CN112300741A - Epoxy adhesive with high elongation at break and high tensile strength and capable of being rapidly cured and preparation method thereof - Google Patents
Epoxy adhesive with high elongation at break and high tensile strength and capable of being rapidly cured and preparation method thereof Download PDFInfo
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- CN112300741A CN112300741A CN202011281046.7A CN202011281046A CN112300741A CN 112300741 A CN112300741 A CN 112300741A CN 202011281046 A CN202011281046 A CN 202011281046A CN 112300741 A CN112300741 A CN 112300741A
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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
- C09J11/06—Non-macromolecular additives organic
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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
Abstract
The invention discloses a high-elongation-at-break and high-tensile-strength epoxy adhesive capable of being rapidly cured, which comprises a component A and a component B; the component A comprises bisphenol F type epoxy resin, polyphenoxy resin, low molecular weight solid epoxy resin, a diluent and a silane coupling agent; the component B comprises modified fatty amine, thiol monomer, polythiol and accelerator; the epoxy adhesive is cured at 25 ℃, and has ShoreD 60-80, the tensile strength is more than 10MPa, the elongation at break is up to more than 100%, and the epoxy adhesive has strong tensile shear strength to stainless steel, cold-rolled steel and aluminum base materials and good bonding strength to PC and ABS; meanwhile, the epoxy adhesive contains lower halogen, the total chlorine content is lower than 700ppm, and the epoxy adhesive has good humidity, heat and aging resistance and creep resistance; therefore, the epoxy adhesive with high elongation at break and high tensile strength, which can be rapidly cured, has wide application prospects in the electronic industry and the general industry, and can show strong competitiveness in the market.
Description
Technical Field
The invention relates to the field of room-temperature fast curing adhesives, in particular to a fast-curing epoxy adhesive with high elongation at break and high tensile strength.
Background
Epoxy adhesives have emerged to date from around 1950, only for over 50 years. However, with the successive proposition of various bonding theories in the middle of the 20 th century and the deep progress of basic research works such as adhesive chemistry, adhesive rheology, adhesive failure mechanism and the like, the performance, variety and application of the adhesive have been developed dramatically. The epoxy resin and the curing system thereof have unique and excellent performance, and the continuous emergence of novel epoxy resin, novel curing agent and additive, so that the epoxy resin and the curing system thereof become important adhesives with excellent performance, various varieties and wide adaptability. Meanwhile, the epoxy adhesive has the advantages of sufficient and easily-obtained raw materials, simple manufacturing process and excellent performance, and is widely applied to the fields of aviation, aerospace, weapons, electronic and electrical appliances, machinery, buildings, vehicles and daily life of people.
As is well known, bisphenol a epoxy resin, bisphenol F epoxy resin and the like which are commonly used in the market at present are linear structures, and when reacting with a curing agent, a three-dimensional network structure with a complex form is generated by reaction according to different structures of the curing agent, and the characteristics of high hardness and high brittleness are shown.
In the current market, most epoxy adhesives have elongation of no more than 25 percent and slow curing speed, and cannot meet the flexibility requirements of the industry and other specific industries, and a patent CN108546535A (an epoxy resin adhesive with high elongation at break) discloses an epoxy resin adhesive with high elongation at break, wherein the problems of slow curing speed and relatively weak tensile strength exist although the elongation at break reaches 170 percent and the tensile strength reaches 5 MPa. Therefore, in order to meet the requirements of high elongation, high body tensile strength and high curing speed of epoxy adhesives on the market, the epoxy adhesive with high breaking elongation and high tensile strength, which can be cured quickly, needs to be developed.
Disclosure of Invention
In order to meet the market requirements for epoxy adhesives with high curing speed, high elongation at break and high tensile strength, for example, the epoxy adhesives with high elongation at break and high tensile strength, which can be cured quickly, are required in the filter industry to bond the middle joint of the filter element of the product, the invention provides a novel epoxy adhesive with high elongation at break and high tensile strength, which can be cured quickly, and is used for meeting the requirements of quick curing speed, high elongation at break and high tensile strength in application occasions and other specific occasions.
