WO2023000582A1 - Preparation method for two-component epoxy resin adhesive and two-component epoxy resin adhesive prepared thereby - Google Patents

Preparation method for two-component epoxy resin adhesive and two-component epoxy resin adhesive prepared thereby Download PDF

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Publication number
WO2023000582A1
WO2023000582A1 PCT/CN2021/135760 CN2021135760W WO2023000582A1 WO 2023000582 A1 WO2023000582 A1 WO 2023000582A1 CN 2021135760 W CN2021135760 W CN 2021135760W WO 2023000582 A1 WO2023000582 A1 WO 2023000582A1
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epoxy
epoxy resin
component
preparation
compound
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PCT/CN2021/135760
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French (fr)
Chinese (zh)
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胡利杰
梁松苗
金焱
王兵辉
刘忠操
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沃顿科技股份有限公司
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Publication of WO2023000582A1 publication Critical patent/WO2023000582A1/en

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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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • 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
    • 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
    • C08G59/20—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 epoxy compounds used
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/04—Epoxynovolacs

Definitions

  • the present disclosure relates to the technical field of two-component epoxy resin adhesives, and more particularly to a preparation method of a two-component epoxy resin adhesive used in a separation membrane module and a two-component epoxy resin adhesive prepared by the method.
  • Alkali-resistant nanofiltration membrane technology is an advanced and energy-saving membrane separation technology used in extremely harsh working conditions such as alkali recovery of viscose fiber, chitin alkali boiling wastewater and strong alkali cleaning solution recovery.
  • the common alkali-resistant nanofiltration membrane module is a spiral-wound structure. From the perspective of its application field, the main factors affecting the service life of the alkali-resistant nanofiltration membrane and the destructive ability to deal with actual working conditions are membrane surface pollution, functional layer (also known as Separation layer) is damaged by strong alkali and glue line leakage, etc. Among them, membrane surface pollution and functional layer damage by strong alkali can be solved by designing new alkali-resistant nanofiltration membrane materials.
  • Alkali-resistant nanofiltration membranes generally refer to nanofiltration membranes that can withstand aqueous solutions with a concentration of 20% by mass of inorganic strong alkalis such as sodium hydroxide, potassium hydroxide, cesium hydroxide, barium hydroxide, and calcium hydroxide.
  • inorganic strong alkalis such as sodium hydroxide, potassium hydroxide, cesium hydroxide, barium hydroxide, and calcium hydroxide.
  • the glue line of the membrane module is a very important link in the sealing of the whole membrane.
  • the bonding strength of the glue line directly determines the ability of the membrane module to withstand the impact of the strong alkali solution flow.
  • the high bonding strength of the glue line means that it has strong resistance to the impact of water flow and strong alkali. On the contrary, it will cause the overall performance of the entire membrane system to decline or even be scrapped.
  • Patent Document 1 Yue Li et al. added preservatives and oxygen scavengers to the adhesive components to form interpenetrating polymer networks through the chemical combination of polyurethane prepolymers and epoxy resins.
  • Polyurethane-modified epoxy resin adhesives have good corrosion resistance or electrochemical oxidation resistance; however, due to the introduction of ester bonds, the hydrolysis of ester groups in alkaline environments leads to bond breakage, making them resistant to strong alkalis poor.
  • Patent Document 2 Xue Gang et al. provided a preparation method of graphene oxide reinforced epoxy resin adhesive, which solved the difficulty of dispersing graphene oxide and the use of organic solvents in the dispersion process to pollute the environment.
  • the highly dispersed graphene oxide-reinforced epoxy adhesive has higher toughness and heat resistance, its modulus is 10.3% higher than before, and its impact strength is 89.5% higher than before; however, the graphene oxide suspension and epoxy resin Due to the introduction of water in the mixing step, the bonding strength of the adhesive is reduced, which is not conducive to the sealing of the alkali-resistant nanofiltration membrane module with glue lines.
  • the purpose of this disclosure is to provide a method for preparing a two-component epoxy resin adhesive and the method The resulting two-component epoxy adhesive.
  • the molecular structure of the two-component epoxy resin adhesive prepared by the method of the present disclosure does not contain a functional group that is easily hydrolyzed in a strong alkali environment to cause bond breakage, so the adhesive has a stronger ability to withstand strong alkali;
  • the two-component epoxy resin adhesive prepared by the disclosed method has a high degree of network crosslinking of the polymer chain, thus enhancing the adhesive strength of the adhesive.
  • component A epoxy compounds and/or epoxy resins containing two or more epoxy groups are used as matrix materials, and epoxy compounds containing terminal amino groups are used as base materials.
  • the prepolymer undergoes a cross-linking reaction and introduces an alcohol substance as an adhesive strength modifier, so that the hydroxyl group in the alcohol substance and the epoxy compound and/or epoxy resin containing more than two epoxy groups
  • the chemical reaction of the group can enhance the network cross-linking degree of the polymer chain, thereby improving the bonding strength of the adhesive;
  • the polymer undergoes a cross-linking reaction; then component A and component B are mixed in proportion, and the molecular structure of the resulting adhesive material does not contain functional groups that are easily hydrolyzed in a strong alkali environment and cause bond breaks, so the obtained
  • the two-component epoxy resin adhesive has strong resistance to strong alkali.
  • the present disclosure provides a preparation method of a two-component epoxy resin adhesive, which comprises the following steps:
  • the epoxy compound and/or epoxy resin containing two or more epoxy groups and the polyamine compound are in a mass ratio of (10-70): (100-200) in Mixing at a temperature of 50-95°C, the polyamine compound is selected from aromatic diamine compounds, aliphatic di- to tetra-amine compounds, alicyclic di- to tetra-amine compounds at least one of;
  • component A wherein the epoxy compound and/or epoxy resin containing more than two epoxy groups and the prepolymer containing terminal amino groups are mixed at a temperature of 50-95° C., and then alcohol is added Class substances, wherein the mass ratio of the epoxy compound and/or epoxy resin comprising two or more epoxy groups, the prepolymer comprising terminal amino groups, and the alcohols is (50-250): (5-30): (5-40);
  • the prepolymer that comprises terminal epoxy group wherein will comprise the epoxy compound and/or epoxy resin of more than two epoxy groups and polyamine compound with mass ratio (100-200): (5-20 ) mixed at a temperature of 50-95°C, and the polyamine compound is selected from the group consisting of aromatic diamine compounds, aliphatic di- to tetra-amine compounds, alicyclic di-to-quaternary amines at least one of the class of compounds;
  • component B wherein the polyamine compound and the prepolymer containing epoxy groups are mixed at a mass ratio of (50-250):(5-50) at a temperature of 50-95°C,
  • the polyamine compound is at least one selected from aromatic diamine compounds, aliphatic di- to tetra-amine compounds, and alicyclic di- to tetra-amine compounds;
  • a two-component epoxy resin adhesive is prepared, wherein the component A and the component B are mixed in a mass ratio of (100-200):(30-100).
  • the epoxy compound containing two or more epoxy groups is at least one selected from the following epoxy compounds: tetraglycidyl ether tetraphenylethane, triphenyl Glycidyl ether methane, tetraglycidyl xylylene diamine, triglycidyl-p-aminophenol, tetraglycidyl diamino dimethylene benzene, diglycidyl phthalate.
  • the epoxy resin containing two or more epoxy groups is at least one selected from the following epoxy resins: bisphenol A type epoxy resin, bisphenol F type epoxy resin Oxygen resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac type epoxy resin, aliphatic glycidyl ether resin, brominated epoxy resin, hydantoin epoxy resin.
  • the aromatic diamine compound is at least one selected from the following compounds: 4,4'-diaminodiphenylmethane, m-phenylenediamine, m-xylylene Amine, 4,4'-diaminodiphenylsulfone, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylylenediamine;
  • the aliphatic dibasic to tetrabasic amine compounds are selected from the following compounds At least one of: ethylenediamine, hexamethylenediamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, triethylenetetramine;
  • the alicyclic binary to tetravalent amine compounds is at least one selected from the following compounds: diethylenetriamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis(
  • the amount of the polyamine compound calculated by the molar amount of the amino group is equal to the amount of the polyamine compound calculated by the molar amount of the epoxy group
  • the ratio of the amount of the epoxy compound and/or epoxy resin containing two or more epoxy groups is in the range of greater than 1 and less than or equal to 10.
  • the alcohol substance is at least one of alcohol monomers or polymers containing at least one hydroxyl group.
  • the alcohol monomer or polymer containing at least one hydroxyl group is at least one selected from the group consisting of methanol, ethanol, ethylene glycol, propanol, isopropanol, 1- Butanol, 2-butanol, 2-methyl-2-propanol, cyclohexanol, castor oil, soybean oil, glycerol, trimethylolpropane, xylitol, sorbitol, triose, tetrose , pentose, hexose, heptose, mannitol, sucrose, benzyl alcohol, pentaerythritol, hexanehexanol, macrogol-200, macrogol-400, macrogol-600, macrogol- 1000, Polypropylene Glycol-400, Polyglycerol-1000.
  • the epoxy compound containing two or more epoxy groups in terms of the molar weight of epoxy groups And/or the ratio of the amount of the epoxy resin to the amount of the polyamine compound based on the molar amount of the amino group is in the range of greater than 1 and less than or equal to 15.
  • the present disclosure provides a two-component epoxy resin adhesive obtained through the preparation method according to the present disclosure.
  • the preparation method of the two-component epoxy resin adhesive provided by the present disclosure has simple sources of raw materials, low method cost, easy preparation and operation, and is suitable for large-scale industrial production.
  • the two-component epoxy resin adhesive obtained by the present disclosure has Strong resistance to strong alkali and high bonding strength.
  • Fig. 1 shows the change curve of edge glue peel strength and bottom glue peel strength in the process of soaking in 20% NaOH aqueous solution for 180 days after the two-component epoxy resin adhesive prepared in Example 1 is used to seal the nanofiltration membrane module.
  • Fig. 2 shows the change curve of edge glue peel strength and bottom glue peel strength in the process of soaking in 20% KOH aqueous solution for 180 days after the two-component epoxy resin adhesive prepared in Example 1 is used to seal the nanofiltration membrane module.
  • FIG. 3 and (b) of Fig. 3 show respectively that when the two-component epoxy resin adhesive prepared by embodiment 3 is used to seal the nanofiltration membrane assembly, the cross-section of the edge glue line and the bottom glue line Scanning electron microscope photo.
