1. The double-component stone binder is characterized in that: the adhesive comprises a component A and a component B, wherein the component A comprises:

32-58 parts of epoxy resin, preferably 37-54 parts of epoxy resin, and more preferably 42-52 parts of epoxy resin;

1-9 parts by weight of reactive diluent, preferably 2-8 parts by weight, more preferably 3-7 parts by weight;

5-20 parts of toughening agent, preferably 7-18 parts, more preferably 9-15 parts;

13-33 parts of modified calcium carbonate, preferably 15-30 parts of modified calcium carbonate, and more preferably 18-28 parts of modified calcium carbonate;

1-5 parts by weight of thixotropic agent, preferably 1.5-4.5 parts by weight, more preferably 2-4 parts by weight;

0.05 to 1.5 parts by weight of antioxidant, preferably 0.08 to 1 part by weight, more preferably 0.1 to 0.8 part by weight;

1-9 parts of white carbon black, preferably 2-5 parts of white carbon black, and more preferably 3-4 parts of white carbon black;

wherein the component B comprises:

60-88 parts of modified curing agent, preferably 65-85 parts, more preferably 70-80 parts;

0.5 to 7 parts by weight of an accelerator, preferably 0.8 to 5.5 parts by weight, more preferably 1 to 4 parts by weight;

1-11 parts by weight of silane coupling agent, preferably 2-9 parts by weight, more preferably 3-7 parts by weight;

0.01 to 1 part by weight of a thixotropic agent, preferably 0.05 to 0.8 part by weight, more preferably 0.08 to 0.5 part by weight;

0.5 to 3 parts by weight, preferably 0.8 to 2.8 parts by weight, more preferably 1 to 2.5 parts by weight of tungsten nitride;

0.5-5 parts of white carbon black, preferably 0.8-4 parts of white carbon black, and more preferably 1-3 parts of white carbon black;

7-24 parts of modified calcium carbonate, preferably 9-22 parts, more preferably 12-20 parts;

wherein the modified curing agent is a mixture of polyether amine modified curing agent and fatty amine modified curing agent.

2. The two-component stone binder as claimed in claim 1, wherein: the epoxy resin is selected from one or more of bisphenol A type, bisphenol F type and bisphenol S type epoxy resin; preferably a mixture of E-51 epoxy resin and 133L epoxy resin; and/or

The polyether amine modified curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine by epoxy resin; preferably a polyether amine modified curing agent which is modified by polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine by E-51 epoxy resin and then is further treated by benzyl alcohol;

The aliphatic amine modified curing agent is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and m-xylene diamine which are modified by nonyl phenol glycidyl ether;

preferably, the amount of the benzyl alcohol is 1 to 8 wt%, preferably 2 to 6 wt%, based on the total mass of the polyether amine modified curing agent; and/or

In the mixed modified curing agent consisting of the polyether amine modified curing agent and the fatty amine modified curing agent, the mass ratio of the polyether amine modified curing agent to the fatty amine modified curing agent is 1:0.5-3, preferably 1: 0.8-2.

3. The two-component stone binder as claimed in claim 1 or 2, wherein: the reactive diluent is one or more selected from C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, glycerol triglycidyl ether, 1,4 butanediol glycidyl ether, ethylene glycol diglycidyl ether and neopentyl glycol glycidyl ether; preferably glycerol triglycidyl ether and/or 1, 4-butanediol glycidyl ether; and/or

The toughening agent is an active polyurethane toughening agent.

4. The two-component stone binder as claimed in any one of claims 1 to 3, wherein: the modified calcium carbonate is obtained by modifying calcium carbonate by adopting aminobenzoic acid; the aminobenzoic acid is selected from one of anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-3, 4,5, 6-tetrafluorobenzoic acid, 4-amino-2, 3,5, 6-tetrafluorobenzoic acid, 2-amino-3, 4, 5-trifluorobenzoic acid, 3-amino-2, 5, 6-trifluorobenzoic acid and 6-amino-2, 3, 4-trifluorobenzoic acid, preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid and/or 4-amino-2, 3,5, 6-tetrafluorobenzoic acid;

Preferably, the particle size composition of the modified calcium carbonate is as follows: 10-30% of particle size less than 100 meshes, 25-55% of particle size 100-200 meshes, 18-35% of particle size 300-500 meshes and 12-28% of particle size more than 500 meshes.

5. The two-component stone binder as claimed in any one of claims 1 to 4, wherein: the promoter is selected from one or more of 2,4, 6-tri (dimethylaminomethyl) phenol (DMP-30), tri- (2-ethylhexanoic acid) salt of 2,4, 6-tri (dimethylaminomethyl) phenol, triethanolamine and thiourea; preferably 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30); and/or

The antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) or antioxidant 1076; and/or

The white carbon black is fumed silica.

6. The two-component stone binder as claimed in any one of claims 1 to 5, wherein: the silane coupling agent is dialkoxysilane or trialkoxysilane coupling agent containing amino or hydroxyl functional groups; preferably one or more of gamma-aminopropyltriethoxysilane (KH-550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), and diethylenetriaminopropyltriethoxysilane; and/or

The thixotropic agent is one or more of hydrogenated castor oil, cellulose and bentonite.

7. Method for preparing a two-component stone binder as claimed in any one of claims 1 to 6, characterized in that: the method comprises the following steps:

s1: preparation of the component A: firstly, mixing epoxy resin, an active diluent, a toughening agent, an antioxidant and white carbon black; then adding the modified calcium carbonate and the thixotropic agent, and continuously mixing to obtain a component A after uniform mixing;

s2: preparation of the component B: firstly, mixing a modified curing agent and an accelerant; then adding a thixotropic agent and a silane coupling agent and continuously mixing uniformly; finally, adding the modified calcium carbonate, the tungsten nitride and the white carbon black, and continuously mixing to obtain a component B after uniform mixing;

s3: preparing a two-component stone binder: bottling the component A and the component B according to a proportion to obtain the double-component stone binder;

wherein the modified curing agent is a mixed modified curing agent consisting of a polyether amine modified curing agent and a fatty amine modified curing agent according to the mass ratio of 1:0.5-3 (preferably 1: 0.8-2); the modified calcium carbonate is modified calcium carbonate obtained by modifying calcium carbonate with aminobenzoic acid;

preferably, the aminobenzoic acid is selected from one of anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-3, 4,5, 6-tetrafluorobenzoic acid, 4-amino-2, 3,5, 6-tetrafluorobenzoic acid, 2-amino-3, 4, 5-trifluorobenzoic acid, 3-amino-2, 5, 6-trifluorobenzoic acid, 6-amino-2, 3, 4-trifluorobenzoic acid, and preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid and/or 4-amino-2, 3,5, 6-tetrafluorobenzoic acid.

