High-performance epoxy resin modified filling material for metal floor and preparation method of high-performance epoxy resin modified filling material

Abstract

The invention discloses a high-performance epoxy resin modified filling material for a metal floor and a preparation method of the high-performance epoxy resin modified filling material, and relates to the technical field of epoxy resin-based filling materials. The epoxy resin is modified by using the imidogroup modified polybutadiene liquid rubber, an imide structure is introduced to improve the overall polarity, improve the bonding strength and enhance the bonding effect between metal plates and the ground, and then the epoxy resin is mixed with the alkenylated epoxy resin and the alkenylated nano filler and cured to form a high-crosslinking structure, so that the deformation shrinkage is reduced; the size stability of the adhesive layer at high temperature or in long-term use is ensured, and the damage of the adhesive layer caused by deformation is avoided. The alkenylation nanofiller is modified by alkenylation, has good compatibility with an epoxy resin system, is uniformly dispersed and is not easy to settle, and the porous structure of the alkenylation nanofiller enables liquid resin to be fully permeated into micropores during curing so as to fill gaps generated by shrinkage of resin chains.

Description

Technical Field

[0001] This invention relates to the field of epoxy resin materials technology, specifically to a high-performance epoxy resin modified filler material for metal flooring and its preparation method. Background Technology

[0002] Metal flooring is widely used in electronic factories, data centers, medical cleanrooms, industrial workshops, and other locations with stringent requirements for cleanliness, anti-static properties, load-bearing capacity, and dimensional stability. Its installation typically relies on high-performance filler materials for leveling, bonding, and sealing to ensure the floor's flatness, integrity, and long-term reliability. Epoxy resin, due to its excellent adhesion, mechanical strength, chemical resistance, and low shrinkage, is the preferred matrix resin for this type of filler.

[0003] However, traditional epoxy resin-based fillers still have some significant limitations in practical applications. First, conventional epoxy resins, after curing, have a high cross-linking density and poor molecular chain mobility, resulting in brittleness and insufficient toughness. When the metal floor is subjected to dynamic loads, thermal expansion and contraction, or slight deformation of the substrate, the filler layer is prone to micro-cracks or even cracking, affecting the sealing effect and service life. Second, epoxy resins inevitably undergo a certain amount of volume shrinkage during curing. This shrinkage stress may cause voids within the adhesive layer, weakening interfacial bonding strength, or, due to temperature changes, causing deformation and warping due to a mismatch in the thermal expansion coefficients with the metal substrate, ultimately affecting the flatness and stability of the metal floor. Furthermore, to improve performance or reduce costs, various fillers are often added to the resin. However, ordinary fillers often have poor compatibility with the resin matrix, easily agglomerating and settling, which not only affects the storage stability of the system but may also become stress concentration points, impairing the material's uniformity and final performance.

[0004] To overcome these shortcomings, the industry has made many attempts at improvement, such as adding liquid rubber to toughen epoxy resin. However, such simple blending modifications often face compatibility challenges, are prone to phase separation, resulting in limited toughening efficiency and potentially sacrificing the material's modulus and heat resistance. Some studies have also used nanofillers such as silica and montmorillonite to enhance and reduce shrinkage, but their high surface energy makes them difficult to disperse uniformly in the resin, and their insufficient interfacial bonding strength with the resin limits their ability to fully exert their reinforcing effect.

[0005] Therefore, developing an epoxy resin modified filler material that combines excellent toughness, high strength, low shrinkage, high dimensional stability, and outstanding adhesion to metal substrates is of great significance for improving the overall performance and reliability of metal flooring. Summary of the Invention

[0006] The purpose of this invention is to provide a high-performance epoxy resin modified filler material for metal flooring and its preparation method, so as to solve the problems existing in the prior art.

[0007] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a high-performance epoxy resin modified filler material for metal flooring, composed of component A and component B, wherein the volume ratio of component A to component B is 1.5-2.5:1, and component A is composed of alkenylated epoxy resin, solvent, monomer, alkenylated nanofiller, initiator, modified epoxy resin, and tri(2-hydroxyethyl)isocyanurate triacrylate in a mass ratio of 70-85:30-40:20-25:6-15:1-5:95-105:2-4; The modified epoxy resin is obtained by modifying epoxy resin with imide-modified polybutadiene liquid rubber.