  • the present disclosure provides a preparation method of a two-component epoxy resin adhesive, which comprises the following steps:
  • the epoxy compound and/or epoxy resin containing two or more epoxy groups and the polyamine compound are in a mass ratio of (10-70): (100-200) in Mixing at a temperature of 50-95°C, the polyamine compound is selected from aromatic diamine compounds, aliphatic di- to tetra-amine compounds, alicyclic di- to tetra-amine compounds at least one of;
  • component A wherein the epoxy compound and/or epoxy resin containing more than two epoxy groups and the prepolymer containing terminal amino groups are mixed at a temperature of 50-95° C., and then alcohol is added Class substances, wherein the mass ratio of the epoxy compound and/or epoxy resin comprising two or more epoxy groups, the prepolymer comprising terminal amino groups, and the alcohols is (50-250): (5-30): (5-40);
  • the prepolymer that comprises terminal epoxy group wherein will comprise the epoxy compound and/or epoxy resin of more than two epoxy groups and polyamine compound with mass ratio (100-200): (5-20 ) mixed at a temperature of 50-95°C, and the polyamine compound is selected from the group consisting of aromatic diamine compounds, aliphatic di- to tetra-amine compounds, alicyclic di-to-quaternary amines at least one of the class of compounds;
  • component B wherein the polyamine compound and the prepolymer containing epoxy groups are mixed at a mass ratio of (50-250):(5-50) at a temperature of 50-95°C,
  • the polyamine compound is at least one selected from aromatic diamine compounds, aliphatic di- to tetra-amine compounds, and alicyclic di- to tetra-amine compounds;
  • a two-component epoxy resin adhesive is prepared, wherein the component A and the component B are mixed in a mass ratio of (100-200):(30-100).
  • the technical idea of the preparation method of the present disclosure is that, in component A, the epoxy compound and/or epoxy resin containing two or more epoxy groups is used as the matrix material, and the prepolymer containing the terminal amino group is used for cross-linking reaction and Introducing an alcohol substance as an adhesive strength regulator, making the hydroxyl group contained in the alcohol substance chemically react with the epoxy compound containing two or more epoxy groups and/or the epoxy group contained in the epoxy resin, thereby Enhance the degree of network crosslinking of polymer chains, so it has the effect of enhancing the bonding strength of the adhesive.
  • the polyamine compound is used as a base material to carry out cross-linking reaction with the prepolymer containing epoxy groups.
  • component A and component B are mixed in proportion, and the molecular structure of the resulting adhesive material does not contain functional groups that are easily hydrolyzed in a strong alkali environment and cause bond breakage, so the obtained two-component epoxy resin adhesive It has a strong resistance to strong alkali performance.
  • the epoxy compound containing more than two epoxy groups is at least one selected from the following epoxy compounds: tetraglycidyl ether tetraphenylethane, triphenylglycidol Ether methane, tetraglycidyl xylylenediamine, triglycidyl-p-aminophenol and tetraglycidyl diamino dimethylenebenzene, diglycidyl phthalate.
  • the epoxy resin containing more than two epoxy groups is at least one selected from the following epoxy resins: bisphenol A type epoxy resin, bisphenol F type epoxy resin, Bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac type epoxy resin, aliphatic glycidyl ether resin, brominated epoxy resin, hydantoin epoxy resin.
  • the aromatic diamine compound is at least one selected from the following compounds: 4,4'-diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, 4 , 4'-diaminodiphenylsulfone, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylylenediamine;
  • the aliphatic binary to tetravalent amine compounds are at least one selected from the following compounds One: ethylenediamine, hexamethylenediamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, triethylenetetramine;
  • the alicyclic binary to tetraamine compounds are selected from At least one of the following compounds: diethylenetriamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl
  • the amount of the polyamine compound in terms of molar amounts of amino groups is different from the amount of the polyamine compounds in terms of molar amounts of epoxy groups
  • the ratio of the amount of epoxy compounds and/or epoxy resins with two or more epoxy groups is within a range of greater than 1 and less than or equal to 10. If the ratio of the two is greater than 10, the resulting prepolymer containing amino groups will solidify to form massive gel particles or clusters, thereby affecting performance.
  • the alcohol substance is at least one of alcohol monomers or polymers containing at least one hydroxyl group.
  • the alcohol monomer or polymer containing at least one hydroxyl group is at least one selected from the group consisting of methanol, ethanol, ethylene glycol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, cyclohexanol, castor oil, soybean oil, glycerol, trimethylolpropane, xylitol, sorbitol, triose, tetrose, pentose , hexose, heptose, mannitol, sucrose, benzyl alcohol, pentaerythritol, hexyl alcohol, macrogol-200, macrogol-400, macrogol-600, macrogol-1000, polyethylene glycol Propylene Glycol-400, Polyglycerol-1000.
  • the epoxy compound containing two or more epoxy groups and/or The ratio of the amount of the epoxy resin to the amount of the polyamine compound based on the molar amount of the amino group is in the range of greater than 1 and less than or equal to 15. If the ratio of the two is greater than 15, the resulting prepolymer containing epoxy groups will cure to form massive gel particles or clusters, thereby affecting performance.
  • the preparation method of the disclosed two-component epoxy resin adhesive comprises the following steps:
  • Preparation of prepolymers containing terminal amino groups react epoxy compounds or epoxy resins containing two or more epoxy groups with polyamine compounds at 50-90°C for 2-5 hours, which contain more than two epoxy groups
  • the mass ratio of the base epoxy compound or epoxy resin to the polyamine compound is (10-70): (100-200);
  • Preparation of prepolymers containing epoxy groups react epoxy compounds or epoxy resins containing two or more epoxy groups with polyamine compounds at 50-90°C for 2-5 hours, which The mass ratio of the epoxy compound or epoxy resin to the polyamine compound of the epoxy group is (100-200): (5-20);
  • Preparation of component A Mix the epoxy compound or epoxy resin containing two or more epoxy groups with the prepared prepolymer containing amino groups, adjust the temperature to 50-95°C, and use a stirring speed of 100-200r/ min for stirring, after it reacts for 0.5-3h, then add alcohols as a bonding strength regulator, keep stirring at a temperature of 50-95°C for 1-4h, then place it at room temperature and let it cool naturally Component A is available for use;
  • Preparation of component B Mix the polyamine compound and the prepared prepolymer containing epoxy groups, adjust the reaction temperature to 50-95°C, and stir at a stirring speed of 100-200r/min, and wait for the reaction for 1h -4h, then place it at room temperature, and cool naturally to obtain component B, which is ready for use.
  • Preparation of two-component epoxy resin adhesive The prepared components A and B are stored separately, and the components A and B are mixed evenly according to the mass ratio (100-200): (30-100) during use, that is Two-part epoxy adhesives are available.
  • the present disclosure also provides a two-component epoxy resin adhesive, which is obtained through the preparation method described in the present disclosure.
  • the two-component epoxy resin adhesive of the present disclosure has strong strong alkali resistance and high bonding strength.
  • mass ratio described in the present disclosure refers to the mass ratio calculated according to the sequence of the substances described.
  • “Components A and B are mixed in a mass ratio (100-200): (30-100)” means “Component A and component B are mixed according to the mass ratio of component A: component B (100-200 ): (30-100) mixed”.
  • the prepared components A and B are stored in separate containers.
  • the prepared components A and B are stored in separate containers.
  • the prepared components A and B are stored in separate containers.
  • the prepared components A and B are stored in separate containers.
  • the prepared components A and B are stored in separate containers.
  • the two-component epoxy resin adhesive that makes among the embodiment 1 to 5 is used for sealing nanofiltration membrane assembly respectively, then the nanofiltration membrane assembly through sealing is soaked in the aqueous solution of 20%NaOH 180 days, and to membrane assembly
  • the peel strength of the side glue line and bottom glue line before soaking and soaking for 30 days, 60 days, 90 days, 120 days, 150 days and 180 days were tested.
  • the test steps and test conditions are: cut The glue line splines (length 10cm, width 2cm) of the water inlet, water outlet and bottom of the module, the spline is the composition of the light net and the diaphragm bonded by adhesive, and the glued area is 2cm*2cm (located in the sample strip ends). Clamp both ends of the sample on the fixture of the universal tensile testing machine with the glued part as the center to do a 180° peel test, peel vertically at a rate of 50mm/min for 30s, and record the peel strength of the glue line.
  • the alkali-resistant nanofiltration membrane assembly sealed with the two-component epoxy resin adhesive prepared in Examples 1-5 of the present disclosure was soaked in 20% NaOH aqueous solution for 180 days, while The glue line peel strength of the glue and the glue line peel strength of the bottom glue are all consistent with the initial value, therefore, it has been proved that after long-term storage in the strong alkali solution environment, good bonding strength is still maintained, which also shows that the implementation of the present disclosure
  • the adhesive obtained in Examples 1-5 not only has good alkali resistance performance, but also has good bonding strength, therefore, the adhesive is suitable for sealing alkali-resistant nanofiltration membrane modules.
  • the inventor used the two-component epoxy resin adhesive prepared in Example 1 to seal the nanofiltration membrane module, and soaked it in 20% NaOH aqueous solution and 20% KOH aqueous solution for 180 days respectively, and glued the edge of the membrane module.
  • the peeling strength of the primer line before soaking and after soaking for different days was tested, and the results were tabulated as shown in Figure 1 and Figure 2, respectively.
  • the peel strength of the glue line is greater than 5N/20mm , which solves the long-standing technical bottleneck of the sealing problem of alkali-resistant nanofiltration membrane products in field application, and is conducive to the improvement of the sealing performance of alkali-resistant nanofiltration membranes and the market promotion of products.
  • the inventor used the two-component epoxy resin adhesive prepared in Example 3 to seal the nanofiltration membrane module, and observed the cross-sections of the edge glue line and the bottom glue line respectively using a scanning electron microscope, as shown in Figure 3 ( As shown in a) and (b), it can be clearly seen that the adhesive exists between the diaphragm and the freshwater spacer with an interpenetrating network structure, which also shows that the strong alkali-resistant two-component epoxy resin prepared by the present disclosure High strength properties of the adhesive.
  • the preparation method of the two-component epoxy resin adhesive provided by the present disclosure has simple sources of raw materials, low method cost, easy preparation and operation, and is suitable for large-scale industrial production.
  • the two-component epoxy resin adhesive obtained by the present disclosure has Strong alkali resistance performance, high bonding strength.

Abstract

The present disclosure relates to a preparation method for a two-component epoxy resin adhesive and the two-component epoxy resin adhesive prepared thereby. The preparation method comprises the following steps: mixing an epoxy compound and/or epoxy resin that contains more than two epoxy groups with an excess polyamine compound to prepare a prepolymer containing a terminal amino group; mixing the epoxy compound and/or epoxy resin that contains more than two epoxy groups with the prepolymer containing a terminal amino group, and then adding an alcohol substance to prepare component A; mixing an excess epoxy compound and/or epoxy resin that contains more than two epoxy groups with a polyamine compound to prepare a prepolymer containing a terminal epoxy group; mixing the polyamine compound with the prepolymer containing a terminal epoxy group to prepare component B; and mixing the component A and the component B to prepare the two-component epoxy resin adhesive. The two-component epoxy resin adhesive of the present disclosure has strong alkali resistance and high bonding strength.