8. The method of claim 7, wherein: the dosage of each component is as follows: wherein the component A is as follows:

32-58 parts of epoxy resin, preferably 37-54 parts of epoxy resin, and more preferably 42-52 parts of epoxy resin;

1-9 parts by weight of reactive diluent, preferably 2-8 parts by weight, more preferably 3-7 parts by weight;

5-20 parts of toughening agent, preferably 7-18 parts, more preferably 9-15 parts;

13-33 parts of modified calcium carbonate, preferably 15-30 parts of modified calcium carbonate, and more preferably 18-28 parts of modified calcium carbonate;

1-5 parts by weight of thixotropic agent, preferably 1.5-4.5 parts by weight, more preferably 2-4 parts by weight;

0.05 to 1.5 parts by weight of antioxidant, preferably 0.08 to 1 part by weight, more preferably 0.1 to 0.8 part by weight;

1-9 parts of white carbon black, preferably 2-5 parts of white carbon black, and more preferably 3-4 parts of white carbon black;

wherein the component B is as follows:

60-88 parts of modified curing agent, preferably 65-85 parts, more preferably 70-80 parts;

0.5 to 7 parts by weight of an accelerator, preferably 0.8 to 5.5 parts by weight, more preferably 1 to 4 parts by weight;

1-11 parts by weight of silane coupling agent, preferably 2-9 parts by weight, more preferably 3-7 parts by weight;

0.01 to 1 part by weight of a thixotropic agent, preferably 0.05 to 0.8 part by weight, more preferably 0.08 to 0.5 part by weight;

0.5 to 3 parts by weight, preferably 0.8 to 2.8 parts by weight, more preferably 1 to 2.5 parts by weight of tungsten nitride;

0.5-5 parts of white carbon black, preferably 0.8-4 parts of white carbon black, and more preferably 1-3 parts of white carbon black;

the modified calcium carbonate is 7 to 24 parts by weight, preferably 9 to 22 parts by weight, and more preferably 12 to 20 parts by weight.

9. The method according to claim 7 or 8, characterized in that: the epoxy resin is selected from one or more of bisphenol A type, bisphenol F type and bisphenol S type epoxy resin; preferably a mixture of E-51 epoxy resin and 133L epoxy resin; and/or

The polyether amine modified curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine by epoxy resin; preferably a polyether amine modified curing agent which is modified by polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine by E-51 epoxy resin and then is further treated by benzyl alcohol; the aliphatic amine modified curing agent is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and m-xylene diamine which are modified by nonyl phenol glycidyl ether; preferably, the amount of benzyl alcohol is 1 to 8 wt%, preferably 2 to 6 wt%, based on the total mass of the polyetheramine modified curing agent; and/or

The reactive diluent is one or more selected from C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, glycerol triglycidyl ether, 1,4 butanediol glycidyl ether, ethylene glycol diglycidyl ether and neopentyl glycol glycidyl ether; and/or

The promoter is selected from one or more of 2,4, 6-tri (dimethylaminomethyl) phenol (DMP-30), tri- (2-ethylhexanoic acid) salt of 2,4, 6-tri (dimethylaminomethyl) phenol, triethanolamine and thiourea; and/or

The toughening agent is an active polyurethane toughening agent; and/or

The antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) or antioxidant 1076; and/or

The white carbon black is fumed silica; and/or

The silane coupling agent is one or more of gamma-aminopropyltriethoxysilane (KH-550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560) and diethylenetriaminopropyltriethoxysilane; and/or

The thixotropic agent is one or more of hydrogenated castor oil, cellulose and bentonite.

10. The method of claim 9, wherein: s1 specifically includes: preparation of the component A: firstly, uniformly mixing the epoxy resin, the reactive diluent, the flexibilizer, the antioxidant and the fumed silica under the condition of heating (for example, uniformly stirring and mixing at 50-95 ℃, preferably 60-80 ℃); then starting high-speed stirring and vacuumizing (for example, vacuumizing to-0.01 MPa to-0.09 MPa), wherein the high-speed stirring time is 10-60 min; finally, adding the modified calcium carbonate and the thixotropic agent, continuing stirring for 10-40min, cooling, stopping stirring for 30min, and then stopping vacuumizing to obtain a component A; and/or

S2 specifically includes: preparation of the component B: firstly, uniformly mixing the modified curing agent according to the proportion, then adding the accelerant and continuously uniformly mixing (for example, stirring and mixing for 10-60 min); then adding the thixotropic agent and the silane coupling agent and uniformly mixing (for example, stirring and mixing); after a period of time, starting high-speed stirring and vacuumizing (for example, vacuumizing to-0.01 MPa to-0.09 MPa), wherein the high-speed stirring time is 10-60 min; finally, adding the modified calcium carbonate, the tungsten nitride and the gas-phase white carbon black, continuously stirring (stirring for 10-40min), cooling, stopping stirring for 30min, and then stopping vacuumizing to obtain a component B; and/or

S3 specifically includes: preparing a two-component stone binder: and respectively bottling the component A and the component B according to the mass ratio of 1:1.0-1.5 (preferably 1:1.1-1.3) to obtain the double-component stone binder.

Background

The natural stone slab has elegant texture and unique and beautiful texture, and is often used as a facing material for inner and outer walls, floors, ceilings, windowsills, table tops and sanitary wares of buildings. With the development of economy, the living standard of people is improved and the culture is improved, and the quantity of the decorative materials is increased. With the wide application of stone in the construction industry, the market demand of the stone bonding adhesive is continuously expanded, which is particularly embodied in the bonding and reinforcing operation of repairing, installing and positioning the stone, and the bonding and reinforcing material for repairing, installing and positioning the stone at the present stage mainly adopts unsaturated polyester adhesive (marble adhesive); it has a lot of not enoughly when the location of stone material is consolidated, if: the volatilization is serious, the volatile matter is toxic, the unsaturated polyester adhesive contains 20-30% of styrene monomer, and is volatile at room temperature, the styrene has larger toxicity and irritation, the industrial sanitation and labor protection are influenced, and the leukemia can be caused by long-term contact; the shrinkage rate is large, and large stress is generated by curing shrinkage; high brittleness, poor ageing resistance and the like. After the epoxy adhesive is cured, the epoxy adhesive has excellent adhesiveness and mechanical strength, excellent aging resistance, environmental protection, small shrinkage rate and good toughness after modification, accelerates the curing speed on the basis of common epoxy adhesive, can completely replace unsaturated polyester adhesive (marble adhesive), and meets the requirement of quick positioning and bonding of stone dry hanging in the building industry.

The epoxy resin contains various polar groups and epoxy groups with high activity, so that the epoxy resin has high adhesive force with materials with high surface activity, and the epoxy cured material has high cohesive strength, so that the adhesive strength is high, the curing shrinkage is small, the size stability of the cured product is good, the hardness of the cured product is high, and the polishing processing is easy. Therefore, in the stone processing industry at present, the adhesive prepared by taking the epoxy resin as the raw material gradually occupies the leading position of the market.

