Wear-resistant self-repairing plastic-wood board and preparation method thereof

Abstract

The present application relates to the technical field of plastic-wood materials, in particular to a wear-resistant self-repairing plastic-wood board and a preparation method thereof; and is used to solve the problems of poor wear resistance and poor self-repairing ability of the existing plastic-wood board; the plastic-wood board is prepared from polydopamine-furan triazine branched polybenzimidazole; firstly, a triazine-based benzoic acid compound is prepared, then a tetraamino benzoate-based furan is prepared, and the two are polymerized with 4,4'-diphenyl ether dicarboxylic acid to obtain furan triazine branched polybenzimidazole; dopamine is self-polymerized on the surface of the polymer to obtain polydopamine-furan triazine branched polybenzimidazole; polydopamine provides good self-repairing function; furan ring and imidazole ring have low surface energy, which reduces the friction coefficient and the wear rate; when added to the plastic-wood board, the maintenance frequency and cost of the board can be reduced, and the service life and convenience of the board are improved.

Description

Technical Field

[0001] This invention relates to the field of wood-plastic composite materials technology, specifically to a wear-resistant, self-healing wood-plastic composite board and its preparation method. Background Technology

[0002] In the current fields of construction, landscaping, and outdoor furniture, wood-plastic composite (WPC) panels are widely used due to their combination of the texture of wood and the durability of plastic. WPC panels are a material made by mixing wood powder and plastic, and then processing them using specific techniques. While traditional WPC panels have solved the problems of wood's susceptibility to rot and deformation to some extent, their wear resistance and self-healing capabilities still need improvement, failing to meet the requirements of some applications with high durability demands. Therefore, this invention provides a wear-resistant, self-healing WPC panel and its preparation method, enabling WPC panels to provide a more durable and stable user experience in various environments. Summary of the Invention

[0003] In order to overcome the above-mentioned technical problems, the present invention aims to provide: a wear-resistant self-healing wood-plastic composite board and its preparation method, which solves the problems of poor wear resistance and poor self-healing ability of existing wood-plastic composite boards.

[0004] The objective of this invention can be achieved through the following technical solutions: In a first aspect, this application provides a wear-resistant, self-healing wood-plastic composite board, comprising the following parts by weight: 100 parts wood flour, 60-80 parts polydopamine-furan triazine branched polybenzimidazole, 10-20 parts polyethylene, 8-10 parts calcium carbonate, 1.5-2 parts polyethylene wax, and 0.4-0.6 parts zinc stearate; The polydopamine-furan triazine-branched polybenzimidazole is prepared by the following steps: Step A1: Add p-hydroxybenzonitrile, sodium hydroxide, acetone and deionized water to a single-necked flask equipped with a stirrer, stir for 10-20 minutes to obtain solution 1; Step A2: Add cyanuric chloride and acetone to a three-necked flask equipped with a thermometer and a stirrer, transfer to an ice bath, add ice water and stir for 10-20 min, add solution 1 dropwise, react at 0℃ for 2 h, raise the temperature to 24-26℃ and stir for 2 h, reflux at 60℃ for 18 h, wash with ice water 3-5 times, place in a drying oven and dry at 60℃ for 12 h to obtain triazine benzonitrile compound;

[0005] Step A3: Add the triazine benzonitrile compound, potassium hydroxide, deionized water and anhydrous ethanol to a three-necked flask equipped with a reflux condenser, transfer to an oil bath, heat to 90°C and reflux for 10-12 hours, cool, remove ethanol by rotary evaporation, recrystallize with an ethanol / water mixture, and dry to obtain the triazine benzoic acid compound.

[0006] Step A4: Add 2,5-furandiethanol, 3,4-diaminobenzoic acid, tetrabutyl titanate, triethylamine, dibutylhydroxytoluene, and N,N-dimethylformamide to a three-necked flask equipped with a stirrer and thermometer. Seal the nitrogen gas inlet and transfer the flask to an oil bath. Stir at 120-130℃ for 2-3 hours. After cooling, adjust the pH to 3 with hydrochloric acid. Add the flask to ice water, filter, wash with deionized water 3-5 times, and dry to obtain tetraaminobenzoic acid furan.

[0007] Step A5: Place polyphosphoric acid in a forced-air drying oven and heat at 80℃ for 30 min. Add it to a three-necked flask equipped with a magnetic stirrer and a reflux condenser. Purge with nitrogen and stir at 140℃ and 1500 r / min for 10-20 min. Add tetraaminobenzoic acid ester-based furan at 1000 r / min and stir for 6 h. Add triazine benzoic acid compound and 4,4'-diphenyl ether dicarboxylic acid and react for 3 h. Add deionized water to precipitate the precipitate. Adjust the pH to 8-10 with sodium bicarbonate and stir for 10-12 h. Filter and wash with deionized water 5-7 times. Soak in deionized water and stir for 2 h. Filter and soak in anhydrous ethanol at 80℃ for 2 h. Filter and place in an oven to vacuum dry at 120℃ for 24 h to obtain furan triazine-based branched polybenzimidazole.

