Basalt fiber component reinforced modified epoxy resin adhesive, preparation method and application thereof, epoxy mortar material and application thereof

Abstract

The invention belongs to the technical field of epoxy resin adhesives, and particularly relates to a basalt fiber component reinforced modified epoxy resin adhesive, a preparation method and application thereof, an epoxy mortar material and application thereof. According to the basalt fiber component reinforced modified epoxy resin adhesive disclosed by the invention, a modified epoxy resin adhesive matrix contains an-NCO group, so that the basalt fiber component reinforced modified epoxy resin adhesive can have very good flexibility and rigidity balance, and the-NCO group and an epoxy group can generate an oxazolidinone structure, so that the stability of the basalt fiber component reinforced modified epoxy resin adhesive is improved; the basalt fiber powder is added into a modified epoxy resin adhesive matrix as a reinforcing material, and the basalt fiber powder is dispersed in a resin system to form particles with a certain concentration, so that the mechanical strength, the impact resistance, the corrosion resistance, the wear resistance and the thermal stability of the basalt fiber powder reinforced modified epoxy resin adhesive are improved; when the composite material is applied to defect repair of a concrete structure, the bending resistance, the tensile strength, the compressive strength and the crack resistance of concrete are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of epoxy resin adhesives, and specifically relates to a basalt fiber component reinforced modified epoxy resin adhesive and a preparation method and application thereof, an epoxy mortar and an application thereof. Background Art

[0002] Epoxy resin glue generally refers to an adhesive made of epoxy resin as the main body. It has good chemical stability and high bonding strength to both metal and non-metal materials. It is known as a universal glue and is widely used in coatings, fiber composite materials and other fields. However, the current epoxy resin glue has poor impact resistance, toughness and thermal stability. When used in the repair of defects in concrete structures, the tensile strength of the concrete is low, which limits the application of epoxy resin glue in the concrete field. Summary of the invention

[0003] The purpose of the present invention is to provide a basalt fiber component reinforced modified epoxy resin adhesive and a preparation method and application thereof, an epoxy mortar and an application thereof. When the basalt fiber component reinforced modified epoxy resin adhesive provided by the present invention is used in defect repair of concrete structure, the tensile strength of the concrete is high.

[0004] In order to achieve the above object, the present invention provides the following technical solutions:

[0005] The present invention provides a basalt fiber component reinforced modified epoxy resin adhesive, comprising a modified epoxy resin adhesive matrix and a fiber component dispersed in the modified epoxy resin adhesive matrix;

[0006] The fiber component includes fiber powder and / or short fibers; the fiber powder includes basalt fiber powder and / or basalt fiber powder modified by silane coupling agent; the short fibers include basalt filamentary fibers and / or basalt flocculent fibers;

[0007] The raw materials for preparing the modified epoxy resin adhesive matrix include bisphenol A epoxy resin, polyether, alicyclic diisocyanate and esterification catalyst;

[0008] The mass ratio of the modified epoxy resin matrix to the fiber component is 100:10-30.

[0009] Preferably, the alicyclic diisocyanate comprises isophorone diisocyanate;

[0010] The esterification catalyst includes dibutyltin oxide and / or dihydroxybutyltin chloride.

[0011] Preferably, the polyether comprises polyethylene glycol and / or polypropylene glycol;

[0012] The mass ratio of the bisphenol A epoxy resin to the polyether is 65-70:10-20;

[0013] The mass ratio of the bisphenol A epoxy resin to the alicyclic diisocyanate is 65-70:5-10;

[0014] The mass ratio of the bisphenol A epoxy resin to the esterification catalyst is 65-70:1-2.

[0015] Preferably, the preparation method of the modified epoxy resin adhesive matrix comprises the following steps:

[0016] Bisphenol A epoxy resin, polyether, alicyclic diisocyanate and esterification catalyst are mixed and subjected to esterification reaction to obtain the modified epoxy resin adhesive matrix.

[0017] Preferably, the temperature of the esterification reaction is 60-80° C., and the time is 5.5-8.5 h.

[0018] Preferably, the method for preparing the silane coupling agent modified basalt fiber powder comprises the following steps:

[0019] Mixing a silane coupling agent, a lower alcohol and water to obtain a silane coupling agent hydrolyzate;

[0020] The silane coupling agent hydrolyzate is mixed with basalt fiber powder and surface modified to obtain the silane coupling agent modified basalt fiber powder.

[0021] Preferably, the surface modification temperature is 50-60° C. and the time is 5.25-6.5 h.

[0022] The present invention provides a method for preparing the basalt fiber component reinforced modified epoxy resin adhesive described in the above technical solution, comprising the following steps:

[0023] The modified epoxy resin adhesive matrix and the fiber powder are mixed to obtain the basalt fiber component reinforced modified epoxy resin adhesive.