Although the epoxy resin material is widely used, the epoxy resin material has a plurality of defects when used as a stone adhesive, and the stone adhesive has relatively small adhesive area in the repairing, installing and positioning processes, so that the adhesive is relatively large in stress, and the performance requirements on the adhesive are high, especially the adhesive strength, stability, wear resistance, stain resistance and the like of the adhesive.

Disclosure of Invention

The invention provides a double-component stone binder, which is a reactive adhesive, has few volatile matters and low shrinkage rate in the curing process, and simultaneously adopts two modified curing agent compositions, thereby having excellent adhesion and a certain stress relaxation function. The stone binder also adopts modified calcium carbonate, so that on one hand, the appearance of the cured rubber material is as close as possible to that of the stone, and simultaneously, the bonding strength, wear resistance, aging resistance, stain resistance and other properties of the stone binder can be enhanced.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

according to a first embodiment of the present invention, a two-component stone binder is provided.

The double-component stone binder comprises a component A and a component B, wherein the component A comprises:

the epoxy resin is 32 to 58 parts by weight, preferably 37 to 54 parts by weight, and more preferably 42 to 52 parts by weight.

The reactive diluent is 1 to 9 parts by weight, preferably 2 to 8 parts by weight, and more preferably 3 to 7 parts by weight.

The toughening agent is 5-20 parts by weight, preferably 7-18 parts by weight, and more preferably 9-15 parts by weight.

The modified calcium carbonate is 13 to 33 parts by weight, preferably 15 to 30 parts by weight, and more preferably 18 to 28 parts by weight.

The thixotropic agent is 1 to 5 parts by weight, preferably 1.5 to 4.5 parts by weight, and more preferably 2 to 4 parts by weight.

The antioxidant is 0.05 to 1.5 parts by weight, preferably 0.08 to 1 part by weight, and more preferably 0.1 to 0.8 part by weight.

1-9 parts of white carbon black, preferably 2-5 parts of white carbon black, and more preferably 3-4 parts of white carbon black.

Wherein the component B comprises:

60-88 parts by weight of modified curing agent, preferably 65-85 parts by weight, and more preferably 70-80 parts by weight.

0.5 to 7 parts by weight of accelerator, preferably 0.8 to 5.5 parts by weight, more preferably 1 to 4 parts by weight.

1 to 11 parts by weight of the silane coupling agent, preferably 2 to 9 parts by weight, and more preferably 3 to 7 parts by weight.

The thixotropic agent is 0.01 to 1 part by weight, preferably 0.05 to 0.8 part by weight, and more preferably 0.08 to 0.5 part by weight.

0.5 to 3 parts by weight, preferably 0.8 to 2.8 parts by weight, more preferably 1 to 2.5 parts by weight of tungsten nitride.

0.5-5 parts of white carbon black, preferably 0.8-4 parts of white carbon black, and more preferably 1-3 parts of white carbon black.

The modified calcium carbonate is 7 to 24 parts by weight, preferably 9 to 22 parts by weight, and more preferably 12 to 20 parts by weight.

Wherein the modified curing agent is a mixture of polyether amine modified curing agent and fatty amine modified curing agent.

The sum of the components in the component A is 100 parts by weight. The sum of the components in the component B is 100 parts by weight.

Preferably, the epoxy resin is selected from one or more of bisphenol A type, bisphenol F type and bisphenol S type epoxy resins. Preferably a mixture of E-51 epoxy and 133L epoxy.

Preferably, the polyether amine modified curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an epoxy resin. Preferably, the curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an E-51 epoxy resin and then further treating the modified curing agent with benzyl alcohol.

Preferably, the aliphatic amine modified curing agent is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and m-xylene diamine modified by nonylphenol glycidyl ether.

Preferably, the amount of benzyl alcohol is 1 to 8 wt%, preferably 2 to 6 wt%, based on the total mass of the polyetheramine-modified curing agent.

Preferably, in the mixed modified curing agent consisting of the polyether amine modified curing agent and the fatty amine modified curing agent, the mass ratio of the polyether amine modified curing agent to the fatty amine modified curing agent is 1:0.5-3, and preferably 1: 0.8-2.

Preferably, the reactive diluent is one or more selected from C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, glycerol triglycidyl ether, 1,4 butanediol glycidyl ether, ethylene glycol diglycidyl ether and neopentyl glycol glycidyl ether. Preferably glycerol triglycidyl ether and/or 1, 4-butanediol glycidyl ether.

Preferably, the toughening agent is an active polyurethane toughening agent.

Preferably, the modified calcium carbonate is obtained by modifying calcium carbonate with aminobenzoic acid. The aminobenzoic acid is selected from one of anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-3, 4,5, 6-tetrafluorobenzoic acid, 4-amino-2, 3,5, 6-tetrafluorobenzoic acid, 2-amino-3, 4, 5-trifluorobenzoic acid, 3-amino-2, 5, 6-trifluorobenzoic acid and 6-amino-2, 3, 4-trifluorobenzoic acid, and is preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid and/or 4-amino-2, 3,5, 6-tetrafluorobenzoic acid.

Preferably, the particle size composition of the modified calcium carbonate is as follows: 10-30% of particle size less than 100 meshes, 25-55% of particle size 100-200 meshes, 18-35% of particle size 300-500 meshes and 12-28% of particle size more than 500 meshes.

Preferably, the accelerator is selected from one or more of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), tris- (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, triethanolamine, thiourea. 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) is preferred.

Preferably, the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) or antioxidant 1076.

Preferably, the white carbon black is fumed silica.

Preferably, the silane coupling agent is a dialkoxysilane or trialkoxysilane coupling agent containing an amino or hydroxyl functional group. Preferably one or more of gamma-aminopropyltriethoxysilane (KH-550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560) and diethylenetriaminopropyltriethoxysilane.

Preferably, the thixotropic agent is one or more of hydrogenated castor oil, cellulose and bentonite.

According to a second embodiment of the present invention, there is provided a method of preparing a two-component stone binder or a method of preparing the two-component stone binder of the first embodiment.

A method for preparing a two-component stone binder comprises the following steps:

s1: preparation of the component A: firstly, mixing epoxy resin, active diluent, toughening agent, antioxidant and white carbon black. Then adding the modified calcium carbonate and the thixotropic agent, and continuously mixing to obtain the component A after uniform mixing.

S2: preparation of the component B: firstly, mixing the modified curing agent and the accelerator. Then adding the thixotropic agent and the silane coupling agent and continuously mixing uniformly. Finally, adding the modified calcium carbonate, the tungsten nitride and the white carbon black, and continuously mixing to obtain the component B after uniform mixing.

S3: preparing a two-component stone binder: bottling the component A and the component B according to the proportion to obtain the double-component stone binder.

