CN113736402A - Environment-friendly abrasion-resistant anti-degradation epoxy resin daub and preparation method thereof - Google Patents
Environment-friendly abrasion-resistant anti-degradation epoxy resin daub and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
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- C08K2003/323—Ammonium polyphosphate
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- C08L2201/02—Flame or fire retardant/resistant
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention relates to the field of buildings and building materials, in particular to a high-molecular environment-friendly abrasion-resistant deterioration-resistant epoxy resin mortar and a preparation method thereof. The composite material is prepared by mixing and reacting epoxy resin, a surface active auxiliary agent, epoxy cyclohexyl-cage polysilsesquioxane, a silane coupling agent, fumed silica, unsaturated polyester resin, brominated nano light calcium, a curing agent, a DMP-30 accelerator, an ultraviolet absorbent, aramid fiber powder, a flame retardant, graphene oxide nanosheets and the like. The invention has the advantages that: the epoxy daub prepared by the invention has higher strength, toughness, impact resistance and abrasion resistance, the ultraviolet aging resistance, flame retardance, thermal linear expansion coefficient and the like of the epoxy daub are obviously improved, the problems of curling, shelling and cracking in the construction process are solved, the comprehensive performance is good, and the epoxy daub can be used for hydraulic and hydroelectric engineering, bridge engineering, high-speed rail traffic engineering, building engineering and the like.
Description
Technical Field
The invention belongs to the field of buildings and building materials, and particularly relates to high-molecular environment-friendly abrasion-resistant deterioration-resistant epoxy resin mortar and a preparation method thereof.
Background
The epoxy daub is a novel thin-layer repairing material which is composed of epoxy resin, curing agent and hard filler and has high strength, erosion resistance and firm bonding, has the functions of seepage prevention, sealing, corrosion prevention and the like in bonding repair, can be used for repairing thin-layer defects of air holes, small honeycombs, pitted surfaces, sand lines and the like on the surface of concrete, performing seepage prevention, carbonization prevention, degradation prevention protection, fine crack sealing and appearance beautifying treatment on the concrete, and is also suitable for repairing surface defects of special train beams and track plates for high-speed railway passenger transportation and repairing or anti-erosion protection treatment on slight abrasion after overflowing the surface of concrete of hydraulic buildings. Epoxy resin is one of thermosetting resins which are widely used in modern industry, has excellent corrosion resistance and chemical resistance, good moisture resistance and solvent resistance, excellent adhesion and easy curing, but has high crosslinking density after curing and a three-dimensional network structure, so that the epoxy resin has the defects of large internal stress, brittleness, poor impact resistance, poor weather resistance and the like. The high temperature resistance is poor, the coefficient of thermal linear expansion cannot meet the ideal requirement, and the matching property with concrete is poor; in the construction process of the conventional epoxy daub material, the phenomena of curling, shelling and falling off can be generated when the surface of a matrix is coated and scraped, and a cured daub layer can crack and pulverize, so that the impermeability is reduced. When the relatively closed water outlet structure is constructed in a circulating environment, the conventional material has no flame retardance, and is not beneficial to fire prevention and construction environment safety.
The epoxy resin is used for a plurality of products of walls, and the products used in hydraulic engineering such as hydropower stations and the like are not specially disclosed, and particularly, the products which need to use the epoxy resin in the underwater operation process do not form a standard research result.
Disclosure of Invention
Aiming at the defects and shortcomings of the epoxy daub, the epoxy daub material disclosed by the invention is designed to improve the toughness of the epoxy daub material, improve the ultraviolet aging resistance, the flame retardant property, the thermal linear expansion coefficient and other properties, solve the problems of curling, shelling and cracking in the construction process and obtain the epoxy daub with excellent performance and convenience in construction. The material of the invention is planned to add aramid fiber powder to improve the toughness of the epoxy daub, improve the high temperature resistance and reduce the coefficient of thermal linear expansion; the unsaturated polyester resin is added in the mortar, so that the coating scraping and flexibility of the mortar are improved, the porosity is reduced, and the anti-permeability capability of the mortar is improved; adding an ultraviolet absorbent to improve the ultraviolet resistance and the ageing resistance of the cured daub and delay the pulverization and the light loss of the resin; the flame retardant is added to improve the flame retardant property of the epoxy daub.