Description

双组分环氧树脂胶粘剂的制备方法及由其制备的双组分环氧树脂胶粘剂Preparation method of two-component epoxy resin adhesive and two-component epoxy resin adhesive prepared therefrom 技术领域technical field
本公开涉及双组分环氧树脂胶粘剂的技术领域，更具体地涉及用于分离膜组件中的双组分环氧树脂胶粘剂的制备方法及由该方法制备的双组分环氧树脂胶粘剂。The present disclosure relates to the technical field of two-component epoxy resin adhesives, and more particularly to a preparation method of a two-component epoxy resin adhesive used in a separation membrane module and a two-component epoxy resin adhesive prepared by the method.
背景技术Background technique
耐碱纳滤膜技术是一种用于处理粘胶纤维的碱回收、甲壳素碱煮废水和强碱清洗液回收等极端苛刻工况中的先进和节能的膜分离技术。常见的耐碱纳滤膜组件为螺旋卷式结构，从其应用领域来看，影响耐碱纳滤膜使用寿命和应对实际工况等破坏能力的主要因素有膜面污染、功能层(又称分离层)受强碱破坏和胶线渗漏等，其中膜面污染和功能层受强碱破坏可以通过设计新型耐碱纳滤膜材料来解决。Alkali-resistant nanofiltration membrane technology is an advanced and energy-saving membrane separation technology used in extremely harsh working conditions such as alkali recovery of viscose fiber, chitin alkali boiling wastewater and strong alkali cleaning solution recovery. The common alkali-resistant nanofiltration membrane module is a spiral-wound structure. From the perspective of its application field, the main factors affecting the service life of the alkali-resistant nanofiltration membrane and the destructive ability to deal with actual working conditions are membrane surface pollution, functional layer (also known as Separation layer) is damaged by strong alkali and glue line leakage, etc. Among them, membrane surface pollution and functional layer damage by strong alkali can be solved by designing new alkali-resistant nanofiltration membrane materials.
耐碱纳滤膜通常指能够耐受例如氢氧化钠、氢氧化钾、氢氧化铯、氢氧化钡和氢氧化钙等无机强碱的质量百分比浓度为20％的水溶液的纳滤膜。这不仅要求膜片具有较强的耐受强碱性能，更重要的是，对膜组件在强碱环境中的密封性能提出了更高的要求和标准。膜组件的胶线在整个膜内部密封中是非常重要的一个环节，胶线的粘接强度直接决定了膜组件应对强碱溶液流冲击的能力。胶线的粘接强度高，则抗水流冲击力和耐受强碱的性能强，反之，则导致整个膜***的整体性能下降甚至报废。Alkali-resistant nanofiltration membranes generally refer to nanofiltration membranes that can withstand aqueous solutions with a concentration of 20% by mass of inorganic strong alkalis such as sodium hydroxide, potassium hydroxide, cesium hydroxide, barium hydroxide, and calcium hydroxide. This not only requires the diaphragm to have a strong strong alkali resistance performance, but more importantly, it puts forward higher requirements and standards for the sealing performance of the membrane module in a strong alkali environment. The glue line of the membrane module is a very important link in the sealing of the whole membrane. The bonding strength of the glue line directly determines the ability of the membrane module to withstand the impact of the strong alkali solution flow. The high bonding strength of the glue line means that it has strong resistance to the impact of water flow and strong alkali. On the contrary, it will cause the overall performance of the entire membrane system to decline or even be scrapped.
然而，耐强碱型胶粘剂方面的研究开展的非常少，也一直成为耐碱纳滤膜未能规模市场化的重要技术瓶颈，其相关专利也较少。常见的膜组件用胶粘剂多为聚氨酯体系，但由于在强碱环境中酯基的水解导致化学键的断裂使其不具有较好的耐受强碱性能。However, very little research has been carried out on alkali-resistant adhesives, and it has always been an important technical bottleneck for alkali-resistant nanofiltration membranes not to be marketed on a large scale, and there are few related patents. Common adhesives for membrane modules are mostly polyurethane systems, but due to the hydrolysis of ester groups in a strong alkali environment, the chemical bonds are broken, so they do not have good resistance to strong alkali.
在专利文献1(CN 111909620A)中，岳利等通过在胶粘剂组分中加入防腐剂和除氧剂，经聚氨酯预聚体和环氧树脂的化学结合形成互穿聚合物网络，使制得的聚氨酯改性的环氧树脂胶粘剂具有良好的抗腐蚀或抗电化学氧化性能；但是由于酯键的引入，使其在碱性环境中发生酯基的水解导致键的断裂，使其耐强碱性能较差。In Patent Document 1 (CN 111909620A), Yue Li et al. added preservatives and oxygen scavengers to the adhesive components to form interpenetrating polymer networks through the chemical combination of polyurethane prepolymers and epoxy resins. Polyurethane-modified epoxy resin adhesives have good corrosion resistance or electrochemical oxidation resistance; however, due to the introduction of ester bonds, the hydrolysis of ester groups in alkaline environments leads to bond breakage, making them resistant to strong alkalis poor.
在专利文献2(CN 108342177A)中，薛刚等提供了一种氧化石墨烯增强环氧树脂胶粘剂的制备方法，解决了氧化石墨烯的难分散以及分散过程中使用有机溶剂污染环境的问 题，制备的高分散氧化石墨烯增强的环氧树脂胶粘剂具有更高的韧性和耐热性，其模量较之前提高10.3％，冲击强度较之前提高89.5％；然而氧化石墨烯的悬浮液与环氧树脂的混合步骤中由于水的引入，使得胶粘剂的粘接强度有所降低，不利于耐碱纳滤膜组件用胶线密封。In Patent Document 2 (CN 108342177A), Xue Gang et al. provided a preparation method of graphene oxide reinforced epoxy resin adhesive, which solved the difficulty of dispersing graphene oxide and the use of organic solvents in the dispersion process to pollute the environment. The highly dispersed graphene oxide-reinforced epoxy adhesive has higher toughness and heat resistance, its modulus is 10.3% higher than before, and its impact strength is 89.5% higher than before; however, the graphene oxide suspension and epoxy resin Due to the introduction of water in the mixing step, the bonding strength of the adhesive is reduced, which is not conducive to the sealing of the alkali-resistant nanofiltration membrane module with glue lines.
因此，提升胶粘剂的耐受强碱性能和粘接强度为目前需要解决的两大技术难题。这将有利于胶粘剂在强碱溶液环境中的应用，为耐碱纳滤膜产品的推广具有重要的现实意义。Therefore, improving the strong alkali resistance and bonding strength of the adhesive is the two major technical problems that need to be solved at present. This will be beneficial to the application of the adhesive in the strong alkali solution environment, and has important practical significance for the promotion of alkali-resistant nanofiltration membrane products.
发明内容Contents of the invention
发明要解决的问题The problem to be solved by the invention
针对现有的胶粘剂难以兼具较强的耐受强碱的性能和较高的粘接强度的技术问题，本公开的目的在于提供一种双组分环氧树脂胶粘剂的制备方法和由该方法得到的双组分环氧树脂胶粘剂。在通过本公开的方法制得的双组分环氧树脂胶粘剂的分子结构中不含有在强碱环境中容易水解导致键的断裂的官能团，因此胶粘剂具有较强的耐受强碱的性能；通过本公开的方法制得的双组分环氧树脂胶粘剂的聚合物链的网络交联程度高，因此增强了胶粘剂的粘接强度。Aiming at the technical problem that it is difficult for existing adhesives to have strong strong alkali resistance and high bonding strength, the purpose of this disclosure is to provide a method for preparing a two-component epoxy resin adhesive and the method The resulting two-component epoxy adhesive. The molecular structure of the two-component epoxy resin adhesive prepared by the method of the present disclosure does not contain a functional group that is easily hydrolyzed in a strong alkali environment to cause bond breakage, so the adhesive has a stronger ability to withstand strong alkali; The two-component epoxy resin adhesive prepared by the disclosed method has a high degree of network crosslinking of the polymer chain, thus enhancing the adhesive strength of the adhesive.
用于解决问题的方案solutions to problems
本公开的发明人等为了实现以上目的，进行深入研究之后发现：在组分A中以包含两个以上的环氧基的环氧化合物和/或环氧树脂为基体材料、与包含端氨基的预聚物进行交联反应并且引入作为粘接强度调节剂的醇类物质，使醇类物质中的羟基与包含两个以上的环氧基的环氧化合物和/或环氧树脂中的环氧基进行化学反应，可以增强聚合物链的网络交联程度，从而起到提高胶粘剂的粘接强度的效果；在组分B中以多元胺类化合物为基体材料、与包含端环氧基的预聚物进行交联反应；进而将组分A和组分B按比例混合，在由此得到的胶粘剂材料的分子结构中不含有在强碱环境中容易水解导致键的断裂的官能团，因此得到的双组分环氧树脂胶粘剂具有较强的耐受强碱的性能。In order to achieve the above purpose, the inventors of the present disclosure have conducted in-depth research and found that: in component A, epoxy compounds and/or epoxy resins containing two or more epoxy groups are used as matrix materials, and epoxy compounds containing terminal amino groups are used as base materials. The prepolymer undergoes a cross-linking reaction and introduces an alcohol substance as an adhesive strength modifier, so that the hydroxyl group in the alcohol substance and the epoxy compound and/or epoxy resin containing more than two epoxy groups The chemical reaction of the group can enhance the network cross-linking degree of the polymer chain, thereby improving the bonding strength of the adhesive; The polymer undergoes a cross-linking reaction; then component A and component B are mixed in proportion, and the molecular structure of the resulting adhesive material does not contain functional groups that are easily hydrolyzed in a strong alkali environment and cause bond breaks, so the obtained The two-component epoxy resin adhesive has strong resistance to strong alkali.