In order to achieve the purpose, the invention provides the following technical scheme:
the utility model provides a high elongation at break, high tensile strength epoxy gluing agent that can fast cure which characterized in that: comprises a component A and a component B; wherein the component A comprises bisphenol F type epoxy resin, polyphenoxy resin, low molecular weight solid epoxy resin, a diluent and a silane coupling agent; the component B comprises modified fatty amine, thiol monomer, polythiol and accelerator.
In a further preferred embodiment, the mass ratio of the component A to the component B is 1: 1.
In a further preferred embodiment, the component A consists of 30 to 60wt% of bisphenol F type epoxy resin, 10 to 30wt% of polyphenol oxygen resin, 10 to 30wt% of low molecular weight solid epoxy resin, 5 to 25wt% of diluent and 1 to 5wt% of silane coupling agent based on the total mass of the component A.
In a further preferred embodiment, the component B consists of 30 to 55wt% of modified fatty amine, 10 to 30wt% of thiol monomer, 30 to 55wt% of polythiol and 1 to 10wt% of accelerator based on the total mass of the component B.
In a further preferred embodiment, the phenoxy resin is any one or combination of more of PKHM-85, PKHM-30, PKHM-301, PXCP-67, PXCP-80, JER-1256, JER-4250.
In a further preferred embodiment, the low molecular weight solid epoxy resin is any one or more of DER671, DER662E, DER663U and DER 664U.
In a further preferred embodiment, the diluent is at least one or more of dibromoneopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil triglycidyl ether and pentaerythritol tetraglycidyl ether.
In a further preferred embodiment, the silane coupling agent is gamma-epoxypropyletherpropyltriethoxysilane.
In a further preferred embodiment, the modified fatty amine is at least one or more of Ancamide2741, Ancamide 2727, Ancamide 2914, Sunmide CX-1151, Ancamide 1636, and Ancamide 1922.
In a further preferred embodiment, the thiol monomer is at least one or more of ethanethiol, propanethiol, 2- (1, 2-ethanediylbis-oxo) bisethanethiol, 2-thiobis (ethanethiol), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) ester.
In a further preferred embodiment, the polythiol is at least one or more of Capcure 3-800, Capcure 3830-CB, Capcure40SEC HV, JH-9044S, JH-3380S, JH-3380M.
In a further preferred embodiment, the accelerator is at least one or a combination of 2, 4, 6-tris (dimethylaminomethyl) phenol, resorcinol, salicylic acid, triphenylphosphine, 1, 8-diazabicycloundec-7-ene.
The invention also provides a method for preparing the epoxy adhesive with high elongation at break and high tensile strength, which can be rapidly cured, and the method comprises the following steps:
(1) preparation of component A
The preparation method comprises the following steps of: 30-60 wt% of bisphenol F type epoxy resin, 10-30 wt% of polyphenol oxygen resin, 10-30 wt% of low molecular weight solid epoxy resin, 5-25 wt% of diluent and 1-5 wt% of silane coupling agent;
pouring bisphenol F epoxy resin into a stirring kettle in advance, heating to 130 ℃, grinding low molecular weight solid epoxy, adding into the stirring kettle, starting stirring for 500 r/min-800 r/min, heating to 200 ℃ after complete melting, adding poly phenol-oxygen resin, starting stirring for 500 r/min-800 r/min, cooling to normal temperature after complete melting to obtain modified epoxy resin;
thirdly, adding the modified epoxy resin, the diluent and the silane coupling agent into a stirring kettle, stirring at the normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain a component A;
(2) preparation of component B
The raw materials are prepared according to the components and the parts by weight: 30-55 wt% of modified fatty amine, 10-30 wt% of mercaptan monomer, 30-55 wt% of polythiol and 1-10 wt% of accelerator.
Adding modified fatty amine, thiol monomer, polythiol and accelerant into a stirring kettle, stirring at normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then carrying out vacuum defoaming to obtain a component B;
(3) according to the mass ratio of the main agent of the epoxy resin of the component A to the epoxy curing agent of the component B of 1: and 1, selecting the A component epoxy resin main agent and the B component epoxy curing agent, and fully mixing to obtain the epoxy adhesive with high elongation at break and high tensile strength, which can be rapidly cured.