The product of the application is tested in the fields of hydraulic and hydroelectric engineering, high-speed rail engineering, constructional engineering and the like. The developed product is subjected to field verification tests on projects such as a Wudongde hydropower station of a power plant, a Baihe beach hydropower station and a Jinghong hydropower station under China Huaneng group company, indexes of the developed product can meet requirements, and a product prototype is formed preliminarily. When the product is applied to water conservancy and hydropower engineering, a professional construction enterprise is required to carry out construction, the ratio of product technical consultants to constructors is 1:8 according to the past engineering experience, and after popularization and application, company technical consultants are arranged according to national partitions, so that employment increasing opportunities are indirectly driven.
The invention is realized by the following technical scheme:
the environment-friendly abrasion-resistant deterioration-resistant epoxy resin daub is characterized by consisting of a component A and a component B, wherein the use ratio of the component A to the component B is 3-6: 1;
the component A comprises the following components in parts by mass:
the component B comprises the following components in parts by mass:
wherein the epoxy cyclohexyl-cage polysilsesquioxane has the following structure:
The epoxy resin is a base material of epoxy daub, and has excellent corrosion resistance, chemical resistance, moisture resistance and solvent resistance, strong adhesive force and easy curing. The surface active agent can obviously reduce the surface tension of a system, improve the dispersibility and the permeability of materials, improve the bonding strength of a coating and a base surface, and select proper oily surface active agent to have important influence on the quality of a product. The epoxy cyclohexyl-cage polysilsesquioxane is a main component for forming a high molecular alloy structure, has excellent solvent resistance, can enhance the chemical and thermal stability of the material, enlarge the use temperature range of a system, improve the mechanical property, improve the processing property of the material and enable the material to have obvious delayed combustion characteristic. The silane coupling agent can modify the surface of the filler, and improve the dispersibility and the bonding strength of the filler in the resin. Due to the variety of fillers, the performance of the product can be effectively influenced and improved by selecting a specific preparation. The fumed silica has large specific surface area and strong surface adsorption capacity, can be uniformly and fully dispersed into a resin material, and obviously improves the dispersibility of the system; in addition, the fumed silica has the effects of improving the strength and the elongation of the material, improving the thixotropic property of a system and preventing sagging. The nanometer light calcium bromide is a composition of the nanometer light calcium and a bromine-containing flame retardant, and has a system filling effect and a flame retardant effect.
The curing agent chemically reacts with the epoxy resin to convert the linear resin into a tough, cross-linked, network-like solid resin. DMP-30 is used as an accelerant to accelerate the curing time of epoxy resin, the curing time requirement in the construction process is higher, the faster the construction process is, and the proper curing time needs to be selected according to the requirement and the characteristics in the construction process. The ultraviolet absorbent is a light stabilizer, can improve the ultraviolet aging resistance of materials, has super-strong ultraviolet absorption capacity, good thermal stability, good chemical stability and good miscibility, and has good photochemical stability, no color, no toxicity and no odor. The aramid fiber powder can realize the toughening effect, can resist high temperature, can reduce the coefficient of thermal linear expansion of the material, and has good matching property with the base concrete. The graphene oxide nanosheet is a graphene-based carbon nanomaterial functionalized by oxygen-containing groups, has high hydrophilicity and surface activity, has a certain effect of inhibiting the growth of aquatic organisms and bacteria on the surface of the coating, and can also improve the thermal stability of the coating and play a toughening role. Flame retardants function as flame retardants, and as such, there are many types of flame retardants that can be adapted for use in the specific applications and situations of the present application, which require constant testing by skilled artisans.
Preferably, in the environment-friendly abrasion-resistant deterioration-resistant epoxy resin mortar, the epoxy resin is composed of an adhesion main body and a modification main body, the adhesion main body is bisphenol A type epoxy resin or bisphenol F type epoxy resin, the modification main body is epoxy-terminated polysiloxane with the epoxy equivalent of 400-900g/mol, and the mass ratio of the adhesion main body to the modification main body is 8-12: 1.
Preferably, the modified main body in the environment-friendly abrasion-resistant deterioration-resistant epoxy resin mortar further comprises 15-25% by mass of fused ring aromatic group epoxy resin; the condensed ring aromatic hydrocarbon group epoxy resin is naphthyl epoxy resin or anthryl epoxy resin.