本公开提供一种双组分环氧树脂胶粘剂的制备方法，其包括以下步骤：The present disclosure provides a preparation method of a two-component epoxy resin adhesive, which comprises the following steps:
制备包含端氨基的预聚物，其中将包含两个以上的环氧基的环氧化合物和/或环氧树 脂与多元胺类化合物以质量比为(10-70)：(100-200)在温度为50-95℃的条件下混合，所述多元胺类化合物为选自芳香族二元胺类化合物、脂肪族二元至四元胺类化合物、脂环族二元至四元胺类化合物中的至少一种；Prepare a prepolymer containing terminal amino groups, wherein the epoxy compound and/or epoxy resin containing two or more epoxy groups and the polyamine compound are in a mass ratio of (10-70): (100-200) in Mixing at a temperature of 50-95°C, the polyamine compound is selected from aromatic diamine compounds, aliphatic di- to tetra-amine compounds, alicyclic di- to tetra-amine compounds at least one of;
制备组分A，其中将包含两个以上的环氧基的环氧化合物和/或环氧树脂、所述包含端氨基的预聚物在温度为50-95℃的条件下混合，然后加入醇类物质，其中所述包含两个以上的环氧基的环氧化合物和/或环氧树脂、所述包含端氨基的预聚物、所述醇类物质的质量比为(50-250)：(5-30)：(5-40)；Preparation of component A, wherein the epoxy compound and/or epoxy resin containing more than two epoxy groups and the prepolymer containing terminal amino groups are mixed at a temperature of 50-95° C., and then alcohol is added Class substances, wherein the mass ratio of the epoxy compound and/or epoxy resin comprising two or more epoxy groups, the prepolymer comprising terminal amino groups, and the alcohols is (50-250): (5-30): (5-40);
制备包含端环氧基的预聚物，其中将包含两个以上的环氧基的环氧化合物和/或环氧树脂与多元胺类化合物以质量比为(100-200)：(5-20)在温度为50-95℃的条件下混合，所述多元胺类化合物为选自芳香族二元胺类化合物、脂肪族二元至四元胺类化合物、脂环族二元至四元胺类化合物中的至少一种；Prepare the prepolymer that comprises terminal epoxy group, wherein will comprise the epoxy compound and/or epoxy resin of more than two epoxy groups and polyamine compound with mass ratio (100-200): (5-20 ) mixed at a temperature of 50-95°C, and the polyamine compound is selected from the group consisting of aromatic diamine compounds, aliphatic di- to tetra-amine compounds, alicyclic di-to-quaternary amines at least one of the class of compounds;
制备组分B，其中将多元胺类化合物和所述包含端环氧基的预聚物以质量比为(50-250)：(5-50)在温度为50-95℃的条件下混合，所述多元胺类化合物为选自芳香族二元胺类化合物、脂肪族二元至四元胺类化合物、脂环族二元至四元胺类化合物中的至少一种；Preparation of component B, wherein the polyamine compound and the prepolymer containing epoxy groups are mixed at a mass ratio of (50-250):(5-50) at a temperature of 50-95°C, The polyamine compound is at least one selected from aromatic diamine compounds, aliphatic di- to tetra-amine compounds, and alicyclic di- to tetra-amine compounds;
制备双组分环氧树脂胶粘剂，其中将所述组分A和所述组分B以质量比为(100-200)：(30-100)混合。A two-component epoxy resin adhesive is prepared, wherein the component A and the component B are mixed in a mass ratio of (100-200):(30-100).
根据本公开所述的制备方法，其中所述包含两个以上的环氧基的环氧化合物为选自以下环氧化合物中的至少一种：四缩水甘油醚基四苯基乙烷、三苯基缩水甘油醚基甲烷、四缩水甘油基二甲苯二胺、三缩水甘油基-p-氨基苯酚、四缩水甘油基二胺基二亚甲基苯、邻苯二甲酸二缩水甘油酯。According to the preparation method described in the present disclosure, wherein the epoxy compound containing two or more epoxy groups is at least one selected from the following epoxy compounds: tetraglycidyl ether tetraphenylethane, triphenyl Glycidyl ether methane, tetraglycidyl xylylene diamine, triglycidyl-p-aminophenol, tetraglycidyl diamino dimethylene benzene, diglycidyl phthalate.
根据本公开所述的制备方法，其中所述包含两个以上的环氧基的环氧树脂为选自以下环氧树脂中的至少一种：双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、氢化双酚A型环氧树脂、线性酚醛型环氧树脂、脂肪族缩水甘油醚树脂、溴化环氧树脂、海因环氧树脂。According to the preparation method described in the present disclosure, wherein the epoxy resin containing two or more epoxy groups is at least one selected from the following epoxy resins: bisphenol A type epoxy resin, bisphenol F type epoxy resin Oxygen resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac type epoxy resin, aliphatic glycidyl ether resin, brominated epoxy resin, hydantoin epoxy resin.
根据本公开所述的制备方法，其中所述芳香族二元胺类化合物为选自以下化合物中的至少一种：4,4’-二氨基二苯甲烷、间苯二胺、间苯二甲胺、4,4’-二氨基二苯砜、二氨 基二苯基甲烷、二氨基二苯基砜、间二甲苯二胺；所述脂肪族二元至四元胺类化合物为选自以下化合物中的至少一种：乙二胺、己二胺、N,N-二甲氨基丙胺、N,N-二乙氨基丙胺、三乙烯四胺；所述脂环族二元至四元胺类化合物为选自以下化合物中的至少一种：二乙烯三胺、异佛尔酮二胺、N-氨乙基哌嗪、3,9-双(3-氨丙基)-2,4,8,10-四氧杂螺[5.5]十一烷、双(4-氨基-3-甲基环己基)甲烷、双(4-氨基环己基)甲烷。According to the preparation method described in the present disclosure, wherein the aromatic diamine compound is at least one selected from the following compounds: 4,4'-diaminodiphenylmethane, m-phenylenediamine, m-xylylene Amine, 4,4'-diaminodiphenylsulfone, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylylenediamine; the aliphatic dibasic to tetrabasic amine compounds are selected from the following compounds At least one of: ethylenediamine, hexamethylenediamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, triethylenetetramine; the alicyclic binary to tetravalent amine compounds is at least one selected from the following compounds: diethylenetriamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)-2,4,8, 10-tetraoxaspiro[5.5]undecane, bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane.
根据本公开所述的制备方法，其中在所述制备包含端氨基的预聚物的步骤中，以氨基的摩尔量计的所述多元胺类化合物的量与以环氧基的摩尔量计的所述包含两个以上的环氧基的环氧化合物和/或环氧树脂的量之比在大于1且小于等于10的范围内。According to the preparation method of the present disclosure, wherein in the step of preparing the prepolymer containing an amino group, the amount of the polyamine compound calculated by the molar amount of the amino group is equal to the amount of the polyamine compound calculated by the molar amount of the epoxy group The ratio of the amount of the epoxy compound and/or epoxy resin containing two or more epoxy groups is in the range of greater than 1 and less than or equal to 10.
根据本公开所述的制备方法，其中所述醇类物质为包含至少一个羟基的醇类单体或聚合物中的至少一种。According to the preparation method of the present disclosure, wherein the alcohol substance is at least one of alcohol monomers or polymers containing at least one hydroxyl group.
根据本公开所述的制备方法，其中所述包含至少一个羟基的醇类单体或聚合物为选自以下的至少一种：甲醇、乙醇、乙二醇、丙醇、异丙醇、1-丁醇、2-丁醇、2-甲基-2-丙醇、环己醇、蓖麻油、大豆油、丙三醇、三羟甲基丙烷、木糖醇、山梨醇、丙糖、丁糖、戊糖、己糖、庚糖、甘露醇、蔗糖、苯甲醇、季戊四醇、己六醇、聚乙二醇-200、聚乙二醇-400、聚乙二醇-600、聚乙二醇-1000、聚丙二醇-400、聚丙三醇-1000。According to the preparation method of the present disclosure, wherein the alcohol monomer or polymer containing at least one hydroxyl group is at least one selected from the group consisting of methanol, ethanol, ethylene glycol, propanol, isopropanol, 1- Butanol, 2-butanol, 2-methyl-2-propanol, cyclohexanol, castor oil, soybean oil, glycerol, trimethylolpropane, xylitol, sorbitol, triose, tetrose , pentose, hexose, heptose, mannitol, sucrose, benzyl alcohol, pentaerythritol, hexanehexanol, macrogol-200, macrogol-400, macrogol-600, macrogol- 1000, Polypropylene Glycol-400, Polyglycerol-1000.
根据本公开所述的制备方法，其中在所述制备包含端环氧基的预聚物的步骤中，以环氧基的摩尔量计的所述包含两个以上的环氧基的环氧化合物和/或环氧树脂的量与以氨基的摩尔量计的所述多元胺类化合物的量之比在大于1且小于等于15的范围内。According to the preparation method of the present disclosure, wherein in the step of preparing the prepolymer containing epoxy groups, the epoxy compound containing two or more epoxy groups in terms of the molar weight of epoxy groups And/or the ratio of the amount of the epoxy resin to the amount of the polyamine compound based on the molar amount of the amino group is in the range of greater than 1 and less than or equal to 15.
本公开提供一种双组分环氧树脂胶粘剂，其通过根据本公开的制备方法得到。The present disclosure provides a two-component epoxy resin adhesive obtained through the preparation method according to the present disclosure.
发明的效果The effect of the invention
本公开提供的双组分环氧树脂胶粘剂的制备方法，采用的原料来源简单，方法成本低廉，制备操作容易，适于工业上的规模化生产，本公开得到的双组分环氧树脂胶粘剂具备较强的耐受强碱的性能并且粘接强度高。The preparation method of the two-component epoxy resin adhesive provided by the present disclosure has simple sources of raw materials, low method cost, easy preparation and operation, and is suitable for large-scale industrial production. The two-component epoxy resin adhesive obtained by the present disclosure has Strong resistance to strong alkali and high bonding strength.
附图说明Description of drawings
图1示出实施例1制备的双组分环氧树脂胶粘剂用于密封纳滤膜组件后，浸泡于20％NaOH水溶液180天的过程中边胶剥离强度和底胶剥离强度的变化曲线。Fig. 1 shows the change curve of edge glue peel strength and bottom glue peel strength in the process of soaking in 20% NaOH aqueous solution for 180 days after the two-component epoxy resin adhesive prepared in Example 1 is used to seal the nanofiltration membrane module.
图2示出实施例1制备的双组分环氧树脂胶粘剂用于密封纳滤膜组件后，浸泡于20％KOH水溶液180天的过程中边胶剥离强度和底胶剥离强度的变化曲线。Fig. 2 shows the change curve of edge glue peel strength and bottom glue peel strength in the process of soaking in 20% KOH aqueous solution for 180 days after the two-component epoxy resin adhesive prepared in Example 1 is used to seal the nanofiltration membrane module.
图3的(a)和图3的(b)分别示出将实施例3制备的双组分环氧树脂胶粘剂用于密封纳滤膜组件时，边胶胶线和底胶胶线的断面的扫描电子显微镜照片。(a) of Fig. 3 and (b) of Fig. 3 show respectively that when the two-component epoxy resin adhesive prepared by embodiment 3 is used to seal the nanofiltration membrane assembly, the cross-section of the edge glue line and the bottom glue line Scanning electron microscope photo.
