CN113896863A - Epoxy resin glass high polymer material, three-component epoxy solution, preparation method and application - Google Patents

Epoxy resin glass high polymer material, three-component epoxy solution, preparation method and application Download PDF

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CN113896863A
CN113896863A CN202111318105.8A CN202111318105A CN113896863A CN 113896863 A CN113896863 A CN 113896863A CN 202111318105 A CN202111318105 A CN 202111318105A CN 113896863 A CN113896863 A CN 113896863A
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epoxy
compound
polymer material
epoxy resin
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邓煜东
闫磊
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Jiangsu Fuqisen New Materials Co ltd
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    • 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
    • C08G59/5033—Amines aromatic
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • 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
    • C08G59/5006—Amines aliphatic
    • C08G59/5013—Amines aliphatic containing more than seven carbon atoms, e.g. fatty amines
    • 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
    • C08G59/5026—Amines cycloaliphatic
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C09J163/10—Epoxy resins modified by unsaturated compounds

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Epoxy Resins (AREA)

Abstract

The embodiment of the application provides an epoxy resin glass high polymer material, a three-component epoxy solution, a preparation method and an application, and relates to the field of high polymer resin. The epoxy resin glass polymer material is mainly obtained by reacting an epoxy compound, an amine compound and a propiolic acid ester compound. The preparation method of the epoxy resin glass polymer material mainly comprises the steps of dissolving an epoxy compound, an amine compound and a propiolic acid ester compound in a solvent, removing the solvent and reacting at 100-130 ℃. The epoxy resin glass polymer material is easy to prepare and obtain, has excellent mechanical strength and can be recycled.

Description

Epoxy resin glass high polymer material, three-component epoxy solution, preparation method and application
Technical Field
The application relates to the field of polymer resin, in particular to an epoxy resin glass polymer material, a three-component epoxy solution, a preparation method and application.
Background
The waste high polymer materials cause global environmental pollution and resource waste, however, due to the lack of effective recycling technology, the recovery rate of the high polymer materials is less than 10%. In particular, epoxy resins, although having excellent properties, can be used for the production of a variety of articles of daily use, some types of epoxy resins are not recyclable. For example, thermosetting epoxy resin has a dense three-dimensional network structure and high mechanical strength, but is difficult to melt, dissolve and degrade, and recycling of the thermosetting epoxy resin is a difficult problem to be solved.
Most of the thermosetting epoxy resins reported at present degrade the epoxy resin into small molecules under high temperature and high pressure, but the reaction selectivity is poor, so that the product composition is complex and difficult to reuse. In recent years, epoxy resin systems with high mechanical strength and recyclability have been continuously studied, and most commonly, epoxy-carboxylic acid systems are obtained by a catalytic method by adding metal zinc ions, and cannot be obtained by a reaction in the absence of a catalyst.
Disclosure of Invention
The embodiment of the application aims to provide an epoxy resin glass high polymer material, a three-component epoxy solution, a preparation method and an application.
In a first aspect, the present application provides an epoxy glass polymer material, which is mainly obtained by reacting an epoxy compound, an amine compound, and a propiolic acid ester compound.
In the technical scheme, three specific components are selected for reaction, the amine compound enables an epoxy group in the epoxy compound to be subjected to ring opening, and an acetylene bond of the acrylate compound can react with secondary amine subjected to ring opening of the epoxy group, so that a cross-linked network is formed; in addition, the acrylate compound and the amine compound are subjected to click reaction, and the formed secondary amine and epoxy are subjected to ring opening to form a cross-linked network structure, so that the material has excellent mechanical strength. Moreover, the chemical bonds (inter-vinyl ester bonds) in such a cross-linked network structure are not fixed, but are in dynamic equilibrium: namely, the chemical bond can be broken under a certain temperature condition, the material is in a molten state, and then reaches a certain temperature pressure condition, the chemical bond can be reformed and restored into a complete cross-linked network structure, so that the material can realize plastic processing when the temperature changes, has the functions of self-repairing, shape memory and processing molding, and can be recycled.
In one possible implementation, the epoxy compound is one or a mixture of two or more of ethylene glycol diglycidyl ether, poly (ethylene glycol) diglycidyl ether, poly (propylene glycol) diglycidyl ether, epoxidized soybean oil, triglycidyl isocyanurate, bisphenol F diglycidyl ether, and bisphenol a diglycidyl ether.