Compared with the prior art, the invention has the following beneficial effects:
1) the epoxy adhesive disclosed by the invention introduces the polyphenoxy resin, and the polyphenoxy resin and the epoxy resin can be well and stably dissolved mutually by using a hot melting process.
2) The epoxy adhesive has the advantages that the initial binding power forming time is 10-15 min at 25 ℃, the cured ShoreD 60-70 has the tensile strength of more than 10MPa, and the elongation at break is up to more than 100%.
3) The epoxy adhesive has stronger tensile shear strength to metal base materials such as stainless steel, cold-rolled steel and aluminum base materials;
4) the epoxy adhesive disclosed by the invention contains lower halogen, has the total chlorine content lower than 700ppm, and has good damp-heat aging resistance and creep resistance.
Detailed Description
The technical solution of the present invention will be clearly and completely described by the following detailed description.
Example 1
(1) Preparation of component A
The preparation method comprises the following steps of: 42 parts by weight of a bisphenol F type epoxy resin, 10 parts by weight of a polyphenol oxygen resin, 30 parts by weight of a low molecular weight solid epoxy resin, 16 parts by weight of a diluent, and 2 parts by weight of a silane coupling agent.
Pouring bisphenol F epoxy resin into a stirring kettle in advance, heating to 130 ℃, grinding low molecular weight solid epoxy, adding into the stirring kettle, starting stirring for 500 r/min-800 r/min, heating to 200 ℃ after complete melting, adding poly phenol-oxygen resin, starting stirring for 500 r/min-800 r/min, cooling to normal temperature after complete melting, and taking the mixture as modified epoxy resin.
Thirdly, adding the modified epoxy resin, the diluent and the silane coupling agent into a stirring kettle, stirring at the normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain the component A.
(2) Preparation of component B
The preparation method comprises the following steps of: 51 parts by weight of modified fatty amine, 15 parts by weight of thiol monomer, 30 parts by weight of polythiol and 4 parts by weight of accelerator.
Secondly, adding the modified aliphatic amine, the mercaptan monomer, the polythiol and the accelerant into a stirring kettle, stirring at normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain a component B.
(3) When in use, the mass ratio of the main agent of the epoxy resin of the component A to the epoxy curing agent of the component B is 1: and 1, selecting the A component epoxy resin main agent and the B component epoxy curing agent, and fully mixing to obtain the epoxy adhesive with high elongation at break and high tensile strength, which can be rapidly cured.
Example 2
(1) Preparation of component A
The preparation method comprises the following steps of: 36 parts by weight of a bisphenol F type epoxy resin, 15 parts by weight of a polyphenol oxygen resin, 29 parts by weight of a low molecular weight solid epoxy resin, 16 parts by weight of a diluent and 2 parts by weight of a silane coupling agent.
Pouring bisphenol F epoxy resin into a stirring kettle in advance, heating to 130 ℃, grinding low molecular weight solid epoxy, adding into the stirring kettle, starting stirring for 500 r/min-800 r/min, heating to 200 ℃ after complete melting, adding poly phenol-oxygen resin, starting stirring for 500 r/min-800 r/min, cooling to normal temperature after complete melting, and taking the mixture as modified epoxy resin.
Thirdly, adding the modified epoxy resin, the diluent and the silane coupling agent into a stirring kettle, stirring at the normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain the component A.
(2) Preparation of component B
The preparation method comprises the following steps of: 39 parts by weight of modified fatty amine, 19 parts by weight of thiol monomer, 38 parts by weight of polythiol and 4 parts by weight of accelerator.
Secondly, adding the modified aliphatic amine, the mercaptan monomer, the polythiol and the accelerant into a stirring kettle, stirring at normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain a component B.
(3) When in use, the mass ratio of the main agent of the epoxy resin of the component A to the epoxy curing agent of the component B is 1: and 1, selecting the A component epoxy resin main agent and the B component epoxy curing agent, and fully mixing to obtain the epoxy adhesive with high elongation at break and high tensile strength, which can be rapidly cured.