具体实施方式detailed description
本公开提供一种双组分环氧树脂胶粘剂的制备方法，其包括以下步骤：The present disclosure provides a preparation method of a two-component epoxy resin adhesive, which comprises the following steps:
制备包含端氨基的预聚物，其中将包含两个以上的环氧基的环氧化合物和/或环氧树脂与多元胺类化合物以质量比为(10-70)：(100-200)在温度为50-95℃的条件下混合，所述多元胺类化合物为选自芳香族二元胺类化合物、脂肪族二元至四元胺类化合物、脂环族二元至四元胺类化合物中的至少一种；Prepare a prepolymer containing terminal amino groups, wherein the epoxy compound and/or epoxy resin containing two or more epoxy groups and the polyamine compound are in a mass ratio of (10-70): (100-200) in Mixing at a temperature of 50-95°C, the polyamine compound is selected from aromatic diamine compounds, aliphatic di- to tetra-amine compounds, alicyclic di- to tetra-amine compounds at least one of;
制备组分A，其中将包含两个以上的环氧基的环氧化合物和/或环氧树脂、所述包含端氨基的预聚物在温度为50-95℃的条件下混合，然后加入醇类物质，其中所述包含两个以上的环氧基的环氧化合物和/或环氧树脂、所述包含端氨基的预聚物、所述醇类物质的质量比为(50-250)：(5-30)：(5-40)；Preparation of component A, wherein the epoxy compound and/or epoxy resin containing more than two epoxy groups and the prepolymer containing terminal amino groups are mixed at a temperature of 50-95° C., and then alcohol is added Class substances, wherein the mass ratio of the epoxy compound and/or epoxy resin comprising two or more epoxy groups, the prepolymer comprising terminal amino groups, and the alcohols is (50-250): (5-30): (5-40);
制备包含端环氧基的预聚物，其中将包含两个以上的环氧基的环氧化合物和/或环氧树脂与多元胺类化合物以质量比为(100-200)：(5-20)在温度为50-95℃的条件下混合，所述多元胺类化合物为选自芳香族二元胺类化合物、脂肪族二元至四元胺类化合物、脂环族二元至四元胺类化合物中的至少一种；Prepare the prepolymer that comprises terminal epoxy group, wherein will comprise the epoxy compound and/or epoxy resin of more than two epoxy groups and polyamine compound with mass ratio (100-200): (5-20 ) mixed at a temperature of 50-95°C, and the polyamine compound is selected from the group consisting of aromatic diamine compounds, aliphatic di- to tetra-amine compounds, alicyclic di-to-quaternary amines at least one of the class of compounds;
制备组分B，其中将多元胺类化合物和所述包含端环氧基的预聚物以质量比为(50-250)：(5-50)在温度为50-95℃的条件下混合，所述多元胺类化合物为选自芳香族二元胺类化合物、脂肪族二元至四元胺类化合物、脂环族二元至四元胺类化合物中的至少一种；Preparation of component B, wherein the polyamine compound and the prepolymer containing epoxy groups are mixed at a mass ratio of (50-250):(5-50) at a temperature of 50-95°C, The polyamine compound is at least one selected from aromatic diamine compounds, aliphatic di- to tetra-amine compounds, and alicyclic di- to tetra-amine compounds;
制备双组分环氧树脂胶粘剂，其中将所述组分A和所述组分B以质量比为(100-200)：(30-100)混合。A two-component epoxy resin adhesive is prepared, wherein the component A and the component B are mixed in a mass ratio of (100-200):(30-100).
本公开制备方法的技术构思在于，在组分A中以包含两个以上的环氧基的环氧化合物和/或环氧树脂为基体材料、与包含端氨基的预聚物进行交联反应并且引入作为粘接强 度调节剂的醇类物质，使醇类物质中包含的羟基与包含两个以上的环氧基的环氧化合物和/或环氧树脂中包含的环氧基进行化学反应，从而增强聚合物链的网络交联程度，因此起到增强胶粘剂的粘接强度的效果。在组分B中以多元胺类化合物为基体材料、与包含端环氧基的预聚物进行交联反应。进而将组分A和组分B按比例混合，在由此得到的胶粘剂材料的分子结构中不含有在强碱环境中容易水解导致键的断裂的官能团，因此得到的双组分环氧树脂胶粘剂具有较强的耐受强碱的性能。The technical idea of the preparation method of the present disclosure is that, in component A, the epoxy compound and/or epoxy resin containing two or more epoxy groups is used as the matrix material, and the prepolymer containing the terminal amino group is used for cross-linking reaction and Introducing an alcohol substance as an adhesive strength regulator, making the hydroxyl group contained in the alcohol substance chemically react with the epoxy compound containing two or more epoxy groups and/or the epoxy group contained in the epoxy resin, thereby Enhance the degree of network crosslinking of polymer chains, so it has the effect of enhancing the bonding strength of the adhesive. In component B, the polyamine compound is used as a base material to carry out cross-linking reaction with the prepolymer containing epoxy groups. Furthermore, component A and component B are mixed in proportion, and the molecular structure of the resulting adhesive material does not contain functional groups that are easily hydrolyzed in a strong alkali environment and cause bond breakage, so the obtained two-component epoxy resin adhesive It has a strong resistance to strong alkali performance.
在优选的实施方案中，所述包含两个以上的环氧基的环氧化合物为选自以下环氧化合物中的至少一种：四缩水甘油醚基四苯基乙烷、三苯基缩水甘油醚基甲烷、四缩水甘油基二甲苯二胺、三缩水甘油基-p-氨基苯酚和四缩水甘油基二胺基二亚甲基苯、邻苯二甲酸二缩水甘油酯。In a preferred embodiment, the epoxy compound containing more than two epoxy groups is at least one selected from the following epoxy compounds: tetraglycidyl ether tetraphenylethane, triphenylglycidol Ether methane, tetraglycidyl xylylenediamine, triglycidyl-p-aminophenol and tetraglycidyl diamino dimethylenebenzene, diglycidyl phthalate.
在优选的实施方案中，所述包含两个以上的环氧基的环氧树脂为选自以下环氧树脂中的至少一种：双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、氢化双酚A型环氧树脂、线性酚醛型环氧树脂、脂肪族缩水甘油醚树脂、溴化环氧树脂、海因环氧树脂。In a preferred embodiment, the epoxy resin containing more than two epoxy groups is at least one selected from the following epoxy resins: bisphenol A type epoxy resin, bisphenol F type epoxy resin, Bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac type epoxy resin, aliphatic glycidyl ether resin, brominated epoxy resin, hydantoin epoxy resin.
在优选的实施方案中，所述芳香族二元胺类化合物为选自以下化合物中的至少一种：4,4’-二氨基二苯甲烷、间苯二胺、间苯二甲胺、4,4’-二氨基二苯砜、二氨基二苯基甲烷、二氨基二苯基砜、间二甲苯二胺；所述脂肪族二元至四元胺类化合物为选自以下化合物中的至少一种：乙二胺、己二胺、N,N-二甲氨基丙胺、N,N-二乙氨基丙胺、三乙烯四胺；所述脂环族二元至四元胺类化合物为选自以下化合物中的至少一种：二乙烯三胺、异佛尔酮二胺、N-氨乙基哌嗪、3,9-双(3-氨丙基)-2,4,8,10-四氧杂螺[5.5]十一烷、双(4-氨基-3-甲基环己基)甲烷、双(4-氨基环己基)甲烷。In a preferred embodiment, the aromatic diamine compound is at least one selected from the following compounds: 4,4'-diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, 4 , 4'-diaminodiphenylsulfone, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylylenediamine; the aliphatic binary to tetravalent amine compounds are at least one selected from the following compounds One: ethylenediamine, hexamethylenediamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, triethylenetetramine; the alicyclic binary to tetraamine compounds are selected from At least one of the following compounds: diethylenetriamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetra Oxaspiro[5.5]undecane, bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane.
在优选的实施方案中，在所述制备包含端氨基的预聚物的步骤中，以氨基的摩尔量计的所述多元胺类化合物的量与以环氧基的摩尔量计的所述包含两个以上的环氧基的环氧化合物和/或环氧树脂的量之比在大于1且小于等于10的范围内。如果两者之比大于10，则所得的包含端氨基的预聚物会固化形成块状的凝胶颗粒或团簇，从而影响性能。In a preferred embodiment, in the step of preparing the prepolymer containing terminal amino groups, the amount of the polyamine compound in terms of molar amounts of amino groups is different from the amount of the polyamine compounds in terms of molar amounts of epoxy groups The ratio of the amount of epoxy compounds and/or epoxy resins with two or more epoxy groups is within a range of greater than 1 and less than or equal to 10. If the ratio of the two is greater than 10, the resulting prepolymer containing amino groups will solidify to form massive gel particles or clusters, thereby affecting performance.
在优选的实施方案中，所述醇类物质为包含至少一个羟基的醇类单体或聚合物中的至少一种。In a preferred embodiment, the alcohol substance is at least one of alcohol monomers or polymers containing at least one hydroxyl group.
在优选的实施方案中，所述包含至少一个羟基的醇类单体或聚合物为选自以下的至少一种：甲醇、乙醇、乙二醇、丙醇、异丙醇、1-丁醇、2-丁醇、2-甲基-2-丙醇、环己醇、蓖麻油、大豆油、丙三醇、三羟甲基丙烷、木糖醇、山梨醇、丙糖、丁糖、戊糖、己糖、庚糖、甘露醇、蔗糖、苯甲醇、季戊四醇、己六醇、聚乙二醇-200、聚乙二醇-400、聚乙二醇-600、聚乙二醇-1000、聚丙二醇-400、聚丙三醇-1000。In a preferred embodiment, the alcohol monomer or polymer containing at least one hydroxyl group is at least one selected from the group consisting of methanol, ethanol, ethylene glycol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, cyclohexanol, castor oil, soybean oil, glycerol, trimethylolpropane, xylitol, sorbitol, triose, tetrose, pentose , hexose, heptose, mannitol, sucrose, benzyl alcohol, pentaerythritol, hexyl alcohol, macrogol-200, macrogol-400, macrogol-600, macrogol-1000, polyethylene glycol Propylene Glycol-400, Polyglycerol-1000.
在优选的实施方案中，在所述制备包含端环氧基的预聚物的步骤中，以环氧基的摩尔量计的所述包含两个以上的环氧基的环氧化合物和/或环氧树脂的量与以氨基的摩尔量计的所述多元胺类化合物的量之比在大于1且小于等于15的范围内。如果两者之比大于15，则所得的包含端环氧基的预聚物会固化形成块状的凝胶颗粒或团簇，从而影响性能。In a preferred embodiment, in the step of preparing the prepolymer containing epoxy groups, the epoxy compound containing two or more epoxy groups and/or The ratio of the amount of the epoxy resin to the amount of the polyamine compound based on the molar amount of the amino group is in the range of greater than 1 and less than or equal to 15. If the ratio of the two is greater than 15, the resulting prepolymer containing epoxy groups will cure to form massive gel particles or clusters, thereby affecting performance.