Wherein the modified curing agent is a mixed modified curing agent consisting of polyether amine modified curing agent and fatty amine modified curing agent according to the mass ratio of 1:0.5-3 (preferably 1: 0.8-2). The modified calcium carbonate is modified calcium carbonate obtained by modifying calcium carbonate with aminobenzoic acid.

Preferably, the aminobenzoic acid is selected from one of anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-3, 4,5, 6-tetrafluorobenzoic acid, 4-amino-2, 3,5, 6-tetrafluorobenzoic acid, 2-amino-3, 4, 5-trifluorobenzoic acid, 3-amino-2, 5, 6-trifluorobenzoic acid, 6-amino-2, 3, 4-trifluorobenzoic acid, and preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid and/or 4-amino-2, 3,5, 6-tetrafluorobenzoic acid.

Preferably, the amounts of the components are as follows: wherein the component A is as follows:

the epoxy resin is 32 to 58 parts by weight, preferably 37 to 54 parts by weight, and more preferably 42 to 52 parts by weight.

The reactive diluent is 1 to 9 parts by weight, preferably 2 to 8 parts by weight, and more preferably 3 to 7 parts by weight.

The toughening agent is 5-20 parts by weight, preferably 7-18 parts by weight, and more preferably 9-15 parts by weight.

The modified calcium carbonate is 13 to 33 parts by weight, preferably 15 to 30 parts by weight, and more preferably 18 to 28 parts by weight.

The thixotropic agent is 1 to 5 parts by weight, preferably 1.5 to 4.5 parts by weight, and more preferably 2 to 4 parts by weight.

The antioxidant is 0.05 to 1.5 parts by weight, preferably 0.08 to 1 part by weight, and more preferably 0.1 to 0.8 part by weight.

1-9 parts of white carbon black, preferably 2-5 parts of white carbon black, and more preferably 3-4 parts of white carbon black.

Wherein the component B is as follows:

60-88 parts by weight of modified curing agent, preferably 65-85 parts by weight, and more preferably 70-80 parts by weight.

0.5 to 7 parts by weight of accelerator, preferably 0.8 to 5.5 parts by weight, more preferably 1 to 4 parts by weight.

1 to 11 parts by weight of the silane coupling agent, preferably 2 to 9 parts by weight, and more preferably 3 to 7 parts by weight.

The thixotropic agent is 0.01 to 1 part by weight, preferably 0.05 to 0.8 part by weight, and more preferably 0.08 to 0.5 part by weight.

0.5 to 3 parts by weight, preferably 0.8 to 2.8 parts by weight, more preferably 1 to 2.5 parts by weight of tungsten nitride.

0.5-5 parts of white carbon black, preferably 0.8-4 parts of white carbon black, and more preferably 1-3 parts of white carbon black.

The modified calcium carbonate is 7 to 24 parts by weight, preferably 9 to 22 parts by weight, and more preferably 12 to 20 parts by weight.

Preferably, the epoxy resin is selected from one or more of bisphenol A type, bisphenol F type and bisphenol S type epoxy resins. Preferably a mixture of E-51 epoxy and 133L epoxy.

Preferably, the polyether amine modified curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an epoxy resin. Preferably, the curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an E-51 epoxy resin and then further treating the modified curing agent with benzyl alcohol. The aliphatic amine modified curing agent is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and m-xylene diamine which are modified by nonyl phenol glycidyl ether. Preferably, the amount of benzyl alcohol is 1 to 8 wt%, preferably 2 to 6 wt%, based on the total mass of the polyetheramine-modified curing agent.

Preferably, the reactive diluent is one or more selected from C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, glycerol triglycidyl ether, 1,4 butanediol glycidyl ether, ethylene glycol diglycidyl ether and neopentyl glycol glycidyl ether. And/or

Preferably, the accelerator is selected from one or more of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), tris- (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, triethanolamine, thiourea.

Preferably, the toughening agent is an active polyurethane toughening agent.

The antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) or antioxidant 1076.

Preferably, the white carbon black is fumed silica.

Preferably, the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane (KH-550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), and diethylenetriaminopropyltriethoxysilane.

Preferably, the thixotropic agent is one or more of hydrogenated castor oil, cellulose and bentonite.

Preferably, S1 is specifically: preparation of the component A: the epoxy resin, the reactive diluent, the toughening agent, the antioxidant and the fumed silica are uniformly mixed under the condition of raising the temperature (for example, the epoxy resin, the reactive diluent, the toughening agent, the antioxidant and the fumed silica are uniformly stirred and mixed at 50-95 ℃ and preferably at 60-80 ℃). Then starting high-speed stirring and vacuumizing (for example, vacuumizing to-0.01 MPa to-0.09 MPa), wherein the high-speed stirring time is 10-60 min. And finally, adding the modified calcium carbonate and the thixotropic agent, continuously stirring for 10-40min, cooling, stopping stirring for 30min, and then stopping vacuumizing to obtain the component A.

Preferably, S2 is specifically: preparation of the component B: the modified curing agent is firstly mixed uniformly according to the proportion, and then the accelerant is added to continue mixing uniformly (for example, stirring and mixing for 10-60 min). Then adding the thixotropic agent and the silane coupling agent and mixing uniformly (for example, stirring and mixing). After a period of time, high-speed stirring is started and vacuum is pumped (for example, the vacuum pumping is from-0.01 MPa to-0.09 MPa), and the high-speed stirring time is 10-60 min. And finally, adding the modified calcium carbonate, the tungsten nitride and the gas-phase white carbon black, continuously stirring (stirring for 10-40min), cooling, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.

Preferably, S3 is specifically: preparing a two-component stone binder: and respectively bottling the component A and the component B according to the mass ratio of 1:1.0-1.5 (preferably 1:1.1-1.3) to obtain the two-component stone binder.

In the present invention, a mixture of E-51 epoxy resin and 133L epoxy resin is preferably used as the epoxy resin. The 133L epoxy resin, the E-51 epoxy resin and the reactive diluent form an IPN interpenetrating polymer network structure, so that the adhesive density of the system is improved, and the toughness is improved without sacrificing the strength. And 133L of epoxy resin can improve the compatibility of the E-51 epoxy resin and the reactive diluent. (E51 epoxy resin and 133L epoxy resin are both from south Asia electronic materials Co., Ltd.)

