A polyurethane modified epoxy resin and its preparation method and application

Abstract

The present invention discloses a polyurethane-modified epoxy resin, its preparation method, and application, belonging to the field of resin materials. The polyurethane-modified epoxy resin provided by the present invention comprises the following raw materials: epoxy resin, organic amine, and polyurethane prepolymer; the hydrogen atoms connected to the nitrogen atoms in the organic amine are active hydrogen atoms, the molar ratio of the epoxy groups of the epoxy resin to the active hydrogen atoms is 100:(1-50), and the mass ratio of the epoxy resin to the polyurethane prepolymer is 100:(1-200). The present invention adjusts the ring-opening ratio of the epoxy groups of the epoxy resin by using the organic amine, thereby increasing the hydroxyl content of the epoxy resin, thereby significantly improving the grafting capacity and compatibility of the polyurethane, so that the prepared polyurethane-modified epoxy resin has high tensile strength and elongation at break, and good thermal properties. After the polyurethane-modified epoxy resin is prepared into a grouting adhesive, the grouting adhesive has a suitable curing time and high tensile strength and elongation at break.

Description

Technical Field

[0001] The present invention belongs to the field of resin materials, and in particular relates to a polyurethane-modified epoxy resin and a preparation method and application thereof. Background Art

[0002] Epoxy resin has excellent mechanical properties, electrical insulation properties, bonding properties, etc., but due to its poor toughness, the application of epoxy resin in road repair, crack repair and other fields is limited. Therefore, the study of high-toughness epoxy resin has important theoretical and practical significance.

[0003] Existing research has proposed a variety of epoxy resin toughening modification methods, such as directly adding epoxy resin to nitrile rubber, and directly configuring it into epoxy resin concrete repair material with coupling agent, filler and polyamine. The tensile strength can reach 60MPa, but the elongation at break is low, about 3.5%; other studies have used epoxy resin curing agent containing flexible chain segments to obtain high-strength and high-toughness epoxy resin, but the synthesis method of its curing agent is relatively complex and the cost is high; one study proposed using polyurethane prepolymer to react with hydroxyl groups on epoxy resin to graft polyurethane segments to improve toughness. This study produced a polyurethane-modified epoxy resin with a mass ratio of PU / EP = 15 / 85. The configured grouting material has low cost and long operating time. The tensile strength after curing is about 25.1MPa, but most epoxy resin raw materials have low hydroxyl content and low amount that can be incorporated, making it difficult to obtain epoxy resin with a high polyurethane content. Summary of the Invention

[0004] In order to overcome the problems existing in the above-mentioned prior art, one of the objects of the present invention is to provide a polyurethane-modified epoxy resin, which is modified by polyurethane and has high tensile strength and elongation at break, and good thermal properties.

[0005] A second object of the present invention is to provide a method for preparing the polyurethane-modified epoxy resin, which has simple reaction steps, mild conditions, little harm to the environment, and low production cost.

[0006] A third object of the present invention is to provide a polyurethane-modified epoxy resin grouting adhesive comprising the above-mentioned polyurethane-modified epoxy resin, wherein the grouting adhesive has a suitable curing time and has high tensile strength and elongation at break.

[0007] A fourth object of the present invention is to provide an application of the above-mentioned polyurethane modified epoxy resin grouting adhesive in the field of road repair and crack repair.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is:

[0009] The first aspect of the present invention provides a polyurethane-modified epoxy resin, which includes the following preparation raw materials: epoxy resin, organic amine, and polyurethane prepolymer; the hydrogen connected to the nitrogen atom in the organic amine is active hydrogen, the molar ratio of the epoxy group of the epoxy resin to the active hydrogen of the organic amine is 100:(1-50), and the mass ratio of the epoxy resin to the polyurethane prepolymer is 100:(1-200).

[0010] Preferably, in the polyurethane-modified epoxy resin, the molar ratio of the epoxy groups of the epoxy resin to the active hydrogen of the organic amine is 100:(1-45); further preferably, in the polyurethane-modified epoxy resin, the molar ratio of the epoxy groups of the epoxy resin to the active hydrogen of the organic amine is 100:(3-40); even further preferably, in the polyurethane-modified epoxy resin, the molar ratio of the epoxy groups of the epoxy resin to the active hydrogen of the organic amine is 100:(5-30).

[0011] Preferably, in the polyurethane-modified epoxy resin, the mass ratio of the epoxy resin to the polyurethane prepolymer is 100:(1-200); further preferably, in the polyurethane-modified epoxy resin, the mass ratio of the epoxy resin to the polyurethane prepolymer is 100:(25-130); even further preferably, in the polyurethane-modified epoxy resin, the mass ratio of the epoxy resin to the polyurethane prepolymer is 100:(25-50).

[0012] Preferably, in the polyurethane-modified epoxy resin, the epoxy resin includes at least one of a glycidylamine epoxy resin, an aliphatic epoxy resin or an epoxy resin prepolymer; further preferably, in the polyurethane-modified epoxy resin, the epoxy resin includes at least one of a glycidylamine epoxy resin or an epoxy resin prepolymer; even further preferably, in the polyurethane-modified epoxy resin, the epoxy resin is selected from an epoxy resin prepolymer.

[0013] Preferably, in the epoxy resin, the epoxy resin prepolymer includes at least one of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, triglycidyl ether, tetrabromobisphenol A diglycidyl ether or phthalic acid diglycidyl ether; further preferably, in the epoxy resin, the epoxy resin prepolymer includes at least one of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or triglycidyl ether; even further preferably, in the epoxy resin, the epoxy resin prepolymer includes at least one of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or bisphenol S diglycidyl ether.

[0014] Preferably, in the polyurethane-modified epoxy resin, the organic amine includes organic amine A, organic amine B or a combination thereof, wherein the organic amine A is an organic amine having an active hydrogen number greater than 1 per molecule, and the organic amine B is an organic amine having an active hydrogen number equal to 1 per molecule.

[0015] Preferably, among the organic amines, the organic amine A includes at least one of ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, cyclopentylamine, cyclohexylamine, aniline, p-phenylenediamine, benzylamine or piperazine; further preferably, among the organic amines, the organic amine A includes at least one of ethylamine, propylamine, butylamine, cyclopentylamine, cyclohexylamine, aniline, benzylamine or piperazine; even further preferably, among the organic amines, the organic amine A includes at least one of ethylamine, propylamine or piperazine.

