts of diluent, 2 parts of filler and 0.5 part of antioxidant into a stirring tank A, and stirring for 30min under the condition of 500r/min to obtain a component A;
(2) mixing 45 parts of composite curing agent and 10 parts of curing accelerator into a stirring tank B, and stirring for 30min under the condition of 500r/min to obtain a component B;
(3) mixing the component A and the component B at room temperature to obtain the product.
Comparative example 5
The dual-curing flexible epoxy adhesive comprises, by weight, 100 parts of toughened epoxy resin, 15 parts of diluent, 45 parts of composite curing agent, 10 parts of curing accelerator, 2 parts of filler and 0.5 part of antioxidant, wherein the toughened epoxy resin is polyether modified epoxy resin which is purchased from complex advanced materials (Shanghai) Limited company under the brand number: japanese ADEKA, epoxy equivalent 320 g/eq. The diluent is an ether solvent, the ether solvent is diglycidyl ether, the composite curing agent is a mixture of hexamethylene diamine and polyether amine, and the mass ratio of the hexamethylene diamine to the polyether amine is 1: 1. the polyether amine curing agent is polyether amine D220, and the polyether amine D220 is purchased from the special industrial product business of Weijia in the Nanshan region of Shenzhen. The curing accelerator is 2-ethyl-4-methylimidazole, and the 2-ethyl-4-methylimidazole is purchased from Jinchuan chemical Co., Ltd, Jinan, and has a CAS number of 931-36-2. The filler is mica powder, the particle size of the mica powder is 500 meshes, and the mica powder is purchased from a Gantai mineral product processing factory in Lingshou county and has the grade of 500 meshes. The antioxidant is selected from antioxidant 1010, and the antioxidant 1010 is purchased from Gaozogalping Co., Ltd.
A second aspect of the present invention provides a method for preparing a dual-curing flexible epoxy glue, comprising the following steps:
(1) mixing 100 parts of toughened epoxy resin, 15 parts of diluent, 2 parts of filler and 0.5 part of antioxidant into a stirring tank A, and stirring for 30min at the speed of 500r/min to obtain a component A;
(2) mixing 45 parts of composite curing agent and 10 parts of curing accelerator into a stirring tank B, and stirring for 30min under the condition of 500r/min to obtain a component B;
(3) mixing the component A and the component B at room temperature to obtain the product.
Performance test
Performance test one
10 parts of each of the epoxy adhesives obtained in examples 1 to 2 and comparative examples 1 to 5 were prepared, gel time was measured with reference to GB12007.7-89 standard to characterize the curing rate thereof, and the average gel time in each example and comparative example was calculated, with gel times of less than 60min being recorded as passed and gel times of greater than 60min being recorded as failed.
Performance test 2
The fully cured epoxy adhesives obtained in examples 1-2 and comparative examples 1-5 were subjected to an impact toughness test to evaluate flexibility of the epoxy adhesives with reference to the GB/T1451-2005 standard, 10 specimens were tested in each example and comparative example, and an average value of 10 specimens was calculated, with an impact toughness of 235J/M or more being recorded as an impact toughness pass and an impact toughness of less than 235J/M being recorded as an impact toughness fail.
Gel time Impact toughness
Example 1 Qualified Qualified
Example 2 Qualified Qualified
Comparative example 1 Qualified Fail to be qualified
Comparative example 2 Fail to be qualified Fail to be qualified
Comparative example 3 Fail to be qualified Qualified
Comparative example 4 Qualified Fail to be qualified
Comparative example 5 Qualified Fail to be qualified
According to the data, the inventor can increase the impact toughness and flexibility of the whole material by applying the polyether modified epoxy resin, the practicability of the whole material is improved, the whole material has higher curing speed by compounding different curing agents, and the efficiency of epoxy glue bonding devices is improved.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.

Claims (10)

1. The dual-curing flexible epoxy adhesive is characterized by comprising, by weight, 80-120 parts of toughened epoxy resin, 1-30 parts of diluent, 20-55 parts of composite curing agent, 5-15 parts of curing accelerator, 1-3 parts of filler and 0.5-2 parts of antioxidant, wherein the toughened epoxy resin is polyether modified epoxy resin.
2. The dual-curing flexible epoxy adhesive as claimed in claim 1, wherein the epoxy equivalent of the polyether modified epoxy resin is 300-400 g/eq.
3. The dual cure flexible epoxy glue of claim 1 or 2, wherein the diluent is an ether solvent.
4. The dual cure flexible epoxy glue of claim 3, wherein the ether solvent is selected from at least one of diglycidyl ether, polyglycidyl ether, propylene oxide butyl ether, propylene oxide phenyl ether, propylene oxide ethyl ether, and propylene oxide propyl ether.
5. The dual cure flexible epoxy glue of claim 1, wherein the composite curing agent is selected from at least one of aliphatic amines, alicyclic amines, and aromatic amines.
6. The dual cure flexible epoxy glue of claim 5, wherein the aliphatic amine is selected from at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, and polyetheramine.
7. The dual cure flexible epoxy glue of claim 1, wherein the curing accelerator comprises an imidazole group in a molecule.
8. The dual-curing flexible epoxy adhesive as claimed in claim 1, wherein the filler has a particle size of 300-400 mesh.
9. The dual cure flexible epoxy glue of claim 1, wherein the antioxidant is selected from the group consisting of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 1024, antioxidant 697, antioxidant 565, antioxidant DSTDP, antioxidant DLTDP, antioxidant 618, antioxidant 168, antioxidant 626.
10. A method for preparing a dual cure flexible epoxy glue according to any of claims 1-9, characterized in that it comprises at least the following steps:
(1) mixing 80-120 parts of toughened epoxy resin, 1-30 parts of diluent, 1-3 parts of filler and 0.5-2 parts of antioxidant into a stirring tank A, and stirring to obtain a component A;
(2) mixing 20-55 parts of composite curing agent and 5-15 parts of curing accelerator into a stirring tank B, and stirring to obtain a component B;
(3) mixing the component A and the component B at room temperature to obtain the product.
CN202110381344.1A 2021-04-09 2021-04-09 Dual-curing flexible epoxy adhesive and preparation method thereof Withdrawn CN114539957A (en)

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CN114539957A true CN114539957A (en) 2022-05-27

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Application publication date: 20220527