In the invention, the modified curing agent is a mixture of polyether amine modified curing agent and fatty amine modified curing agent. The polyether amine modified curing agent is self-made and is prepared by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with E-51 epoxy resin. Preferably, the polyether amine modified curing agent is a curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with E-51 epoxy resin to obtain the polyether amine modified curing agent, and then treating the polyether amine modified curing agent with benzyl alcohol. Still preferably, the amount of the benzyl alcohol is 1 to 8 wt%, preferably 2 to 6 wt%, based on the total mass of the polyetheramine-modified curing agent. The aliphatic amine modified curing agent is also self-made, and refers to the aliphatic amine modified curing agent which is prepared by modifying one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and m-xylene diamine by using nonyl phenol glycidyl ether. Through modification of the polyether amine, the defects of low hardness, small adhesion, poor moisture resistance, long curing time and the like of the polyether amine are overcome; the defects of high normal-temperature volatility, high toxicity and the like of aliphatic amines are overcome by modifying the aliphatic amines; meanwhile, the polyether amine modified curing agent and the fatty amine modified curing agent are compounded according to a certain proportion (for example, the mass ratio of the polyether amine modified curing agent to the fatty amine modified curing agent is 1:0.5-3, preferably 1:0.8-2), so that excellent complementation can be realized, the bonding strength, the tensile strength, the shear strength and the bending strength of the epoxy cured product are greatly improved, the high temperature resistance, the corrosion resistance, the wear resistance and the like are greatly improved, the maximum elongation is improved, the flexibility is good, and the later-stage secondary cracking and stripping can be effectively avoided.

According to the invention, the specific epoxy resin and the specific curing agent are combined for use, so that the curing effect is good, on one hand, a compact film layer is formed, and the internal stress is effectively eliminated after curing. After a long time (e.g., 2 years) has elapsed after the construction, the film layer section is sampled, and the sample is examined by a Scanning Electron Microscope (SEM), and no micro-cracks or micro-pores are found on the sample surface of the film layer.

In the invention, the cracking resistance of the colloid is improved and the stability and the ageing resistance of the material are improved by adding the active polyurethane toughening agent. The toughening agent does not generate chemical reaction when blending epoxy resin and a diluent, but has good physical blending stability, is not layered and can stably exist for a long time. The toughening agent contains terminal epoxy group which is active to amino group and can generate chemical reaction. The elastomer structure with a 'polyurethane-urea' structure is generated by the reaction of the active polyurethane and the amino, meanwhile, the epoxy group and the amino of the epoxy resin react to generate a body type polymer containing a flexible chain, the two reactions are carried out simultaneously to form an IPN polymer interpenetrating network, and finally, the cured product changes the molecular structure of the polymer to increase the elongation and toughness of the polymer, thereby improving the cracking resistance of the colloid, avoiding the phenomenon that the plasticizer migrates to the surface of the colloid along with the time extension in different degrees when the flexibility is increased by simply depending on external plasticization, and further obtaining more effective material stability and aging hard and brittle life compared with the method of simply adding the external plasticizer for plasticization.

In the present invention, the reactive diluent is or includes one or more selected from C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, glycerol triglycidyl ether, 1,4 butanediol glycidyl ether, ethylene glycol diglycidyl ether, and neopentyl glycol glycidyl ether, and preferably one or two selected from glycerol triglycidyl ether and 1,4 butanediol glycidyl ether are used. The reactive diluent can improve the consistency and optimize the construction performance.

In the present invention, the silane coupling agent is a dialkoxysilane-based or trialkoxysilane-based coupling agent containing an amino or hydroxyl functional group. Preferably one or more of gamma-aminopropyltriethoxysilane (KH-550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560) and diethylenetriaminopropyltriethoxysilane. The coupling agent can increase the adhesive property.

In the present invention, the accelerator is selected from one or more of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), tris- (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, triethanolamine, thiourea. 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) is preferred. The accelerator can accelerate the reaction speed.

In the present invention, the modified calcium carbonate is modified calcium carbonate. The grain size composition is as follows: 10-30% of particle size less than 100 meshes, 25-55% of particle size 100-200 meshes, 18-35% of particle size 300-500 meshes and 12-28% of particle size more than 500 meshes. In general, when calcium carbonate is directly used as a filler, since it has a small particle size, a high surface energy, unstable thermodynamic properties, and easy agglomeration of particles affects its filling effect, aminobenzoic acid having both amino and carboxyl groups (e.g., anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid, 4-amino-2, 3,5, 6-tetrafluorobenzoic acid, 2-amino-3, 4, 5-trifluorobenzoic acid, 3-amino-2, 5, 6-trifluorobenzoic acid, 6-amino-2, 3, 4-trifluorobenzoic acid, and more preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid and/or 4-amino-2, 3,5, 6-tetrafluorobenzoic acid) as a modifier to obtain modified calcium carbonate; on one hand, the modified calcium carbonate is in composite bonding with special groups (such as carboxyl) contained in the modifier, so that the van der Waals force among calcium carbonate particles can be effectively reduced, the agglomeration phenomenon among the calcium carbonate particles is avoided, and the dispersibility of the modified calcium carbonate is improved; on the other hand, the calcium carbonate is bonded on the epoxy group through the special group (such as amino group) contained in the modifier and the epoxy resin, so that the adhesive property and the adhesive strength of the epoxy adhesive are greatly improved. When the fluorine-substituted aminobenzoic acid is used as a modifier, the aminobenzoic acid containing the fluorine-substituted group is not only used as a bonding bridge between the filler and the resin, but also can be used as a side chain group on the main chain of the resin after being bonded with an epoxy group of the resin through a chemical bond due to the fluorine-substituted group, so that the epoxy adhesive has better weather resistance, cold resistance, high temperature resistance and corrosion resistance, and also has higher thermal stability and surface self-cleaning performance due to the carbon-fluorine bond length and large bond energy. The modified calcium carbonate is used as the filler, so that the mechanical strength of the colloid can be increased, the curing shrinkage is reduced, the thermal expansion coefficient of a cured material is reduced, and the sensitivity of the rubber material to high and low temperature changes is reduced, so that the internal stress is reduced, and secondary cracking is avoided.

In the invention, the tungsten nitride is a tungsten nitride fiber which is mainly used for improving the tear resistance and the hardness of the silica gel, and the tungsten nitride fiber with the length of 10-50 microns is generally adopted. In the process of crosslinking and curing the sizing material, the tungsten nitride fibers are inserted into the hard framework, so that after the sizing material is cured, the hardness and strength of the cured sizing material can be greatly improved, and the curing rate and the crosslinking degree of the sizing material cannot be influenced. By adopting the tungsten nitride fiber, a multi-layer three-dimensional framework can be formed in the sizing material, and the thermal stability of the cured sizing material can be further improved. The length of the tungsten nitride fiber is not too long or too short, the too short length can cause the hardness and strength of the adhesive to be insufficient, the thermal stability is poor, and the too long length can cause the interface of the adhesive to be rough, thereby affecting the adhesive property of the adhesive.

Compared with the prior art, the invention has the following beneficial technical effects:

1. the self-made polyether amine modified curing agent is matched with the polyamide curing agent for use, so that the defect of a single curing agent is overcome, the self-made polyether amine modified curing agent and the polyamide curing agent are complementary and mutually assisted, and the self-made polyether amine modified curing agent has high strength, high maximum elongation and good flexibility; the prepared stone binder has excellent adhesion and certain stress relaxation function. The preparation method and operation of the stone binder are relatively simple and convenient, the material utilization rate is high, the stone has higher strength after being bound by the stone binder, and the secondary cracking in the later period can be effectively avoided.