[0016] Preferably, in the organic amine, the organic amine B includes at least one of a chain unsaturated secondary amine, dimethylamine, diethylamine, diisopropylamine, dipropylamine, dibutylamine, N-ethylmethylamine, piperidine, tetrahydropyrrole, imidazole or morpholine; further preferably, in the organic amine, the organic amine B includes at least one of a chain unsaturated secondary amine, diethylamine, N-ethylmethylamine, piperidine, tetrahydropyrrole, imidazole or morpholine; even further preferably, in the organic amine, the organic amine B includes at least one of a chain unsaturated secondary amine, diethylamine or piperidine.

[0017] Preferably, in the organic amine B, the chain unsaturated secondary amine includes the following preparation raw materials:

[0018]

[0019] H2N-R3 formula (II);

[0020] In the formula (I), R1 is a cyano group, a carbonyl group, an ester group or an amide group, and R2 is hydrogen or a C1-C6 alkyl group;

[0021] In the formula (II), R3 is a benzyl group, a C1-C10 straight-chain or branched alkyl group, or a C3-C7 cycloalkyl group.

[0022] Preferably, in the formula (I), R1 is a cyano group, a carbonyl group or an ester group; further preferably, in the formula (I), R1 is a cyano group or an ester group.

[0023] Preferably, in the formula (I), R2 is hydrogen or a C1-C4 alkyl group; further preferably, in the formula (I), R2 is selected from hydrogen.

[0024] Preferably, in the formula (II), R3 is a C1-C10 alkyl group, isopropyl group, cyclopentyl group or cyclohexyl group; more preferably, in the formula (II), R3 is a C1-C10 alkyl group, cyclopentyl group or cyclohexyl group; and even more preferably, in the formula (II), R3 is an ethyl group or a propyl group.

[0025] Preferably, in the raw materials for preparing the chain unsaturated secondary amine, the molar ratio of the compound represented by formula (I) to the compound represented by formula (II) is 1:(1 to 3); further preferably, in the raw materials for preparing the chain unsaturated secondary amine, the molar ratio of the compound represented by formula (I) to the compound represented by formula (II) is 1:(1 to 2); even further preferably, in the raw materials for preparing the chain unsaturated secondary amine, the molar ratio of the compound represented by formula (I) to the compound represented by formula (II) is 1:(1 to 1.5).

[0026] Preferably, among the raw materials for preparing the chain unsaturated secondary amine, the compound represented by formula (I) and the compound represented by formula (II) both participate in the reaction in the form of solution.

[0027] Preferably, the solvent of the solution of the compound represented by formula (I) includes at least one of water, ethanol, acetone or tetrahydrofuran; further preferably, the solvent of the solution of the compound represented by formula (I) includes at least one of water or ethanol; even more preferably, the solvent of the solution of the compound represented by formula (I) is water or a mixed solution of ethanol and water.

[0028] Preferably, the solvent of the solution of the compound represented by formula (II) includes at least one of water, ethanol, acetone or tetrahydrofuran; further preferably, the solvent of the solution of the compound represented by formula (II) includes at least one of water or ethanol; further preferably, the solvent of the solution of the compound represented by formula (II) is water or a mixed solution of ethanol and water.

[0029] Preferably, the solution concentration of the compound represented by formula (I) is 10 to 90 wt %, further preferably, the solution concentration of the compound represented by formula (I) is 40 to 80 wt %; further preferably, the solution concentration of the compound represented by formula (I) is 50 to 70 wt %.

[0030] Preferably, the solution concentration of the compound represented by formula (II) is 10 to 90 wt %, further preferably, the solution concentration of the compound represented by formula (II) is 40 to 80 wt %; further preferably, the solution concentration of the compound represented by formula (II) is 50 to 70 wt %.

[0031] Preferably, the chain unsaturated secondary amine is prepared in the presence of water.

[0032] Preferably, the reaction temperature for preparing the chain unsaturated secondary amine is the first reaction temperature, and the first reaction temperature is 10 to 50°C; further preferably, the first reaction temperature is 20 to 45°C; further preferably, the first reaction temperature is 20 to 35°C.

[0033] Preferably, the preparation reaction time of the chain unsaturated secondary amine is the first reaction time, and the first reaction time is 0.2 to 4 hours; further preferably, the first reaction time is 0.2 to 2 hours; further preferably, the first reaction time is 0.5 to 1 hour.

[0034] Preferably, in the organic amine B, the structural formula of the chain unsaturated secondary amine is as shown in formula (VI):

[0035]

[0036] In the formula (VI), R4 is a cyano group, a carbonyl group, an ester group or an amide group, R5 is hydrogen or a C1-C6 alkyl group, and R6 is a benzyl group, a C1-C10 straight-chain or branched alkyl group, or a C3-C7 cycloalkyl group.

[0037] Preferably, in the formula (VI), R4 is a cyano group, a carbonyl group or an ester group; further preferably, in the formula (VI), R4 is a cyano group or an ester group.

[0038] Preferably, in the formula (VI), R5 is hydrogen or a C1-C4 alkyl group; further preferably, in the formula (VI), R5 is selected from hydrogen.

[0039] Preferably, in the formula (VI), R6 is a C1-C10 straight chain or branched alkyl group, or a C3-C7 cycloalkyl group; further preferably, in the formula (VI), R6 is a C1-C10 straight chain or branched alkyl group; even further preferably, in the formula (VI), R6 is an ethyl group or a propyl group.

[0040] Preferably, in the polyurethane-modified epoxy resin, the raw materials for preparing the polyurethane prepolymer include isocyanate and polyol.

[0041] Preferably, among the raw materials for preparing the polyurethane prepolymer, the isocyanate includes at least one of monoisocyanate, diisocyanate or polyisocyanate; further preferably, among the raw materials for preparing the polyurethane prepolymer, the isocyanate includes at least one of monoisocyanate or diisocyanate; even further preferably, among the raw materials for preparing the polyurethane prepolymer, the isocyanate is selected from diisocyanate.

[0042] Preferably, among the isocyanates, the diisocyanate includes at least one of 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or 4,4'-dicyclohexylmethane diisocyanate; further preferably, among the isocyanates, the diisocyanate includes at least one of 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate or hexamethylene diisocyanate; even further preferably, among the isocyanates, the diisocyanate includes at least one of 4,4'-diphenylmethane diisocyanate, toluene diisocyanate or 1,5-naphthalene diisocyanate.

[0043] Preferably, in the raw materials for preparing the polyurethane prepolymer, the polyol includes polyether polyol, polyester polyol or a combination thereof.