[0024] The present invention provides an epoxy mortar material, the preparation raw materials of which include epoxy resin glue, basalt fiber powder and mortar filler; the epoxy resin glue is the basalt fiber component reinforced modified epoxy resin glue described in the above technical solution or the basalt fiber component reinforced modified epoxy resin glue prepared by the preparation method described in the above technical solution;

[0025] The mortar filler includes cement powder and / or quartz sand.

[0026] The present invention provides the use of the basalt fiber component reinforced modified epoxy resin adhesive described in the above technical scheme, the basalt fiber component reinforced modified epoxy resin adhesive prepared by the preparation method described in the above technical scheme, or the epoxy mortar described in the above technical scheme in epoxy concrete, composite reinforcement connection anchoring, concrete structure defect repair, steel-concrete structure connection, reinforcement or structural paving.

[0027] The present invention provides a basalt fiber component reinforced modified epoxy resin adhesive, comprising a modified epoxy resin adhesive matrix and a fiber component dispersed in the modified epoxy resin adhesive matrix; the fiber component comprises fiber powder and / or short fine fibers; the fiber powder comprises basalt fiber powder and / or basalt fiber powder modified by a silane coupling agent; the short fine fibers comprise basalt filamentary fibers and / or basalt flocculent fibers; the raw materials for preparing the modified epoxy resin adhesive matrix comprise bisphenol A type epoxy resin, polyether, alicyclic diisocyanate and an esterification catalyst. In the present invention, the modified epoxy resin adhesive matrix contains -NCO groups, so that the basalt fiber component reinforced modified epoxy resin adhesive can have a good balance of flexibility and rigidity, and the -NCO group and the epoxy group can generate an oxazolidinone structure, which is very stable and improves the stability of the basalt fiber component reinforced modified epoxy resin adhesive; the present invention adds basalt fiber powder as a reinforcing material into the modified epoxy resin adhesive matrix, and the basalt fiber powder is dispersed in the resin system to form particles of a certain concentration, and then interacts with other components in the system through physical and chemical effects, thereby increasing the viscosity of the liquid system, thereby increasing the adhesion of the system, and improving the mechanical strength, impact resistance, corrosion resistance, wear resistance and thermal stability of the basalt fiber powder reinforced modified epoxy resin adhesive. When applied to defect repair of concrete structures, the concrete has high tensile strength. Moreover, the present invention adopts silane coupling agent modified basalt fiber powder as a reinforcing material and adds it to the modified epoxy resin adhesive matrix. The surface of the silane coupling agent modified basalt fiber powder has an organic layer of silane coupling agent molecules, which can form Si-O-Si chemical bonds in the modified epoxy resin adhesive matrix, thereby forming a "bridging" effect between the interfaces of the two substances, constructing a multi-dimensional network structure, and can be better combined with the modified epoxy resin adhesive matrix, and has good compatibility with the modified epoxy resin adhesive matrix. Moreover, the present invention uses bisphenol A epoxy resin, polyether, alicyclic diisocyanate (IPDI) and esterification catalyst as raw materials for preparing modified epoxy resin adhesive matrix. Polyether can increase the flexibility of epoxy resin, and the esterification catalyst can accelerate the esterification reaction of alicyclic diisocyanate and epoxy resin. The obtained basalt fiber powder reinforced modified epoxy resin adhesive has good bonding performance and toughness, which broadens the application field of the material. In addition, the present invention adds (basalt) short fine fibers as reinforcing materials into the modified epoxy resin adhesive matrix. When applied to epoxy concrete, the flexural strength and compressive strength of the concrete are improved.

[0028] The preparation method provided by the invention has the advantages of simple operation, low cost, little environmental pollution and is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a line graph showing the effect of basalt fiber powder before and after modification with silane coupling agent on the flexural strength of epoxy resin. DETAILED DESCRIPTION

[0030] The present invention provides a basalt fiber component reinforced modified epoxy resin adhesive, comprising a modified epoxy resin adhesive matrix and a fiber component dispersed in the modified epoxy resin adhesive matrix; the fiber component comprises fiber powder and / or short fine fibers; the fiber powder comprises basalt fiber powder and / or basalt fiber powder modified by a silane coupling agent; the short fine fibers comprise basalt filamentary fibers and / or basalt flocculent fibers; the raw materials for preparing the modified epoxy resin adhesive matrix comprise bisphenol A type epoxy resin, polyether, alicyclic diisocyanate and an esterification catalyst; the mass ratio of the modified epoxy resin adhesive matrix to the fiber powder is 100:10-30.

[0031] In the present invention, unless otherwise specified, the reagents used are commercially available products well known to those skilled in the art.