2. The invention adopts the matching use of the modified calcium carbonate and the hydrophobic fumed silica, so that the paste property of the stone binder is ensured, the dispersibility of the calcium carbonate in resin is further improved, the binding property of the binder is greatly improved, and simultaneously, the weather resistance, the cold resistance, the high temperature resistance and the corrosion resistance of the stone binder are further improved by introducing the side chain fluorine group, so that the stone binder has higher thermal stability, surface self-cleaning property and the like. Further, the hardness and strength of the stone binder are improved by adding tungsten nitride, and the tear resistance and the thermal stability of the binder are greatly enhanced.

3. The stone binder disclosed by the invention is simple in preparation method, wide in raw material source, simple and convenient in construction method, greatly improves the construction efficiency, and has the advantages of low cost, good binding performance and low curing shrinkage rate.

Detailed Description

The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.

The double-component stone binder comprises a component A and a component B, wherein the component A comprises:

the epoxy resin is 32 to 58 parts by weight, preferably 37 to 54 parts by weight, and more preferably 42 to 52 parts by weight.

The reactive diluent is 1 to 9 parts by weight, preferably 2 to 8 parts by weight, and more preferably 3 to 7 parts by weight.

The toughening agent is 5-20 parts by weight, preferably 7-18 parts by weight, and more preferably 9-15 parts by weight.

The modified calcium carbonate is 13 to 33 parts by weight, preferably 15 to 30 parts by weight, and more preferably 18 to 28 parts by weight.

The thixotropic agent is 1 to 5 parts by weight, preferably 1.5 to 4.5 parts by weight, and more preferably 2 to 4 parts by weight.

The antioxidant is 0.05 to 1.5 parts by weight, preferably 0.08 to 1 part by weight, and more preferably 0.1 to 0.8 part by weight.

1-9 parts of white carbon black, preferably 2-5 parts of white carbon black, and more preferably 3-4 parts of white carbon black.

Wherein the component B comprises:

60-88 parts by weight of modified curing agent, preferably 65-85 parts by weight, and more preferably 70-80 parts by weight.

0.5 to 7 parts by weight of accelerator, preferably 0.8 to 5.5 parts by weight, more preferably 1 to 4 parts by weight.

1 to 11 parts by weight of the silane coupling agent, preferably 2 to 9 parts by weight, and more preferably 3 to 7 parts by weight.

The thixotropic agent is 0.01 to 1 part by weight, preferably 0.05 to 0.8 part by weight, and more preferably 0.08 to 0.5 part by weight.

0.5 to 3 parts by weight, preferably 0.8 to 2.8 parts by weight, more preferably 1 to 2.5 parts by weight of tungsten nitride.

0.5-5 parts of white carbon black, preferably 0.8-4 parts of white carbon black, and more preferably 1-3 parts of white carbon black.

The modified calcium carbonate is 7 to 24 parts by weight, preferably 9 to 22 parts by weight, and more preferably 12 to 20 parts by weight.

Wherein the modified curing agent is a mixture of polyether amine modified curing agent and fatty amine modified curing agent.

Preferably, the epoxy resin is selected from one or more of bisphenol A type, bisphenol F type and bisphenol S type epoxy resins. Preferably a mixture of E-51 epoxy and 133L epoxy.

Preferably, the polyether amine modified curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an epoxy resin. Preferably, the curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an E-51 epoxy resin and then further treating the modified curing agent with benzyl alcohol.

Preferably, the aliphatic amine modified curing agent is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and m-xylene diamine modified by nonylphenol glycidyl ether.

Preferably, the amount of benzyl alcohol is 1 to 8 wt%, preferably 2 to 6 wt%, based on the total mass of the polyetheramine-modified curing agent.

Preferably, in the mixed modified curing agent consisting of the polyether amine modified curing agent and the fatty amine modified curing agent, the mass ratio of the polyether amine modified curing agent to the fatty amine modified curing agent is 1:0.5-3, and preferably 1: 0.8-2.

Preferably, the reactive diluent is one or more selected from C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, glycerol triglycidyl ether, 1,4 butanediol glycidyl ether, ethylene glycol diglycidyl ether and neopentyl glycol glycidyl ether. Preferably glycerol triglycidyl ether and/or 1, 4-butanediol glycidyl ether.

Preferably, the toughening agent is an active polyurethane toughening agent.

Preferably, the modified calcium carbonate is obtained by modifying calcium carbonate with aminobenzoic acid. The aminobenzoic acid is selected from one of anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-3, 4,5, 6-tetrafluorobenzoic acid, 4-amino-2, 3,5, 6-tetrafluorobenzoic acid, 2-amino-3, 4, 5-trifluorobenzoic acid, 3-amino-2, 5, 6-trifluorobenzoic acid and 6-amino-2, 3, 4-trifluorobenzoic acid, and is preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid and/or 4-amino-2, 3,5, 6-tetrafluorobenzoic acid.

Preferably, the particle size composition of the modified calcium carbonate is as follows: 10-30% of particle size less than 100 meshes, 25-55% of particle size 100-200 meshes, 18-35% of particle size 300-500 meshes and 12-28% of particle size more than 500 meshes.

Preferably, the accelerator is selected from one or more of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), tris- (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, triethanolamine, thiourea. 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) is preferred.

Preferably, the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010) or antioxidant 1076.

Preferably, the white carbon black is fumed silica.

Preferably, the silane coupling agent is a dialkoxysilane or trialkoxysilane coupling agent containing an amino or hydroxyl functional group. Preferably one or more of gamma-aminopropyltriethoxysilane (KH-550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560) and diethylenetriaminopropyltriethoxysilane.

Preferably, the thixotropic agent is one or more of hydrogenated castor oil, cellulose and bentonite.

A method for preparing a two-component stone binder comprises the following steps:

s1: preparation of the component A: firstly, mixing epoxy resin, active diluent, toughening agent, antioxidant and white carbon black. Then adding the modified calcium carbonate and the thixotropic agent, and continuously mixing to obtain the component A after uniform mixing.

S2: preparation of the component B: firstly, mixing the modified curing agent and the accelerator. Then adding the thixotropic agent and the silane coupling agent and continuously mixing uniformly. Finally, adding the modified calcium carbonate, the tungsten nitride and the white carbon black, and continuously mixing to obtain the component B after uniform mixing.

S3: preparing a two-component stone binder: bottling the component A and the component B according to the proportion to obtain the double-component stone binder.

Wherein the modified curing agent is a mixed modified curing agent consisting of polyether amine modified curing agent and fatty amine modified curing agent according to the mass ratio of 1:0.5-3 (preferably 1: 0.8-2). The modified calcium carbonate is modified calcium carbonate obtained by modifying calcium carbonate with aminobenzoic acid.