In the technical scheme, the epoxy compound provides an active epoxy bond and is easy to open a ring; but also can be crosslinked with other two components to form a crosslinked network structure.
In one possible implementation, the amine compound has the formula:
Figure BDA0003344464660000021
wherein, when n is 1, R1Is C2H4、C3H6、C4H8、C5H10、C6H12、C7H14、C8H16、C9H18、C10H20、C11H22、C12H24、(C2H4)2S2、(C6H4)2S2、C6H4、(C6H4)2、(C6H4)2CH2、C6H4(CH2)2、C6H4C2H4、C6H10Or (C)6H10)2CH2(ii) a When n is 2, R1Is (C)2H4)3N；
The amine compound is one or a mixture of more than two of the compounds with the structural formula.
In the technical scheme, the amine compound has polyamine groups and can provide a skeleton structure for forming a cross-linked network structure.
In one possible implementation, the propiolate compound has the formula:
Figure BDA0003344464660000031
wherein, when n is 1, R2Is C2H4、C3H6、C4H8、C5H10、C6H12、C7H14、C8H16、C9H18、C10H20、C11H22、C12H24、(C2H4)2S2、(C6H4)2S2、C6H4,(C6H4)2、(C6H4)2CH2、C6H10、(C6H10)2CH2Or (C)6H10)2C(CH3)2；
When n is 2, R2Is (C)2H4)3N、(C6H4)3CCH3Or (C)2H4)3CCH3；
When n is 3, R2Is that
Figure BDA0003344464660000032
The propiolate compound is one or a mixture of two or more of the compounds having the structural formula.
In the above technical scheme, the propiolate compound has a polypropionate group, and can provide a skeleton structure for forming a cross-linked network structure.
In one possible implementation mode, the molar ratio of the epoxy group of the epoxy compound, the amine group of the amine compound and the propiolate group of the propiolate compound is 1-2: 1-2: 1 to 2.
In a second aspect, an embodiment of the present application provides a method for preparing an epoxy resin glass polymer material provided in the first aspect, which mainly includes dissolving an epoxy compound, an amine compound, and a propiolate compound in a solvent, removing the solvent, and reacting at a high temperature of 100-130 ℃.
In the technical scheme, the preparation method is simple and does not need a catalyst.
In one possible implementation, the solvent is one or a mixture of two or more of dichloromethane, chloroform, tetrahydrofuran, acetone, methanol, ethanol, and butanone.
In the above technical scheme, the solvent can dissolve the above three components, thereby forming a reaction system.
In a third aspect, an embodiment of the present application provides an application of the epoxy resin glass polymer material provided in the first aspect, where the epoxy resin glass polymer material is used to form a resin product, and a melting point of the resin product is 110 to 150 ℃.
In the technical scheme, the resin product formed by the material has high mechanical strength and can realize plastic processing in a lower temperature range.
In a fourth aspect, the present application provides a three-component epoxy solution for preparing the epoxy resin glass polymer material provided in the first aspect, which includes a solvent, and an epoxy compound, an amine compound, and a propiolate compound dissolved in the solvent.
In a fifth aspect, the present application provides a use of the three-component epoxy solution provided in the fourth aspect, where the three-component epoxy solution is used as a coating or an adhesive.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and that those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is a nuclear magnetic spectrum of a propiolate compound in example 1 of the present application;
FIG. 2 is a drawing chart showing the results of recovering a resin layer of an epoxy resin based glass polymer material of example 1 of the present application for a plurality of times.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The epoxy resin glass polymer material, the three-component epoxy solution, the preparation method and the application of the epoxy resin glass polymer material and the three-component epoxy solution of the embodiment of the present application are specifically described below.
The embodiment of the application provides an epoxy resin glass high polymer material which is mainly obtained by reacting an epoxy compound, an amine compound and a propiolic acid ester compound.