[0044] Preferably, in the polyol, the polyether polyol includes at least one of polypropylene glycol, polyethylene glycol, polyoxypropylene glycol or polytetramethylene glycol; further preferably, in the polyol, the polyether polyol includes at least one of polypropylene glycol, polyethylene glycol or polyoxypropylene glycol; even further preferably, in the polyol, the polyether polyol includes at least one of polypropylene glycol or polyethylene glycol.

[0045] Preferably, among the polyols, the polyester polyol includes polycarbonate diol ester, polyadipate diol ester or a combination thereof; further preferably, among the polyols, the polyester polyol is selected from polycarbonate diol ester.

[0046] Preferably, among the raw materials for preparing the polyurethane prepolymer, the polyol includes at least one of polypropylene glycol, polyethylene glycol, polyoxypropylene glycol, polytetramethylene glycol, polycarbonate diol ester or polyadipate diol ester; further preferably, among the raw materials for preparing the polyurethane prepolymer, the polyol includes at least one of polypropylene glycol, polyethylene glycol, polyoxypropylene glycol or polycarbonate diol ester; even further preferably, among the raw materials for preparing the polyurethane prepolymer, the polyol includes at least one of polypropylene glycol, polyethylene glycol or polycarbonate diol ester.

[0047] Preferably, the molecular weight of the polyol in the raw materials for preparing the polyurethane prepolymer is 100-14000; further preferably, the molecular weight of the polyol in the raw materials for preparing the polyurethane prepolymer is 200-12000; even further preferably, the molecular weight of the polyol in the raw materials for preparing the polyurethane prepolymer is 1000-4000.

[0048] Preferably, in the raw materials for preparing the polyurethane prepolymer, the molar ratio of -OH of polyol to -NCO of isocyanate is 1:(0.5~4); further preferably, in the raw materials for preparing the polyurethane prepolymer, the molar ratio of -OH of polyol to -NCO of isocyanate is 1:(1~3); even further preferably, in the raw materials for preparing the polyurethane prepolymer, the molar ratio of -OH of polyol to -NCO of isocyanate is 1:(1.5~2.5).

[0049] Preferably, the polyurethane prepolymer is prepared by reaction under the catalysis of a catalyst.

[0050] Preferably, the catalyst for the polyurethane prepolymer includes at least one of bismuth neodecanoate, dibutyltin dilaurate, bis(2-dimethylaminoethyl) ether, N,N'-dimethylpyridine or 1,8-diazabicycloundec-7-ene; further preferably, the catalyst for the polyurethane prepolymer includes at least one of bismuth neodecanoate, dibutyltin dilaurate or bis(2-dimethylaminoethyl) ether; even more preferably, the catalyst for the polyurethane prepolymer is selected from bismuth neodecanoate.

[0051] Preferably, the amount of the catalyst for the polyurethane prepolymer is 0.1 to 2 wt% of the raw materials for preparing the polyurethane prepolymer; further preferably, the amount of the catalyst for the polyurethane prepolymer is 0.3 to 1.5 wt% of the raw materials for preparing the polyurethane prepolymer; even more preferably, the amount of the catalyst for the polyurethane prepolymer is 0.5 to 1 wt% of the raw materials for preparing the polyurethane prepolymer.

[0052] Preferably, the preparation reaction temperature of the polyurethane prepolymer is the second reaction temperature, and the second reaction temperature is 30-120°C; further preferably, the second reaction temperature is 40-110°C; further preferably, the second reaction temperature is 50-100°C.

[0053] Preferably, the preparation reaction time of the polyurethane prepolymer is the second reaction time, and the second reaction time is 0.5 to 8 hours; further preferably, the second reaction time is 0.8 to 7 hours; further preferably, the second reaction time is 1 to 6 hours.

[0054] Preferably, the structural formula of the structural unit of the polyurethane-modified epoxy resin is as described in Formula (III), Formula (IV) or Formula (V):

[0055]

[0056]

[0057] Among the raw materials for preparing the polyurethane-modified epoxy resin, when the organic amine is organic amine A, the polyurethane-modified epoxy resin is a grafted polyurethane-modified epoxy resin with polyurethane as the branch chain, and the structural formula of its structural unit is shown in Formula (III) or Formula (IV); when the organic amine is organic amine B, the polyurethane-modified epoxy resin is a segmented polyurethane-modified epoxy resin with a long polyether chain segment in the main chain, and the structural formula of its structural unit is shown in Formula (V).

[0058] The second aspect of the present invention provides a method for preparing the polyurethane-modified epoxy resin described in the first aspect of the present invention, the preparation method comprising the following steps: mixing an epoxy resin and an organic amine to react to obtain a pre-ring-opened epoxy resin, and then adding a polyurethane prepolymer to react to obtain the polyurethane-modified epoxy resin.

[0059] Preferably, in the preparation method of the polyurethane-modified epoxy resin, the ring-opening ratio of the epoxy groups of the pre-ring-opened epoxy resin is 2 to 50%; further preferably, in the preparation method of the polyurethane-modified epoxy resin, the ring-opening ratio of the epoxy groups of the pre-ring-opened epoxy resin is 3 to 40%; even further preferably, in the preparation method of the polyurethane-modified epoxy resin, the ring-opening ratio of the epoxy groups of the pre-ring-opened epoxy resin is 5 to 30%.

[0060] Preferably, in the preparation method of the polyurethane-modified epoxy resin, the molar ratio of -OH of the pre-ring-opened epoxy resin to -NCO of the polyurethane prepolymer is 100:(1~150); further preferably, in the preparation method of the polyurethane-modified epoxy resin, the molar ratio of -OH of the pre-ring-opened epoxy resin to -NCO of the polyurethane prepolymer is 100:(30~140); even further preferably, in the preparation method of the polyurethane-modified epoxy resin, the molar ratio of -OH of the pre-ring-opened epoxy resin to -NCO of the polyurethane prepolymer is 100:(80~130).

[0061] Preferably, in the preparation method of the polyurethane-modified epoxy resin, the temperature at which the epoxy resin and the organic amine are mixed and reacted is the third reaction temperature, and the third reaction temperature is 50-120°C; further preferably, the third reaction temperature is 60-100°C; even further preferably, the third reaction temperature is 70-90°C.

[0062] Preferably, in the preparation method of the polyurethane-modified epoxy resin, the time for the epoxy resin and the organic amine to mix and react is the third reaction time, and the third reaction time is 1 to 5 hours; further preferably, the third reaction time is 1.5 to 4.5 hours; even more preferably, the third reaction time is 2 to 4 hours.