[0008] Furthermore, the epoxy resin used in the alkenylated epoxy resin and modified epoxy resin is one or a mixture of more than one of epoxy resin E-44 and epoxy resin E-51.

[0009] Furthermore, the modified epoxy resin is prepared by: dehydrating the epoxy resin at high temperature, and then mixing and reacting it with imide-modified polybutadiene liquid rubber at a mass ratio of 75-100:10-25 to obtain the modified epoxy resin.

[0010] Furthermore, the imide-modified polybutadiene liquid rubber is composed of hydroxyl-terminated polybutadiene liquid rubber and N-(P-maleimide-phenyl) isocyanate in an n-... -NCO / n -OH It was prepared by a mixed reaction of 3.5-4.5.

[0011] Furthermore, the hydroxyl-terminated polybutadiene liquid rubber has a number average molecular weight of 3000-3500, a molecular weight distribution index of 1.4-1.7, a viscosity of <5.0 Pa·s, an average functionality of 2-2.3 at 40℃, a hydroxyl value of 0.60-0.75 mmol / g, and a moisture content of <300 ppm.

[0012] Furthermore, the alkenylated nanofiller is prepared by modifying porous shell powder with a silane coupling agent, wherein the silane coupling agent is at least one of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, and γ-methacryloyloxypropyltrimethoxysilane.

[0013] Furthermore, the preparation method of component A is as follows: the alkenylated epoxy resin and solvent are mixed and stirred, and under nitrogen protection, the mixture is stirred and heated to 110-125°C. The monomer, alkenylated nanofiller and initiator are added, and the mixture is reacted at a constant temperature for 4-5 hours. After cooling to room temperature, the modified epoxy resin and tri(2-hydroxyethyl)isocyanurate triacrylate are added and stirred evenly.

[0014] Furthermore, the solvent is one or more selected from n-butanol, isobutanol, sec-butanol, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol propyl ether, dipropylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, propylene glycol phenyl ether, propylene glycol methyl ether acetate, and dipropylene glycol methyl ether acetate; the initiator is one selected from benzoyl peroxide, azobisisobutyronitrile, di-tert-butyl peroxide, and di-tert-pentyl peroxide; and the monomer is at least one selected from butyl acrylate, butyl methacrylate, isobutyl acrylate, sec-butyl acrylate, and isobutyl methacrylate.

[0015] Furthermore, component B comprises a long-chain fatty amine modified curing agent, a polyether amine with a number average molecular weight of 200-400, and an accelerator DMP-30 in a mass ratio of 1:5-7:0.2-0.3.

[0016] Furthermore, the long-chain fatty amine modified curing agent is T30 long-chain fatty amine modified curing agent, with an amine value of 490-580 mgKOH and a viscosity of 800-1500 mPa·s at 25℃.

[0017] Furthermore, the high-performance epoxy resin modified filler material used in the metal floor is cured at room temperature.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are: (1) The present invention uses imide-modified polybutadiene liquid rubber as a modifier to modify epoxy resin. Due to the introduction of the imide structure, the overall polarity is improved, which helps to improve the overall bonding strength and the bonding effect between metal sheets and between metal sheets and the ground. At the same time, the reaction between the imide-modified polybutadiene liquid rubber and epoxy resin avoids phase separation and forms flexible segments in the cured network, which significantly improves the toughness of the material and overcomes the problem of high brittleness and easy cracking of traditional epoxy resin after curing.

[0019] (2) This invention uses a mixture of modified epoxy resin, alkenylated epoxy resin, and alkenylated nanofiller, which can form a highly cross-linked structure after the epoxy resin is cured. This reduces the deformation and shrinkage caused by the curing of epoxy resin, ensuring that the adhesive layer can maintain good dimensional stability under high temperature or long-term use conditions, and avoiding damage to the adhesive layer due to excessive deformation. The alkenylated nanofiller has an alkenylated surface, which has excellent compatibility with the epoxy resin system, is uniformly dispersed, and is not easy to settle. Its porous structure allows the liquid resin to fully penetrate into the micropores during the curing process, effectively filling the local gaps that may be caused by resin chain shrinkage. Detailed Implementation