作为一个非限制性实例，本公开的双组分环氧树脂胶粘剂的制备方法包括以下步骤：As a non-limiting example, the preparation method of the disclosed two-component epoxy resin adhesive comprises the following steps:
制备包含端氨基的预聚物：将包含两个以上的环氧基的环氧化合物或环氧树脂与多元胺类化合物在50-90℃下反应2-5h，其中包含两个以上的环氧基的环氧化合物或环氧树脂与多元胺类化合物的质量比为(10-70)：(100-200)；Preparation of prepolymers containing terminal amino groups: react epoxy compounds or epoxy resins containing two or more epoxy groups with polyamine compounds at 50-90°C for 2-5 hours, which contain more than two epoxy groups The mass ratio of the base epoxy compound or epoxy resin to the polyamine compound is (10-70): (100-200);
制备包含端环氧基的预聚物：将包含两个以上的环氧基的环氧化合物或环氧树脂和多元胺类化合物在50-90℃下反应2-5h，其中包含两个以上的环氧基的环氧化合物或环氧树脂与多元胺类化合物的质量比为(100-200)：(5-20)；Preparation of prepolymers containing epoxy groups: react epoxy compounds or epoxy resins containing two or more epoxy groups with polyamine compounds at 50-90°C for 2-5 hours, which The mass ratio of the epoxy compound or epoxy resin to the polyamine compound of the epoxy group is (100-200): (5-20);
制备组分A：将包含两个以上的环氧基的环氧化合物或环氧树脂和制备的包含端氨基的预聚物混合，调整温度为50-95℃，采用搅拌速度为100-200r/min进行搅拌，待其反应0.5-3h后，再加入醇类物质作为粘接强度调节剂，在温度为50-95℃下持续搅拌1-4h，而后将其置于室温环境中，自然冷却即可得组分A，待用；Preparation of component A: Mix the epoxy compound or epoxy resin containing two or more epoxy groups with the prepared prepolymer containing amino groups, adjust the temperature to 50-95°C, and use a stirring speed of 100-200r/ min for stirring, after it reacts for 0.5-3h, then add alcohols as a bonding strength regulator, keep stirring at a temperature of 50-95°C for 1-4h, then place it at room temperature and let it cool naturally Component A is available for use;
制备组分B：将多元胺类化合物和制备的包含端环氧基的预聚物混合，调整反应温度为50-95℃，并采用搅拌速度为100-200r/min进行搅拌，待其反应1h-4h,而后将其置于室温环境中，自然冷却即可得组分B，待用。Preparation of component B: Mix the polyamine compound and the prepared prepolymer containing epoxy groups, adjust the reaction temperature to 50-95°C, and stir at a stirring speed of 100-200r/min, and wait for the reaction for 1h -4h, then place it at room temperature, and cool naturally to obtain component B, which is ready for use.
制备双组分环氧树脂胶粘剂：将制备得到的组分A和B，进行单独盛装保存，使用时将组分A和B按照质量比(100-200)：(30-100)混合均匀，即可获得双组分环氧树脂胶粘剂。Preparation of two-component epoxy resin adhesive: The prepared components A and B are stored separately, and the components A and B are mixed evenly according to the mass ratio (100-200): (30-100) during use, that is Two-part epoxy adhesives are available.
本公开还提供一种双组分环氧树脂胶粘剂，其通过本公开所述的制备方法得到。本公开的双组分环氧树脂胶粘剂具备较强的耐受强碱的性能并且粘接强度高。The present disclosure also provides a two-component epoxy resin adhesive, which is obtained through the preparation method described in the present disclosure. The two-component epoxy resin adhesive of the present disclosure has strong strong alkali resistance and high bonding strength.
需要说明的是，在本公开中所述的质量比是指按照所述的物质先后顺序计算的质量比。例如，“组分A和B以质量比(100-200)：(30-100)混合”是指“组分A与组分B按照组分A：组分B的质量比为(100-200)：(30-100)混合”。It should be noted that the mass ratio described in the present disclosure refers to the mass ratio calculated according to the sequence of the substances described. For example, "Components A and B are mixed in a mass ratio (100-200): (30-100)" means "Component A and component B are mixed according to the mass ratio of component A: component B (100-200 ): (30-100) mixed".
实施例Example
下面结合具体的实施例进一步详细说明本公开，但本公开的技术方案绝不限于以下实施例。需要说明的是，实施例中采用的试剂和原料除非特别说明，皆为商购可得的常规产品。The present disclosure will be further described in detail below in conjunction with specific examples, but the technical solutions of the present disclosure are by no means limited to the following examples. It should be noted that, unless otherwise specified, the reagents and raw materials used in the examples are commercially available conventional products.
实施例1Example 1
将10kg双酚A型环氧树脂和120kg 4,4’-二氨基二苯甲烷在60℃下反应3h制得包含端氨基的预聚物；10kg bisphenol A epoxy resin and 120kg 4,4'-diaminodiphenylmethane were reacted at 60°C for 3h to obtain a prepolymer comprising terminal amino groups;
将80kg双酚A型环氧树脂和6kg前述制备得到的包含端氨基的预聚物在75℃和搅拌速度为120r/min下反应1h,再向其中加入8kg聚乙二醇-400，在75℃下持续搅拌反应1.5h，置于室温环境中自然冷却，即可得组分A，待用；80kg of bisphenol A type epoxy resin and 6kg of the prepolymer containing terminal amino groups prepared above were reacted at 75°C and a stirring speed of 120r/min for 1h, then 8kg of polyethylene glycol-400 was added thereto, and the Continue to stir and react at ℃ for 1.5h, and then cool naturally at room temperature to obtain component A, which is ready for use;
将150kg四缩水甘油醚基四苯基乙烷和18kg间苯二胺在60℃下反应3h制得包含端环氧基的预聚物；150 kg of tetraglycidyl ether tetraphenylethane and 18 kg of m-phenylenediamine were reacted at 60 ° C for 3 h to prepare a prepolymer containing an epoxy group;
将80kg 4,4’-二氨基二苯甲烷和15kg包含端环氧基的预聚物在80℃和搅拌速度120r/min下反应2h，将其置于室温环境中自然冷却，即可得组分B，待用；React 80kg of 4,4'-diaminodiphenylmethane and 15kg of prepolymers containing epoxy groups at 80°C and a stirring speed of 120r/min for 2 hours, and place them at room temperature to cool naturally to obtain the compound Point B, to be used;
制备得到的组分A、组分B，进行单独盛装保存。The prepared components A and B are stored in separate containers.
将组分A、组分B按照质量比100:30混合均匀，即可获得双组分环氧树脂胶粘剂。Mix component A and component B evenly according to the mass ratio of 100:30 to obtain a two-component epoxy resin adhesive.
实施例2Example 2
将30kg双酚F型环氧树脂和160kg 4,4’-二氨基二苯甲烷在65℃下反应3h制得包含端氨基的预聚物；30kg of bisphenol F type epoxy resin and 160kg of 4,4'-diaminodiphenylmethane were reacted at 65°C for 3h to obtain a prepolymer comprising terminal amino groups;
将100kg双酚F型环氧树脂和20kg前述制备得到的包含端氨基的预聚物在75℃和搅拌速度为150r/min下反应1h,再向其中加入10kg山梨醇，在70℃下持续搅拌反应2h，置于室温环境中自然冷却，即可得组分A，待用；React 100kg of bisphenol F-type epoxy resin and 20kg of the prepolymer containing terminal amino groups prepared above at 75°C and a stirring speed of 150r/min for 1 hour, then add 10kg of sorbitol to it, and continue stirring at 70°C After reacting for 2 hours, place it at room temperature and cool naturally to obtain component A, which is ready for use;
将40kg四缩水甘油醚基四苯基乙烷和5kg 4,4’-二氨基二苯基甲烷在70℃下反应3h制 得包含端环氧基的预聚物；40kg tetraglycidyl ether base tetraphenylethane and 5kg 4,4'-diaminodiphenylmethane were reacted at 70 DEG C for 3h to obtain a prepolymer comprising an epoxy-terminated group;
将200kg 4,4’-二氨基二苯甲烷和30kg包含端环氧基的预聚物在85℃和搅拌速度100r/min下反应2h,将其置于室温环境中自然冷却，即可得组分B，待用；React 200kg of 4,4'-diaminodiphenylmethane and 30kg of prepolymers containing epoxy groups at 85°C and a stirring speed of 100r/min for 2 hours, and place them at room temperature to cool naturally to obtain the compound Point B, to be used;
制备得到的组分A、组分B，进行单独盛装保存。The prepared components A and B are stored in separate containers.
将组分A、组分B按照质量比100:40混合均匀，即可获得双组分环氧树脂胶粘剂。Mix component A and component B evenly according to the mass ratio of 100:40 to obtain a two-component epoxy resin adhesive.
实施例3Example 3
将50kg四缩水甘油基二胺基二亚甲基苯和180kg间苯二甲胺在70℃下反应2h制得包含端氨基的预聚物；50kg of tetraglycidyldiaminodimethylbenzene and 180kg of m-xylylenediamine were reacted at 70°C for 2h to prepare a prepolymer containing terminal amino groups;
将230kg四缩水甘油基二胺基二亚甲基苯和25kg包含前述制备得到的端氨基的预聚物在90℃和搅拌速度为180r/min下反应1h，再向其中加入30kg丙三醇，在80℃下持续搅拌反应2h，置于室温环境中自然冷却，即可得组分A，待用；230 kg of tetraglycidyl diamino dimethylene benzene and 25 kg of the prepolymer containing the terminal amino groups prepared above were reacted at 90 ° C and a stirring speed of 180 r/min for 1 h, and then 30 kg of glycerol was added thereto, Continue to stir and react at 80°C for 2 hours, and cool naturally at room temperature to obtain component A, which is ready for use;
将150kg三苯基缩水甘油醚基甲烷和15kg间苯二甲胺在80℃下反应2.5h制得包含端环氧基的预聚物；150kg of triphenylglycidyl ether methane and 15kg of m-xylylenediamine were reacted at 80°C for 2.5h to prepare a prepolymer containing an epoxy-terminated group;
将180kg间苯二甲胺和80kg包含端环氧基的预聚物在80℃和搅拌速度150r/min下反应2h，将其置于室温环境中自然冷却，即可得组分B，待用；React 180kg of m-xylylenediamine and 80kg of prepolymers containing epoxy groups at 80°C and a stirring speed of 150r/min for 2h, place them at room temperature and cool naturally to obtain component B, ready to use ;
制备得到的组分A、组分B，进行单独盛装保存。The prepared components A and B are stored in separate containers.