In the embodiment of the present application, the epoxy compound is one or a mixture of two or more of ethylene glycol diglycidyl ether, poly (ethylene glycol) diglycidyl ether, poly (propylene glycol) diglycidyl ether, epoxidized soybean oil, triglycidyl isocyanurate, bisphenol F diglycidyl ether, and bisphenol a diglycidyl ether. In the present application, "above" and "below" include the present numbers. In one embodiment, the epoxy compound is ethylene glycol diglycidyl ether or poly (ethylene glycol) diglycidyl ether, or a mixture of poly (propylene glycol) diglycidyl ether and epoxidized soybean oil, or a mixture of triglycidyl isocyanurate, bisphenol F diglycidyl ether, and bisphenol a diglycidyl ether.
In the examples of the present application, the structural formula of the amine compound is:
Figure BDA0003344464660000051
wherein, when n is 1, R1Is C2H4、C3H6、C4H8、C5H10、C6H12、C7H14、C8H16、C9H18、C10H20、C11H22、C12H24、(C2H4)2S2、(C6H4)2S2、C6H4、(C6H4)2、(C6H4)2CH2、C6H4(CH2)2、C6H4C2H4、C6H10Or (C)6H10)2CH2(ii) a When n is 2, R1Is (C)2H4)3N。
The amine compound is one or a mixture of more than two of the compounds with the structural formula. As an embodiment, the amine compound is
Figure BDA0003344464660000052
n＝1，R1Is C2H4And
Figure BDA0003344464660000053
n＝1，R1is C3H6A mixture of (a).
In the examples of the present application, the propiolate compound has the structural formula:
Figure BDA0003344464660000054
wherein, when n is 1, R2Is C2H4、C3H6、C4H8、C5H10、C6H12、C7H14、C8H16、C9H18、C10H20、C11H22、C12H24、(C2H4)2S2、(C6H4)2S2、C6H4,(C6H4)2、(C6H4)2CH2、C6H10、(C6H10)2CH2Or (C)6H10)2C(CH3)2(ii) a When n is 2, R2Is (C)2H4)3N、(C6H4)3CCH3Or (C)2H4)3CCH3(ii) a When n is 3, R2Is that
Figure BDA0003344464660000055
The propiolate compound is one or a mixture of two or more of the compounds having the structural formula. As an embodiment, the propiolate compound is
Figure BDA0003344464660000056
n＝1，R1Is C2H4And
Figure BDA0003344464660000061
n＝1，R1is C3H6A mixture of (a).
The propiolate compound can be purchased or manufactured by self, and in general, the propiolate compound is prepared by esterification reaction of polyalcohol and propiolic acid at room temperature, wherein the polyalcohol has a structural formula
Figure BDA0003344464660000062
The ratio of the total functionality of the polyol to the propiolic acid is 1: 1.5.
the embodiment of the application provides a preparation method of the epoxy resin glass polymer material, which is mainly characterized by dissolving an epoxy compound, an amine compound and a propiolic acid ester compound in a solvent, removing the solvent and reacting at a high temperature of 100-130 ℃. The mixing mode of the three components can be that the three components are mixed simultaneously, mixed two by two or the single components are added into the system respectively. The molar ratio of the epoxy group of the epoxy compound, the amino group of the amine compound and the propiolic acid ester group of the propiolic acid ester compound is 1-2: 1-2: 1 to 2.
The solvent is one or a mixture of more than two of dichloromethane, trichloromethane, tetrahydrofuran, acetone, methanol, ethanol and butanone.
The embodiment of the application also provides an application of the epoxy resin glass polymer material, the epoxy resin glass polymer material is used for forming a resin product, the material of the resin product is the epoxy resin glass polymer material, and the melting point of the resin product is usually 110-150 ℃. The recovery method of the resin product comprises the steps of crushing an original resin product, carrying out hot pressing at 110-150 ℃ and 2-10 MPa for 30-60 min, and matching with a corresponding die to obtain a new resin product, wherein the process is a one-step recovery; and repeating the recovery process to realize multiple recovery.
The embodiment of the application also provides a three-component epoxy solution for preparing the epoxy resin glass polymer material, which comprises a solvent, and an epoxy compound, an amine compound and a propiolate compound which are dissolved in the solvent.