Preferably, the diluent in the environment-friendly anti-abrasion and anti-deterioration epoxy resin mortar is one or more of C12-14 alkyl glycidyl ether, 1, 6-hexanediol diglycidyl ether and polypropylene glycol diglycidyl ether; and a reactive diluent in a certain proportion, specifically alicyclic glycidyl ether, ethylene glycol diglycidyl ether, or benzyl glycidyl ether; the part ratio of the diluent to the active diluent is 1-3: 1.
preferably, the curing agent in the component B in the environment-friendly, abrasion-resistant and deterioration-resistant epoxy resin mortar is a composite curing agent consisting of a modified fatty amine adduct, phenolic amine, vinyl-terminated butadiene-acrylonitrile rubber (methacrylic acid-terminated butadiene-acrylonitrile copolymer) and a polyether nitrile hydrogenated polycondensate, and the mass ratio of the curing agent to the polyether nitrile hydrogenated polycondensate is 1:1: 0.2-0.5: 0.2-0.5.
Preferably, the ultraviolet absorber in the environment-friendly abrasion-resistant deterioration-resistant epoxy resin mortar is a triazine ultraviolet absorber or a benzotriazole ultraviolet absorber.
Preferably, the flame retardant in the environment-friendly, abrasion-resistant and deterioration-resistant epoxy resin mortar is one of tris (2-chloroethyl) phosphate, ammonium polyphosphate, dimethyl methyl phosphate or tris-dichloropropyl phosphate.
The preparation method of the environment-friendly abrasion-resistant deterioration-resistant epoxy resin daub is characterized by comprising the following steps of:
(1) mixing the epoxy resin, the diluent and the surface active auxiliary agent in the component A, uniformly stirring, adding into a shear dispersion machine, adding the epoxy cyclohexyl-cage polysilsesquioxane, the silane coupling agent, the fumed silica and the brominated nano light calcium, and shearing and dispersing until the fineness is less than 50;
(2) mixing the curing agent and the DMP-30 accelerator in the component B, uniformly stirring, adding into a shear dispersion machine, adding the ultraviolet absorbent, the aramid fiber powder, the flame retardant and the graphene oxide nanosheet, and grinding until the fineness is less than 50;
(3) and (3) mixing the mixtures prepared in the step (1) and the step (2) in proportion, and shearing and dispersing by using a shearing disperser to obtain the daub.
Preferably, in the preparation method of the environment-friendly abrasion-resistant deterioration-resistant epoxy resin mortar, the epoxy resin is prepared into particles by curing the modified main body and the partially bonded main body, and then the particles are added into the component A.
Preferably, the preparation method of the environment-friendly abrasion-resistant deterioration-resistant epoxy resin mortar comprises the following steps: (1) mixing a modified main body containing epoxy-terminated polysiloxane and condensed ring aromatic hydrocarbon epoxy resin with an equivalent amount of bisphenol A epoxy resin or bisphenol F epoxy resin, adding a diluent with an equivalent amount of the modified main body, and fully mixing and stirring 2% of a surface active auxiliary agent to obtain a solution A;
(2) dissolving polyethylene glycol and sodium dodecyl sulfate in deionized water to prepare solutions with mass concentrations of 10% and 10%, and adding the solutions into the solution B;
(3) adding the solution A into the solution B under rapid stirring, wherein the mixing volume ratio is 1-2:1, continuously stirring for 20min after mixing, controlling the temperature at 30-40 ℃, filtering out a product after reacting for 4h, washing and drying to obtain the particles;
(4) mixing the rest of the epoxy resin, the diluent and the active diluent in the component A, uniformly stirring, adding into a shear dispersion machine, adding epoxy cyclohexyl-cage polysilsesquioxane, a silane coupling agent, fumed silica, nano calcium bromide and the particles prepared in the step (3), and shearing and dispersing until the fineness is less than 50;
(5) mixing the rest of the curing agent and the DMP-30 accelerator in the component B, uniformly stirring, adding into a shear dispersion machine, adding the ultraviolet absorbent, the aramid fiber powder, the flame retardant and the graphene oxide nanosheet, and shearing and dispersing until the fineness is less than 50;
(6) and (5) mixing the mixtures prepared in the steps (4) and (5) in proportion, and shearing and dispersing by using a shearing disperser to obtain the daub.
Has the advantages that: the product of the invention improves the toughness of the epoxy daub material, improves the ultraviolet aging resistance, the flame retardant property, the thermal linear expansion coefficient and other properties, solves the problems of curling, shelling and cracking in the construction process, and obtains the epoxy daub with excellent performance and convenient construction.