[0032] In the present invention, the basalt filamentary fibers are preferably chopped and dispersed basalt continuous fibers; the basalt flocculent fibers are preferably flocculent fibers made by sawing basalt continuous fibers through a spraying process. In the present invention, the length of the short fine fibers is preferably 5 to 10 cm, more preferably 6 to 9 cm, and most preferably 7 to 8 cm; the diameter of the short fine fibers is preferably 7 to 13 μm, more preferably 8 to 12 μm, and most preferably 9 to 10 μm. The present invention adds the short fine fibers as reinforcing materials to the modified epoxy resin matrix, and when applied to epoxy concrete, the flexural strength and compressive strength of the concrete are improved.

[0033] In the present invention, the mass ratio of the modified epoxy resin matrix to the fiber component is 100:10-30, preferably 100:12-25, more preferably 100:15-20, and most preferably 100:16-18.

[0034] In the present invention, the raw materials for preparing the modified epoxy resin adhesive matrix include bisphenol A epoxy resin, polyether, alicyclic diisocyanate and esterification catalyst. In the present invention, the bisphenol A epoxy resin preferably includes one or more of epoxy resin E44, epoxy resin E51 and epoxy resin E56; the polyether preferably includes polyethylene glycol and / or polypropylene glycol; the polyethylene glycol preferably includes polyethylene glycol PEG400; the mass ratio of the bisphenol A epoxy resin and the polyether is preferably 65-70:10-20, more preferably 66-69:12-18, and most preferably 67-68:14-16. The present invention uses polyethylene glycol PEG400 to increase the flexibility of the modified epoxy resin adhesive matrix.

[0035] In the present invention, the alicyclic diisocyanate is preferably isophorone diisocyanate; the mass ratio of the bisphenol A epoxy resin to the alicyclic diisocyanate is preferably 65-70:5-10, more preferably 66-69:6-9, and most preferably 67-68:7-8.

[0036] In the present invention, the esterification catalyst preferably includes dibutyltin oxide and / or dihydroxybutyltin chloride, more preferably dibutyltin oxide; the mass ratio of the bisphenol A epoxy resin to the esterification catalyst is preferably 65-70:1-2, more preferably 66-69:1-2, and most preferably 67-68:1-2.

[0037] In the present invention, the preparation method of the modified epoxy resin adhesive matrix preferably comprises the following steps: mixing bisphenol A epoxy resin, polyether, alicyclic diisocyanate and an esterification catalyst, and performing an esterification reaction to obtain the modified epoxy resin adhesive matrix.

[0038] In the present invention, the mixing preferably includes first mixing bisphenol A epoxy resin, polyether and alicyclic diisocyanate to obtain a premix; and second mixing the premix and an esterification catalyst.

[0039] After obtaining the premix, the present invention preferably further comprises preheating the premix; the preheating temperature is preferably 50-60°C, more preferably 54-60°C, and most preferably 58-60°C.

[0040] In the present invention, the temperature of the esterification reaction is preferably 60-80°C, more preferably 65-80°C, and most preferably 75-80°C; the time of the esterification reaction is preferably 5.5-8.5h, more preferably 6-8h, and most preferably 6-7h; the esterification reaction is preferably carried out in an inert gas atmosphere; the inert gas atmosphere preferably includes nitrogen and / or argon. The present invention adjusts the esterification reaction time by controlling the temperature of the esterification reaction, and the reaction time is shortened when the reaction temperature is increased.

[0041] In the present invention, the basalt fiber powder is preferably prepared by chopping, breaking up and crushing basalt fibers. The present invention has no special limitation on the breaking up, and it is sufficient to obtain chopped basalt fibers that are not entangled and united. In the present invention, the particle size of the basalt fiber powder is preferably 300-400 mesh, more preferably 320-380 mesh, and most preferably 340-360 mesh; the diameter of the basalt fiber is preferably 9-17 μm, more preferably 10-15 μm, and most preferably 11-13 μm; the elongation at break of the basalt fiber is preferably 3.5-4%, more preferably 3.6-3.9%, and most preferably 3.8-3.9%; the density of the basalt fiber is preferably 2.6-2.8 kg / m 3 , more preferably 2.6 to 2.7 kg / m 3 As a green inorganic fiber material, basalt fiber has the characteristics of high and low temperature resistance and corrosion resistance. The present invention enhances the modified epoxy resin adhesive by adding basalt fiber powder, which can not only improve the mechanical strength of the modified epoxy resin adhesive, but also improve the thermal stability and corrosion resistance of the modified epoxy resin adhesive.

[0042] In the present invention, the preparation method of the silane coupling agent modified basalt fiber powder preferably comprises the following steps: mixing a silane coupling agent, ethanol and water to obtain a silane coupling agent hydrolyzate; mixing the silane coupling agent hydrolyzate with basalt fiber powder, performing surface modification, and obtaining the silane coupling agent modified basalt fiber powder.