[0020] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0021] Example 1 A high-performance epoxy resin modified filler material for metal flooring is composed of component A and component B, with a volume ratio of component A to component B of 1.5:1. Component B comprises T30 long-chain fatty amine modified curing agent, polyether amine with a number average molecular weight of 200, and accelerator DMP-30 in a mass ratio of 1:5.0:0.2. The preparation of component A is as follows: (1) Hydroxyl-terminated polybutadiene liquid rubber was heated to 90°C and vacuum-dehydrated for 0.5 h, then cooled to 50°C, according to n -NCO / n -OH =3.5 Add N-(P-maleimide phenyl) isocyanate, heat to 85℃, react for 2 hours, cool down and discharge to obtain imide-modified polybutadiene liquid rubber; (2) Epoxy resin E-44 was stirred and dehydrated at 100℃ and 650mmHg for 1h. Then, imide-modified polybutadiene liquid rubber was added under nitrogen gas. The mass ratio of epoxy resin E-44 to imide-modified polybutadiene liquid rubber was 75:10. The mixture was stirred for 20min, and stannous octoate catalyst was added. The mixture was reacted at 75℃ for 2h. Then, the mixture was degassed under vacuum to obtain modified epoxy resin. (3) Add the shells to a 0.1 mol / L hydrochloric acid solution at a solid-liquid ratio of 1 g: 5 mL for acid hydrolysis treatment for 30 min. After filtration, washing, and drying, grind the shells to 500 nm to obtain porous shell powder. Mix the porous shell powder with anhydrous ethanol at a solid-liquid ratio of 1 g: 30 mL and ultrasonically disperse the mixture to obtain a dispersion. Adjust the pH of the dispersion to 9. Add a vinyltrimethoxysilane hydrolysate with a mass fraction of 7.3 wt% at 70 °C. Reflux the mixture for 4 hours. After the reaction is complete, wash the reaction solution repeatedly with anhydrous ethanol and filter until the filtrate is clear and transparent. Place the filter cake in a vacuum drying oven and dry it at 70 °C for 12 h to obtain alkenylated nanofiller. (4) First, add 1 / 6 of the total amount of epoxy resin E-44 to the reactor and heat it to 100°C to completely melt it. Then, add the remaining epoxy resin, methacrylic acid and the catalyst tetraethylammonium bromide to the reactor all at once, stir, and after 1 hour, raise the temperature to 110°C to continue the reaction. Stop the reaction when the acid value reaches 3 mg KOH / g to obtain alkenylated epoxy resin. The mass ratio of the epoxy resin, methacrylic acid and catalyst is 90:20:2. (5) Mix and stir the alkenylated epoxy resin and solvent propylene glycol methyl ether. Under nitrogen protection, stir and heat to 110°C, add butyl methacrylate, alkenylated nanofiller and benzoyl peroxide, react at constant temperature for 4 hours, cool to room temperature, and add modified epoxy resin and tri(2-hydroxyethyl) isocyanurate triacrylate. The alkenylated epoxy resin, solvent, monomer, alkenylated nanofiller, initiator, modified epoxy resin and tri(2-hydroxyethyl) isocyanurate triacrylate are in a mass ratio of 70:30:20:6:1:95:2.