Detailed Description
The following is a detailed description of the practice of the invention:
the embodiment of the application relates to an environment-friendly, abrasion-resistant and deterioration-resistant epoxy resin daub which comprises a component A and a component B, wherein the use ratio of the component A to the component B is (3-6) to 1, and the component A comprises the following components in parts by mass: 40-60 parts of epoxy resin, 8-15 parts of diluent, 5-8 parts of reactive diluent, 8-12 parts of surface active auxiliary agent, 3-5 parts of epoxy cyclohexyl-cage polysilsesquioxane, 5-8 parts of silane coupling agent, 10-14 parts of fumed silica, 8-12 parts of unsaturated polyester resin and 18-25 parts of brominated nano light calcium; the component B comprises the following components in parts by mass: 60-80 parts of curing agent, 10-20 parts of DMP-30 accelerator, 15-20 parts of ultraviolet absorbent, 2-5 parts of aramid fiber powder, 2-5 parts of flame retardant and 2-5 parts of graphene oxide nanosheet.
The epoxy resin is composed of an adhesion main body and a modification main body, wherein the adhesion main body is bisphenol A type epoxy resin or bisphenol F type epoxy resin, the modification main body is epoxy group terminated polysiloxane with the epoxy equivalent of 400-900g/mol, and the mass ratio of the adhesion main body to the modification main body is (8-12): 1.
The composite curing agent comprises a modified fatty amine adduct, phenolic amine, vinyl-terminated nitrile rubber (methacrylic acid-terminated nitrile copolymer) and a polyether nitrile hydrogenated polycondensate, and the mass ratio of the composite curing agent to the polyether nitrile hydrogenated polycondensate is 1:1 (0.2-0.5): (0.2-0.5).
The modified main body also comprises 15-25% of fused ring aromatic epoxy resin. The condensed ring aromatic hydrocarbon group epoxy resin is naphthyl epoxy resin or anthryl epoxy resin.
The diluent is one or more of C12-14 alkyl glycidyl ether, 1, 6-hexanediol diglycidyl ether and polypropylene glycol diglycidyl ether.
The ultraviolet absorbent is triazine ultraviolet absorbent or benzotriazole ultraviolet absorbent.
The flame retardant is tris (2-chloroethyl) phosphate, ammonium polyphosphate, dimethyl methyl phosphate or tris-dichloropropyl phosphate.
The embodiment of the application also relates to a preparation method of the environment-friendly abrasion-resistant deterioration-resistant epoxy resin daub, which comprises the following steps:
(1) mixing the epoxy resin, the diluent, the reactive diluent and the surface active additive in the component A, uniformly stirring, adding into a shear dispersion machine, adding the epoxy cyclohexyl-cage polysilsesquioxane, the silane coupling agent, the fumed silica and the brominated nano light calcium, and shearing and dispersing until the fineness is less than 50;
(2) mixing the curing agent and the DMP-30 accelerator in the component B, uniformly stirring, adding into a shear dispersion machine, adding the ultraviolet absorbent, the aramid fiber powder, the flame retardant and the graphene oxide nanosheet, and grinding until the fineness is less than 50;
(3) and (3) mixing the mixtures prepared in the step (1) and the step (2) in proportion, and shearing and dispersing by using a shearing disperser to obtain the daub.
As a further optimized scheme, the application also provides another preparation method of the environment-friendly abrasion-resistant deterioration-resistant epoxy resin mortar, specifically, a modified main body and a part of a cementing main body are cured to prepare particles, and then the particles are added into the component a, wherein the preparation method comprises the following steps:
(1) mixing a modified main body containing epoxy-terminated polysiloxane and condensed ring aromatic hydrocarbon epoxy resin with an equivalent amount of bisphenol A epoxy resin or bisphenol F epoxy resin, adding a diluent with an equivalent amount of the modified main body, and fully mixing and stirring 2% of a surface active auxiliary agent to obtain a solution A;
(2) dissolving polyethylene glycol and sodium dodecyl sulfate in deionized water to prepare solutions with the concentrations of 10% and 10% respectively to obtain a solution B;
(3) adding the solution A into the solution B under rapid stirring, wherein the mixing volume ratio is (1-2) to 1, continuously stirring for 20min after mixing, controlling the temperature at 30-40 ℃, reacting for 4h, filtering out a product, washing and drying to obtain the particles;
(4) mixing the rest of the epoxy resin, the diluent and the active diluent in the component A, uniformly stirring, adding into a shear dispersion machine, adding epoxy cyclohexyl-cage polysilsesquioxane, a silane coupling agent, fumed silica, nano calcium bromide and the particles prepared in the step (3), and shearing and dispersing until the fineness is less than 50;
(5) mixing the rest of the curing agent and the DMP-30 accelerator in the component B, uniformly stirring, adding into a shear dispersion machine, adding the ultraviolet absorbent, the aramid fiber powder, the flame retardant and the graphene oxide nanosheet, and shearing and dispersing until the fineness is less than 50;
(6) and (5) mixing the mixtures prepared in the steps (4) and (5) in proportion, and shearing and dispersing by using a shearing disperser to obtain the daub.