Example 3
(1) Preparation of component A
The preparation method comprises the following steps of: 32 parts by weight of a bisphenol F type epoxy resin, 20 parts by weight of a polyphenol oxygen resin, 27 parts by weight of a low molecular weight solid epoxy resin, 18 parts by weight of a diluent, and 2 parts by weight of a silane coupling agent.
Pouring bisphenol F epoxy resin into a stirring kettle in advance, heating to 130 ℃, grinding low molecular weight solid epoxy, adding into the stirring kettle, starting stirring for 500 r/min-800 r/min, heating to 200 ℃ after complete melting, adding poly phenol-oxygen resin, starting stirring for 500 r/min-800 r/min, cooling to normal temperature after complete melting, and taking the mixture as modified epoxy resin.
Thirdly, adding the modified epoxy resin, the diluent and the silane coupling agent into a stirring kettle, stirring at the normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain the component A.
(2) Preparation of component B
The preparation method comprises the following steps of: 30 parts by weight of modified fatty amine, 23 parts by weight of thiol monomer, 43 parts by weight of polythiol and 4 parts by weight of accelerator.
Secondly, adding the modified aliphatic amine, the mercaptan monomer, the polythiol and the accelerant into a stirring kettle, stirring at normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain a component B.
(3) When in use, the mass ratio of the main agent of the epoxy resin of the component A to the epoxy curing agent of the component B is 1: and 1, selecting the A component epoxy resin main agent and the B component epoxy curing agent, and fully mixing to obtain the epoxy adhesive with high elongation at break and high tensile strength, which can be rapidly cured.
Example 4
(1) Preparation of component A
The preparation method comprises the following steps of: 26 parts by weight of a bisphenol F type epoxy resin, 25 parts by weight of a polyphenol oxy resin, 25 parts by weight of a low molecular weight solid epoxy resin, 22 parts by weight of a diluent, and 2 parts by weight of a silane coupling agent.
Pouring bisphenol F epoxy resin into a stirring kettle in advance, heating to 130 ℃, grinding low molecular weight solid epoxy, adding into the stirring kettle, starting stirring for 500 r/min-800 r/min, heating to 200 ℃ after complete melting, adding poly phenol-oxygen resin, starting stirring for 500 r/min-800 r/min, cooling to normal temperature after complete melting, and taking the mixture as modified epoxy resin.
Thirdly, adding the modified epoxy resin, the diluent and the silane coupling agent into a stirring kettle, stirring at the normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain the component A.
(2) Preparation of component B
The preparation method comprises the following steps of: 27 parts by weight of a modified fatty amine, 26 parts by weight of a thiol monomer, 43 parts by weight of a polythiol and 4 parts by weight of an accelerator.
Secondly, adding the modified aliphatic amine, the mercaptan monomer, the polythiol and the accelerant into a stirring kettle, stirring at normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain a component B.
(3) When in use, the mass ratio of the main agent of the epoxy resin of the component A to the epoxy curing agent of the component B is 1: and 1, selecting the A component epoxy resin main agent and the B component epoxy curing agent, and fully mixing to obtain the epoxy adhesive with high elongation at break and high tensile strength, which can be rapidly cured.
Example 5
(1) Preparation of component A
The preparation method comprises the following steps of: 22 parts by weight of a bisphenol F type epoxy resin, 30 parts by weight of a polyphenol oxygen resin, 22 parts by weight of a low molecular weight solid epoxy resin, 24 parts by weight of a diluent, and 2 parts by weight of a silane coupling agent.
Pouring bisphenol F epoxy resin into a stirring kettle in advance, heating to 130 ℃, grinding low molecular weight solid epoxy, adding into the stirring kettle, starting stirring for 500 r/min-800 r/min, heating to 200 ℃ after complete melting, adding poly phenol-oxygen resin, starting stirring for 500 r/min-800 r/min, cooling to normal temperature after complete melting, and taking the mixture as modified epoxy resin.
Thirdly, adding the modified epoxy resin, the diluent and the silane coupling agent into a stirring kettle, stirring at the normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain the component A.
(2) Preparation of component B
The preparation method comprises the following steps of: 20 parts by weight of modified fatty amine, 30 parts by weight of thiol monomer, 47 parts by weight of polythiol and 4 parts by weight of accelerator.