[0063] Preferably, in the preparation method of the polyurethane-modified epoxy resin, the temperature for adding the polyurethane prepolymer to react is the fourth reaction temperature, and the fourth reaction temperature is 50-120°C; further preferably, the fourth reaction temperature is 60-100°C; even more preferably, the fourth reaction temperature is 70-90°C.

[0064] Preferably, in the preparation method of the polyurethane-modified epoxy resin, the time for adding the polyurethane prepolymer to react is the fourth reaction time, and the fourth reaction time is 1 to 5 hours; further preferably, the fourth reaction time is 1.5 to 4.5 hours; even more preferably, the fourth reaction time is 2 to 4 hours.

[0065] The third aspect of the present invention provides a polyurethane modified epoxy resin grouting adhesive comprising the polyurethane modified epoxy resin described in the first aspect of the present invention, the grouting adhesive comprising the following preparation raw materials: polyurethane modified epoxy resin, accelerator, curing agent, and diluent; the curing agent is selected from an amine curing agent, and the hydrogen connected to the nitrogen atom in the amine curing agent is active hydrogen; the molar ratio of the epoxy group of the polyurethane modified epoxy resin to the active hydrogen of the curing agent is 1:(0.5~2); the mass ratio of the polyurethane modified epoxy resin to the diluent is 100:(0.1~80); the mass ratio of the polyurethane modified epoxy resin to the accelerator is 100:(0.01~1.2).

[0066] Preferably, in the raw materials for preparing the grouting glue, the molar ratio of the epoxy groups of the polyurethane-modified epoxy resin to the active hydrogen of the curing agent is 1:(0.6~1.8); further preferably, in the raw materials for preparing the grouting glue, the molar ratio of the epoxy groups of the polyurethane-modified epoxy resin to the active hydrogen of the curing agent is 1:(0.8~1.6); even further preferably, in the raw materials for preparing the grouting glue, the molar ratio of the epoxy groups of the polyurethane-modified epoxy resin to the active hydrogen of the curing agent is 1:(1~1.3).

[0067] Preferably, in the raw materials for preparing the grouting glue, the mass ratio of the polyurethane modified epoxy resin to the diluent is 100:(1~70); further preferably, in the raw materials for preparing the grouting glue, the mass ratio of the polyurethane modified epoxy resin to the diluent is 100:(5~65); even further preferably, in the raw materials for preparing the grouting glue, the mass ratio of the polyurethane modified epoxy resin to the diluent is 100:(10~50).

[0068] Preferably, in the raw materials for preparing the grouting glue, the mass ratio of the polyurethane modified epoxy resin to the accelerator is 100:(0.03~1); further preferably, in the raw materials for preparing the grouting glue, the mass ratio of the polyurethane modified epoxy resin to the accelerator is 100:(0.05~0.8); even further preferably, in the raw materials for preparing the grouting glue, the mass ratio of the polyurethane modified epoxy resin to the accelerator is 100:(0.08~0.7).

[0069] Preferably, in the preparation raw materials of the polyurethane modified epoxy resin grouting adhesive, the accelerator includes at least one of 2,4,6-tris(dimethylaminomethyl)phenol, triethylamine, triethanolamine or pyridine; further preferably, in the preparation raw materials of the polyurethane modified epoxy resin grouting adhesive, the accelerator includes at least one of 2,4,6-tris(dimethylaminomethyl)phenol, triethylamine or triethanolamine; even further preferably, in the preparation raw materials of the polyurethane modified epoxy resin grouting adhesive, the accelerator includes at least one of 2,4,6-tris(dimethylaminomethyl)phenol or triethylamine.

[0070] Preferably, in the preparation raw materials of the polyurethane modified epoxy resin grouting adhesive, the curing agent includes at least one of diethylenetriamine, triethylenetetramine, 4-4'-diaminodiphenylmethane or phenolic amine; further preferably, in the preparation raw materials of the polyurethane modified epoxy resin grouting adhesive, the curing agent includes at least one of diethylenetriamine, triethylenetetramine or 4-4'-diaminodiphenylmethane; even further preferably, in the preparation raw materials of the polyurethane modified epoxy resin grouting adhesive, the curing agent includes at least one of diethylenetriamine or triethylenetetramine.

[0071] Preferably, among the raw materials for preparing the polyurethane modified epoxy resin grouting adhesive, the diluent includes at least one of acetone, toluene, xylene, dichloromethane, ether, furfural, benzophenone, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether or small molecule diglycidyl ether diglycidyl ether; further preferably, among the raw materials for preparing the polyurethane modified epoxy resin grouting adhesive, the diluent includes at least one of acetone, toluene, xylene, dichloromethane, ether, furfural, benzophenone or polypropylene glycol diglycidyl ether; even further preferably, among the raw materials for preparing the polyurethane modified epoxy resin grouting adhesive, the diluent includes at least one of acetone, furfural, benzophenone or polypropylene glycol diglycidyl ether.

[0072] Preferably, the raw materials for preparing the polyurethane modified epoxy resin grouting adhesive also include a degassing agent; further preferably, the degassing agent includes at least one of a polyether degassing agent, a higher alcohol degassing agent, a modified silicon degassing agent or a polysiloxane degassing agent; even further preferably, the degassing agent includes at least one of a polyether degassing agent, a higher alcohol degassing agent or a polysiloxane degassing agent; more preferably, the degassing agent is selected from a polysiloxane degassing agent.

[0073] Preferably, in the preparation raw materials of the polyurethane modified epoxy resin grouting glue, the mass ratio of the polyurethane modified epoxy resin to the defoaming agent is 100:(0~1); further preferably, in the preparation raw materials of the polyurethane modified epoxy resin grouting glue, the mass ratio of the polyurethane modified epoxy resin to the defoaming agent is 100:(0.03~0.8); even further preferably, in the preparation raw materials of the polyurethane modified epoxy resin grouting glue, the mass ratio of the polyurethane modified epoxy resin to the defoaming agent is 100:(0.05~0.6); more preferably, in the preparation raw materials of the polyurethane modified epoxy resin grouting glue, the mass ratio of the polyurethane modified epoxy resin to the defoaming agent is 100:(0.08~0.4).

[0074] The fourth aspect of the present invention provides an application of the polyurethane modified epoxy resin grouting adhesive described in the third aspect of the present invention in the fields of road repair and crack repair.

