Antibacterial flame-retardant gasified slag-based artificial board and preparation method thereof

Abstract

The invention belongs to the technical field of artificial boards, and particularly discloses an antibacterial flame-retardant gasified slag-based artificial board and a preparation method thereof, and the artificial board is prepared from the following raw materials: antibacterial flame-retardant modified gasified slag, recycled fibers and waterborne polyurethane glue. Wherein the antibacterial flame-retardant modified gasified slag is prepared by performing activation, sulfydryl modification, phosphoric acid modification and acylating chlorination treatment on gasified slag and finally reacting with polyhexamethylene guanidine hydrochloride. Vinyl phosphoric acid is grafted to the surface of sulfydryl silane modified gasified slag through click reaction, acylating chlorination treatment is further carried out, reaction with polyhexamethylene guanidine hydrochloride is carried out, antibacterial flame-retardant modified gasified slag is obtained, and then the antibacterial flame-retardant modified gasified slag is mixed with recycled fibers and waterborne polyurethane glue to prepare the artificial board, so that the artificial board has excellent flame-retardant and antibacterial performance; the defects in the prior art are overcome.

Description

Technical Field

[0001] The present invention belongs to the technical field of wood-based panels, and particularly relates to an antibacterial and flame-retardant gasification slag-based wood-based panel and a preparation method thereof. Background Art

[0003] Wood-based panels are widely used in the building decoration and furniture industries. Solid wastes such as gasification slag and waste textile fibers can be used as raw materials for wood-based panels. However, waste textile fibers are flammable materials, and the wood-based panels prepared using them cannot meet the specified fire protection standards without flame retardant treatment. In addition, in some public places with high environmental sanitation requirements, there are certain requirements for the antibacterial properties of decorative panels, and it is also difficult for the wood-based panels prepared by conventional processes to meet the requirements.

[0004] In view of the above problems, wood-based panels made of gasification slag and waste textile fibers still need further research to improve their antibacterial and flame retardant properties to meet the existing usage requirements. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide an antibacterial and flame-retardant gasification slag-based wood-based panel and a preparation method thereof, grafting vinyl phosphoric acid and polyhexamethylene guanidine hydrochloride onto the surface of gasification slag in sequence, and mixing with recycled fibers and waterborne polyurethane glue to prepare a wood-based panel, so that it has excellent flame retardant and antibacterial properties, effectively solving the problems in the background art.

[0006] The present invention is realized through the following technical solutions: An antibacterial and flame-retardant gasification slag-based wood-based panel is prepared from the following raw materials in parts by weight: 55 - 70 parts of antibacterial and flame-retardant modified gasification slag; 15 - 20 parts of recycled fibers; 15 - 25 parts of waterborne polyurethane glue; Wherein, the antibacterial and flame-retardant modified gasification slag is prepared by activating gasification slag, modifying it with mercapto group, phosphoric acid modification, acyl chlorination treatment, and finally reacting with polyhexamethylene guanidine hydrochloride.

[0007] The further improvement scheme of the present invention is as follows: The recycled fibers are one or a mixture of two or more of recycled polyester, recycled hemp fiber or recycled rock wool; And / or, the solid content of the waterborne polyurethane glue is 50% - 70%.

[0008] The further improvement scheme of the present invention is as follows: The specific preparation steps of the antibacterial and flame-retardant modified gasification slag are as follows: S1: Mix the gasification slag and sodium hydroxide, react under a nitrogen atmosphere, cool, add water and conduct the first stirring, filter, add hydrochloric acid to the filter cake, continue with the second stirring, and after the reaction is completed, wash, filter, and dry to obtain the active material; S2: Add the active material and mercapto siloxane to an ethanol aqueous solution, adjust the pH with hydrochloric acid, conduct the third stirring, and after the reaction is completed, wash, filter, and dry to obtain the mercapto-modified gasification slag; S3: Disperse the mercapto-modified gasification slag, vinyl phosphoric acid, and azobisisobutyronitrile in acetonitrile, protect with nitrogen, heat and reflux for reaction, and after the reaction is completed, wash, filter, and dry to obtain the phosphoric acid-modified gasification slag; S4: Disperse the phosphoric acid-modified gasification slag and 1-chloro-N,N,2-trimethylpropenylamine in chloroform, conduct the fourth stirring, filter after the reaction is completed, disperse the filter cake in dichloromethane, add polyhexamethylene guanidine hydrochloride, conduct the fifth stirring, and after the reaction is completed, wash, filter, and dry to obtain the antibacterial and flame-retardant modified gasification slag.