Secondly, adding the modified aliphatic amine, the mercaptan monomer, the polythiol and the accelerant into a stirring kettle, stirring at normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain a component B.
(3) When in use, the mass ratio of the main agent of the epoxy resin of the component A to the epoxy curing agent of the component B is 1: and 1, selecting the A component epoxy resin main agent and the B component epoxy curing agent, and fully mixing to obtain the epoxy adhesive with high elongation at break and high tensile strength, which can be rapidly cured.
Example 6
(1) Preparation of component A
The preparation method comprises the following steps of: 60 parts by weight of a bisphenol F type epoxy resin, 30 parts by weight of a polyphenol oxygen resin, 30 parts by weight of a low molecular weight solid epoxy resin, 25 parts by weight of a diluent, and 5 parts by weight of a silane coupling agent.
Pouring bisphenol F epoxy resin into a stirring kettle in advance, heating to 130 ℃, grinding low molecular weight solid epoxy, adding into the stirring kettle, starting stirring for 500 r/min-800 r/min, heating to 200 ℃ after complete melting, adding poly phenol-oxygen resin, starting stirring for 500 r/min-800 r/min, cooling to normal temperature after complete melting, and taking the mixture as modified epoxy resin.
Thirdly, adding the modified epoxy resin, the diluent and the silane coupling agent into a stirring kettle, stirring at the normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain the component A.
(2) Preparation of component B
The preparation method comprises the following steps of: 55 parts by weight of modified fatty amine, 10 parts by weight of thiol monomer, 55 parts by weight of polythiol and 1 part by weight of accelerator.
Secondly, adding the modified aliphatic amine, the mercaptan monomer, the polythiol and the accelerant into a stirring kettle, stirring at normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain a component B.
(3) When in use, the mass ratio of the main agent of the epoxy resin of the component A to the epoxy curing agent of the component B is 1: and 1, selecting the A component epoxy resin main agent and the B component epoxy curing agent, and fully mixing to obtain the epoxy adhesive with high elongation at break and high tensile strength, which can be rapidly cured.
Example 7
(1) Preparation of component A
The preparation method comprises the following steps of: 30 parts by weight of bisphenol F type epoxy resin, 10 parts by weight of polyphenoxy resin, 10 parts by weight of low molecular weight solid epoxy resin, 5 parts by weight of diluent and 1 part by weight of silane coupling agent.
Pouring bisphenol F epoxy resin into a stirring kettle in advance, heating to 130 ℃, grinding low molecular weight solid epoxy, adding into the stirring kettle, starting stirring for 500 r/min-800 r/min, heating to 200 ℃ after complete melting, adding poly phenol-oxygen resin, starting stirring for 500 r/min-800 r/min, cooling to normal temperature after complete melting, and taking the mixture as modified epoxy resin.
Thirdly, adding the modified epoxy resin, the diluent and the silane coupling agent into a stirring kettle, stirring at the normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain the component A.
(2) Preparation of component B
The preparation method comprises the following steps of: 30 parts by weight of modified fatty amine, 30 parts by weight of thiol monomer, 45 parts by weight of polythiol and 10 parts by weight of accelerator.
Secondly, adding the modified aliphatic amine, the mercaptan monomer, the polythiol and the accelerant into a stirring kettle, stirring at normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain a component B.
(3) When in use, the mass ratio of the main agent of the epoxy resin of the component A to the epoxy curing agent of the component B is 1: and 1, selecting the A component epoxy resin main agent and the B component epoxy curing agent, and fully mixing to obtain the epoxy adhesive with high elongation at break and high tensile strength, which can be rapidly cured.
Comparative example 1
(1) Preparation of component A
The preparation method comprises the following steps of: 52 parts by weight of a bisphenol F type epoxy resin, 30 parts by weight of a low molecular weight solid epoxy resin, 16 parts by weight of a diluent, and 2 parts by weight of a silane coupling agent.
Secondly, pouring bisphenol F epoxy resin into a stirring kettle in advance, heating to 130 ℃, grinding low molecular weight solid epoxy, adding into the stirring kettle, starting stirring for 500 r/min-800 r/min, cooling to normal temperature after complete melting, and taking the epoxy resin as modified epoxy resin.