Example 1
The environment-friendly abrasion-resistant deterioration-resistant epoxy resin daub comprises a component A and a component B, wherein the use ratio of the component A to the component B is 4: 1, the component A comprises the following components in parts by mass: 50 parts of epoxy resin, 11 parts of diluent, 6 parts of reactive diluent, 10 parts of surface active additive, 4 parts of epoxy cyclohexyl-cage polysilsesquioxane, 6 parts of silane coupling agent, 12 parts of fumed silica, 10 parts of unsaturated polyester resin and 20 parts of brominated nano light calcium; the component B comprises the following components in parts by mass: 70 parts of curing agent, 12 parts of DMP-30 accelerator, 15 parts of ultraviolet absorbent, 3 parts of aramid fiber powder, 3 parts of tris (2-chloroethyl) phosphate flame retardant and 3 parts of graphene oxide nanosheet;
the epoxy resin comprises an adhesion main body and a modification main body, wherein the adhesion main body is bisphenol A type epoxy resin or bisphenol F type epoxy resin, the modification main body is epoxy terminated polysiloxane with the epoxy equivalent of 400-900g/mol, and the mass ratio of the adhesion main body to the modification main body is 10: 1;
the curing agent is a composite curing agent consisting of a condensation modified fatty amine adduct, phenolic amine, vinyl-terminated butadiene-acrylonitrile rubber (methacrylic acid-terminated butadiene-acrylonitrile copolymer) and polyether nitrile hydrogenated polycondensate, and the mass ratio of the curing agent to the polyether nitrile hydrogenated polycondensate is 1:1: 0.3: 0.2;
the diluent is a composite diluent consisting of C12-14 alkyl glycidyl ether and 1, 6-hexanediol diglycidyl ether, and the mass ratio of the diluent is 0.2: 1;
the ultraviolet absorber is a triazine ultraviolet absorber.
The preparation method of the environment-friendly abrasion-resistant deterioration-resistant epoxy resin daub comprises the following steps:
(1) mixing the epoxy resin, the diluent, the reactive diluent and the surface active additive in the component A, uniformly stirring, adding into a shear dispersion machine, adding the epoxy cyclohexyl-cage polysilsesquioxane, the silane coupling agent, the fumed silica and the brominated nano light calcium, and shearing and dispersing until the fineness is less than 50;
(2) mixing the curing agent and the DMP-30 accelerator in the component B, uniformly stirring, adding into a shear dispersion machine, adding the ultraviolet absorbent, the aramid fiber powder, the flame retardant and the graphene oxide nanosheet, and grinding until the fineness is less than 50;
(3) and (3) mixing the mixtures prepared in the step (1) and the step (2) in proportion, and shearing and dispersing by using a shearing disperser to obtain the daub.
Example 2
The environment-friendly abrasion-resistant deterioration-resistant epoxy resin daub comprises a component A and a component B, wherein the use ratio of the component A to the component B is 4: 1, the component A comprises the following components in parts by mass: 50 parts of epoxy resin, 11 parts of diluent, 6 parts of reactive diluent, 10 parts of surface active additive, 4 parts of epoxy cyclohexyl-cage polysilsesquioxane, 6 parts of silane coupling agent, 12 parts of fumed silica, 10 parts of unsaturated polyester resin and 20 parts of brominated nano light calcium; the component B comprises the following components in parts by mass: 70 parts of curing agent, 12 parts of DMP-30 accelerator, 15 parts of ultraviolet absorbent, 3 parts of aramid fiber powder, 3 parts of tris (2-chloroethyl) phosphate flame retardant and 3 parts of graphene oxide nanosheet;
the epoxy resin comprises an adhesion main body and a modification main body, wherein the adhesion main body is bisphenol A type epoxy resin or bisphenol F type epoxy resin, the modification main body is epoxy terminated polysiloxane with the epoxy equivalent of 400-900g/mol, and the mass ratio of the adhesion main body to the modification main body is 10: 1;
the modified body further comprises 20% of naphthyl epoxy resin;
the curing agent is a composite curing agent consisting of a condensation modified fatty amine adduct, phenolic amine, vinyl-terminated butadiene-acrylonitrile rubber (methacrylic acid-terminated butadiene-acrylonitrile copolymer) and polyether nitrile hydrogenated polycondensate, and the mass ratio of the curing agent to the polyether nitrile hydrogenated polycondensate is 1:1: 0.3: 0.2;
the diluent is a composite diluent consisting of C12-14 alkyl glycidyl ether and 1, 6-hexanediol diglycidyl ether, and the mass ratio of the diluent to the composite diluent is 0.2: 1;
the ultraviolet absorber is a triazine ultraviolet absorber.