[0075] The present invention has the following beneficial effects: by adjusting the ring-opening ratio of epoxy groups in the epoxy resin using an organic amine, the hydroxyl content of the epoxy resin is increased, thereby significantly improving the grafting capacity and compatibility of the polyurethane. The resulting polyurethane-modified epoxy resin exhibits high tensile strength and elongation at break, as well as good thermal properties. When the polyurethane-modified epoxy resin is prepared into a grouting adhesive, the adhesive exhibits a suitable curing time and high tensile strength and elongation at break.

[0076] Specifically, compared with the prior art, the present invention has the following advantages:

[0077] 1) The polyurethane-modified epoxy resin prepared by the present invention increases the hydroxyl content of the epoxy resin by pre-ring-opening the epoxy group ring-opening ratio, thereby significantly improving the grafting amount and compatibility of polyurethane in the epoxy resin. The mass ratio of epoxy resin to polyurethane prepolymer can be adjusted between 100:(1-200), thereby making the prepared polyurethane-modified epoxy resin have high tensile strength and elongation at break, as well as good thermal properties. At the same time, the present invention can adjust the tensile strength and elongation at break of the polyurethane-modified epoxy resin by adjusting the mass ratio of epoxy resin to polyurethane prepolymer.

[0078] 2) After the polyurethane-modified epoxy resin is prepared into a grouting adhesive, its surface drying time is appropriate and the initial setting strength is high. After curing for 24 hours, the tensile strength of the grouting adhesive can reach more than 50% of the final tensile strength. It takes about 5 days to fully cure. The fully cured grouting adhesive has high tensile strength and elongation at break.

[0079] 3) The present invention utilizes an amine compound to undergo an addition reaction with a compound containing a double bond to synthesize a secondary amine having a cyano group, a carbonyl group, an ester group, or an amide group. The reaction steps are simple, the conditions are mild, the environmental hazard is small, and the production cost is low. The polyurethane-modified epoxy resin and polyurethane-modified epoxy resin grouting adhesive prepared using the secondary amine have high tensile strength and elongation at break. BRIEF DESCRIPTION OF THE DRAWINGS

[0080] Figure 1 This is the H NMR spectrum of the chain unsaturated secondary amine of Example 1.

[0081] Figure 2 This is the C NMR spectrum of the chain unsaturated secondary amine of Example 1. DETAILED DESCRIPTION

[0082] The content of the present invention is further described in detail below through specific examples. It should be understood that the following examples are only used to further illustrate the present invention and cannot be interpreted as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the principles set forth in the present invention all fall within the scope of protection of the present invention. The specific process parameters and the like in the following examples are only examples within a suitable range, and those skilled in the art can make selections within a suitable range through the description herein, and are not limited to the specific data exemplified below. The raw materials, reagents or devices used in the following examples and comparative examples, unless otherwise specified, can be obtained from conventional commercial sources, or can be obtained by existing known methods.

[0083] In one embodiment of the present invention, the organic amine used is a chain unsaturated secondary amine, and the chain unsaturated secondary amine is prepared by reacting a compound represented by formula (I) with a compound represented by formula (II), and the chain unsaturated secondary amine is prepared by rapid reaction in water or at the interface of a water-organic solvent, with a reaction time of about 0.5 to 1 hour, and water acts as a catalyst. Due to the presence of a cyano group, a carbonyl group, an ester group or an amide group in the compound represented by formula (I), it can react with the compound represented by formula (II) under simple conditions to obtain the chain unsaturated secondary amine. During the preparation process of the secondary amine, the compound represented by formula (I) is dissolved into a solution and then slowly dripped into the solution of the compound represented by formula (II).

[0084] The defoaming agent used in the embodiment of the present invention is German Merck MOK6019.

[0085] Example 1

[0086] Preparation of chain unsaturated secondary amine: Add 50 ml of water and 1.06 g of acrylonitrile to a three-necked flask and stir evenly. Then, add 1.3 g of a 70 wt% aqueous ethylamine solution dropwise using an atmospheric funnel. Stir at 30°C for 1 hour. Remove excess ethylamine and water by rotary evaporation and dry to obtain a chain unsaturated secondary amine with a cyano group. The structural formula of the chain unsaturated secondary amine is shown in Formula (VII). Its H NMR spectrum is shown in Figure 1 As shown, the NMR carbon spectrum is Figure 2 As shown, its nuclear magnetic hydrogen spectrum data is: 1 H-NMR (δ, D2O): 2.74, 2.52, 2.49, 2.46, 0.95.

[0087]

[0088] Preparation of polyurethane prepolymer 1: Add 10 g of polypropylene glycol with a molecular weight of 1000 to a three-necked flask, first raise the temperature to 120°C, remove water under vacuum for 2 hours, then cool to 60°C, add 5 g of 4,4'-diphenylmethane diisocyanate and 0.15 g of bismuth neodecanoate dropwise using a normal pressure funnel, raise the temperature to 80°C, react for 2 hours to obtain polyurethane prepolymer 1, and cool to room temperature for use.

[0089] Preparation of polyurethane-modified epoxy resin 1: 0.98 g of the above-mentioned chain unsaturated secondary amine and 16.3 g of bisphenol F diglycidyl ether were added to a three-necked flask at a molar ratio of 100 / 10 between the epoxy group and the chain unsaturated secondary amine. The mixture was stirred and reacted at 80° C. for 3 hours to obtain an epoxy resin with an epoxy group opening ratio of 10%. Subsequently, 7.5 g of prefabricated polyurethane prepolymer 1 was added at a ratio of n(-OH) / n(-NCO)=100 / 100 and a mass ratio of bisphenol F diglycidyl ether to polyurethane prepolymer 1 of 100:46. The reaction was continued for 3 hours to obtain polyurethane-modified epoxy resin 1, which was then cooled to room temperature for use. Take 24.78 g of polyurethane-modified epoxy resin 1, add 2.193 g of triethylenetetramine at a molar ratio of epoxy group to active hydrogen of 1 / 1, stir evenly, and then pour the prepolymer into a mold. After curing at room temperature for 24 hours, demold and obtain a cured sample 1 of polyurethane-modified epoxy resin 1.

[0090] Preparation of polyurethane-modified epoxy resin grouting adhesive 1: 100 grams of polyurethane-modified epoxy resin 1 was added to 10 grams of polypropylene glycol diglycidyl ether, 10 grams of furfural, and 3 grams of acetone. The mixture was stirred evenly and then discharged to obtain grouting adhesive 1. 2.85 grams of triethylenetetramine and 30.48 grams of grouting adhesive 1 were then mixed at a molar ratio of 1:1.3 (epoxy group / active hydrogen). 0.3 grams of 2,4,6-tris(dimethylaminomethyl)phenol and 0.3 grams of deaerator MOK6019 were added, stirred evenly, and poured into a mold. The mixture was cured at room temperature for 3 hours, demolded, and then cured for another 5 days to obtain polyurethane-modified epoxy resin grouting adhesive 1.