[0043] The present invention mixes a silane coupling agent, a lower alcohol and water (referred to as the third mixing) to obtain a silane coupling agent hydrolyzate.

[0044] In the present invention, the silane coupling agent preferably includes one or more of KH550, KH560 and KH570; the lower alcohol preferably includes ethanol; the volume ratio of the silane coupling agent to the lower alcohol is preferably 1:40-60, more preferably 1:45-55, most preferably 1:50-60; the volume ratio of the silane coupling agent to water is preferably 1:4-6, more preferably 1:4.5-5.5, more preferably 1:5-5.2. The present invention uses silane coupling agent as a modifier and impregnating agent for basalt fiber powder, so that the silane coupling agent and basalt fiber powder can be fully contacted and reacted, and an organic layer of coupling agent molecules is formed on the surface of the basalt fiber powder modified by the silane coupling agent. When dispersed in the modified epoxy resin glue, part of the groups in the silane coupling agent are connected to the skeleton (inorganic fiber), and the other part of the groups are connected to the organic molecules, forming Si-O-Si chemical bonds in the modified epoxy resin glue matrix, thereby forming a "bridging" effect between the interfaces of the two substances, which can better combine with the modified epoxy resin glue matrix and has good compatibility with the modified epoxy resin glue matrix.

[0045] In the present invention, the temperature of the third mixing is preferably room temperature, more preferably 10-35°C, most preferably 15-30°C; the time of the third mixing is preferably 10-15min, more preferably 10-14min, most preferably 10-12min; the third mixing preferably includes stirring mixing.

[0046] After obtaining the silane coupling agent hydrolyzate, the present invention mixes the silane coupling agent hydrolyzate with basalt fiber powder (referred to as the fourth mixing) and performs surface modification to obtain the silane coupling agent-modified basalt fiber powder.

[0047] The present invention has no particular limitation on the fourth mixing, as long as the raw materials can be mixed uniformly.

[0048] Before the fourth mixing, the present invention preferably further comprises washing the basalt fiber powder and then drying it. In the present invention, the drying temperature is preferably 105-115°C, more preferably 107-112°C, and most preferably 108-110°C; the drying time is preferably 8-10h, more preferably 8-9h, and most preferably 8-8.5h.

[0049] In the present invention, the temperature of the surface modification is preferably 50-60°C, more preferably 52-60°C, and most preferably 55-60°C; the time of the surface modification is preferably 5.25-6.5h. In the present invention, the surface modification includes stirring modification and ultrasonic modification in sequence; the time of the stirring modification is preferably 5-6h, more preferably 5.2-6h, and most preferably 5.5-6h; the time of the ultrasonic modification is preferably 15-30min, more preferably 20-30min, and most preferably 25-30min.

[0050] After completing the surface modification, the present invention preferably further comprises cooling the modified powder obtained by the surface modification and then performing solid-liquid separation, and drying the obtained solid component. The present invention has no special restrictions on the cooling method and rate, and the modified powder can be cooled to room temperature. The present invention has no special restrictions on the solid-liquid separation method, and conventional solid-liquid separation in the art can be used, such as centrifugal separation; the speed of the centrifugal separation is preferably 2000-3000rpm, more preferably 2000-2500rpm, and most preferably 2000-2200rpm; the time of the centrifugal separation is preferably 3-5min, more preferably 3.5-4.5min, and most preferably 4-4.3min. In the present invention, the drying temperature is preferably 110-120℃, more preferably 113-120℃, and most preferably 115-120℃; the drying time is preferably 6-8h, more preferably 7-8h, and most preferably 7.5-8h.

[0051] The present invention provides a method for preparing the basalt fiber component reinforced modified epoxy resin adhesive described in the above technical solution, comprising the following steps: mixing the modified epoxy resin adhesive matrix and the basalt fiber component (referred to as the fifth mixing) to obtain the basalt fiber component reinforced modified epoxy resin adhesive.

[0052] The present invention has no particular limitation on the fifth mixing, as long as the raw materials can be mixed uniformly.

[0053] The present invention provides an epoxy mortar material, the raw materials for preparation include epoxy resin glue, basalt fiber powder and mortar filler; the epoxy resin glue is the basalt fiber component reinforced modified epoxy resin glue described in the above technical solution or the basalt fiber component reinforced modified epoxy resin glue prepared by the preparation method described in the above technical solution. In the present invention, the mortar filler includes cement powder and / or quartz sand. The present invention does not specifically limit the type of the cement powder, and conventional silicate cement powder in the art can be used. In the present invention, the quartz sand is preferably clean and free of impurities, and the mud content is preferably ≤3%, more preferably 1-2.5%, and most preferably 1.5-2%; the particle size of the quartz sand is preferably 80-120 mesh, more preferably 90-110 mesh, and most preferably 100-105 mesh; the mass ratio of epoxy resin glue and basalt fiber powder in the epoxy mortar is preferably 1:0.5-0.6, more preferably 1:0.52-0.58, and most preferably 1:0.54-0.56; the mass ratio of epoxy resin glue and mortar filler in the epoxy mortar is preferably 1:1.4-1.6, more preferably 1:1.45-1.55, and most preferably 1:1.5-1.52. The present invention adopts basalt fiber component reinforced modified epoxy resin glue in combination with basalt fiber powder and mortar filler, which can repair and strengthen micro cracks and peeling parts of concrete structure, improve the tensile strength of concrete structure, and extend the service life of concrete. The tensile strength of the repaired concrete surface can be increased to 4-6MPa, which is much higher than the conventional concrete surface tensile strength of 2-4MPa.