Thirdly, adding the modified epoxy resin, the diluent and the silane coupling agent into a stirring kettle, stirring at the normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain the component A.
(2) Preparation of component B
The preparation method comprises the following steps of: 51 parts by weight of modified fatty amine, 15 parts by weight of thiol monomer, 30 parts by weight of polythiol and 4 parts by weight of accelerator.
Secondly, adding the modified aliphatic amine, the mercaptan monomer, the polythiol and the accelerant into a stirring kettle, stirring at normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain a component B.
(3) When in use, the mass ratio of the main agent of the epoxy resin of the component A to the epoxy curing agent of the component B is 1:1, selecting the epoxy resin main agent of the component A and the epoxy curing agent of the component B, and fully mixing to obtain the epoxy adhesive.
Comparative example 2
(1) Preparation of component A
The preparation method comprises the following steps of: 52 parts by weight of a bisphenol F type epoxy resin, 30 parts by weight of a low molecular weight solid epoxy resin, 16 parts by weight of a diluent, and 2 parts by weight of a silane coupling agent.
Secondly, pouring bisphenol F epoxy resin into a stirring kettle in advance, heating to 130 ℃, grinding low molecular weight solid epoxy, adding into the stirring kettle, starting stirring for 500 r/min-800 r/min, cooling to normal temperature after complete melting, and taking the epoxy resin as modified epoxy resin.
Thirdly, adding the modified epoxy resin, the diluent and the silane coupling agent into a stirring kettle, stirring at the normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain the component A.
(2) Preparation of component B
The preparation method comprises the following steps of: 96 parts of modified fatty amine and 4 parts of accelerator.
Secondly, adding the modified fatty amine and the accelerant into a stirring kettle, stirring at the normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain a component B.
(3) When in use, the mass ratio of the main agent of the epoxy resin of the component A to the epoxy curing agent of the component B is 1:1, selecting the epoxy resin main agent of the component A and the epoxy curing agent of the component B, and fully mixing to obtain the epoxy adhesive.
The epoxy adhesives with high elongation at break and high tensile strength, which can be rapidly cured, obtained in examples 1,2, 3, 4, 5, 1 and 2 of the present application were tested as comparative examples, and the test methods were as follows:
tensile strength test method: GB1040.1-2006 determination of tensile properties of plastics;
the shear strength test method comprises the following steps: GB/T7124 and 2008 adhesive tensile shear strength (rigid material to rigid material);
elongation at break test method: GB1040.1-2006 determination of tensile properties of plastics;
the hardness test method comprises the following steps: GB/T2411-2008 plastic and hard rubber indentation hardness (Shore hardness) was determined using a durometer. The test data are shown in the following table:
the comparison between the examples and the comparative examples shows that the elongation at break and the tensile strength of the epoxy adhesive of the present invention are significantly increased.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention.
Claims (14)
1. The utility model provides a high elongation at break, high tensile strength epoxy gluing agent that can fast cure which characterized in that: comprises a component A and a component B; wherein the component A comprises bisphenol F type epoxy resin, polyphenoxy resin, low molecular weight solid epoxy resin, a diluent and a silane coupling agent; the component B comprises modified fatty amine, thiol monomer, polythiol and accelerator.
2. The epoxy adhesive with high elongation at break and high tensile strength capable of being rapidly cured according to claim 1, wherein: the mass ratio of the component A to the component B is 1: 1.
3. The epoxy adhesive with high elongation at break and high tensile strength capable of being rapidly cured according to claim 1, wherein: based on the total mass of the component A, the component A is composed of 30-60 wt% of bisphenol F type epoxy resin, 10-30 wt% of poly phenol-oxygen resin, 10-30 wt% of low molecular weight solid epoxy resin, 5-25 wt% of diluent and 1-5 wt% of silane coupling agent.
4. The epoxy adhesive with high elongation at break and high tensile strength capable of being rapidly cured according to claim 1, wherein: based on the total mass of the component B, the component B consists of 30-55 wt% of modified fatty amine, 10-30 wt% of mercaptan monomer, 30-55 wt% of polythiol and 1-10 wt% of accelerator.