The preparation method of the environment-friendly abrasion-resistant deterioration-resistant epoxy resin daub comprises the following steps:
(1) mixing the epoxy resin, the diluent, the reactive diluent and the surface active additive in the component A, uniformly stirring, adding into a shear dispersion machine, adding the epoxy cyclohexyl-cage polysilsesquioxane, the silane coupling agent, the fumed silica and the brominated nano light calcium, and shearing and dispersing until the fineness is less than 50;
(2) mixing the curing agent and the DMP-30 accelerator in the component B, uniformly stirring, adding into a shear dispersion machine, adding the ultraviolet absorbent, the aramid fiber powder, the flame retardant and the graphene oxide nanosheet, and grinding until the fineness is less than 50;
(3) and (3) mixing the mixtures prepared in the step (1) and the step (2) in proportion, and shearing and dispersing by using a shearing disperser to obtain the daub.
Example 3
The environment-friendly abrasion-resistant deterioration-resistant epoxy resin daub comprises a component A and a component B, wherein the use ratio of the component A to the component B is 4: 1, the component A comprises the following components in parts by mass: 50 parts of epoxy resin, 11 parts of diluent, 6 parts of reactive diluent, 10 parts of surface active additive, 4 parts of epoxy cyclohexyl-cage polysilsesquioxane, 6 parts of silane coupling agent, 12 parts of fumed silica, 10 parts of unsaturated polyester resin and 20 parts of brominated nano light calcium; the component B comprises the following components in parts by mass: 70 parts of curing agent, 12 parts of DMP-30 accelerator, 15 parts of ultraviolet absorbent, 3 parts of aramid fiber powder, 3 parts of tris (2-chloroethyl) phosphate flame retardant and 3 parts of graphene oxide nanosheet;
the epoxy resin comprises an adhesion main body and a modification main body, wherein the adhesion main body is bisphenol A type epoxy resin or bisphenol F type epoxy resin, the modification main body is epoxy terminated polysiloxane with the epoxy equivalent of 400-900g/mol, and the mass ratio of the adhesion main body to the modification main body is 10: 1;
the modified body further comprises 20% of naphthyl epoxy resin;
the curing agent is a composite curing agent consisting of a condensation modified fatty amine adduct, phenolic amine, vinyl-terminated butadiene-acrylonitrile rubber (methacrylic acid-terminated butadiene-acrylonitrile copolymer) and polyether nitrile hydrogenated polycondensate, and the mass ratio of the curing agent to the polyether nitrile hydrogenated polycondensate is 1:1: 0.3: 0.2;
the diluent is a composite diluent consisting of C12-14 alkyl glycidyl ether and 1, 6-hexanediol diglycidyl ether, and the mass ratio of the diluent to the composite diluent is 0.2: 1;
the preparation method of the environment-friendly abrasion-resistant deterioration-resistant epoxy resin daub is characterized in that a modified main body and a part of a cementing main body are cured to prepare particles, and then the particles are added into a component A, and the preparation method comprises the following steps:
(1) mixing a modified main body containing epoxy-terminated polysiloxane and condensed ring aromatic hydrocarbon epoxy resin with an equivalent amount of bisphenol A epoxy resin or bisphenol F epoxy resin, adding a diluent with an equivalent amount of the modified main body, and fully mixing and stirring 2% of a surface active auxiliary agent to obtain a solution A;
(2) dissolving polyethylene glycol and sodium dodecyl sulfate in deionized water to prepare solutions with the concentrations of 10% and 10% respectively to obtain a solution B;
(3) adding the solution A into the solution B under rapid stirring, wherein the mixing volume ratio is (1-2) to 1, continuously stirring for 20min after mixing, controlling the temperature at 30-40 ℃, reacting for 4h, filtering out a product, washing and drying to obtain the particles;
(4) mixing the rest of the epoxy resin, the diluent and the active diluent in the component A, uniformly stirring, adding into a shear dispersion machine, adding epoxy cyclohexyl-cage polysilsesquioxane, a silane coupling agent, fumed silica, nano calcium bromide and the particles prepared in the step (3), and shearing and dispersing until the fineness is less than 50;
(5) mixing the rest of the curing agent and the DMP-30 accelerator in the component B, uniformly stirring, adding into a shear dispersion machine, adding the ultraviolet absorbent, the aramid fiber powder, the flame retardant and the graphene oxide nanosheet, and grinding to a fineness of less than 50;
(6) and (5) mixing the mixtures prepared in the steps (4) and (5) in proportion, and shearing and dispersing by using a shearing disperser to obtain the daub.