[0054] In the present invention, the epoxy mortar preferably further comprises an epoxy resin curing agent; the epoxy resin curing agent preferably comprises one or more of diethylenetriamine, triethylamine and polyethylenepolyamine.

[0055] In the present invention, the preparation method of the epoxy mortar preferably includes the following steps: mixing the modified epoxy resin adhesive matrix and the epoxy resin curing agent for the sixth time, and then mixing with the fiber component for the seventh time to obtain a basalt fiber component reinforced modified epoxy resin adhesive curing system; mixing the basalt fiber component reinforced modified epoxy resin adhesive curing system and the mortar powder for the eighth time to obtain an epoxy mortar. In the present invention, the mass ratio of the modified epoxy resin adhesive matrix and the epoxy resin curing agent is preferably 2 to 3:1, more preferably 2.2 to 2.8:1, and most preferably 2.4 to 2.6:1. The present invention has no special restrictions on the sixth mixing, the seventh mixing and the eighth mixing, and the raw materials can be mixed evenly. In the present invention, the modified epoxy resin adhesive matrix and the epoxy resin curing agent are first mixed for the sixth time, and the two will not be cured immediately after mixing (≥3h), and the fiber component or the mortar powder can be stirred and then mixed.

[0056] The present invention provides the use of the basalt fiber component reinforced modified epoxy resin glue described in the above technical solution, the basalt fiber component reinforced modified epoxy resin glue obtained by the preparation method described in the above technical solution, or the epoxy mortar described in the above technical solution in epoxy concrete, composite reinforcement connection and anchoring, defect repair of concrete structure, connection, reinforcement or structural pavement of steel-concrete structure. In the present invention, when applied to epoxy concrete, the fiber component used in the basalt fiber component reinforced modified epoxy resin glue or epoxy mortar is preferably short fine fiber; when applied to composite reinforcement connection and anchoring, defect repair of concrete structure, connection, reinforcement or structural pavement of steel-concrete structure, the fiber component used in the basalt fiber component reinforced modified epoxy resin glue or epoxy mortar is preferably fiber powder. The basalt fiber powder reinforced modified epoxy resin adhesive provided by the present invention has high mechanical strength, impact resistance, corrosion resistance, wear resistance and thermal stability, and has good bonding performance and toughness. When used in defect repair of concrete structure, the concrete has high tensile strength; the metal sleeve can be used to connect and anchor composite reinforcement materials, thereby ensuring the tensile strength of the reinforcement connection parts; the basalt short fine fiber reinforced modified epoxy resin adhesive improves the flexural strength and compressive strength of the concrete.

[0057] In the present invention, when the fiber component is fiber powder, the method for using the basalt fiber component reinforced modified epoxy resin adhesive in repairing defects in concrete structures preferably further comprises: mixing the basalt fiber component reinforced modified epoxy resin adhesive with crushed stone to obtain epoxy resin concrete. The epoxy resin concrete obtained by the present invention can repair large cracks and potholes in the original concrete structure.

[0058] In order to further illustrate the present invention, the basalt fiber component reinforced modified epoxy resin adhesive and its preparation method and application, and epoxy mortar provided by the present invention are described in detail below in conjunction with the accompanying drawings and examples, but they should not be understood as limiting the scope of protection of the present invention.

[0059] In all embodiments of the present invention, the chopped basalt fibers are produced by Jiangsu Tianlong Basalt Continuous Fiber Co., Ltd., and the fiber length is 30 mm. After being chopped, the basalt fibers are put into a special disperser to break them up, and after ensuring that the fibers are not entangled and united, they are crushed by a grinder to obtain basalt fiber powder.

[0060] Preparation of silane coupling agent modified basalt fiber powder: wash the basalt fiber powder with clean water and dry it at 110°C for 8h; mix ethanol, water and silane coupling agent KH560 in a mass ratio of 50:5:1 and stir for 10min to obtain a silane coupling agent hydrolyzate; add the dried basalt fiber powder to the silane coupling agent hydrolyzate, stir and modify it at 60°C for 6h, then ultrasonically modify it for 30min, cool the modified powder, centrifuge it at 2000rpm for 5min, and dry the obtained solid component at 120°C for 8h to obtain silane coupling agent modified basalt fiber powder.