The embodiment of the application also provides an application of the three-component epoxy solution, the three-component epoxy solution is used as a coating or an adhesive, and a coating film or an adhesive layer formed by curing the three-component epoxy solution is made of an epoxy resin glass high polymer material.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
The embodiment provides an epoxy resin glass polymer material resin layer, which is prepared according to the following preparation method:
according to the molar ratio of three groups of epoxy group in ethylene glycol diglycidyl ether, amido group in 1, 12-dodecane diamine and acrylate group in 1, 12-dodecane dipropionate being 1: 1: 1, sampling; mixing ethylene glycol diglycidyl ether, 1, 12-dodecanediamine and 1, 12-dodecanedipropionate, and adding a solvent dichloromethane into the mixed system.
After the solid raw materials in the system are dissolved, pouring the system into a polytetrafluoroethylene film with the thickness of 50mm x 2mm, standing at room temperature until the solvent is volatilized, standing overnight at the high temperature of 110 ℃, and demolding to obtain the epoxy resin glass polymer material resin layer.
The reaction formula of the process is as follows:
Figure BDA0003344464660000071
it should be noted that the right side of the reaction formula only represents that the schematic product is a cross-linked network structure, and does not represent the structural formula of the product.
The nuclear magnetic spectrum of the propiolate compound is shown in figure 1.
The epoxy resin glass polymer material resin layer (initial sample) prepared in the above is recycled for 3 times to obtain 1 recycled resin layer, 2 recycled resin layers and 3 recycled resin layers respectively, and the recycling mode for each time is as follows:
and (3) shearing 1g of the resin layer obtained last time, adding the resin layer into a hot press, and hot-pressing at 130 ℃ and 5MPa for 30min to obtain the recycled coating.
The resin layer prepared in the example 1 and the resin layer obtained by each recovery are subjected to a tensile test by adopting a tensile tester with the test standard of GB/T1039-; the test results are shown in FIG. 2: although the resin layer is thermosetting, it exhibits thermoplastic characteristics due to dynamic exchange of dynamic chemical bonds therein; after many times of recycling, the mechanical strength of the resin layer is hardly changed.
Example 2
The embodiment provides an epoxy resin glass polymer material resin layer, which is prepared according to the following preparation method:
according to the molar ratio of epoxy groups in poly (ethylene glycol) diglycidyl ether, amino groups in m-xylylenediamine and acrylate groups in bisphenol A dipropyl ester of 1: 1: 1, sampling; then poly (ethylene glycol) diglycidyl ether, m-xylylenediamine and bisphenol a dipropynyl ester are mixed, and then methylene chloride as a solvent is added to the system.
And after the solid is dissolved, pouring the system into a polytetrafluoroethylene film with the thickness of 50mm x 2mm, standing at room temperature until the solvent is volatilized, standing at the high temperature of 110 ℃ overnight, and demolding to obtain the epoxy resin glass polymer material resin layer.
The reaction formula of the process is as follows:
Figure BDA0003344464660000081
the epoxy resin glass polymer material resin layer obtained as described above was recovered 1 time in the same manner as in example 1, to obtain 1 recovered resin layer.
Example 3
The embodiment provides an epoxy resin glass polymer material resin layer, which is prepared according to the following preparation method:
according to the mol ratio of three groups of epoxy group in the epoxy soybean oil, amino group in cystamine and acrylate group in 1, 4-cyclohexyl dipropyl ester of 1: 1: 1, sampling; and mixing the epoxidized soybean oil, the cystamine and the 1, 4-cyclohexanedipropynyl ester, and adding a solvent dichloromethane into the system.
And after the solid is dissolved, pouring the system into a polytetrafluoroethylene film with the thickness of 50mm x 2mm, standing at room temperature until the solvent is volatilized, standing at the high temperature of 110 ℃ overnight, and demolding to obtain the epoxy resin glass polymer material resin layer.
The reaction formula of the process is as follows:
Figure BDA0003344464660000091
the epoxy resin glass polymer material resin layer obtained as described above was recovered 1 time in the same manner as in example 1, to obtain 1 recovered resin layer.
Example 4
The embodiment provides an epoxy resin glass polymer material resin layer, which is prepared according to the following preparation method:
according to the molar ratio of epoxy group in bisphenol F diglycidyl ether, amino group in tri (2-aminoethyl) amine and acrylate group in trimethylpropane tripropynyl ester of 1: 1: 1, sampling; then bisphenol F diglycidyl ether, tris (2-aminoethyl) amine and trimethylpropane tripropynyl ester are mixed, and then the solvent dichloromethane is added into the system.