[0008] Step A6: Add deionized water to a single-necked flask equipped with a stirrer, adjust the pH to 8.5 with tris(hydroxymethyl)aminomethane, add dopamine and stir for 10-20 min, add furan triazine-branched polybenzimidazole and stir for 24 h, vacuum filter, place in an oven and dry at 80 °C to obtain polydopamine-furan triazine-branched polybenzimidazole.

[0009] As a further aspect of the present invention: the ratio of p-hydroxybenzonitrile, sodium hydroxide, acetone and deionized water used in step A1 is 0.03-0.06 mol: 1.8-3.6 g: 25-50 mL: 25-50 mL.

[0010] As a further aspect of the present invention: the ratio of the amount of cyanuric chloride, acetone, ice water and solution 1 used in step A2 is 0.01-0.02 mol: 100-200 mL: 100-200 mL: 50-100 mL.

[0011] As a further aspect of the present invention: the ratio of the triazine benzonitrile compound, potassium hydroxide, deionized water and anhydrous ethanol used in step A3 is 5-10g: 13-26g: 80-160mL: 20-40mL.

[0012] As a further aspect of the present invention: the volume ratio of ethanol to water in the ethanol / water mixed solution in step A3 is 3:1.

[0013] As a further embodiment of the present invention: the ratio of the amounts of 2,5-furandimethylethanol, 3,4-diaminobenzoic acid, tetrabutyl titanate, triethylamine, butylated hydroxytoluene, and N,N-dimethylformamide used in step A4 is 0.01-0.02 mol: 0.02-0.04 mol: 0.0068-0.0136 g: 0.0505-0.101 g: 0.0157-0.0314 g: 30-60 mL.

[0014] As a further aspect of the present invention: the molar concentration of hydrochloric acid in step A4 is 1 mol / L.

[0015] As a further embodiment of the present invention: the ratio of polyphosphoric acid, tetraaminobenzoic acid furan, triazine benzoic acid compound and 4,4'-diphenyl ether dicarboxylic acid in step A5 is 20-40g: 3-6mmol: 0.18-0.36mmol: 2.73-5.46mmol.

[0016] As a further aspect of the present invention: the CAS number of the polyphosphoric acid mentioned in step A5 is 8017-16-1.

[0017] As a further aspect of the present invention: the ratio of deionized water, dopamine and furan triazine-branched polybenzimidazole used in step A6 is 100-200mL: 0.2-0.4g: 10-20g.

[0018] Secondly, a method for preparing a wear-resistant, self-healing wood-plastic composite board includes the following steps: Step 1: Weigh out 100 parts by weight of wood flour, 60-80 parts by weight of polydopamine-furan triazine-branched polybenzimidazole, 10-20 parts by weight of polyethylene, 8-10 parts by weight of calcium carbonate, 1.5-2 parts by weight of polyethylene wax, and 0.4-0.6 parts by weight of zinc stearate, and set aside; wherein, the wood flour is wood-plastic composite wood flour; the particle size of the wood flour is 40-160 mesh; the polyethylene is of type DGDB-2480; and the polyethylene wax is of type CH-100A; Step 2: Mix wood flour, polydopamine-furan triazine-branched polybenzimidazole, polyethylene, calcium carbonate, polyethylene wax and zinc stearate, and melt-extrude using an extruder at an extrusion temperature of 173-175℃. After cooling and shaping, wear-resistant self-healing wood-plastic composite board is obtained.

[0019] Beneficial effects:

[0020] The present invention discloses a wear-resistant and self-healing wood-plastic composite board. First, furan triazine-branched polybenzimidazole is prepared. Then, dopamine is used to self-polymerize on the polymer surface to obtain polydopamine-furan triazine-branched polybenzimidazole, which enables the surface of the wood-plastic composite board to withstand heavier loads without easily wearing out, thus greatly improving the service life of the board.