[0022] Example 2 A high-performance epoxy resin modified filler material for metal flooring is composed of component A and component B, with a volume ratio of component A to component B of 1.7:1. Component B comprises T30 long-chain fatty amine modified curing agent, polyether amine with a number average molecular weight of 200, and accelerator DMP-30 in a mass ratio of 1:5.5:0.25. The preparation of component A is as follows: (1) Hydroxyl-terminated polybutadiene liquid rubber was heated to 90°C and vacuum-dehydrated for 0.5 h, then cooled to 50°C, according to n -NCO / n -OH =4.0 N-(P-maleimide phenyl) isocyanate was added, the temperature was raised to 85℃, the reaction was carried out for 3 hours, the temperature was lowered and the material was discharged to obtain imide-modified polybutadiene liquid rubber. (2) The epoxy resin was stirred and dehydrated at 110°C and 700 mmHg for 1.5 h. Then, imide-modified polybutadiene liquid rubber was added under nitrogen gas. The mass ratio of epoxy resin to imide-modified polybutadiene liquid rubber was 85:15. The mixture was stirred for 25 min, and triethylamine was added as a catalyst. The mixture was reacted at 80°C for 2.5 h. Then, the mixture was degassed under vacuum to obtain the modified epoxy resin. The epoxy resin was a mixture of epoxy resin E-44 and epoxy resin E-51 in equal mass. (3) Add the shells to a 0.15 mol / L acetic acid solution at a solid-liquid ratio of 1 g: 5 mL for acid hydrolysis for 30 min. After filtration, washing, and drying, grind the shells to 550 nm to obtain porous shell powder. Mix the porous shell powder with anhydrous ethanol at a solid-liquid ratio of 1 g: 35 mL and ultrasonically disperse the mixture to obtain a dispersion. Adjust the pH of the dispersion to 9.5. Add a vinyltriethoxysilane hydrolysate with a mass fraction of 8.0 wt% at 70 °C. Reflux the mixture for 4 hours. After the reaction is complete, wash the reaction solution repeatedly with anhydrous ethanol and filter until the filtrate is clear and transparent. Place the filter cake in a vacuum drying oven and dry it at 70 °C for 12 h to obtain alkenylated nanofiller. (4) First, add 1 / 6 of the total amount of epoxy resin to the reactor and heat it to 102°C to completely melt it. Then, add the remaining epoxy resin, methacrylic acid and triphenylphosphine catalyst to the reactor all at once, stir, and after 1.2 hours, raise the temperature to 115°C to continue the reaction. Stop the reaction when the acid value reaches 2 mg KOH / g to obtain alkenylated epoxy resin. The epoxy resin is an equal mass mixture of epoxy resin E-44 and epoxy resin E-51. The mass ratio of epoxy resin, methacrylic acid and catalyst is 95:25:2.5. (5) Mix and stir the alkenylated epoxy resin and solvent dipropylene glycol methyl ether. Under nitrogen protection, stir and heat to 115°C. Add monomer butyl acrylate, alkenylated nanofiller and initiator azobisisobutyronitrile. React at a constant temperature for 4.5 h. Cool to room temperature and add modified epoxy resin and tri(2-hydroxyethyl) isocyanurate triacrylate. The alkenylated epoxy resin, solvent, monomer, alkenylated nanofiller, initiator, modified epoxy resin and tri(2-hydroxyethyl) isocyanurate triacrylate are in a mass ratio of 75:35:22:8:3:98:3.

[0023] Example 4 A high-performance epoxy resin modified filler material for metal flooring is composed of component A and component B, with a volume ratio of component A to component B of 1.9:1. Component B comprises T30 long-chain fatty amine modified curing agent, polyether amine with a number average molecular weight of 300, and accelerator DMP-30 in a mass ratio of 1:6.0:0.28. The preparation of component A is as follows: (1) Hydroxyl-terminated polybutadiene liquid rubber was heated to 90°C and vacuum-dehydrated for 0.5 h, then cooled to 50°C, according to n -NCO / n -OH =4.5 Add N-(P-maleimide phenyl) isocyanate, heat to 85℃, react for 4h, cool down and discharge to obtain imide-modified polybutadiene liquid rubber; (2) The epoxy resin was stirred and dehydrated at 120°C and 720 mmHg for 1.8 h. Then, imide-modified polybutadiene liquid rubber was added under nitrogen gas. The mass ratio of epoxy resin to imide-modified polybutadiene liquid rubber was 95:20. The mixture was stirred for 28 min. The catalyst organotin was added and reacted at 85°C for 3 h. Then, the mixture was degassed under vacuum to obtain the modified epoxy resin. The epoxy resin was a mixture of epoxy resin E-44 and epoxy resin E-51 in a mass ratio of 2:1. (3) Add the shells to a 0.2 mol / L nitric acid solution at a solid-liquid ratio of 1 g: 5 mL for acid hydrolysis for 30 min. After filtration, washing, and drying, grind the shells to 580 nm to obtain porous shell powder. Mix the porous shell powder with anhydrous ethanol at a solid-liquid ratio of 1 g: 38 mL and ultrasonically disperse the mixture to obtain a dispersion. Adjust the pH of the dispersion to 10. Add a 9.0 wt% vinyltris(β-methoxyethoxy)silane hydrolysate at 70 °C. Reflux the mixture for 4 hours. After the reaction is complete, wash the reaction solution repeatedly with anhydrous ethanol and filter until the filtrate is clear and transparent. Place the filter cake in a vacuum drying oven and dry it at 70 °C for 12 h to obtain alkenylated nanofiller. (4) First, add 1 / 5 of the total amount of epoxy resin to the reactor and heat it to 104°C to completely melt it. Then, add the remaining epoxy resin, methacrylic acid and the catalyst tetraethylammonium bromide to the reactor all at once. Stir and heat for 1.4 hours. Then, raise the temperature to 122°C to continue the reaction. Stop the reaction when the acid value reaches 1 mg KOH / g to obtain alkenylated epoxy resin. The epoxy resin is a mixture of epoxy resin E-44 and epoxy resin E-51 in a mass ratio of 2:1. The mass ratio of epoxy resin, methacrylic acid and catalyst is 105:30:3. (5) Mix and stir the alkenylated epoxy resin and solvent propylene glycol butyl ether. Under nitrogen protection, stir and heat to 122°C. Add monomer isobutyl acrylate, alkenylated nanofiller and initiator di-tert-butyl peroxide. React at constant temperature for 5 hours. Cool to room temperature and add modified epoxy resin and tri(2-hydroxyethyl) isocyanurate triacrylate. The alkenylated epoxy resin, solvent, monomer, alkenylated nanofiller, initiator, modified epoxy resin and tri(2-hydroxyethyl) isocyanurate triacrylate are in a mass ratio of 80:38:24:12:4:102:3.5.