[0091] Example 2

[0092] Preparation of polyurethane prepolymer 2: Add 20 g of polypropylene glycol with a molecular weight of 2000 to a three-necked flask, first raise the temperature to 120°C, remove water in vacuo for 2 hours, then cool to 60°C, add 3.48 g of toluene diisocyanate and 0.23 g of bismuth neodecanoate dropwise using a normal pressure funnel, raise the temperature to 80°C, react for 2 hours to obtain polyurethane prepolymer 2, and cool to room temperature for use.

[0093] Preparation of polyurethane-modified epoxy resin 2: 0.365 g of diethylamine and 19.6 g of bisphenol A diglycidyl ether were added to a three-necked flask at a molar ratio of 100 / 5 for epoxy groups and diethylamine. The mixture was stirred at 80°C for 3 hours to produce an epoxy resin with an epoxy group ring opening ratio of 5%. 5.283 g of preformed polyurethane prepolymer 2 was then added at a ratio of n(-OH) / n(-NCO)=100 / 90 and a mass ratio of bisphenol A diglycidyl ether to polyurethane prepolymer 2 of 100:27. The reaction continued for another 3 hours to produce polyurethane-modified epoxy resin 2. The mixture was then cooled to room temperature and used. To 25.248 g of polyurethane-modified epoxy resin 2, 2.3116 g of triethylenetetramine was added at a molar ratio of 1 / 1 for epoxy groups and active hydrogen. After stirring, the mixture was poured into a mold, vacuum-degassed, and cured at room temperature for 24 hours. The mold was then demolded to obtain a cured sample 2 of polyurethane-modified epoxy resin 2.

[0094] Preparation of polyurethane-modified epoxy resin grouting adhesive 2: 100 grams of polyurethane-modified epoxy resin 2 was added to 5 grams of furfural and 5 grams of acetone, stirred evenly, and then discharged to obtain grouting adhesive 2. At a molar ratio of epoxy groups to active hydrogen of 1:1.2, 27.773 grams of grouting adhesive 2 and 2.774 grams of triethylenetetramine were added, along with 0.1 grams of 2,4,6-tris(dimethylaminomethyl)phenol and 0.1 grams of deaerator MOK6019. Stir evenly and pour into a mold. Curing at room temperature for 3 hours, demolding, and continuing to cure for 5 days to obtain polyurethane-modified epoxy resin grouting adhesive 2.

[0095] Example 3

[0096] Preparation of polyurethane prepolymer 3: Add 10 g of polypropylene glycol with a molecular weight of 1000 to a three-necked flask, first raise the temperature to 120°C, remove water in vacuo for 2 hours, then cool to 60°C, add 3.48 g of toluene diisocyanate and 0.13 g of bismuth neodecanoate dropwise using a normal pressure funnel, raise the temperature to 80°C, react for 2 hours to obtain polyurethane prepolymer 3, and cool to room temperature for use.

[0097] Preparation of polyurethane-modified epoxy resin 3: 0.87 g of piperazine and 16.3 g of bisphenol F diglycidyl ether were added to a three-necked flask at a molar ratio of 100 / 20 for epoxy groups and active hydrogen. The mixture was stirred at 80°C for 3 hours to produce an epoxy resin with an epoxy group ring opening ratio of 20%. 10.784 g of preformed polyurethane prepolymer 2 was then added at a ratio of n(-OH) / n(-NCO)=80 / 100 and a mass ratio of bisphenol F diglycidyl ether to polyurethane prepolymer 3 of 100:66. The reaction continued for another 3 hours to produce polyurethane-modified epoxy resin 3. The mixture was then cooled to room temperature and used. 27.95 g of polyurethane-modified epoxy resin 3 was then added with 1.648 g of diethylenetriamine at a molar ratio of 1 / 1 for epoxy groups and active hydrogen. After uniform mixing, the mixture was poured into a mold, vacuum-degassed, and cured at room temperature for 24 hours. The mold was then demolded to obtain a cured sample 3 of polyurethane-modified epoxy resin 3.

[0098] Preparation of polyurethane-modified epoxy resin grouting adhesive 3: 100 grams of polyurethane-modified epoxy resin 3 was added to 10 grams of polypropylene glycol diglycidyl ether, 20 grams of furfural, and 20 grams of acetone. The mixture was stirred evenly and discharged to obtain grouting adhesive 3. 42 grams of grouting adhesive 3 and 1.82 grams of diethylenetriamine were added at a molar ratio of 1:1 (epoxy groups / active hydrogen). 0.1 grams of 2,4,6-tris(dimethylaminomethyl)phenol and 0.1 grams of deaerator MOK6019 were added, stirred evenly, and poured into a mold. The mixture was cured at room temperature for 3 hours, demolded, and then cured for another 5 days to obtain polyurethane-modified epoxy resin grouting adhesive 3.

[0099] Example 4

[0100] Preparation of polyurethane prepolymer 4: Add 10 g of polypropylene glycol with a molecular weight of 1000 to a three-necked flask, first raise the temperature to 120°C, remove water in vacuo for 2 hours, then cool to 60°C, add 3.48 g of toluene diisocyanate and 0.13 g of bismuth neodecanoate dropwise using a normal pressure funnel, raise the temperature to 80°C, react for 2 hours to obtain polyurethane prepolymer 4, and cool to room temperature for use.

[0101] Preparation of polyurethane-modified epoxy resin 4: 2.5542 g of piperidine and 16.3 g of bisphenol F diglycidyl ether were added to a three-necked flask at a molar ratio of 100 / 30 for epoxy groups and active hydrogen. The mixture was stirred at 80°C for 3 hours to produce an epoxy resin with an epoxy group ring opening ratio of 30%. 20.22 g of preformed polyurethane prepolymer 4 was then added at a ratio of n(-OH) / n(-NCO)=100 / 100 and a mass ratio of bisphenol F diglycidyl ether to polyurethane prepolymer 4 of 100:124. The reaction continued for another 3 hours to produce polyurethane-modified epoxy resin 4. The mixture was then cooled to room temperature and used. 39 g of polyurethane-modified epoxy resin 4 was then added with 1.703 g of triethylenetetramine at a molar ratio of 1 / 1 for epoxy groups and active hydrogen. After uniform mixing, the mixture was poured into a mold, vacuum-degassed, and cured at room temperature for 24 hours. The mold was then demolded to obtain a cured sample of polyurethane-modified epoxy resin 4.