[0061] Example 1

[0062] In terms of mass fractions, 68 parts of epoxy resin E51, 15 parts of polyethylene glycol PEG400 and 8 parts of isophorone diisocyanate were mixed, placed in a three-necked flask, heated to 60°C under nitrogen atmosphere, and then 2 parts of dibutyltin oxide were added and heated to 80°C for esterification reaction for 6 hours to obtain a modified epoxy resin adhesive matrix.

[0063] 100 parts of modified epoxy resin adhesive matrix and 50 parts of epoxy resin curing agent polyethylene polyamine are mixed and stirred evenly to obtain a premix; 5 parts of silane coupling agent modified basalt fiber powder are added to the premix and stirred thoroughly to obtain a basalt fiber powder reinforced modified epoxy resin adhesive curing system.

[0064] Example 2

[0065] A basalt fiber powder reinforced modified epoxy resin adhesive curing system was prepared according to the method of Example 1, the only difference from Example 1 being that the amount of basalt fiber powder modified by silane coupling agent was 10 parts.

[0066] Example 3

[0067] The basalt fiber powder reinforced modified epoxy resin adhesive curing system was prepared according to the method of Example 1, the only difference from Example 1 was that the amount of basalt fiber powder modified by silane coupling agent was 15 parts.

[0068] Example 4

[0069] The basalt fiber powder reinforced modified epoxy resin adhesive curing system was prepared according to the method of Example 1, the only difference from Example 1 was that the amount of basalt fiber powder modified by silane coupling agent was 20 parts.

[0070] Example 5

[0071] The basalt fiber powder reinforced modified epoxy resin adhesive curing system was prepared according to the method of Example 1, the only difference from Example 1 was that the amount of basalt fiber powder modified by silane coupling agent was 25 parts.

[0072] Example 6

[0073] The basalt fiber powder reinforced modified epoxy resin adhesive curing system was prepared according to the method of Example 1, the only difference from Example 1 was that the amount of basalt fiber powder modified by silane coupling agent was 30 parts.

[0074] Example 7

[0075] In terms of mass fractions, 68 parts of epoxy resin E51, 15 parts of polyethylene glycol PEG400 and 8 parts of isophorone diisocyanate were mixed, placed in a three-necked flask, heated to 60°C under nitrogen atmosphere, and then 2 parts of dibutyltin oxide were added and heated to 80°C for esterification reaction for 6 hours to obtain a modified epoxy resin adhesive matrix.

[0076] 100 parts of modified epoxy resin adhesive matrix and 50 parts of epoxy resin curing agent polyethylene polyamine are mixed and stirred evenly to obtain a premix; 5 parts of basalt fiber powder powder are added to the premix and stirred thoroughly to obtain a basalt fiber powder reinforced modified epoxy resin adhesive curing system.

[0077] Example 8

[0078] The basalt fiber powder reinforced modified epoxy resin adhesive curing system was prepared according to the method of Example 7, the only difference from Example 7 being that the amount of basalt fiber powder modified by silane coupling agent was 10 parts.

[0079] Example 9

[0080] A basalt fiber powder reinforced modified epoxy resin adhesive curing system was prepared according to the method of Example 7, the only difference from Example 7 being that the amount of basalt fiber powder used was 15 parts.

[0081] Example 10

[0082] A basalt fiber powder reinforced modified epoxy resin adhesive curing system was prepared according to the method of Example 7, the only difference from Example 7 being that the amount of basalt fiber powder used was 20 parts.

[0083] Embodiment 11

[0084] A basalt fiber powder reinforced modified epoxy resin adhesive curing system was prepared according to the method of Example 7, the only difference from Example 7 being that the amount of basalt fiber powder used was 25 parts.

[0085] Embodiment 13

[0086] A basalt fiber powder reinforced modified epoxy resin adhesive curing system was prepared according to the method of Example 7, the only difference from Example 7 being that the amount of basalt fiber powder used was 30 parts.

[0087] Comparative Example 1

[0088] In terms of mass fractions, 68 parts of epoxy resin E51, 15 parts of polyethylene glycol PEG400 and 8 parts of isophorone diisocyanate were mixed, placed in a three-necked flask, heated to 60°C under nitrogen atmosphere, and then 2 parts of dibutyltin oxide were added and heated to 80°C for esterification reaction for 6 hours to obtain a modified epoxy resin adhesive matrix.

[0089] 100 parts of modified epoxy resin adhesive matrix and 50 parts of epoxy resin curing agent polyethylene polyamine were mixed and stirred thoroughly to obtain a modified epoxy resin adhesive curing system.