[0024] Example 4 A high-performance epoxy resin modified filler material for metal flooring, consisting of component A and component B, wherein the volume ratio of component A to component B is 2.1:1; Component B comprises T30 long-chain fatty amine modified curing agent, polyether amine with a number average molecular weight of 400, and accelerator DMP-30 in a mass ratio of 1:6.5:0.29. The preparation of component A is as follows: (1) Hydroxyl-terminated polybutadiene liquid rubber was heated to 90°C and vacuum-dehydrated for 0.5 h, then cooled to 50°C, according to n -NCO / n -OH =3.8 Add N-(P-maleimide phenyl) isocyanate, heat to 85℃, react for 2.5h, cool down and discharge to obtain imide-modified polybutadiene liquid rubber; (2) Epoxy resin E-51 was stirred and dehydrated at 130℃ and 750mmHg for 2h. Then, imide-modified polybutadiene liquid rubber was added under nitrogen gas. The mass ratio of epoxy resin to imide-modified polybutadiene liquid rubber was 100:25. The mixture was stirred for 30min, and stannous octoate catalyst was added. The mixture was reacted at 82℃ for 2.2h. Then, the mixture was degassed under vacuum to obtain modified epoxy resin. (3) Add the shells to a 0.12 mol / L hydrochloric acid solution at a solid-liquid ratio of 1 g: 5 mL for acid hydrolysis for 30 min. After filtration, washing, and drying, grind the shells to 600 nm to obtain porous shell powder. Mix the porous shell powder with anhydrous ethanol at a solid-liquid ratio of 1 g: 40 mL and ultrasonically disperse the mixture to obtain a dispersion. Adjust the pH of the dispersion to 9.0. Add γ-methacryloxypropyltrimethoxysilane hydrolysate with a mass fraction of 10 wt% at 70 °C. Reflux the mixture for 4 hours. After the reaction is complete, wash the reaction solution repeatedly with anhydrous ethanol and filter until the filtrate is clear and transparent. Place the filter cake in a vacuum drying oven and dry it at 70 °C for 12 h to obtain alkenylated nanofiller. (4) First, add 1 / 5 of the total amount of epoxy resin E-51 to the reactor and heat it to 105°C to completely melt it. Then, add the remaining epoxy resin E-51, methacrylic acid and triethylamine catalyst to the reactor all at once, stir, and after 1.5 h, raise the temperature to 125°C to continue the reaction. Stop the reaction when the acid value reaches 1.5 mg KOH / g to obtain alkenylated epoxy resin. The mass ratio of epoxy resin, methacrylic acid and catalyst is 100:28:2.8. (5) Mix the alkenylated epoxy resin and the solvent tripropylene glycol methyl ether, stir and heat to 125°C under nitrogen protection, add the monomer isobutyl methacrylate, alkenylated nanofiller and initiator di-tert-amyl peroxide, react at a constant temperature for 4.2 h, cool to room temperature, add the modified epoxy resin and tri(2-hydroxyethyl) isocyanurate triacrylate; the alkenylated epoxy resin, solvent, monomer, alkenylated nanofiller, initiator, modified epoxy resin and tri(2-hydroxyethyl) isocyanurate triacrylate are in a mass ratio of 85:40:25:15:5:105:4.