[0021] To prepare a wear-resistant, self-healing wood-plastic composite board, a triazine benzonitrile compound was first prepared, and the cyano group was converted to a carboxyl group to obtain a triazine benzoic acid compound. Esterification with 2,5-furandimethyl alcohol and 3,4-diaminobenzoic acid yielded tetraaminobenzoate furan. Polymerization of the triazine benzoic acid compound, tetraaminobenzoate furan, and 4,4'-diphenyl ether dicarboxylic acid yielded furan triazine-branched polybenzimidazole. Self-polymerization with dopamine on the surface of the furan triazine-branched polybenzimidazole yielded polydopamine-furan triazine-branched polybenzimidazole. The molecular chain contains rigid aromatic structures such as triazine rings, benzimidazole rings, and furan rings, forming a three-dimensional cross-linked network through π-π stacking and conjugation effects, which can effectively disperse external impacts and reduce wear. The branched structure reduces the propagation of microcracks on the material surface, absorbs energy, and induces crack deflection, avoiding stress concentration. Meanwhile, flexible segments such as ether bonds in the molecular weight buffer impacts and improve material toughness. Furthermore, the furan and imidazole rings have low surface energy, forming a lubricating layer at the friction interface, reducing the friction coefficient and wear rate. Polydopamine contains catechol groups, amino and imino groups, which can form dynamic non-covalent bonds such as hydrogen bonds, π-π stacking, and metal coordination. These bonds break when damaged and recombine under external stimuli (such as heat, light, acids, and alkalis), achieving crack closure and performance recovery, thus enhancing the self-healing ability of wood-plastic composite boards. The combined effect of multiple functional groups not only significantly improves the wear resistance of wood-plastic composite boards but also enhances their self-healing ability, extending service life and optimizing maintenance costs. Detailed Implementation

[0022] 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.

[0023] Example 1:

[0024] This embodiment describes a method for preparing wear-resistant, self-healing wood-plastic composite boards, including the following steps: Step A1: Add 0.03 mol p-hydroxybenzonitrile, 1.8 g sodium hydroxide, 25 mL acetone and 25 mL deionized water to a single-necked flask equipped with a stirrer, stir for 10 min to obtain solution 1; Step A2: Add 0.01 mol cyanuric chloride and 100 mL acetone to a three-necked flask equipped with a thermometer and a stirrer, transfer to an ice bath, add 100 mL ice water and stir for 10 min, add 50 mL solution 1 dropwise, react at 0 °C for 2 h, raise the temperature to 24 °C and stir for 2 h, reflux at 60 °C for 18 h, wash 3 times with ice water, place in a drying oven and dry at 60 °C for 12 h to obtain triazine benzonitrile compound; Step A3: Add 5g of triazine benzonitrile compound, 13g of potassium hydroxide, 80mL of deionized water and 20mL of anhydrous ethanol to a three-necked flask equipped with a reflux condenser, transfer to an oil bath, heat to 90℃ and reflux for 10h, cool, remove ethanol by rotary evaporation, recrystallize with an ethanol / water mixture, and dry to obtain triazine benzoic acid compound; Step A4: Add 0.01 mol 2,5-furandiethanol, 0.02 mol 3,4-diaminobenzoic acid, 0.0068 g tetrabutyl titanate, 0.0505 g triethylamine, 0.0157 g dibutylhydroxytoluene and 30 mL N,N-dimethylformamide to a three-necked flask equipped with a stirrer and thermometer. Seal the flask by introducing nitrogen gas, transfer it to an oil bath, stir at 120 °C for 2 h, cool and adjust the pH to 3 with hydrochloric acid, add it to ice water, filter, wash three times with deionized water, and dry to obtain tetraaminobenzoic acid furan; Step A5: Place 20g of polyphosphoric acid in a forced-air drying oven and heat at 80℃ for 30min. Add the mixture to a three-necked flask equipped with a magnetic stirrer and a reflux condenser. Purge with nitrogen and stir at 140℃ and 1500r / min for 10min. Add 3mmol of tetraaminobenzoic acid ester-based furan at 1000r / min and stir for 6h. Add 0.18mmol of triazine benzoic acid compound and 2.73mmol of 4,4'-diphenyl ether dicarboxylic acid and react for 3h. Add deionized water to precipitate the precipitate. Adjust the pH to 8 with sodium bicarbonate and stir for 10h. Filter and wash 5 times with deionized water. Soak in deionized water and stir for 2h. Filter and soak in anhydrous ethanol at 80℃ for 2h. Filter and place in an oven to vacuum dry at 120℃ for 24h to obtain furan triazine-based branched polybenzimidazole. Step A6: Add 100 mL of deionized water to a single-necked flask equipped with a stirrer, adjust the pH to 8.5 with tris(hydroxymethyl)aminomethane, add 0.2 g of dopamine and stir for 10 min, add 10 g of furan triazine-branched polybenzimidazole and stir for 24 h, vacuum filter, place in an oven and dry at 80 °C to obtain polydopamine-furan triazine-branched polybenzimidazole; Step A7: Weigh out 100 parts by weight of wood flour, 60 parts by weight of polydopamine-furan triazine-branched polybenzimidazole, 10 parts by weight of polyethylene, 8 parts by weight of calcium carbonate, 1.5 parts by weight of polyethylene wax, and 0.4 parts by weight of zinc stearate, and set aside; wherein, the wood flour is wood-plastic composite wood flour; the particle size of the wood flour is 40-160 mesh; the polyethylene is of type DGDB-2480; and the polyethylene wax is of type CH-100A; Step A8: Mix wood flour, polydopamine-furan triazine-branched polybenzimidazole, polyethylene, calcium carbonate, polyethylene wax and zinc stearate, melt extrude using an extruder at an extrusion temperature of 173℃, cool and set to obtain wear-resistant self-healing wood-plastic composite board.