Preferably, the aminobenzoic acid is selected from one of anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, 2-amino-3, 4,5, 6-tetrafluorobenzoic acid, 4-amino-2, 3,5, 6-tetrafluorobenzoic acid, 2-amino-3, 4, 5-trifluorobenzoic acid, 3-amino-2, 5, 6-trifluorobenzoic acid, 6-amino-2, 3, 4-trifluorobenzoic acid, and preferably 2-amino-3, 4,5, 6-tetrafluorobenzoic acid and/or 4-amino-2, 3,5, 6-tetrafluorobenzoic acid.

Preferably, the amounts of the components are as follows: wherein the component A is as follows:

The epoxy resin is 32 to 58 parts by weight, preferably 37 to 54 parts by weight, and more preferably 42 to 52 parts by weight.

The reactive diluent is 1 to 9 parts by weight, preferably 2 to 8 parts by weight, and more preferably 3 to 7 parts by weight.

The toughening agent is 5-20 parts by weight, preferably 7-18 parts by weight, and more preferably 9-15 parts by weight.

The modified calcium carbonate is 13 to 33 parts by weight, preferably 15 to 30 parts by weight, and more preferably 18 to 28 parts by weight.

The thixotropic agent is 1 to 5 parts by weight, preferably 1.5 to 4.5 parts by weight, and more preferably 2 to 4 parts by weight.

The antioxidant is 0.05 to 1.5 parts by weight, preferably 0.08 to 1 part by weight, and more preferably 0.1 to 0.8 part by weight.

1-9 parts of white carbon black, preferably 2-5 parts of white carbon black, and more preferably 3-4 parts of white carbon black.

Wherein the component B is as follows:

60-88 parts by weight of modified curing agent, preferably 65-85 parts by weight, and more preferably 70-80 parts by weight.

0.5 to 7 parts by weight of accelerator, preferably 0.8 to 5.5 parts by weight, more preferably 1 to 4 parts by weight.

1 to 11 parts by weight of the silane coupling agent, preferably 2 to 9 parts by weight, and more preferably 3 to 7 parts by weight.

The thixotropic agent is 0.01 to 1 part by weight, preferably 0.05 to 0.8 part by weight, and more preferably 0.08 to 0.5 part by weight.

0.5 to 3 parts by weight, preferably 0.8 to 2.8 parts by weight, more preferably 1 to 2.5 parts by weight of tungsten nitride.

0.5-5 parts of white carbon black, preferably 0.8-4 parts of white carbon black, and more preferably 1-3 parts of white carbon black.

The modified calcium carbonate is 7 to 24 parts by weight, preferably 9 to 22 parts by weight, and more preferably 12 to 20 parts by weight.

Preferably, the epoxy resin is selected from one or more of bisphenol A type, bisphenol F type and bisphenol S type epoxy resins. Preferably a mixture of E-51 epoxy and 133L epoxy.

Preferably, the polyether amine modified curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an epoxy resin. Preferably, the curing agent is a polyether amine modified curing agent obtained by modifying polyoxypropylene diamine and/or polyoxyethylene diamine and/or polyoxypropylene triamine with an E-51 epoxy resin and then further treating the modified curing agent with benzyl alcohol. The aliphatic amine modified curing agent is one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and m-xylene diamine which are modified by nonyl phenol glycidyl ether. Preferably, the amount of benzyl alcohol is 1 to 8 wt%, preferably 2 to 6 wt%, based on the total mass of the polyetheramine-modified curing agent.

Preferably, the reactive diluent is one or more selected from C12-C14 alkyl glycidyl ether, benzyl glycidyl ether, butyl glycidyl ether, glycerol triglycidyl ether, 1,4 butanediol glycidyl ether, ethylene glycol diglycidyl ether and neopentyl glycol glycidyl ether. And/or

Preferably, the accelerator is selected from one or more of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), tris- (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, triethanolamine, thiourea.

Preferably, the toughening agent is an active polyurethane toughening agent.

The antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) or antioxidant 1076.

Preferably, the white carbon black is fumed silica.

Preferably, the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane (KH-550), 3- (2, 3-glycidoxy) propyltrimethoxysilane (KH-560), and diethylenetriaminopropyltriethoxysilane.

Preferably, the thixotropic agent is one or more of hydrogenated castor oil, cellulose and bentonite.

Preferably, S1 is specifically: preparation of the component A: the epoxy resin, the reactive diluent, the toughening agent, the antioxidant and the fumed silica are uniformly mixed under the condition of raising the temperature (for example, the epoxy resin, the reactive diluent, the toughening agent, the antioxidant and the fumed silica are uniformly stirred and mixed at 50-95 ℃ and preferably at 60-80 ℃). Then starting high-speed stirring and vacuumizing (for example, vacuumizing to-0.01 MPa to-0.09 MPa), wherein the high-speed stirring time is 10-60 min. And finally, adding the modified calcium carbonate and the thixotropic agent, continuously stirring for 10-40min, cooling, stopping stirring for 30min, and then stopping vacuumizing to obtain the component A.

Preferably, S2 is specifically: preparation of the component B: the modified curing agent is firstly mixed uniformly according to the proportion, and then the accelerant is added to continue mixing uniformly (for example, stirring and mixing for 10-60 min). Then adding the thixotropic agent and the silane coupling agent and mixing uniformly (for example, stirring and mixing). After a period of time, high-speed stirring is started and vacuum is pumped (for example, the vacuum pumping is from-0.01 MPa to-0.09 MPa), and the high-speed stirring time is 10-60 min. And finally, adding the modified calcium carbonate, the tungsten nitride and the gas-phase white carbon black, continuously stirring (stirring for 10-40min), cooling, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.

Preferably, S3 is specifically: preparing a two-component stone binder: and respectively bottling the component A and the component B according to the mass ratio of 1:1.0-1.5 (preferably 1:1.1-1.3) to obtain the two-component stone binder.

Example 1

Preparation of the component A: 40.0g of 40.0g E-51 epoxy resin, 10.0g of 133L epoxy resin, 4.0g of 1,4 g of butanediol glycidyl ether, 13.0g of active polyurethane, 0.5g of antioxidant 1010 and 3.5g of fumed silica are stirred and mixed uniformly under the condition of raising the temperature to 70 ℃. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 40 min. Then 26.0g of modified calcium carbonate and 3.0g of hydrogenated castor oil were added and stirring was continued for 30min, the temperature was reduced to room temperature and stirring was stopped. Stopping stirring for 30min, and stopping vacuumizing to obtain component A.

Preparation of the component B: and (3) uniformly mixing 29.0g of polyether amine modified curing agent and 43.0g of fatty amine modified curing agent, then adding 3.0g of DMP-30, and continuously stirring and mixing for 30 min. Then 0.4g of hydrogenated castor oil and 4.5g of KH-550 are added and mixed uniformly. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 30 min. Then adding 16.0g of modified calcium carbonate, 2.1g of tungsten nitride and 2.0g of fumed silica, continuing stirring for 25min, cooling to room temperature, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.