将组分A、组分B按照质量比100:30混合均匀，即可获得双组分环氧树脂胶粘剂。Mix component A and component B evenly according to the mass ratio of 100:30 to obtain a two-component epoxy resin adhesive.
实施例4Example 4
将60kg双酚S型环氧树脂和180kg 4,4’-二氨基二苯甲烷在70℃下反应2h制得包含端氨基的预聚物；60kg of bisphenol S-type epoxy resin and 180kg of 4,4'-diaminodiphenylmethane were reacted at 70°C for 2h to obtain a prepolymer containing terminal amino groups;
将200kg双酚S型环氧树脂和25kg前述制备得到的包含端氨基的预聚物在80℃和搅拌速度为150r/min下反应1h，再向其中加入30kg聚乙二醇-400，在85℃下持续搅拌反应2h，置于室温环境中自然冷却，即可得组分A，待用；200kg of bisphenol S-type epoxy resin and 25kg of the prepolymer containing terminal amino groups prepared above were reacted for 1h at 80°C and a stirring speed of 150r/min, then 30kg of polyethylene glycol-400 was added thereto, and the Continue to stir and react at ℃ for 2 hours, and cool naturally at room temperature to obtain component A, which is ready for use;
将100kg双酚S型环氧树脂和15kg 4,4’-二氨基二苯甲烷在80℃下反应2.5h制得包含端环氧基的预聚物；100kg of bisphenol S-type epoxy resin and 15kg of 4,4'-diaminodiphenylmethane were reacted at 80°C for 2.5h to obtain a prepolymer comprising an epoxy-terminated group;
将160kg 4,4’-二氨基二苯甲烷和80kg包含端环氧基的预聚物在80℃和搅拌速度140r/min下反应2h，将其置于室温环境中自然冷却，即可得组分B，待用；React 160kg of 4,4'-diaminodiphenylmethane and 80kg of prepolymers containing epoxy groups at 80°C and a stirring speed of 140r/min for 2 hours, and place them at room temperature to cool naturally to obtain the compound Point B, to be used;
制备得到的组分A、组分B，进行单独盛装保存。The prepared components A and B are stored in separate containers.
将组分A、组分B按照质量比100:40混合均匀，即可获得双组分环氧树脂胶粘剂。Mix component A and component B evenly according to the mass ratio of 100:40 to obtain a two-component epoxy resin adhesive.
实施例5Example 5
将65kg双酚S型环氧树脂和180kg间苯二甲胺在75℃下反应2h制得包含端氨基的预聚物；65kg of bisphenol S-type epoxy resin and 180kg of m-xylylenediamine were reacted at 75°C for 2h to prepare a prepolymer containing terminal amino groups;
将200kg双酚S型环氧树脂和25kg包含端氨基的预聚物在85℃和搅拌速度为140r/min下反应1h，再向其中加入30kg蓖麻油，在85℃下持续搅拌反应2h，置于室温环境中自然冷却，即可得组分A，待用；React 200kg of bisphenol S-type epoxy resin and 25kg of prepolymer containing terminal amino groups at 85°C and a stirring speed of 140r/min for 1h, then add 30kg of castor oil to it, and continue to stir and react at 85°C for 2h. Cool naturally at room temperature to obtain component A, ready to use;
将100kg双酚S型环氧树脂和15kg间苯二甲胺在80℃下反应2.5h制得包含端环氧基的预聚物；100kg of bisphenol S-type epoxy resin and 15kg of m-xylylenediamine were reacted at 80°C for 2.5h to prepare a prepolymer containing epoxy groups;
将190kg间苯二甲胺和80kg包含端环氧基的预聚物在80℃和搅拌速度140r/min下反应2h，将其置于室温环境中自然冷却，即可得组分B，待用；React 190kg of m-xylylenediamine and 80kg of prepolymers containing epoxy groups at 80°C and a stirring speed of 140r/min for 2 hours, and place them at room temperature to cool naturally to obtain component B, which is ready for use ;
制备得到的组分A、组分B，进行单独盛装保存。The prepared components A and B are stored in separate containers.
将组分A、组分B按照质量比100:50混合均匀，即可获得双组分环氧树脂胶粘剂。Mix component A and component B evenly according to the mass ratio of 100:50 to obtain a two-component epoxy resin adhesive.
双组分环氧树脂胶粘剂的耐强碱性能测试和胶线的剥离强度的测试Two-component epoxy resin adhesive's strong alkali resistance test and the peel strength test of the glue line
将实施例1至5中制得的双组分环氧树脂胶粘剂分别用于密封纳滤膜组件，然后将经密封的纳滤膜组件浸泡于20％NaOH的水溶液中180天，并且对膜组件的边胶胶线和底胶胶线在未浸泡前和分别浸泡30天、60天、90天、120天、150天和180天的剥离强度进行检测，测试步骤和测试条件为：分别裁取组件进水端、出水端和底端的胶线样条(长10cm、宽2cm)，样条为淡网和膜片经胶粘剂粘接后的组合物，其中胶粘面积为2cm*2cm(位于样条端部)。以胶粘部分为中心将样条两端夹在万能拉伸试验机的夹具上做180°剥离测试，在50mm/min的速率下垂直剥离30s，记录胶线剥离强度。The two-component epoxy resin adhesive that makes among the embodiment 1 to 5 is used for sealing nanofiltration membrane assembly respectively, then the nanofiltration membrane assembly through sealing is soaked in the aqueous solution of 20%NaOH 180 days, and to membrane assembly The peel strength of the side glue line and bottom glue line before soaking and soaking for 30 days, 60 days, 90 days, 120 days, 150 days and 180 days were tested. The test steps and test conditions are: cut The glue line splines (length 10cm, width 2cm) of the water inlet, water outlet and bottom of the module, the spline is the composition of the light net and the diaphragm bonded by adhesive, and the glued area is 2cm*2cm (located in the sample strip ends). Clamp both ends of the sample on the fixture of the universal tensile testing machine with the glued part as the center to do a 180° peel test, peel vertically at a rate of 50mm/min for 30s, and record the peel strength of the glue line.
测试数据结果如下表1所示：The test data results are shown in Table 1 below:
表1Table 1
Figure PCTCN2021135760-appb-000001
Figure PCTCN2021135760-appb-000001
从表1中的数据可以看出，分别使用本公开的实施例1-5中制备的双组份环氧树脂胶粘剂密封的耐碱纳滤膜组件在20％NaOH水溶液浸泡180天过程中，边胶的胶线剥离强度和底胶的胶线剥离强度均与初始值一致，因此，证明了在强碱溶液环境中长期保存后仍然保持了较好的粘接强度，这也表明本公开的实施例1-5中得到的胶粘剂既具有较好的耐受强碱的性能，又具有较好的粘接强度，因此，该胶粘剂适用于密封耐碱纳滤膜组件。As can be seen from the data in Table 1, the alkali-resistant nanofiltration membrane assembly sealed with the two-component epoxy resin adhesive prepared in Examples 1-5 of the present disclosure was soaked in 20% NaOH aqueous solution for 180 days, while The glue line peel strength of the glue and the glue line peel strength of the bottom glue are all consistent with the initial value, therefore, it has been proved that after long-term storage in the strong alkali solution environment, good bonding strength is still maintained, which also shows that the implementation of the present disclosure The adhesive obtained in Examples 1-5 not only has good alkali resistance performance, but also has good bonding strength, therefore, the adhesive is suitable for sealing alkali-resistant nanofiltration membrane modules.
发明人将实施例1制备的双组分环氧树脂胶粘剂用于密封纳滤膜组件，并将其分别浸泡在20％NaOH水溶液和20％KOH水溶液中180天，对膜组件的边胶胶线和底胶胶线在未浸泡前和浸泡不同天数后的剥离强度进行检测，将所得结果作表分别如图1和图2所示。The inventor used the two-component epoxy resin adhesive prepared in Example 1 to seal the nanofiltration membrane module, and soaked it in 20% NaOH aqueous solution and 20% KOH aqueous solution for 180 days respectively, and glued the edge of the membrane module. The peeling strength of the primer line before soaking and after soaking for different days was tested, and the results were tabulated as shown in Figure 1 and Figure 2, respectively.
从图1和图2可以看出，将胶线分别浸泡于20％NaOH水溶液和20％KOH水溶液180天后，边胶的剥离强度和底胶的剥离强度均与初始值一致，为大于5N/20mm。这表明胶粘剂能耐受20％NaOH、20％KOH等强碱，可以实现胶粘剂在强碱环境中的应用，使用该胶粘剂卷制耐碱纳滤膜组件时，胶线的剥离强度大于5N/20mm，这解决了长久以来耐碱纳滤膜产品在现场应用时密封问题的技术瓶颈，有利于耐碱纳滤膜密封性能的提升和产品的市场推广。It can be seen from Figure 1 and Figure 2 that after soaking the glue line in 20% NaOH aqueous solution and 20% KOH aqueous solution for 180 days, the peel strength of the edge glue and the peel strength of the bottom glue are consistent with the initial values, which are greater than 5N/20mm . This shows that the adhesive can withstand strong alkalis such as 20% NaOH and 20% KOH, and can realize the application of the adhesive in a strong alkali environment. When the adhesive is used to roll alkali-resistant nanofiltration membrane modules, the peel strength of the glue line is greater than 5N/20mm , which solves the long-standing technical bottleneck of the sealing problem of alkali-resistant nanofiltration membrane products in field application, and is conducive to the improvement of the sealing performance of alkali-resistant nanofiltration membranes and the market promotion of products.
发明人将实施例3制备的双组分环氧树脂胶粘剂用于密封纳滤膜组件，并且分别对边胶胶线和底胶胶线的断面使用扫描电子显微镜进行观察，分别如图3的(a)和(b)所示， 可以明显的看到，胶粘剂以互穿网络结构存在于膜片与淡水隔网之间，这也表明了本公开所制备的耐强碱双组份环氧树脂胶粘剂的高强度特性。The inventor used the two-component epoxy resin adhesive prepared in Example 3 to seal the nanofiltration membrane module, and observed the cross-sections of the edge glue line and the bottom glue line respectively using a scanning electron microscope, as shown in Figure 3 ( As shown in a) and (b), it can be clearly seen that the adhesive exists between the diaphragm and the freshwater spacer with an interpenetrating network structure, which also shows that the strong alkali-resistant two-component epoxy resin prepared by the present disclosure High strength properties of the adhesive.