[0025] Example 2:

[0026] This embodiment describes a method for preparing wear-resistant, self-healing wood-plastic composite boards, including the following steps: Step A1: Add 0.045 mol p-hydroxybenzonitrile, 2.7 g sodium hydroxide, 32.5 mL acetone and 32.5 mL deionized water to a single-necked flask equipped with a stirrer, stir for 15 min to obtain solution 1; Step A2: Add 0.015 mol cyanuric chloride and 150 mL acetone to a three-necked flask equipped with a thermometer and a stirrer, transfer to an ice bath, add 150 mL ice water and stir for 15 min, add 75 mL solution 1 dropwise, react at 0 °C for 2 h, raise the temperature to 25 °C and stir for 2 h, reflux at 60 °C for 18 h, wash 4 times with ice water, place in a drying oven and dry at 60 °C for 12 h to obtain triazine benzonitrile compound; Step A3: Add 7.5g of triazine benzonitrile compound, 19.5g of potassium hydroxide, 120mL of deionized water and 30mL of anhydrous ethanol to a three-necked flask equipped with a reflux condenser, transfer to an oil bath, heat to 90℃ and reflux for 11h, cool, remove ethanol by rotary evaporation, recrystallize with an ethanol / water mixture, and dry to obtain triazine benzoic acid compound; Step A4: Add 0.015 mol 2,5-furandiethanol, 0.03 mol 3,4-diaminobenzoic acid, 0.0102 g tetrabutyl titanate, 0.07575 g triethylamine, 0.02355 g dibutylhydroxytoluene and 45 mL N,N-dimethylformamide to a three-necked flask equipped with a stirrer and thermometer. Seal the flask by introducing nitrogen gas, transfer it to an oil bath, stir at 125 °C for 2.5 h, cool and adjust the pH to 3 with hydrochloric acid, add it to ice water, filter, wash 4 times with deionized water, and dry to obtain tetraaminobenzoate furan; Step A5: Place 30g of polyphosphoric acid in a forced-air drying oven and heat at 80℃ for 30min. Add the mixture to a three-necked flask equipped with a magnetic stirrer and a reflux condenser. Purge with nitrogen and stir at 140℃ and 1500r / min for 15min. Add 4.5mmol of tetraaminobenzoic acid ester-based furan at 1000r / min and stir for 6h. Add 0.27mmol of triazine benzoic acid compound and 4.095mmol of 4,4'-diphenyl ether dicarboxylic acid and react for 3h. Add deionized water to precipitate the precipitate. Adjust the pH to 9 with sodium bicarbonate and stir for 11h. Filter and wash 6 times with deionized water. Soak in deionized water and stir for 2h. Filter and soak in anhydrous ethanol at 80℃ for 2h. Filter and place in an oven to vacuum dry at 120℃ for 24h to obtain furan triazine-based branched polybenzimidazole. Step A6: Add 150 mL of deionized water to a single-necked flask equipped with a stirrer, adjust the pH to 8.5 with tris(hydroxymethyl)aminomethane, add 0.3 g of dopamine and stir for 15 min, add 15 g of furan triazine-branched polybenzimidazole and stir for 24 h, vacuum filter, place in an oven and dry at 80 °C to obtain polydopamine-furan triazine-branched polybenzimidazole; Step A7: Weigh out 100 parts by weight of wood flour, 70 parts by weight of polydopamine-furan triazine-branched polybenzimidazole, 15 parts by weight of polyethylene, 9 parts by weight of calcium carbonate, 1.75 parts by weight of polyethylene wax, and 0.5 parts by weight of zinc stearate, and set aside; wherein, the wood flour is wood-plastic composite wood flour; the particle size of the wood flour is 40-160 mesh; the polyethylene is of type DGDB-2480; and the polyethylene wax is of type CH-100A; Step A8: Mix wood flour, polydopamine-furan triazine-branched polybenzimidazole, polyethylene, calcium carbonate, polyethylene wax and zinc stearate, melt extrude using an extruder at an extrusion temperature of 174℃, cool and set to obtain wear-resistant self-healing wood-plastic composite board.