[0090] The bending strength of the basalt fiber powder reinforced modified epoxy resin adhesive curing system obtained in Examples 1 to 13 and the modified epoxy resin adhesive curing system obtained in Comparative Example 1 after curing was tested respectively. The results are as follows: Figure 1 shown. Figure 1 The following is a line graph showing the effect of basalt fiber powder before and after modification with silane coupling agent on the flexural strength of epoxy resin. Figure 1 It can be seen that the flexural strength of epoxy resin increases with the increase of the amount of basalt fiber powder added, and when the amount exceeds 20%, its flexural strength gradually decreases. In addition, the flexural strength of epoxy resin added with basalt fiber powder modified by silane coupling agent KH560 is higher than that of epoxy resin added with unmodified basalt fiber powder of the same amount.

[0091] Embodiment 14

[0092] In parts by mass, 65 parts of epoxy resin E51, 20 parts of polyethylene glycol PEG400 and 8 parts of isophorone diisocyanate were mixed, placed in a three-necked flask, heated to 60°C under a nitrogen atmosphere, 1.5 parts of dibutyltin oxide were added, and the temperature was raised to 80°C for esterification reaction for 8 hours to obtain a modified epoxy resin adhesive matrix.

[0093] 100 parts of modified epoxy resin adhesive matrix and 50 parts of epoxy resin curing agent polyethylene polyamine are mixed and stirred evenly to obtain a premix; 20 parts of basalt fiber powder before and after modification by silane coupling agent are added to the premix and stirred thoroughly to obtain a basalt fiber powder reinforced modified epoxy resin adhesive curing system.

[0094] The basalt fiber powder reinforced modified epoxy resin adhesive curing system and concrete mortar powder were mixed and stirred in a mass ratio of 1:1.8 to obtain epoxy mortar. The obtained epoxy mortar was used to repair and improve the micro-crack structure on the concrete surface. The comparison results of the pull-out strength of the concrete structure surface before and after the repair are shown in Table 1, where serial numbers 1 to 5 are pull-out tests performed at 5 different positions on the same sample, using a dedicated pull-out tester. The test method refers to the 7.9 bonding strength test method in JC / T 2217--2014 "Epoxy Resin Waterproof Coating", and the pull-out strength is obtained by calculating the average value to ensure the accuracy of the test.

[0095] Table 1 Comparison of tensile strength of concrete structure surface before and after repair

[0096]

[0097]

[0098] As can be seen from Table 1, when the basalt fiber powder reinforced modified epoxy resin adhesive provided by the present invention is mixed with concrete mortar powder to form an epoxy mortar for repairing and improving the micro-crack structure on the concrete surface, the tensile strength of the concrete structure surface can be significantly improved.

[0099] Embodiment 15

[0100] In parts by mass, 65 parts of epoxy resin E51, 20 parts of polyethylene glycol PEG400 and 8 parts of isophorone diisocyanate were mixed, placed in a three-necked flask, heated to 60°C under a nitrogen atmosphere, 1.5 parts of dibutyltin oxide were added, and the temperature was raised to 80°C for esterification reaction for 8 hours to obtain a modified epoxy resin adhesive matrix.

[0101] 100 parts of modified epoxy resin adhesive matrix and 50 parts of epoxy resin curing agent polyethylene polyamine were mixed and stirred evenly to obtain a premix; 20 parts of basalt fiber powder before and after silane coupling agent modification were added to the premix and stirred thoroughly to obtain a basalt fiber powder reinforced modified epoxy resin adhesive curing system; 4.5 parts of basalt short fine fibers were preliminarily mixed with 300 parts of crushed stone and stirred evenly to obtain a fiber crushed stone mixture; the basalt fiber powder reinforced modified epoxy resin adhesive was added to the premix and stirred evenly to obtain a fiber crushed stone mixture; The curing system and the fiber crushed stone mixture are combined and mixed, stirred evenly, and put into a mold for curing and molding to obtain basalt short fine fiber reinforced modified epoxy resin concrete, wherein the length of the basalt short fine fiber is 30 mm; the crushed stone is pyrophyllite with a particle size of 3-5 mm and 5-8 mm and basalt with a particle size of 0.5-3 mm, and the mass ratio of pyrophyllite with a particle size of 3-5 mm, pyrophyllite with a particle size of 5-8 mm and basalt with a particle size of 0.5-3 mm is 35:52:13.

[0102] Comparative Example 2

[0103] In parts by mass, 65 parts of epoxy resin E51, 20 parts of polyethylene glycol PEG400 and 8 parts of isophorone diisocyanate were mixed, placed in a three-necked flask, heated to 60°C under a nitrogen atmosphere, 1.5 parts of dibutyltin oxide were added, and the temperature was raised to 80°C for esterification reaction for 8 hours to obtain a modified epoxy resin adhesive matrix.