以上所述的具体实施例，对本公开的目的、技术方案和有益效果进行了进一步的详细说明，应理解的是，以上所述仅为本公开的实施例而已，并不用于限制本公开，凡在本公开的原则和精神之内，所做的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。The specific embodiments described above have further described the purpose, technical solutions and beneficial effects of the present disclosure in detail. It should be understood that the above descriptions are only examples of the present disclosure and are not intended to limit the present disclosure. Within the principles and spirit of the present disclosure, any modifications, equivalent replacements, improvements, etc., shall be included in the protection scope of the present disclosure.
产业上的可利用性Industrial availability
本公开提供的双组分环氧树脂胶粘剂的制备方法，采用的原料来源简单，方法成本低廉，制备操作容易，适于工业上的规模化生产，本公开得到的双组分环氧树脂胶粘剂具备较强的耐受强碱的性能，粘接强度高。The preparation method of the two-component epoxy resin adhesive provided by the present disclosure has simple sources of raw materials, low method cost, easy preparation and operation, and is suitable for large-scale industrial production. The two-component epoxy resin adhesive obtained by the present disclosure has Strong alkali resistance performance, high bonding strength.

Claims (9)

  1. 一种双组分环氧树脂胶粘剂的制备方法，其特征在于，包括以下步骤：A preparation method of two-component epoxy resin adhesive, is characterized in that, comprises the following steps:
    制备包含端氨基的预聚物，其中将包含两个以上的环氧基的环氧化合物和/或环氧树脂与多元胺类化合物以质量比为(10-70)：(100-200)在温度为50-95℃的条件下混合，所述多元胺类化合物为选自芳香族二元胺类化合物、脂肪族二元至四元胺类化合物、脂环族二元至四元胺类化合物中的至少一种；Prepare a prepolymer containing terminal amino groups, wherein the epoxy compound and/or epoxy resin containing two or more epoxy groups and the polyamine compound are in a mass ratio of (10-70): (100-200) in Mixing at a temperature of 50-95°C, the polyamine compound is selected from aromatic diamine compounds, aliphatic di- to tetra-amine compounds, alicyclic di- to tetra-amine compounds at least one of;
    制备组分A，其中将包含两个以上的环氧基的环氧化合物和/或环氧树脂、所述包含端氨基的预聚物在温度为50-95℃的条件下混合，然后加入醇类物质，其中所述包含两个以上的环氧基的环氧化合物和/或环氧树脂、所述包含端氨基的预聚物、所述醇类物质的质量比为(50-250)：(5-30)：(5-40)；Preparation of component A, wherein the epoxy compound and/or epoxy resin containing more than two epoxy groups and the prepolymer containing terminal amino groups are mixed at a temperature of 50-95° C., and then alcohol is added Class substances, wherein the mass ratio of the epoxy compound and/or epoxy resin comprising two or more epoxy groups, the prepolymer comprising terminal amino groups, and the alcohols is (50-250): (5-30): (5-40);
    制备包含端环氧基的预聚物，其中将包含两个以上的环氧基的环氧化合物和/或环氧树脂与多元胺类化合物以质量比为(100-200)：(5-20)在温度为50-95℃的条件下混合，所述多元胺类化合物为选自芳香族二元胺类化合物、脂肪族二元至四元胺类化合物、脂环族二元至四元胺类化合物中的至少一种；Prepare the prepolymer that comprises terminal epoxy group, wherein will comprise the epoxy compound and/or epoxy resin of more than two epoxy groups and polyamine compound with mass ratio (100-200): (5-20 ) mixed at a temperature of 50-95°C, and the polyamine compound is selected from the group consisting of aromatic diamine compounds, aliphatic di- to tetra-amine compounds, alicyclic di-to-quaternary amines at least one of the class of compounds;
    制备组分B，其中将多元胺类化合物和所述包含端环氧基的预聚物以质量比为(50-250)：(5-50)在温度为50-95℃的条件下混合，所述多元胺类化合物为选自芳香族二元胺类化合物、脂肪族二元至四元胺类化合物、脂环族二元至四元胺类化合物中的至少一种；Preparation of component B, wherein the polyamine compound and the prepolymer containing epoxy groups are mixed at a mass ratio of (50-250):(5-50) at a temperature of 50-95°C, The polyamine compound is at least one selected from aromatic diamine compounds, aliphatic di- to tetra-amine compounds, and alicyclic di- to tetra-amine compounds;
    制备双组分环氧树脂胶粘剂，其中将所述组分A和所述组分B以质量比为(100-200)：(30-100)混合。A two-component epoxy resin adhesive is prepared, wherein the component A and the component B are mixed in a mass ratio of (100-200):(30-100).
  2. 根据权利要求1所述的制备方法，其中所述包含两个以上的环氧基的环氧化合物为选自以下环氧化合物中的至少一种：四缩水甘油醚基四苯基乙烷、三苯基缩水甘油醚基甲烷、四缩水甘油基二甲苯二胺、三缩水甘油基-p-氨基苯酚、四缩水甘油基二胺基二亚甲基苯、邻苯二甲酸二缩水甘油酯。The preparation method according to claim 1, wherein the epoxy compound comprising more than two epoxy groups is at least one selected from the following epoxy compounds: tetraglycidyl ether tetraphenylethane, tris Phenylglycidylmethane, tetraglycidylxylylenediamine, triglycidyl-p-aminophenol, tetraglycidyldiaminodimethylbenzene, diglycidylphthalate.
  3. 根据权利要求1或2所述的制备方法，其中所述包含两个以上的环氧基的环氧树脂为选自以下环氧树脂中的至少一种：双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、氢化双酚A型环氧树脂、线性酚醛型环氧树脂、脂肪族缩水甘油醚树脂、溴化环氧树脂、海因环氧树脂。The preparation method according to claim 1 or 2, wherein the epoxy resin comprising more than two epoxy groups is at least one selected from the following epoxy resins: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac type epoxy resin, aliphatic glycidyl ether resin, brominated epoxy resin, hydantoin epoxy resin.
  4. 根据权利要求1或2所述的制备方法，其中所述芳香族二元胺类化合物为选自以下化合物中的至少一种：4,4’-二氨基二苯甲烷、间苯二胺、间苯二甲胺、4,4’-二氨基二苯砜、二氨基二苯基甲烷、二氨基二苯基砜、间二甲苯二胺；所述脂肪族二元至四元胺类化合物为选自以下化合物中的至少一种：乙二胺、己二胺、N,N-二甲氨基丙胺、N,N-二乙氨基丙胺、三乙烯四胺；所述脂环族二元至四元胺类化合物为选自以下化合物中的至少一种：二乙烯三胺、异佛尔酮二胺、N-氨乙基哌嗪、3,9-双(3-氨丙基)-2,4,8,10-四氧杂螺[5.5]十一烷、双(4-氨基-3-甲基环己基)甲烷、双(4-氨基环己基)甲烷。The preparation method according to claim 1 or 2, wherein the aromatic diamine compound is at least one selected from the following compounds: 4,4'-diaminodiphenylmethane, m-phenylenediamine, m- xylylenediamine, 4,4'-diaminodiphenylsulfone, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylylenediamine; the aliphatic binary to tetravalent amine compounds are optional At least one of the following compounds: ethylenediamine, hexamethylenediamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, triethylenetetramine; the alicyclic binary to quaternary The amine compound is at least one selected from the following compounds: diethylenetriamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)-2,4 ,8,10-tetraoxaspiro[5.5]undecane, bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane.
  5. 根据权利要求1或2所述的制备方法，其中在所述制备包含端氨基的预聚物的步骤中，以氨基的摩尔量计的所述多元胺类化合物的量与以环氧基的摩尔量计的所述包含两个以上的环氧基的环氧化合物和/或环氧树脂的量之比在大于1且小于等于10的范围内。The preparation method according to claim 1 or 2, wherein in the step of preparing the prepolymer containing terminal amino groups, the amount of the polyamine compound in the molar amount of the amino group is different from the molar amount of the epoxy group The ratio of the amount of the epoxy compound containing two or more epoxy groups and/or the epoxy resin is in the range of greater than 1 and less than or equal to 10.
  6. 根据权利要求1或2所述的制备方法，其中所述醇类物质为包含至少一个羟基的醇类单体或聚合物中的至少一种。The preparation method according to claim 1 or 2, wherein the alcohol substance is at least one of alcohol monomers or polymers containing at least one hydroxyl group.
  7. 根据权利要求6所述的制备方法，其中所述包含至少一个羟基的醇类单体或聚合物为选自以下的至少一种：甲醇、乙醇、乙二醇、丙醇、异丙醇、1-丁醇、2-丁醇、2-甲基-2-丙醇、环己醇、蓖麻油、大豆油、丙三醇、三羟甲基丙烷、木糖醇、山梨醇、丙糖、丁糖、戊糖、己糖、庚糖、甘露醇、蔗糖、苯甲醇、季戊四醇、己六醇、聚乙二醇-200、聚乙二醇-400、聚乙二醇-600、聚乙二醇-1000、聚丙二醇-400、聚丙三醇-1000。The preparation method according to claim 6, wherein the alcohol monomer or polymer comprising at least one hydroxyl group is at least one selected from the group consisting of methanol, ethanol, ethylene glycol, propanol, isopropanol, 1 -Butanol, 2-butanol, 2-methyl-2-propanol, cyclohexanol, castor oil, soybean oil, glycerol, trimethylolpropane, xylitol, sorbitol, triose, butyl Sugar, pentose, hexose, heptose, mannitol, sucrose, benzyl alcohol, pentaerythritol, hexyl alcohol, macrogol-200, macrogol-400, macrogol-600, macrogol -1000, Polypropylene Glycol-400, Polyglycerol-1000.
  8. 根据权利要求1或2所述的制备方法，其中在所述制备包含端环氧基的预聚物的步骤中，以环氧基的摩尔量计的所述包含两个以上的环氧基的环氧化合物和/或环氧树脂的量与以氨基的摩尔量计的所述多元胺类化合物的量之比在大于1且小于等于15的范围内。The preparation method according to claim 1 or 2, wherein in the step of preparing the prepolymer containing epoxy groups, the molar weight of epoxy groups containing more than two epoxy groups The ratio of the amount of the epoxy compound and/or epoxy resin to the amount of the polyamine compound based on the molar amount of the amino group is within a range of greater than 1 and less than or equal to 15.
  9. 一种双组分环氧树脂胶粘剂，其通过根据权利要求1-8中任一项所述的制备方法得到。A two-component epoxy resin adhesive obtained by the preparation method according to any one of claims 1-8.
PCT/CN2021/135760 2021-07-19 2021-12-06 Preparation method for two-component epoxy resin adhesive and two-component epoxy resin adhesive prepared thereby WO2023000582A1 (en)

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