[0027] Example 3:

[0028] This embodiment describes a method for preparing wear-resistant, self-healing wood-plastic composite boards, including the following steps: Step A1: Add 0.06 mol p-hydroxybenzonitrile, 3.6 g sodium hydroxide, 50 mL acetone and 50 mL deionized water to a single-necked flask equipped with a stirrer, stir for 20 min to obtain solution 1; Step A2: Add 0.02 mol cyanuric chloride and 200 mL acetone to a three-necked flask equipped with a thermometer and a stirrer, transfer to an ice bath, add 200 mL ice water and stir for 20 min, add 100 mL solution 1 dropwise, react at 0 °C for 2 h, raise the temperature to 26 °C and stir for 2 h, reflux at 60 °C for 18 h, wash 5 times with ice water, place in a drying oven and dry at 60 °C for 12 h to obtain triazine benzonitrile compound; Step A3: Add 10g of triazine benzonitrile compound, 26g of potassium hydroxide, 160mL of deionized water and 40mL of anhydrous ethanol to a three-necked flask equipped with a reflux condenser, transfer to an oil bath, heat to 90℃ and reflux for 12h, cool, remove ethanol by rotary evaporation, recrystallize with an ethanol / water mixture, and dry to obtain triazine benzoic acid compound; Step A4: Add 0.02 mol 2,5-furandiethanol, 0.04 mol 3,4-diaminobenzoic acid, 0.0136 g tetrabutyl titanate, 0.101 g triethylamine, 0.0314 g dibutylhydroxytoluene and 60 mL N,N-dimethylformamide to a three-necked flask equipped with a stirrer and thermometer. Seal the flask by introducing nitrogen gas, transfer it to an oil bath, stir at 130 °C for 3 h, cool and adjust the pH to 3 with hydrochloric acid, add it to ice water, filter and wash 5 times with deionized water, dry to obtain tetraaminobenzoate furan; Step A5: Place 40g of polyphosphoric acid in a forced-air drying oven and heat at 80℃ for 30min. Add the mixture to a three-necked flask equipped with a magnetic stirrer and a reflux condenser. Purge with nitrogen and stir at 140℃ and 1500r / min for 20min. Add 6mmol of tetraaminobenzoic acid ester-based furan at 1000r / min and stir for 6h. Add 0.36mmol of triazine benzoic acid compound and 5.46mmol of 4,4'-diphenyl ether dicarboxylic acid and react for 3h. Add deionized water to precipitate the precipitate. Adjust the pH to 10 with sodium bicarbonate and stir for 12h. Filter and wash 7 times with deionized water. Soak in deionized water and stir for 2h. Filter and soak in anhydrous ethanol at 80℃ for 2h. Filter and place in an oven to vacuum dry at 120℃ for 24h to obtain furan triazine-based branched polybenzimidazole. Step A6: Add 200 mL of deionized water to a single-necked flask equipped with a stirrer, adjust the pH to 8.5 with tris(hydroxymethyl)aminomethane, add 0.4 g of dopamine and stir for 20 min, add 20 g of furan triazine-branched polybenzimidazole and stir for 24 h, vacuum filter, place in an oven and dry at 80 °C to obtain polydopamine-furan triazine-branched polybenzimidazole; Step A7: Weigh out 100 parts by weight of wood flour, 80 parts by weight of polydopamine-furan triazine-branched polybenzimidazole, 20 parts by weight of polyethylene, 10 parts by weight of calcium carbonate, 2 parts by weight of polyethylene wax, and 0.6 parts by weight of zinc stearate, and set aside; wherein, the wood flour is wood-plastic composite wood flour; the particle size of the wood flour is 40-160 mesh; the polyethylene is of type DGDB-2480; and the polyethylene wax is of type CH-100A; Step A8: Mix wood flour, polydopamine-furan triazine-branched polybenzimidazole, polyethylene, calcium carbonate, polyethylene wax and zinc stearate, melt extrude using an extruder at an extrusion temperature of 175℃, cool and set to obtain wear-resistant self-healing wood-plastic composite board.