[0104] 100 parts of modified epoxy resin adhesive matrix and 50 parts of epoxy resin curing agent polyethylene polyamine are mixed and stirred evenly to obtain a premix; 4.5 parts of basalt short fine fibers and 300 parts of crushed stones are preliminarily mixed and stirred evenly to obtain a fiber crushed stone mixture; the basalt fiber powder reinforced modified epoxy resin adhesive curing system and the fiber crushed stone mixture are combined and mixed, stirred evenly, and put into a mold for curing and molding to obtain basalt short fine fiber reinforced epoxy resin concrete.

[0105] With reference to the flexural strength and bending strength test methods in GB / T 17671-2021 "Test Method for Strength of Cement Mortar (ISO Method)", the flexural strength and compressive strength of the concrete test blocks of Example 15 and Comparative Example 2 were tested respectively, and the size of the concrete test blocks was 40mm×40mm×160mm. The flexural strength of the concrete test block of Example 15 was 28.5Mpa and the compressive strength was 75.8Mpa, while the flexural strength of the concrete test block of Comparative Example 2 was 25.6MPa and the compressive strength was 70.4MPa. The flexural strength and compressive strength of the concrete in Example 15 were increased by 11.3% and 7.7% respectively compared with those in Comparative Example 2.

[0106] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A basalt fiber component reinforced modified epoxy resin adhesive, comprising a modified epoxy resin adhesive matrix and a fiber component dispersed in the modified epoxy resin adhesive matrix; The fiber component includes fiber powder and / or short fibers; the fiber powder includes basalt fiber powder and / or basalt fiber powder modified by silane coupling agent; the short fibers include basalt filamentary fibers and / or basalt flocculent fibers; The raw materials for preparing the modified epoxy resin adhesive matrix include bisphenol A epoxy resin, polyether, alicyclic diisocyanate and esterification catalyst; The mass ratio of the modified epoxy resin matrix to the fiber component is 100:10-30.

2. The basalt fiber component reinforced modified epoxy resin adhesive according to claim 1, characterized in that: The alicyclic diisocyanate includes isophorone diisocyanate; The esterification catalyst includes dibutyltin oxide and / or dihydroxybutyltin chloride.

3. The basalt fiber component reinforced modified epoxy resin adhesive according to claim 1 or 2, characterized in that: The polyether includes polyethylene glycol and / or polypropylene glycol; The mass ratio of the bisphenol A epoxy resin to the polyether is 65-70:10-20; The mass ratio of the bisphenol A epoxy resin to the alicyclic diisocyanate is 65-70:5-10; The mass ratio of the bisphenol A epoxy resin to the esterification catalyst is 65-70:1-2.

4. The basalt fiber component reinforced modified epoxy resin adhesive according to claim 1, characterized in that: The preparation method of the modified epoxy resin adhesive matrix comprises the following steps: Bisphenol A epoxy resin, polyether, alicyclic diisocyanate and esterification catalyst are mixed and subjected to esterification reaction to obtain the modified epoxy resin adhesive matrix.

5. The basalt fiber component reinforced modified epoxy resin adhesive according to claim 4, characterized in that: The temperature of the esterification reaction is 60-80° C. and the time is 5.5-8.5 hours.

6. The basalt fiber component reinforced modified epoxy resin adhesive according to claim 1, characterized in that: The preparation method of the silane coupling agent modified basalt fiber powder comprises the following steps: Mixing a silane coupling agent, a lower alcohol and water to obtain a silane coupling agent hydrolyzate; The silane coupling agent hydrolyzate is mixed with basalt fiber powder and surface modified to obtain the silane coupling agent modified basalt fiber powder.

7. The basalt fiber component reinforced modified epoxy resin adhesive according to claim 6, characterized in that: The surface modification temperature is 50-60° C. and the time is 5.25-6.5 hours.

8. The method for preparing the basalt fiber component reinforced modified epoxy resin adhesive according to any one of claims 1 to 7, comprising the following steps: The modified epoxy resin adhesive matrix and the fiber component are mixed to obtain the basalt fiber component reinforced modified epoxy resin adhesive.

9. An epoxy mortar, characterized in that: The preparation raw materials include epoxy resin glue, basalt fiber powder and mortar filler; the epoxy resin glue is the basalt fiber component reinforced modified epoxy resin glue as described in any one of claims 1 to 7 or the basalt fiber component reinforced modified epoxy resin glue prepared by the preparation method as described in claim 8; The mortar filler includes cement powder and / or quartz sand.

10. Application of the basalt fiber component reinforced modified epoxy resin adhesive according to any one of claims 1 to 7, the basalt fiber component reinforced modified epoxy resin adhesive prepared by the preparation method according to claim 8, or the epoxy mortar according to claim 9 in epoxy concrete, composite reinforcement connection anchoring, concrete structure defect repair, steel-concrete structure connection, reinforcement or structural paving.

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