Preparing a two-component stone binder I: and filling the component A and the component B into a double tube according to the mass ratio of 1:1.1 to obtain the double-component stone binder I.

Example 2

Preparation of the component A: 40.0g of 40.0g E-51 epoxy resin, 10.0g of 133L epoxy resin, 4.0g of 1, 4g of butanediol glycidyl ether, 13.0g of active polyurethane, 0.5g of antioxidant 1010 and 3.5g of fumed silica are stirred and mixed uniformly under the condition of raising the temperature to 70 ℃. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 40 min. Then 26.0g of modified calcium carbonate and 3.0g of hydrogenated castor oil were added and stirring was continued for 30min, the temperature was reduced to room temperature and stirring was stopped. Stopping stirring for 30min, and stopping vacuumizing to obtain component A.

Preparation of the component B: and (3) uniformly mixing 29.0g of polyether amine modified curing agent and 43.0g of fatty amine modified curing agent, then adding 3.0g of DMP-30, and continuously stirring and mixing for 30 min. Then 0.4g of hydrogenated castor oil and 4.5g of KH-550 are added and mixed uniformly. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 30 min. Then 18.1g of modified calcium carbonate and 2.0g of fumed silica are added and stirred for 25min, the temperature is reduced to room temperature, the stirring is stopped, and the component B is obtained after the stirring is stopped for 30min and the vacuumizing is stopped.

Preparing a two-component stone binder II: and filling the component A and the component B into a double tube according to the mass ratio of 1:1.1 to obtain the double-component stone binder II.

Example 3

Preparation of the component A: 40.0g of 40.0g E-51 epoxy resin, 10.0g of 133L of epoxy resin, 4.0g of glycerol triglycidyl ether, 13.0g of reactive polyurethane, 0.5g of antioxidant 1076 and 3.5g of fumed silica are stirred and mixed uniformly under the condition of raising the temperature to 70 ℃. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 40 min. Then 26.0g of modified calcium carbonate and 3.0g of hydrogenated castor oil were added and stirring was continued for 30min, the temperature was reduced to room temperature and stirring was stopped. Stopping stirring for 30min, and stopping vacuumizing to obtain component A.

Preparation of the component B: and (3) uniformly mixing 29.0g of polyether amine curing agent and 43.0g of fatty amine curing agent, then adding 3.0g of DMP-30, and continuously stirring and mixing for 30 min. Then 0.4g of hydrogenated castor oil and 4.5g of KH-550 are added and mixed uniformly. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 30 min. Then adding 16.0g of modified calcium carbonate, 2.1g of tungsten nitride and 2.0g of fumed silica, continuing stirring for 25min, cooling to room temperature, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.

Preparing a two-component stone binder III: and filling the component A and the component B into a double tube according to the mass ratio of 1:1.1 to obtain the double-component stone binder III.

Example 4

Preparation of the component A: 40.0g of 40.0g E-51 epoxy resin, 10.0g of 133L of epoxy resin, 4.0g of glycerol triglycidyl ether, 13.0g of reactive polyurethane, 0.5g of antioxidant 1076 and 3.5g of fumed silica are stirred and mixed uniformly under the condition of raising the temperature to 70 ℃. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 40 min. 26.0g of calcium carbonate and 3.0g of hydrogenated castor oil are then added and stirring is continued for 30min, the temperature is reduced to room temperature and the stirring is stopped. Stopping stirring for 30min, and stopping vacuumizing to obtain component A.

Preparation of the component B: and (3) uniformly mixing 29.0g of polyether amine modified curing agent and 43.0g of fatty amine modified curing agent, then adding 3.0g of DMP-30, and continuously stirring and mixing for 30 min. Then 0.4g of hydrogenated castor oil and 4.5g of KH-550 are added and mixed uniformly. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 30 min. Then adding 16.0g of calcium carbonate, 2.1g of tungsten nitride and 2.0g of fumed silica, continuing stirring for 25min, cooling to room temperature, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.

Preparing a two-component stone binder IV: and filling the component A and the component B into a double tube according to the mass ratio of 1:1.1 to obtain the double-component stone binder IV.

Example 5

Preparation of the component A: 40.0g of 40.0g E-51 epoxy resin, 10.0g of 133L epoxy resin, 4.0g of benzyl glycidyl ether, 13.0g of active polyurethane, 0.5g of antioxidant 1010 and 3.5g of fumed silica are stirred and mixed uniformly under the condition of raising the temperature to 70 ℃. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 40 min. Then 26.0g of modified calcium carbonate and 3.0g of hydrogenated castor oil were added and stirring was continued for 30min, the temperature was reduced to room temperature and stirring was stopped. Stopping stirring for 30min, and stopping vacuumizing to obtain component A.

Preparation of the component B: 73.0g of the polyetheramine modified curing agent and 3.0g of DMP-30 were stirred and mixed for 30 min. Then 0.4g of hydrogenated castor oil and 4.5g of KH-560 were added and mixed well with stirring. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 30 min. Then adding 16.0g of modified calcium carbonate, 2.1g of tungsten nitride and 2.0g of fumed silica, continuing stirring for 25min, cooling to room temperature, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.

Preparing a two-component stone binder V: and filling the component A and the component B into a double tube according to the mass ratio of 1:1.1 to obtain the double-component stone binder V.

Example 6

Preparation of the component A: 40.0g of 40.0g E-51 epoxy resin, 10.0g of 133L epoxy resin, 4.0g of benzyl glycidyl ether, 13.0g of active polyurethane, 0.5g of antioxidant 1010 and 3.5g of fumed silica are stirred and mixed uniformly under the condition of raising the temperature to 70 ℃. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 40 min. Then 26.0g of modified calcium carbonate and 3.0g of hydrogenated castor oil were added and stirring was continued for 30min, the temperature was reduced to room temperature and stirring was stopped. Stopping stirring for 30min, and stopping vacuumizing to obtain component A.

Preparation of the component B: 73.0g of the aliphatic amine modified curing agent and 3.0g of DMP-30 were stirred and mixed for 30 min. Then 0.4g of hydrogenated castor oil and 4.5g of KH-550 are added and mixed well. After 25min, starting high-speed stirring and vacuumizing to-0.08 MPa, wherein the high-speed stirring time is 30 min. Then adding 16.0g of modified calcium carbonate, 2.1g of tungsten nitride and 2.0g of fumed silica, continuing stirring for 25min, cooling to room temperature, stopping stirring for 30min, and then stopping vacuumizing to obtain the component B.

Preparing a two-component stone binder VI: and filling the component A and the component B into a double tube according to the mass ratio of 1:1.1 to obtain the double-component stone binder VI.

And (3) effect testing: the stone binders I to VI prepared in examples 1 to 6 were subjected to aging and strength tests, and the results were as follows:

TABLE 1 Performance test one

TABLE 2 Performance test two