[0029] Comparative Example 1: This comparative example illustrates a method for preparing a wear-resistant, self-healing wood-plastic composite board, comprising the following steps: Step A1: Add 0.06 mol p-hydroxybenzonitrile, 3.6 g sodium hydroxide, 50 mL acetone and 50 mL deionized water to a single-necked flask equipped with a stirrer, stir for 20 min to obtain solution 1; Step A2: Add 0.02 mol cyanuric chloride and 200 mL acetone to a three-necked flask equipped with a thermometer and a stirrer, transfer to an ice bath, add 200 mL ice water and stir for 20 min, add 100 mL solution 1 dropwise, react at 0 °C for 2 h, raise the temperature to 26 °C and stir for 2 h, reflux at 60 °C for 18 h, wash 5 times with ice water, place in a drying oven and dry at 60 °C for 12 h to obtain triazine benzonitrile compound; Step A3: Add 10g of triazine benzonitrile compound, 26g of potassium hydroxide, 160mL of deionized water and 40mL of anhydrous ethanol to a three-necked flask equipped with a reflux condenser, transfer to an oil bath, heat to 90℃ and reflux for 12h, cool, remove ethanol by rotary evaporation, recrystallize with an ethanol / water mixture, and dry to obtain triazine benzoic acid compound; Step A4: Place 40g of polyphosphoric acid in a forced-air drying oven and heat at 80℃ for 30min. Add the mixture to a three-necked flask equipped with a magnetic stirrer and a reflux condenser. Purge with nitrogen and stir at 140℃ and 1500r / min for 20min. Add 6mmol of 3,3-diaminobenzidine at 1000r / min and stir for 6h. Add 0.36mmol of triazine benzoic acid compound and 5.46mmol of 4,4'-diphenyl ether dicarboxylic acid and react for 3h. Add deionized water to precipitate the precipitate. Adjust the pH to 10 with sodium bicarbonate and stir for 12h. Filter and wash 7 times with deionized water. Soak in deionized water and stir for 2h. Filter and soak in anhydrous ethanol at 80℃ for 2h. Filter and place in an oven to vacuum dry at 120℃ for 24h to obtain triazine branched polybenzimidazole. Step A5: Add 200 mL of deionized water to a single-necked flask equipped with a stirrer, adjust the pH to 8.5 with tris(hydroxymethyl)aminomethane, add 0.4 g of dopamine and stir for 20 min, add 20 g of furan triazine branched polybenzimidazole and stir for 24 h, vacuum filter, place in an oven and dry at 80 °C to obtain polydopamine-triazine branched polybenzimidazole; Step A6: Weigh out 100 parts by weight of wood flour, 80 parts by weight of polydopamine-triazine-branched polybenzimidazole, 20 parts by weight of polyethylene, 10 parts by weight of calcium carbonate, 2 parts by weight of polyethylene wax, and 0.6 parts by weight of zinc stearate, and set aside; wherein, the wood flour is wood-plastic composite wood flour; the particle size of the wood flour is 40-160 mesh; the polyethylene is of type DGDB-2480; and the polyethylene wax is of type CH-100A; Step A7: Mix wood flour, polydopamine-triazine branched polybenzimidazole, polyethylene, calcium carbonate, polyethylene wax and zinc stearate, melt extrude using an extruder at an extrusion temperature of 175℃, cool and set to obtain wear-resistant self-healing wood-plastic composite board.

[0030] Comparative Example 2: This comparative example illustrates a method for preparing a wear-resistant, self-healing wood-plastic composite board, comprising the following steps: Step A1: 0.02 mol 2,5-furandiethanol, 0.04 mol 3,4-diaminobenzoic acid, 0.0136 g tetrabutyl titanate, 0.101 g triethylamine, 0.0314 g dibutylhydroxytoluene and 60 mL N,N-dimethylformamide were added to a three-necked flask equipped with a stirrer and thermometer. The flask was sealed at the nitrogen gas inlet and transferred to an oil bath. The mixture was stirred at 130 °C for 3 h. After cooling, the pH was adjusted to 3 with hydrochloric acid. The mixture was then added to ice water, filtered, washed 5 times with deionized water, and dried to obtain tetraaminobenzoic acid ester furan. Step A2: Place 40g of polyphosphoric acid in a forced-air drying oven and heat at 80℃ for 30min. Add the mixture to a three-necked flask equipped with a magnetic stirrer and a reflux condenser. Purge with nitrogen and stir at 140℃ and 1500r / min for 20min. Add 6mmol of tetraaminobenzoic acid ester-based furan at 1000r / min and stir for 6h. Add 0.36mmol of trimesic acid and 5.46mmol of 4,4'-diphenyl ether dicarboxylic acid and react for 3h. Add deionized water to precipitate the precipitate. Adjust the pH to 10 with sodium bicarbonate and stir for 12h. Filter the mixture and wash it 7 times with deionized water. Soak the mixture in deionized water and stir for 2h. Filter the mixture and soak it in anhydrous ethanol at 80℃ for 2h. Filter the mixture and place it in an oven to vacuum dry at 120℃ for 24h to obtain furanyl-branched polybenzimidazole. Step A3: Add 200 mL of deionized water to a single-necked flask equipped with a stirrer, adjust the pH to 8.5 with tris(hydroxymethyl)aminomethane, add 0.4 g of dopamine and stir for 20 min, add 20 g of furanyltriazine-branched polybenzimidazole and stir for 24 h, vacuum filter, place in an oven and dry at 80 °C to obtain polydopamine-furanyl-branched polybenzimidazole; Step A4: Weigh out 100 parts by weight of wood flour, 80 parts by weight of polydopamine-furan-branched polybenzimidazole, 20 parts by weight of polyethylene, 10 parts by weight of calcium carbonate, 2 parts by weight of polyethylene wax, and 0.6 parts by weight of zinc stearate, and set aside; wherein, the wood flour is wood-plastic composite wood flour; the particle size of the wood flour is 40-160 mesh; the polyethylene is of type DGDB-2480; and the polyethylene wax is of type CH-100A; Step A5: Mix wood flour, polydopamine-furan-branched polybenzimidazole, polyethylene, calcium carbonate, polyethylene wax and zinc stearate, melt extrude using an extruder at an extrusion temperature of 175℃, cool and set to obtain wear-resistant self-healing wood-plastic composite board.