[0025] Example 5 A high-performance epoxy resin modified filler material for metal flooring is composed of component A and component B, with a volume ratio of component A to component B of 2.5:1. Component B comprises T30 long-chain fatty amine modified curing agent, polyether amine with a number average molecular weight of 400, and accelerator DMP-30 in a mass ratio of 1:7.0:0.3; The preparation of component A is as follows: (1) Hydroxyl-terminated polybutadiene liquid rubber was heated to 90°C and vacuum-dehydrated for 0.5 h, then cooled to 50°C, according to n -NCO / n -OH =4.2 Add N-(P-maleimide phenyl) isocyanate, heat to 85℃, react for 3.5h, cool down and discharge to obtain imide-modified polybutadiene liquid rubber; (2) Epoxy resin E-51 was stirred and dehydrated at 115℃ and 680mmHg for 1.2h. Then, imide-modified polybutadiene liquid rubber was added under nitrogen gas. The mass ratio of epoxy resin to imide-modified polybutadiene liquid rubber was 80:18. After stirring for 22min, a mixture of triethylamine and stannous octoate in a mass ratio of 1:1 was added. The mixture was reacted at 78℃ for 2.8h. Then, the mixture was degassed under vacuum to obtain modified epoxy resin. (3) Add the shells to a 0.18 mol / L acetic acid solution at a solid-liquid ratio of 1 g: 5 mL for acid hydrolysis for 30 min. After filtration, washing, and drying, grind the shells to 520 nm to obtain porous shell powder. Mix the porous shell powder with anhydrous ethanol at a solid-liquid ratio of 1 g: 32 mL and ultrasonically disperse the mixture to obtain a dispersion. Adjust the pH of the dispersion to 9. Add a silane coupling agent of 8.5 wt% vinyltrimethoxysilane hydrolysate at 70 °C. Reflux the mixture for 4 hours. After the reaction is complete, wash the reaction solution repeatedly with anhydrous ethanol and filter until the filtrate is clear and transparent. Place the filter cake in a vacuum drying oven and dry it at 70 °C for 12 h to obtain alkenylated nanofiller. (4) First, add 1 / 6 of the total amount of epoxy resin E-51 to the reactor and heat it to 103°C to completely melt it. Then, add the remaining epoxy resin E-51, methacrylic acid and triphenylphosphine catalyst to the reactor all at once. Stir and heat to 118°C after 1.3 hours to continue the reaction. Stop the reaction when the acid value reaches 2.5 mg KOH / g to obtain alkenylated epoxy resin. The mass ratio of epoxy resin, methacrylic acid and catalyst is 98:26:2.2. (5) Mix and stir the alkenylated epoxy resin and solvent propylene glycol phenyl ether. Under nitrogen protection, stir and heat to 118°C, add monomer sec-butyl acrylate, alkenylated nanofiller and initiator benzoyl peroxide, react at constant temperature for 4.8 h, cool to room temperature, add modified epoxy resin and tri(2-hydroxyethyl) isocyanurate triacrylate; the alkenylated epoxy resin, solvent, monomer, alkenylated nanofiller, initiator, modified epoxy resin and tri(2-hydroxyethyl) isocyanurate triacrylate are in a mass ratio of 82:36:23:10:2:100:2.5.

[0026] Comparative Example 1 The difference between Comparative Example 1 and Example 5 is that epoxy resin E-51 is used instead of alkenylated epoxy resin, and the remaining steps are the same as in Example 5.

[0027] Comparative Example 2 The difference between Comparative Example 2 and Example 5 is that epoxy resin E-51 is used instead of modified epoxy resin, while the other steps are the same as in Example 5.

[0028] Comparative Example 3 The difference between Comparative Example 3 and Example 5 is that the porous shell powder is not modified by a coupling agent, while the other steps are the same as in Example 5.

[0029] Comparative Example 4 The difference between Comparative Example 4 and Example 5 is that the seashells were directly crushed and ground to 520nm without acid hydrolysis, while the remaining steps were the same as in Example 5.

[0030] Comparative Example 5 The difference between Comparative Example 5 and Example 5 is that the seashells were directly crushed and ground to 520nm without acid hydrolysis or coupling agent modification. The remaining steps are the same as in Example 5.