After the solid had dissolved, the system was poured into a 50mm by 2mm teflon membrane, left at room temperature until the solvent had evaporated, and allowed to warm at 110 ℃ overnight.
The reaction formula of the process is as follows:
Figure BDA0003344464660000101
the epoxy resin glass polymer material resin layer obtained as described above was recovered 1 time in the same manner as in example 1, to obtain 1 recovered resin layer.
Example 5
The embodiment provides an epoxy resin glass polymer material resin layer, which is prepared according to the following preparation method:
according to the molar ratio of epoxy groups in bisphenol A diglycidyl ether, amine groups in polyetheramine and acrylate groups in bis (trimethylolpropane) tripropynyl ester of 1: 1: 1, sampling; then mixing bisphenol A diglycidyl ether, polyetheramine and bis (trimethylolpropane) tripropynyl ester, and then adding a solvent into the system.
And after the solid is dissolved, pouring the system into a polytetrafluoroethylene film with the thickness of 50mm x 2mm, standing at room temperature until the solvent is volatilized, standing at the high temperature of 110 ℃ overnight, and demolding to obtain the epoxy resin glass polymer material resin layer.
The reaction formula of the process is as follows:
Figure BDA0003344464660000111
the epoxy resin glass polymer material resin layer obtained as described above was recovered 1 time in the same manner as in example 1, to obtain 1 recovered resin layer.
Example 6
The embodiment provides an epoxy resin glass polymer material resin layer, which is prepared according to the following preparation method:
according to the molar ratio of three groups of epoxy group in triglycidyl isocyanurate, amino group in 4,4' -diaminodicyclohexylmethane and acrylate group in 1, 4-phenyl dipropyl ester being 1: 1: 1, sampling; then, triglycidyl isocyanurate, 4,4' -diaminodicyclohexylmethane and 1, 4-phenyl dipropynyl ester are mixed, and then a solvent dichloromethane is added into the system.
After the solid had dissolved, the system was poured into a 50mm by 2mm teflon membrane, left at room temperature until the solvent had evaporated, and allowed to warm at 110 ℃ overnight.
The reaction formula of the process is as follows:
Figure BDA0003344464660000121
the epoxy resin glass polymer material resin layer obtained as described above was recovered 1 time in the same manner as in example 1, to obtain 1 recovered resin layer.
Comparative example 1:
this comparative example provides a resin layer prepared according to the following preparation method:
according to the molar ratio of the two groups of epoxy group in the bisphenol A epoxy resin and amino group in the 1, 12-dodecane diamine of 2: 1, sampling; the bisphenol a epoxy resin and 1, 12-dodecanediamine were mixed, and then the solvent dichloromethane was added to the system.
After the solid had dissolved, the system was poured into a 50mm by 2mm teflon membrane, left at room temperature until the solvent had evaporated, and allowed to warm at 110 ℃ overnight.
Figure BDA0003344464660000122
Comparative example 2
This comparative example provides a resin layer prepared according to the following preparation method:
according to the molar ratio of two groups of epoxy group in the epoxidized soybean oil and carboxyl group in glutaric acid of 1: 1, sampling; epoxidized soybean oil and glutaric acid were then mixed and the solvent methylene chloride was added to the system.
After the solid had dissolved, the system was poured into a 50mm by 2mm teflon membrane, left at room temperature until the solvent had evaporated, and allowed to warm at 110 ℃ overnight.
Figure BDA0003344464660000131
Firstly, the epoxy resin glass polymer material resin layers in the embodiments 1 to 6 are subjected to a tensile test and a DSC test, and the tensile test method comprises the following steps: DMA (Dynamic thermomechanical analysis), test standard GB/T1039-; DSC test method: differential scanning calorimetry; the standard is as follows: GB/T19466.2-2004, the results are shown in Table 1:
TABLE 1 tensile and DSC test data for examples 1-6
Figure BDA0003344464660000132
As can be seen from table 1, the resin layer of the examples of the present application is very rigid or very elastic, which cannot be achieved by other resin layers.
In summary, the epoxy resin glass polymer material, the three-component epoxy solution, the preparation method and the application of the epoxy resin glass polymer material of the embodiment of the present application are easy to prepare, have excellent mechanical strength, and can be recycled.