[0102] Preparation of polyurethane-modified epoxy resin grouting adhesive 4: 100 grams of polyurethane-modified epoxy resin 4 was added to 25 grams of furfural and 25 grams of acetone, stirred evenly, and then discharged to obtain grouting adhesive 4. At a molar ratio of 1:1 epoxy group / active hydrogen, 58.61 grams of grouting adhesive 4 and 1.703 grams of triethylenetetramine were added, along with 0.6 grams of 2,4,6-tris(dimethylaminomethyl)phenol and 0.1 grams of deaerator MOK6019. Stir evenly and pour into a mold. Curing at room temperature for 3 hours, demolding, and continuing to cure for 5 days to obtain polyurethane-modified epoxy resin grouting adhesive 4.

[0103] Example 5

[0104] Preparation of polyurethane prepolymer 5: Add 10 g of polypropylene glycol with a molecular weight of 1000 to a three-necked flask, first raise the temperature to 120°C, remove water under vacuum for 2 hours, then cool to 60°C, add 5 g of 4,4'-diphenylmethane diisocyanate and 0.15 g of bismuth neodecanoate dropwise using a normal pressure funnel, raise the temperature to 80°C, react for 2 hours to obtain polyurethane prepolymer 5, and cool to room temperature for use.

[0105] Preparation of polyurethane-modified epoxy resin 5: 0.296 g of propylamine and 16.3 g of bisphenol F diglycidyl ether were added to a three-necked flask at a molar ratio of 100 / 10 for epoxy groups and active hydrogen. The mixture was stirred at 80°C for 3 hours to produce an epoxy resin with an epoxy group ring-opening ratio of 10%. 7.5 g of preformed polyurethane prepolymer 5 was then added at a ratio of n(-OH) / n(-NCO)=100 / 100 and a mass ratio of bisphenol F diglycidyl ether to polyurethane prepolymer 5 of 100:46. The reaction continued for another 3 hours to produce polyurethane-modified epoxy resin 5. The mixture was then cooled to room temperature and used. 24.095 g of polyurethane-modified epoxy resin 5 was then added to 2.19 g of triethylenetetramine at a molar ratio of 1 / 1 for epoxy groups and active hydrogen. After stirring, the mixture was poured into a mold, vacuum-degassed, and cured at room temperature for 24 hours. The mold was then demolded to obtain a cured sample 5 of polyurethane-modified epoxy resin 5.

[0106] Preparation of polyurethane-modified epoxy resin grouting adhesive 5: 100 grams of polyurethane-modified epoxy resin 5 was added to 10 grams of polypropylene glycol diglycidyl ether, 10 grams of furfural, and 3 grams of acetone. The mixture was stirred evenly and then discharged to obtain grouting adhesive 5. 36 grams of grouting adhesive 5 and 2.847 grams of triethylenetetramine were added at a molar ratio of 1:1.3 of epoxy groups to active hydrogen. 0.1 grams of 2,4,6-tris(dimethylaminomethyl)phenol and 0.1 grams of deaerator MOK6019 were added and stirred evenly. The mixture was then poured into a mold. Cured at room temperature for 3 hours, demolded, and then cured for another 5 days to obtain polyurethane-modified epoxy resin grouting adhesive 5.

[0107] Example 6

[0108] Preparation of polyurethane prepolymer 6: Add 10 g of polypropylene glycol with a molecular weight of 1000 to a three-necked flask, first raise the temperature to 120°C, remove water in vacuo for 2 hours, then cool to 60°C, add 5 g of 4,4'-diphenylmethane diisocyanate and 0.15 g of bismuth neodecanoate dropwise using a normal pressure funnel, raise the temperature to 80°C, react for 2 hours to obtain polyurethane prepolymer 6, and cool to room temperature for use.

[0109] Preparation of polyurethane-modified epoxy resin 6: 0.225 g of ethylamine and 16.3 g of bisphenol F diglycidyl ether were added to a three-necked flask at a molar ratio of 100 / 10 for epoxy groups and active hydrogen. The mixture was stirred at 80°C for 3 hours to produce an epoxy resin with an epoxy group ring opening ratio of 10%. 7.5 g of preformed polyurethane prepolymer 6 was then added at a ratio of n(-OH) / n(-NCO)=100 / 100 and a mass ratio of bisphenol F diglycidyl ether to polyurethane prepolymer 6 of 100:46. The reaction continued for another 3 hours to produce polyurethane-modified epoxy resin 6. The mixture was then cooled to room temperature and used. 24.025 g of polyurethane-modified epoxy resin 6 was then added to 2.19 g of triethylenetetramine at a molar ratio of 1 / 1 for epoxy groups and active hydrogen. After stirring, the mixture was poured into a mold, vacuum-degassed, and cured at room temperature for 24 hours. The mold was then demolded to obtain a cured sample of polyurethane-modified epoxy resin 6.

[0110] Preparation of polyurethane-modified epoxy resin grouting adhesive 6: Take 100 grams of polyurethane-modified epoxy resin 6, add 10 grams of polypropylene glycol diglycidyl ether, 10 grams of furfural, and 3 grams of acetone, stir well, and then discharge to obtain grouting adhesive 6. At a molar ratio of epoxy groups to active hydrogen of 1:1.3, take 36 grams of grouting adhesive 6 and 2.847 grams of triethylenetetramine, add 0.1 grams of 2,4,6-tris(dimethylaminomethyl)phenol and 0.1 grams of deaerator MOK6019, stir well, and pour into a mold. Curing at room temperature for 3 hours, demolding, and continuing to cure for 5 days to obtain polyurethane-modified epoxy resin grouting adhesive 6.

[0111] Comparative Example 1

[0112] Preparation of epoxy resin cured sample 7: Take 2.06 grams of curing agent triethylenetetramine and 17 grams of bisphenol F diglycidyl ether, stir at room temperature for 10 minutes, prepare a prepolymer liquid, and then pour the prepolymer liquid into a steel mold, cure at room temperature for 24 hours, and demold to obtain epoxy resin cured sample 7.