[0031] Comparative Example 3: This comparative example illustrates a method for preparing a wear-resistant, self-healing wood-plastic composite board, comprising the following steps: Step A1: Place 40g of polyphosphoric acid in a forced-air drying oven and heat at 80℃ for 30min. Add the mixture to a three-necked flask equipped with a magnetic stirrer and a reflux condenser. Purge with nitrogen and stir at 140℃ and 1500r / min for 20min. Add 6mmol of 3,3-diaminobenzidine at 1000r / min and stir for 6h. Add 0.36mmol of trimesic acid and 5.46mmol of 4,4'-diphenyl ether dicarboxylic acid and react for 3h. Add deionized water to precipitate the precipitate. Adjust the pH to 10 with sodium bicarbonate and stir for 12h. Filter the precipitate and wash it 7 times with deionized water. Soak the precipitate in deionized water and stir for 2h. Filter the precipitate and soak it in anhydrous ethanol at 80℃ for 2h. Filter the precipitate and place it in an oven to vacuum dry at 120℃ for 24h to obtain branched polybenzimidazole. Step A2: Add 200 mL of deionized water to a single-necked flask equipped with a stirrer, adjust the pH to 8.5 with tris(hydroxymethyl)aminomethane, add 0.4 g of dopamine and stir for 20 min, add 20 g of furantriazine-branched polybenzimidazole and stir for 24 h, vacuum filter, place in an oven and dry at 80 °C to obtain polydopamine-branched polybenzimidazole; Step A3: Weigh out 100 parts by weight of wood flour, 80 parts by weight of polydopamine-branched polybenzimidazole, 20 parts by weight of polyethylene, 10 parts by weight of calcium carbonate, 2 parts by weight of polyethylene wax, and 0.6 parts by weight of zinc stearate, and set aside; wherein, the wood flour is wood-plastic composite wood flour; the particle size of the wood flour is 40-160 mesh; the polyethylene is of type DGDB-2480; and the polyethylene wax is of type CH-100A; Step A4: Mix wood flour, polydopamine-branched polybenzimidazole, polyethylene, calcium carbonate, polyethylene wax and zinc stearate, melt extrude using an extruder at an extrusion temperature of 175℃, cool and set to obtain wear-resistant self-healing wood-plastic composite board.

[0032] Performance testing: The wood-plastic composite boards of Examples 1-3 and Comparative Examples 1-3 were subjected to abrasion resistance tests according to the standard in GB17657-2022 to obtain abrasion values; The self-healing performance of the wood-plastic composite boards of Examples 1-3 and Comparative Examples 1-3 was tested. A 40-grit metallographic sandpaper with a length of 200cm and a width of 3cm was laid on the surface of the board. A 1kg weight was placed on top of the sandpaper. The sandpaper was then manually pulled horizontally at a speed of 30mm / min to rub back and forth on the surface of the board 3 times. Scratches were produced on the surface of the board. The rubbing was stopped, the sandpaper was removed, and after the surface scratches disappeared, the static bending strength and static bending modulus before and after the rubbing were tested to obtain the retention rate.

[0033]

[0034] Referring to the table above, based on the comparison between Examples 1-3 and Comparative Examples 1-3, it can be seen that the wood-plastic composite board prepared from polydopamine-furan triazine-branched polybenzimidazole has good wear resistance and self-healing ability. Based on the comparison between Example 3 and Comparative Example 1, it can be seen that the wear value of the wood-plastic composite board prepared by polydopamine-furan triazine-branched polybenzimidazole is less than that of the wood-plastic composite board prepared by polydopamine-furan triazine-branched polybenzimidazole, indicating that the wood-plastic composite board prepared by polydopamine-furan triazine-branched polybenzimidazole has excellent wear resistance. Based on the comparison between Example 3 and Comparative Example 2, it can be seen that the wear value of the wood-plastic composite board prepared by polydopamine-furan triazine-branched polybenzimidazole is less than that of the wood-plastic composite board prepared by polydopamine-furan triazine-branched polybenzimidazole, indicating that the wood-plastic composite board prepared by polydopamine-furan triazine-branched polybenzimidazole has excellent wear resistance. Based on the comparison between Example 3 and Comparative Example 3, it can be seen that the wear value of the wood-plastic composite board prepared by polydopamine-furan triazine-branched polybenzimidazole is less than that of the wood-plastic composite board prepared by polydopamine-branched polybenzimidazole, indicating that the wood-plastic composite board prepared by polydopamine-furan triazine-branched polybenzimidazole has excellent wear resistance.

[0035] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0036] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.