[0009] Further, in S1, the reaction temperature under a nitrogen atmosphere is 600 - 900 °C, the reaction time is 1 - 2 h, the time for the first stirring is 30 - 60 min, the temperature for the second stirring is 50 - 70 °C, and the stirring time is 30 - 60 min; And / or, in S2, adjust the pH = 4 - 5 with hydrochloric acid, the temperature for the third stirring is 60 - 70 °C, and the stirring time is 1 - 3 h; And / or, in S3, the time for the heating reflux reaction is 2 - 4 h; And / or, in S4, the temperature for the fourth stirring is 50 - 55 °C, the stirring time is 20 - 30 min, the temperature for the fifth stirring is 0 - 5 °C, and the stirring time is 18 - 24 h.

[0010] Further, in S1, the particle size of the gasification slag is 100 - 300 mesh, and the mass fraction of the hydrochloric acid is 20% - 22%; And / or, in S2, the mercapto siloxane is one or a mixture of two of mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane, and the mass fraction of the ethanol aqueous solution is 75% - 78%.

[0011] Further, calculated by weight, the specific dosages of the raw materials in S1 are as follows: Gasification slag 1 - 1.5 parts; Sodium hydroxide 2 - 4 parts; Water 20 - 30 parts; Hydrochloric acid 10 - 15 parts.

[0012] Further, calculated by weight, the specific dosages of the raw materials in S2 are as follows: 10 - 15 parts of the active material prepared from S1; 1 - 3 parts of mercapto - siloxane; 200 - 250 parts of aqueous ethanol solution.

[0013] Furthermore, calculated by weight parts, the specific dosages of each raw material in S3 are as follows: 100 - 120 parts of mercapto - modified gasification slag prepared from S2; 7 - 9 parts of vinyl phosphoric acid; 0.1 - 0.2 parts of azobisisobutyronitrile; 1500 - 2000 parts of acetonitrile.

[0014] Furthermore, calculated by weight parts, the specific dosages of each raw material in S4 are as follows: 10 - 15 parts of phosphoric acid - modified gasification slag prepared from S3; 3 - 5 parts of 1 - chloro - N,N,2 - trimethylpropeneamine; 200 - 300 parts of chloroform; 200 - 300 parts of dichloromethane; 10 - 20 parts of polyhexamethylene guanidine hydrochloride.

[0015] A further scheme of the present invention is as follows: A preparation method of an antibacterial and flame - retardant gasification - slag - based artificial board, the specific steps are as follows: Mix the antibacterial and flame - retardant modified gasification slag, recycled fiber and water - borne polyurethane glue, and under the conditions of 120 - 140 °C and 20 - 30 Mpa, hot - press for 1 - 3 h to obtain the antibacterial and flame - retardant gasification - slag - based artificial board. Beneficial effects

[0016] Compared with the prior art, the present invention has the following obvious advantages: In the present invention, vinyl phosphoric acid is grafted onto the surface of mercapto - silane - modified gasification slag through click reaction for flame - retardant treatment to obtain phosphoric acid - modified gasification slag. During combustion, the phosphoric acid - modified gasification slag can release phosphorus - containing free radicals, capture highly active free radicals such as HO· and H· generated during combustion, and quench the combustion chain reaction in the gas phase, thus achieving a flame - retardant effect and further endowing the artificial board made from it with good flame - retardant performance.

[0017] The present invention conducts acyl chlorination treatment on the phosphoric acid - modified gasification slag and then reacts it with polyhexamethylene guanidine hydrochloride to obtain the antibacterial and flame - retardant modified gasification slag. Polyhexamethylene guanidine hydrochloride carries strong positive charges, can combine with the negative charges on the surface of the bacterial cell membrane, cause the separation of membrane phospholipids, increase permeability, trigger the outflow of membrane lipids, and finally make the cell membrane lose its function and the bacteria die, achieving an antibacterial effect and further endowing the artificial board made from it with good antibacterial performance.

[0018] III. The present invention uses solid wastes such as gasification slag and waste textile fibers as the main raw materials for artificial boards, which can not only solve the problem of large quantities of solid wastes with wide distribution, but also achieve effective recycling of resources, meeting the concept of green environmental protection. Detailed implementation manners

[0019] The present invention will be introduced in detail below in conjunction with embodiments.