[0113] Preparation of epoxy resin grouting glue 7: Take 17 grams of bisphenol F diglycidyl ether, 1.7 grams of furfural, 0.5 grams of acetone and 1.7 grams of polypropylene glycol diglycidyl ether, stir at room temperature for 30 minutes, then add 2.7 grams of curing agent triethylenetetramine, continue stirring for 10 minutes, prepare into prepolymer liquid, and then pour the prepolymer liquid into a steel mold and cure at room temperature for 5 days to obtain epoxy resin grouting glue 7.

[0114] Test Case

[0115] According to GB / T 528-2009 and GB / T 2410-2008 standards, the mechanical and thermal properties of the cured samples of the epoxy resins obtained in Examples 1 to 6 and Comparative Example 1 were tested, and the results are recorded in Table 1. The mechanical and curing properties of the epoxy resin grouting adhesives obtained in Examples 1 to 6 and Comparative Example 1 were tested, and the results are recorded in Table 2.

[0116] Table 1 Performance test results of epoxy resin cured samples

[0117]

[0118] Table 2 Performance test results of epoxy resin potting glue

[0119]

[0120]

[0121] The polyurethane-modified epoxy resin prepared by the present invention increases the hydroxyl content of the epoxy resin by pre-ring-opening the epoxy group ring-opening ratio, thereby significantly improving the grafting capacity and compatibility of polyurethane in the epoxy resin. The mass ratio of the epoxy resin to the polyurethane prepolymer can be adjusted between 100:1 and 200, resulting in the polyurethane-modified epoxy resin having high tensile strength and elongation at break, as well as good thermal properties. Furthermore, the present invention can adjust the mass ratio of the epoxy resin to the polyurethane prepolymer to adjust the tensile strength and elongation at break of the polyurethane-modified epoxy resin. When the mass ratio of the epoxy resin to the polyurethane prepolymer is 100:46, the cured sample of the polyurethane-modified epoxy resin has good mechanical and thermal properties. According to tests in accordance with GB / T 528-2009 and GB / T 2410-2008, the tensile strength can be 26 to 48 MPa, and the elongation at break can be 16 to 36%.

[0122] The polyurethane-modified epoxy resin grouting adhesive of the present invention has a suitable surface drying time and high initial setting strength. After curing for 24 hours, the tensile strength of the adhesive can reach more than 50% of the final tensile strength, and complete curing requires 5 days or more. When the mass ratio of epoxy resin to polyurethane prepolymer is 100:(27-46), the tensile strength of the polyurethane-modified epoxy resin grouting adhesive can be 20-36 MPa and the elongation at break can be 32-40%.

[0123] The polyurethane-modified epoxy resin and polyurethane-modified epoxy resin grouting adhesive provided by the present invention have simple reaction steps, mild conditions, low environmental harm, and low production cost. The resulting polyurethane-modified epoxy resin grouting adhesive has wide applications in the fields of road repair and crack repair.

Claims

1. A polyurethane modified epoxy resin, characterized in that, The preparation method comprises the following raw materials: epoxy resin, organic amine, and polyurethane prepolymer; the hydrogen connected to the nitrogen atom in the organic amine is active hydrogen, the molar ratio of the epoxy group of the epoxy resin to the active hydrogen of the organic amine is 100:(5-30), and the mass ratio of the epoxy resin to the polyurethane prepolymer is 100:(46-50); The epoxy resin is selected from epoxy resin prepolymers; the epoxy resin prepolymer is selected from bisphenol F diglycidyl ether; The organic amine is selected from organic amine B; the organic amine B is selected from chain unsaturated secondary amine; the chain unsaturated secondary amine is prepared by reacting the following raw materials: Formula (I); Formula (II); In the formula (I), R1 is a cyano group, and R2 is hydrogen or a C1~C6 alkyl group; In the formula (II), R3 is benzyl, C1~C10 straight or branched alkyl, or C3~C7 cycloalkyl; The polyurethane prepolymer is prepared by reacting preparation raw materials including isocyanate and polyol; the isocyanate is selected from diisocyanate; the molar ratio of -OH of the polyol to -NCO of the isocyanate is 1:(1.5-2.5); the diisocyanate is selected from 4,4'-diphenylmethane diisocyanate; the polyol is selected from polypropylene glycol; the molecular weight of the polyol is 1000-4000; the preparation reaction temperature of the polyurethane prepolymer is the second reaction temperature; the second reaction temperature is 80-120°C; the preparation reaction time of the polyurethane prepolymer is the second reaction time; and the second reaction time is 0.5-8 hours.

2. The polyurethane-modified epoxy resin according to claim 1, characterized in that: The structural formula of the structural unit of the polyurethane-modified epoxy resin is shown in formula (V): Formula (V).

3. The method for preparing the polyurethane-modified epoxy resin according to any one of claims 1 to 2, characterized in that: The method comprises the following steps: mixing epoxy resin and organic amine to react to obtain pre-ring-opened epoxy resin, and then adding polyurethane prepolymer to react to obtain the polyurethane-modified epoxy resin.

4. The preparation method according to claim 3, characterized in that The epoxy group opening ratio of the pre-ring-opened epoxy resin is 5 to 30%; And / or, the molar ratio of -OH of the pre-ring-opened epoxy resin to -NCO of the polyurethane prepolymer is 100:(80-130).

5. A polyurethane modified epoxy resin grouting adhesive, characterized in that: The invention comprises the following preparation raw materials: a polyurethane-modified epoxy resin, an accelerator, a curing agent, and a diluent; the polyurethane-modified epoxy resin is the polyurethane-modified epoxy resin according to any one of claims 1 to 2; the curing agent is selected from an amine curing agent, and the hydrogen connected to the nitrogen atom in the amine curing agent is active hydrogen; the molar ratio of the epoxy group of the polyurethane-modified epoxy resin to the active hydrogen of the curing agent is 1:(0.5-2); the mass ratio of the polyurethane-modified epoxy resin to the diluent is 100:(0.1-80); and the mass ratio of the polyurethane-modified epoxy resin to the accelerator is 100:(0.01-1.2).

6. The polyurethane modified epoxy resin grouting adhesive according to claim 5, characterized in that: The accelerator includes at least one of 2,4,6-tris(dimethylaminomethyl)phenol, triethylamine, triethanolamine or pyridine; and / or, the curing agent comprises at least one of diethylenetriamine, triethylenetetramine, 4-4'-diaminodiphenylmethane or phenalkamine; And / or, the diluent includes at least one of acetone, toluene, xylene, dichloromethane, ether, furfural, benzophenone, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether or small molecule diglycidyl ether.

7. Use of the polyurethane modified epoxy resin grouting adhesive according to claim 5 or 6 in the fields of road repair and crack repair.

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