Comparative example
The same as example 1, but the epoxy resin was composed entirely of the bonding host and did not contain the modifying host.
The mechanical properties of the epoxy resin mortar are tested according to the technical specification DL/T5193 of epoxy resin mortar, including compressive strength, tensile strength, bonding strength to concrete, elastic modulus and linear expansion coefficient, and the specific results are as follows:
the abrasion resistance test is tested according to an epoxy mortar sand-containing water flow scouring resistance test method 5.19 in epoxy mortar technical Specification DL/T5193, a concrete test block is formed in advance before the test, a space of 2cm is reserved close to the upper opening of a test film, the test piece is taken out from a curing room after being cured for 28 days, air drying is carried out, epoxy cement is smeared, the test piece is placed in the room and cured for 28 days, and the test piece is soaked in room temperature water 2 days in advance. The specific results are as follows:
the ultraviolet aging degree is tested according to the relevant regulation control of GB/T3681 and GB/T15596 of determination of color and performance change of plastics under sunlight, natural climate or laboratory light source exposure under glass, wherein the minimum 12 test pieces are manufactured in each example test, the experimental test pieces and the comparison test piece are molded under the standard environmental condition, 6 experimental test pieces are placed in an ultraviolet aging test box, and the other 6 test pieces are stored under the standard test environmental condition. And respectively testing the tensile strength of the epoxy daub after the epoxy daub is irradiated by ultraviolet rays for 3 days, 7 days and 28 days, and recording the average tensile strength of the test piece so as to represent the ultraviolet aging degree. The tensile strength measured in the examples is compared with the comparative example, and the corresponding retention rate is calculated, and the larger the retention rate is, the more excellent the material performance is. The specific results are as follows:
according to the material, the aramid fiber powder is added, so that the toughness and the high-temperature resistance of the epoxy daub are improved, and the coefficient of thermal linear expansion is reduced; unsaturated polyester resin is introduced to replace acetone to adjust the resin viscosity, improve the coating and the flexibility of the daub, reduce the porosity and increase the impermeability of the daub; the ultraviolet-resistant and anti-aging performance of the cured daub is improved by adding the ultraviolet absorber, and the chalking and the delustering of the resin are delayed; the material of the invention abandons the conventional flame retardant which is easy to volatilize and has high toxicity, and uses the tris (2-chloroethyl) phosphate flame retardant to improve the flame retardant property of the epoxy daub.
Claims (10)
1. The environment-friendly abrasion-resistant deterioration-resistant epoxy resin daub is characterized by consisting of a component A and a component B, wherein the use ratio of the component A to the component B is 3-6: 1;
the component A comprises the following components in parts by mass:
the component B comprises the following components in parts by mass:
wherein the epoxy cyclohexyl-cage polysilsesquioxane has the following structure:
2. The environment-friendly abrasion-resistant deterioration-resistant epoxy resin mortar as claimed in claim 1, wherein the epoxy resin is composed of an adhesion main body and a modification main body, the adhesion main body is bisphenol A type epoxy resin or bisphenol F type epoxy resin, the modification main body is epoxy-terminated polysiloxane with an epoxy equivalent of 400-900g/mol, and the mass ratio of the adhesion main body to the modification main body is 8-12: 1.
3. The environment-friendly abrasion-resistant deterioration-resistant epoxy resin mortar according to claim 2, wherein the modified main body further comprises 15-25% by mass of a fused ring aromatic hydrocarbon-based epoxy resin; the condensed ring aromatic hydrocarbon group epoxy resin is naphthyl epoxy resin or anthryl epoxy resin.