Claims

1. A wear-resistant, self-healing wood-plastic composite board, characterized in that, Includes the following components by weight: 100 parts wood flour, 60-80 parts polydopamine-furan triazine branched polybenzimidazole, 10-20 parts polyethylene, 8-10 parts calcium carbonate, 1.5-2 parts polyethylene wax, and 0.4-0.6 parts zinc stearate; The polydopamine-furan triazine-branched polybenzimidazole is prepared by the following steps: Step A1: Stir p-hydroxybenzonitrile, sodium hydroxide, acetone and deionized water to obtain solution 1; Step A2: Place cyanuric chloride and acetone in an ice bath, add ice water and stir, add solution 1 to react, heat and stir, reflux to obtain triazine benzonitrile compound; Step A3: The triazine benzonitrile compound, potassium hydroxide, deionized water and anhydrous ethanol were heated to reflux in an oil bath to obtain the triazine benzoic acid compound; Step A4: Mix 2,5-furandiethanol, 3,4-diaminobenzoic acid, tetrabutyl titanate, triethylamine, dibutylhydroxytoluene, and N,N-dimethylformamide in an oil bath and stir to obtain tetraaminobenzoate-based furan. Step A5: Heat the polyphosphoric acid, add it to a flask, purge with nitrogen, stir, add tetraaminobenzoic acid ester-based furan and stir, add triazine benzoic acid compound and 4,4'-diphenyl ether dicarboxylic acid to react and obtain furan triazine-based branched polybenzimidazole; Step A6: Add deionized water to the flask, adjust the pH, add dopamine and stir, then add furan triazine-branched polybenzimidazole and stir to obtain polydopamine-furan triazine-branched polybenzimidazole.

2. The wear-resistant self-healing wood-plastic composite board according to claim 1, characterized in that, The ratio of p-hydroxybenzonitrile, sodium hydroxide, acetone and deionized water used in step A1 is 0.03-0.06 mol: 1.8-3.6 g: 25-50 mL: 25-50 mL.

3. The wear-resistant self-healing wood-plastic composite board according to claim 1, characterized in that, The ratio of cyanuric chloride, acetone, ice water and solution 1 used in step A2 is 0.01-0.02 mol: 100-200 mL: 100-200 mL: 50-100 mL.

4. The wear-resistant self-healing wood-plastic composite board according to claim 1, characterized in that, The ratio of the triazine benzonitrile compound, potassium hydroxide, deionized water and anhydrous ethanol used in step A3 is 5-10g: 13-26g: 80-160mL: 20-40mL.

5. The wear-resistant self-healing wood-plastic composite board according to claim 1, characterized in that, The ratio of 2,5-furandimethylethanol, 3,4-diaminobenzoic acid, tetrabutyl titanate, triethylamine, butylated hydroxytoluene, and N,N-dimethylformamide used in step A4 is 0.01-0.02 mol : 0.02-0.04 mol : 0.0068-0.0136 g : 0.0505-0.101 g : 0.0157-0.0314 g : 30-60 mL.

6. The wear-resistant self-healing wood-plastic composite board according to claim 1, characterized in that, In step A5, the ratio of polyphosphoric acid, tetraaminobenzoic acid furan, triazine benzoic acid compound, and 4,4'-diphenyl ether dicarboxylic acid is 20-40 g: 3-6 mmol: 0.18-0.36 mmol: 2.73-5.46 mmol; the CAS number of the polyphosphoric acid is 8017-16-1.

7. The wear-resistant self-healing wood-plastic composite board according to claim 1, characterized in that, The ratio of deionized water, dopamine, and furan triazine-branched polybenzimidazole used in step A6 is 100-200 mL: 0.2-0.4 g: 10-20 g.

8. A method for preparing a wear-resistant, self-healing wood-plastic composite board, characterized in that, The method for preparing the wear-resistant, self-healing wood-plastic composite board as described in any one of claims 1-7 includes the following steps: Step 1: Weigh out 100 parts wood flour, 60-80 parts polydopamine-furan triazine-branched polybenzimidazole, 10-20 parts polyethylene, 8-10 parts calcium carbonate, 1.5-2 parts polyethylene wax, and 0.4-0.6 parts zinc stearate according to the following weight proportions, and set aside. Step 2: Mix wood flour, polydopamine-furan triazine-branched polybenzimidazole, polyethylene, calcium carbonate, polyethylene wax and zinc stearate, and melt-extrude using an extruder at an extrusion temperature of 173-175℃. After cooling and shaping, wear-resistant self-healing wood-plastic composite board is obtained.

9. The method for preparing a wear-resistant self-healing wood-plastic composite board according to claim 8, characterized in that, The wood powder is wood-plastic composite wood powder; the particle size of the wood powder is 40-160 mesh; the polyethylene is of type DGDB-2480; and the polyethylene wax is of type CH-100A.

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