The above description is only an example of the present application and is not intended to limit the scope of the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. An epoxy resin glass high molecular material is characterized in that the epoxy resin glass high molecular material is mainly obtained by reacting an epoxy compound, an amine compound and a propiolic acid ester compound.
2. The epoxy glass polymer material according to claim 1, wherein the epoxy compound is one or a mixture of two or more of ethylene glycol diglycidyl ether, poly (ethylene glycol) diglycidyl ether, poly (propylene glycol) diglycidyl ether, epoxidized soybean oil, triglycidyl isocyanurate, bisphenol F diglycidyl ether, and bisphenol a diglycidyl ether.
3. The epoxy resin glass polymer material according to claim 1, wherein the amine compound has a structural formula:
Figure FDA0003344464650000011
wherein, when n is 1, R1Is C2H4、C3H6、C4H8、C5H10、C6H12、C7H14、C8H16、C9H18、C10H20、C11H22、C12H24、(C2H4)2S2、(C6H4)2S2、C6H4、(C6H4)2、(C6H4)2CH2、C6H4(CH2)2、C6H4C2H4、C6H10Or (C)6H10)2CH2(ii) a When n is 2, R1Is (C)2H4)3N；
The amine compound is one or a mixture of more than two of the compounds with the structural formula.
4. The epoxy glass polymer material according to claim 1, wherein the propiolate compound has a structural formula of:
Figure FDA0003344464650000012
wherein, when n is 1, R2Is C2H4、C3H6、C4H8、C5H10、C6H12、C7H14、C8H16、C9H18、C10H20、C11H22、C12H24、(C2H4)2S2、(C6H4)2S2、C6H4,(C6H4)2、(C6H4)2CH2、C6H10、(C6H10)2CH2Or (C)6H10)2C(CH3)2；
When n is 2, R2Is (C)2H4)3N、(C6H4)3CCH3Or (C)2H4)3CCH3；
When n is 3, R2Is that
Figure FDA0003344464650000013
The propiolate compound is one or a mixture of more than two of the compounds with the structural formula.
5. The epoxy resin based glass polymer material according to claim 1, wherein the molar ratio of the epoxy group of the epoxy compound, the amine group of the amine compound, and the propiolate group of the propiolate compound is 1 to 2: 1-2: 1 to 2.
6. A method for preparing the epoxy resin glass polymer material according to any one of claims 1 to 5, wherein the epoxy compound, the amine compound and the propiolate compound are dissolved in a solvent, and then the solvent is removed and the reaction is carried out at 100 to 130 ℃.
7. The method according to claim 6, wherein the solvent is one or a mixture of two or more of dichloromethane, chloroform, tetrahydrofuran, acetone, methanol, ethanol, and methyl ethyl ketone.
8. Use of the epoxy glass polymer material according to any one of claims 1 to 5 to form a resin product having a melting point of 110 to 150 ℃.
9. A three-component epoxy solution for producing the epoxy resin glass polymer material according to claim 1, comprising a solvent, and an epoxy compound, an amine compound and a propiolate compound dissolved in the solvent.
10. Use of the three-component epoxy solution according to claim 9 as a coating or adhesive.
CN202111318105.8A 2021-11-09 2021-11-09 Epoxy resin glass high polymer material, three-component epoxy solution, preparation method and application Pending CN113896863A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004224890A (en) * 2003-01-22 2004-08-12 Dainippon Ink & Chem Inc Method for manufacturing cured epoxy resin composition
CN112876652A (en) * 2021-03-01 2021-06-01 桂林理工大学 Rosin-based epoxy glass polymer material and preparation method thereof
WO2021105127A1 (en) * 2019-11-26 2021-06-03 Universiteit Gent Epoxy-derived covalent adaptable networks and methods of their production

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004224890A (en) * 2003-01-22 2004-08-12 Dainippon Ink & Chem Inc Method for manufacturing cured epoxy resin composition
WO2021105127A1 (en) * 2019-11-26 2021-06-03 Universiteit Gent Epoxy-derived covalent adaptable networks and methods of their production
CN112876652A (en) * 2021-03-01 2021-06-01 桂林理工大学 Rosin-based epoxy glass polymer material and preparation method thereof

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