4. The environment-friendly abrasion-resistant deterioration-resistant epoxy resin mortar according to claim 1, wherein the diluent is one or more of C12-14 alkyl glycidyl ether, 1, 6-hexanediol diglycidyl ether, and polypropylene glycol diglycidyl ether; and adding a certain proportion of reactive diluent, wherein the proportion of the diluent to the reactive diluent is 1-3: 1.
5. the environment-friendly, abrasion-resistant and deterioration-resistant epoxy resin mortar as claimed in claim 1, wherein the curing agent in the component B is a composite curing agent consisting of a modified fatty amine adduct, phenolic amine, vinyl-terminated nitrile rubber (methacrylic acid terminated nitrile copolymer) and a polyether nitrile hydrogenated polycondensate, and the mass ratio of the composite curing agent to the polyether nitrile hydrogenated polycondensate is 1:1: 0.2-0.5: 0.2-0.5.
6. The environment-friendly abrasion-resistant deterioration-resistant epoxy resin mastic as claimed in claim 1, wherein the ultraviolet absorber is a triazine ultraviolet absorber or a benzotriazole ultraviolet absorber.
7. The environment-friendly, abrasion-resistant and deterioration-resistant epoxy resin mastic as claimed in claim 1, wherein the flame retardant is one of tris (2-chloroethyl) phosphate, ammonium polyphosphate, dimethyl methyl phosphate, or tris-dichloropropyl phosphate.
8. The method for preparing the environment-friendly abrasion-resistant deterioration-resistant epoxy resin mortar as claimed in claims 1 to 7, characterized by comprising the steps of:
(1) mixing the epoxy resin, the diluent and the surface active auxiliary agent in the component A, uniformly stirring, adding into a shear dispersion machine, adding the epoxy cyclohexyl-cage polysilsesquioxane, the silane coupling agent, the fumed silica and the brominated nano light calcium, and shearing and dispersing until the fineness is less than 50;
(2) mixing the curing agent and the DMP-30 accelerator in the component B, uniformly stirring, adding into a shear dispersion machine, adding the ultraviolet absorbent, the aramid fiber powder, the flame retardant and the graphene oxide nanosheet, and grinding until the fineness is less than 50;
(3) and (3) mixing the mixtures prepared in the step (1) and the step (2) in proportion, and shearing and dispersing by using a shearing disperser to obtain the daub.
9. The preparation method of the environment-friendly abrasion-resistant deterioration-resistant epoxy resin mortar according to claim 8, characterized in that: the epoxy resin is prepared by curing the modified main body and the part of the bonding main body into particles, and then is added into the component A.
10. The preparation method of the environment-friendly abrasion-resistant deterioration-resistant epoxy resin mortar according to claim 8, characterized in that: (1) mixing a modified main body containing epoxy-terminated polysiloxane and condensed ring aromatic hydrocarbon epoxy resin with an equivalent amount of bisphenol A epoxy resin or bisphenol F epoxy resin, adding a diluent with an equivalent amount of the modified main body, and fully mixing and stirring 2% of a surface active auxiliary agent to obtain a solution A;
(2) dissolving polyethylene glycol and sodium dodecyl sulfate in deionized water to prepare solutions with mass concentrations of 10% and 10%, and adding the solutions into the solution B;
(3) adding the solution A into the solution B under rapid stirring, wherein the mixing volume ratio is 1-2:1, continuously stirring for 20min after mixing, controlling the temperature at 30-40 ℃, filtering out a product after reacting for 4h, washing and drying to obtain the particles;
(4) mixing the rest of the epoxy resin, the diluent and the active diluent in the component A, uniformly stirring, adding into a shear dispersion machine, adding epoxy cyclohexyl-cage polysilsesquioxane, a silane coupling agent, fumed silica, nano calcium bromide and the particles prepared in the step (3), and shearing and dispersing until the fineness is less than 50;
(5) mixing the rest of the curing agent and the DMP-30 accelerator in the component B, uniformly stirring, adding into a shear dispersion machine, adding the ultraviolet absorbent, the aramid fiber powder, the flame retardant and the graphene oxide nanosheet, and shearing and dispersing until the fineness is less than 50;
(6) and (5) mixing the mixtures prepared in the steps (4) and (5) in proportion, and shearing and dispersing by using a shearing disperser to obtain the daub.
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