[0031] Performance testing 1. Test method for tensile shear strength: GB / T7124-2008 Determination of tensile shear strength of adhesives (rigid material to rigid material).

[0032] 2. Curing shrinkage rate was tested according to ISO 3521-1997 standard.

[0033] Example of effect Table 1 below shows the performance analysis results of the filler materials used in Examples 1 to 5 and Comparative Examples 1 to 5 of the present invention.

[0034] Table 1

[0035] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A high-performance epoxy resin modified filler material for metal flooring, comprising component A and component B, wherein the volume ratio of component A to component B is 1.5-2.5:1, characterized in that, Component A is composed of alkenylated epoxy resin, solvent, monomer, alkenylated nanofiller, initiator, modified epoxy resin, and tri(2-hydroxyethyl)isocyanurate triacrylate in a mass ratio of 70-85:30-40:20-25:6-15:1-5:95-105:2-4. The modified epoxy resin is obtained by modifying epoxy resin with imide-modified polybutadiene liquid rubber.

2. The high-performance epoxy resin modified filler material for metal flooring according to claim 1, characterized in that, The epoxy resin used in the alkenylated epoxy resin and modified epoxy resin is one or a mixture of more than one of epoxy resin E-44 and epoxy resin E-51.

3. The high-performance epoxy resin modified filler material for metal flooring according to claim 1, characterized in that, The modified epoxy resin is prepared by: dehydrating the epoxy resin at high temperature, and then mixing it with imide-modified polybutadiene liquid rubber at a mass ratio of 75-100:10-25 to obtain the modified epoxy resin.

4. The high-performance epoxy resin modified filler material for metal flooring according to claim 3, characterized in that, The imide-modified polybutadiene liquid rubber is composed of hydroxyl-terminated polybutadiene liquid rubber and N-(P-maleimide-phenyl) isocyanate in accordance with n -NCO / n -OH It was prepared by a mixed reaction of 3.5-4.

5.

5. The high-performance epoxy resin modified filler material for metal flooring according to claim 4, characterized in that, The hydroxyl-terminated polybutadiene liquid rubber has a number average molecular weight of 3000-3500, a molecular weight distribution index of 1.4-1.7, a viscosity of <5.0 Pa·s, an average functionality of 2-2.3 at 40℃, a hydroxyl value of 0.60-0.75 mmol / g, and a moisture content of <300 ppm.

6. The high-performance epoxy resin modified filler material for metal flooring according to claim 1, characterized in that, The alkenylated nanofiller is prepared by modifying porous shell powder with a silane coupling agent, wherein the silane coupling agent is at least one of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, and γ-methacryloyloxypropyltrimethoxysilane.

7. The high-performance epoxy resin modified filler material for metal flooring according to claim 1, characterized in that, The preparation method of component A is as follows: the alkenylated epoxy resin and solvent are mixed and stirred, and under nitrogen protection, the mixture is stirred and heated to 110-125℃. The monomer, alkenylated nanofiller and initiator are added, and the mixture is reacted at a constant temperature for 4-5 hours. After cooling to room temperature, the modified epoxy resin and tri(2-hydroxyethyl) isocyanurate triacrylate are added and stirred evenly.

8. The high-performance epoxy resin modified filler material for metal flooring according to claim 7, characterized in that, The solvent is one or more of n-butanol, isobutanol, sec-butanol, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol propyl ether, dipropylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, propylene glycol phenyl ether, propylene glycol methyl ether acetate, and dipropylene glycol methyl ether acetate; the initiator is one of benzoyl peroxide, azobisisobutyronitrile, di-tert-butyl peroxide, and di-tert-pentyl peroxide; the monomer is at least one of butyl acrylate, butyl methacrylate, isobutyl acrylate, sec-butyl acrylate, and isobutyl methacrylate.

9. The high-performance epoxy resin modified filler material for metal flooring according to claim 1, characterized in that, Component B comprises a long-chain fatty amine modified curing agent, a polyether amine with a number average molecular weight of 200-400, and an accelerator DMP-30 in a mass ratio of 1:5-7:0.2-0.

3.

10. A high-performance epoxy resin modified filler material for metal flooring according to claim 9, characterized in that, The long-chain fatty amine modified curing agent is T30 long-chain fatty amine modified curing agent, with an amine value of 490-580 mgKOH and a viscosity of 800-1500 mPa·s at 25℃.

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