[0020] Example 1: Preparation of antibacterial and flame-retardant modified gasification slag After mixing 1 kg of gasification slag with a particle size of 200 mesh and 2 kg of sodium hydroxide, reacting under a nitrogen atmosphere at 800 °C for 1 h, cooling and then adding it to 20 kg of water and stirring for 30 min, filtering and then adding the filter cake to 15 kg of hydrochloric acid with a mass fraction of 20%, stirring and reacting at 50 °C for 60 min, washing, filtering and drying to obtain an active material; Taking 1 kg of the above-mentioned active material and 200 g of mercaptopropyltrimethoxysilane and adding them to 20 kg of an ethanol aqueous solution with a mass fraction of 75%, adjusting the pH of the solution to 5 with hydrochloric acid, stirring and reacting at 70 °C for 1 h, washing, filtering and drying to obtain mercapto-modified gasification slag; Taking 1 kg of the above-mentioned mercapto-modified gasification slag, 90 g of vinyl phosphoric acid and 2 g of azobisisobutyronitrile, dispersing them in 16 kg of acetonitrile, introducing nitrogen protection, heating and refluxing for 2 h, washing, filtering and drying to obtain phosphoric acid-modified gasification slag; Taking 1 kg of the above-mentioned phosphoric acid-modified gasification slag and 500 g of 1-chloro-N,N,2-trimethylallylamine, dispersing them in 30 kg of chloroform, stirring at 50 °C for 30 min, filtering and then dispersing the filter cake in 30 kg of dichloromethane, adding 2 kg of polyhexamethylene guanidine hydrochloride, stirring and reacting at 5 °C for 18 h, washing, filtering and drying to obtain antibacterial and flame-retardant modified gasification slag.

[0021] Example 2: Preparation of antibacterial and flame-retardant gasification slag-based artificial board Taking 33 kg of the antibacterial and flame-retardant modified gasification slag prepared in Example 1 above, 12 kg of recycled polyester and 15 kg of aqueous polyurethane glue with a solid content of 50%, mixing them and loading them into a mold, hot-pressing at 140 °C and 25 Mpa for 2 h to obtain an antibacterial and flame-retardant gasification slag-based artificial board.

[0022] Example 3: Preparation of antibacterial and flame-retardant gasification slag-based artificial board Taking 36 kg of the antibacterial and flame-retardant modified gasification slag prepared in Example 1 above, 12 kg of recycled hemp fiber and 12 kg of aqueous polyurethane glue with a solid content of 60%, mixing them and loading them into a mold, hot-pressing at 140 °C and 25 Mpa for 2 h to obtain an antibacterial and flame-retardant gasification slag-based artificial board.

[0023] Example 4: Preparation of antibacterial and flame-retardant gasification slag-based artificial board Take 39 kg of the antibacterial and flame-retardant modified gasification slag prepared in Example 1 above, 12 kg of recycled rock wool, and 9 kg of a water-based polyurethane glue with a solid content of 70%, mix them, load them into a mold, and hot press for 2 h at 140 °C and 25 Mpa to obtain an antibacterial and flame-retardant gasification slag-based artificial board.

[0024] Comparative Example 1 Mix 33 kg of gasification slag with a particle size of 200 mesh, 12 kg of recycled polyester, and 15 kg of a water-based polyurethane glue with a solid content of 50%, load them into a mold, and hot press for 2 h at 140 °C and 25 Mpa to obtain a gasification slag-based artificial board.

[0025] Carry out relevant performance tests on the artificial boards obtained in Examples 2 to 4 and Comparative Example 1 above, and compare their combustion performance, antibacterial performance, and bending strength. The results are shown in Table 1.

[0026] Among them, the combustion performance grade is tested according to the GB 8624-2006 standard, the antibacterial rate is tested according to the LY / T 1926-2020 standard, and the flexural strength is tested according to the GB / T 17657-2022 standard.

[0027] Table 1 Performance test data of the artificial boards obtained in Examples 2 to 4 and Comparative Example 1

[0028] Conclusion: The comparative example uses unmodified gasification slag, and Examples 2 to 4 use gasification slag after antibacterial and flame-retardant modification treatment. In Examples 2 to 4, the content of antibacterial and flame-retardant modified gasification slag gradually increases, and the content of polyurethane glue gradually decreases, and the rest of the process conditions remain unchanged. From the data in the above table, it can be seen that the antibacterial and flame-retardant gasification slag-based artificial board provided by the present invention has excellent flame retardant and antibacterial effects, the combustion grade is B1, the antibacterial rate exceeds 99%, meeting the requirements of Class I antibacterial. And the flexural strength of the artificial board exceeds 25 Mpa, meeting the use strength requirements of ordinary density boards.

[0029] The above embodiments are only used to illustrate the technical concept and characteristics of the present invention, and their purpose is to enable those who are familiar with this technology to understand the content of the present invention and implement it accordingly, and cannot be used to limit the protection scope of the present invention. All equivalent transformations or modifications made according to the spirit and essence of the present invention should be covered within the protection scope of the present invention.

Claims

1. An antibacterial and flame-retardant gasifiable slag-based artificial board, characterized in that: It is prepared from the following raw materials in parts by weight: 55-70 parts of antibacterial and flame-retardant modified gasified slag; 15-20 parts of recycled fiber; 15-25 parts of water-based polyurethane glue; The antibacterial and flame-retardant modified gasified slag is prepared by activating the gasified slag, modifying it with thiol, modifying it with phosphoric acid, treating it with chlorination, and finally reacting it with polyhexamethyleneguanidine hydrochloride.