5. The epoxy adhesive with high elongation at break and high tensile strength capable of being rapidly cured according to claim 1, wherein: the polyphenolic oxygen resin is any one or combination of more of PKHM-85, PKHM-30, PKHM-301, PXCP-67, PXCP-80, JER-1256 and JER-4250.
6. The epoxy adhesive with high elongation at break and high tensile strength capable of being rapidly cured according to claim 1, wherein: the low molecular weight solid epoxy resin is any one or combination of DER671, DER662E, DER663U and DER 664U.
7. The epoxy adhesive with high elongation at break and high tensile strength capable of being rapidly cured according to claim 1, wherein: the diluent is at least one or a combination of more of dibromo neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil triglycidyl ether and pentaerythritol tetraglycidyl ether.
8. The epoxy adhesive with high elongation at break and high tensile strength capable of being rapidly cured according to claim 1, wherein: the silane coupling agent is gamma-epoxypropyl ether propyl triethoxysilane.
9. The epoxy adhesive with high elongation at break and high tensile strength capable of being rapidly cured according to claim 1, wherein: the modified fatty amine is at least one or a combination of Ancamide2741, Ancamide 2727, Ancamide 2914, Sunmide CX-1151, Ancamine1636 and Ancamine 1922.
10. The epoxy adhesive with high elongation at break and high tensile strength capable of being rapidly cured according to claim 1, wherein: the mercaptan monomer is at least one or a combination of more of ethanethiol, propanethiol, 2- (1, 2-ethanediylbis oxo) bisethanethiol, 2-thiobis (ethanethiol), trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptopropionate).
11. The epoxy adhesive with high elongation at break and high tensile strength capable of being rapidly cured according to claim 1, wherein: the polythiol is at least one or a combination of more of Capcure 3-800, Capcure 3830-CB, Capcure40SEC HV and JH-9044S, JH-3380S, JH-3380M.
12. The epoxy adhesive with high elongation at break and high tensile strength capable of being rapidly cured according to claim 1, wherein: the accelerator is at least one or a combination of 2, 4, 6-tri (dimethylaminomethyl) phenol, resorcinol, salicylic acid, triphenylphosphine and 1, 8-diazabicycloundecan-7-ene.
13. The method for preparing the epoxy adhesive with high elongation at break and high tensile strength, which can be rapidly cured, according to claim 1, is characterized in that: the method comprises the following steps:
(1) preparation of component A
The preparation method comprises the following steps of: 30-60 wt% of bisphenol F type epoxy resin, 10-30 wt% of polyphenol oxygen resin, 10-30 wt% of low molecular weight solid epoxy resin, 5-25 wt% of diluent and 1-5 wt% of silane coupling agent;
pouring bisphenol F epoxy resin into a stirring kettle in advance, heating to 130 ℃, grinding low molecular weight solid epoxy, adding into the stirring kettle, starting stirring for 500 r/min-800 r/min, heating to 200 ℃ after complete melting, adding poly phenol-oxygen resin, starting stirring for 500 r/min-800 r/min, cooling to normal temperature after complete melting to obtain modified epoxy resin;
thirdly, adding the modified epoxy resin, the diluent and the silane coupling agent into a stirring kettle, stirring at the normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then performing vacuum defoaming to obtain a component A;
(2) preparation of component B
The raw materials are prepared according to the components and the parts by weight: 30-55 wt% of modified fatty amine, 10-30 wt% of mercaptan monomer, 30-55 wt% of polythiol and 1-10 wt% of accelerator.
14. Adding modified fatty amine, thiol monomer, polythiol and accelerant into a stirring kettle, stirring at normal temperature for 25-30 min at the rotating speed of 500-800 r/min, and then carrying out vacuum defoaming to obtain a component B;
(3) according to the mass ratio of the main agent of the epoxy resin of the component A to the epoxy curing agent of the component B of 1: and 1, selecting the A component epoxy resin main agent and the B component epoxy curing agent, and fully mixing to obtain the epoxy adhesive with high elongation at break and high tensile strength, which can be rapidly cured.
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