2. The antibacterial and flame-retardant gasifiable slag-based artificial board according to claim 1, characterized in that: The recycled fiber is one or a mixture of two or more of recycled polyester, recycled hemp fiber or recycled rock wool; And / or, the solid content of the water-based polyurethane glue is 50% to 70%.

3. The antibacterial and flame-retardant gasifiable slag-based artificial board according to claim 1, characterized in that: The specific preparation steps of the antibacterial and flame-retardant modified gasified slag are as follows: S1: Mix the gasified slag and sodium hydroxide, react under a nitrogen atmosphere, add water after cooling and stir for the first time, filter, add hydrochloric acid to the filter cake, continue stirring for the second time, wash, filter and dry after the reaction to obtain an active material; S2: adding the active material and mercaptosiloxane to an ethanol aqueous solution, adjusting the pH with hydrochloric acid, stirring for the third time, and after the reaction is completed, washing, filtering, and drying to obtain mercapto-modified gasified slag; S3: dispersing the mercapto-modified gasified slag, vinyl phosphoric acid and azobisisobutyronitrile in acetonitrile, introducing nitrogen protection, heating under reflux reaction, and after the reaction is completed, washing, filtering and drying to obtain phosphoric acid-modified gasified slag; S4: Dispersing the phosphoric acid-modified gasified slag and 1-chloro-N,N,2-trimethylpropyleneamine in chloroform, stirring for the fourth time, filtering after the reaction is completed, and dispersing the filter cake in dichloromethane, adding polyhexamethyleneguanidine hydrochloride, stirring for the fifth time, washing, filtering, and drying after the reaction is completed to obtain antibacterial and flame-retardant modified gasified slag.

4. The antibacterial and flame-retardant gasifiable slag-based artificial board according to claim 3, characterized in that: In S1, the reaction temperature under nitrogen atmosphere is 600-900°C, the reaction time is 1-2h, the first stirring time is 30-60min, the second stirring temperature is 50-70°C, and the stirring time is 30-60min; and / or, in S2, adjusting the pH value to 4-5 with hydrochloric acid, the temperature of the third stirring is 60-70° C., and the stirring time is 1-3 h; And / or, in S3, the heating reflux reaction time is 2 to 4 hours; And / or, in S4, the temperature of the fourth stirring is 50-55° C., the stirring time is 20-30 min, and the temperature of the fifth stirring is 0-5° C., the stirring time is 18-24 h.

5. The antibacterial and flame-retardant gasifiable slag-based artificial board according to claim 3, characterized in that: In S1, the particle size of the gasified slag is 100-300 mesh, and the mass fraction of the hydrochloric acid is 20%-22%; And / or, in S2, the mercaptosiloxane is one or a mixture of mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane, and the mass fraction of the ethanol aqueous solution is 75% to 78%.

6. The antibacterial and flame-retardant gasifiable slag-based artificial board according to claim 3, characterized in that: Calculated by weight, the specific amount of each raw material in S1 is as follows: 1~1.5 parts of gasified slag; 2-4 parts of sodium hydroxide; 20-30 parts water; 10~15 parts of hydrochloric acid.

7. The antibacterial and flame-retardant gasifiable slag-based artificial board according to claim 3, characterized in that: Calculated by weight, the specific amount of each raw material in S2 is as follows: 10-15 parts of active material prepared from S1; 1-3 parts of mercaptosiloxane; 200~250 parts of ethanol aqueous solution.

8. The antibacterial and flame-retardant gasifiable slag-based artificial board according to claim 3, characterized in that: Calculated by weight, the specific amount of each raw material in S3 is as follows: S2: 100-120 parts of mercapto-modified gasified slag; 7-9 parts of vinyl phosphate; 0.1-0.2 parts of azobisisobutyronitrile; 1500~2000 parts of acetonitrile.

9. The antibacterial and flame-retardant gasifiable slag-based artificial board according to claim 3, characterized in that: Calculated by weight, the specific amount of each raw material in S4 is as follows: 10-15 parts of phosphoric acid modified gasified slag prepared in S3; 3-5 parts of 1-chloro-N,N,2-trimethylpropyleneamine; 200~300 parts of chloroform; 200-300 parts of dichloromethane; 10-20 parts of polyhexamethyleneguanidine hydrochloride.

10. A method for preparing the antibacterial and flame-retardant gasifiable slag-based artificial board according to any one of claims 1 to 9, characterized in that: The specific steps are as follows: the antibacterial and flame-retardant modified gasified slag, recycled fiber and water-based polyurethane glue are mixed, and hot-pressed for 1 to 3 hours at 120 to 140° C. and 20 to 30 MPa to obtain an antibacterial and flame-retardant gasified slag-based artificial board.

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