A flame-retardant activated carbon formaldehyde-free board and its preparation method

Abstract

The present invention relates to the technical field of formaldehyde-free boards, and discloses a flame-retardant activated carbon formaldehyde-free board and a preparation method thereof. The present invention prepares a flame-retardant activated carbon formaldehyde-free board by adding sodium sulfonate-modified boric acid, modified bentonite, activated carbon, wood powder, cerium oxide, and animal protein glue into a blender, stirring and mixing, and then laminating to obtain a plain board. The plain board is then cut and placed for curing, and then surface polished to obtain a flame-retardant activated carbon formaldehyde-free board. The phosphorus element, boron element, sodium sulfonate group, and bentonite in the sodium sulfonate-modified boric acid and modified bentonite all have flame-retardant effects and together constitute a flame-retardant system. The phosphorus element contained therein can generate phosphoric acid when heated, which can promote the dehydration of the material into carbon, thereby achieving a flame-retardant effect; under high temperature conditions, the boron element can release bound water, and this process absorbs a large amount of heat, slows down the combustion rate, and achieves a flame-retardant effect; the sodium sulfonate group can promote the release of carbon dioxide and water at high temperatures, thereby achieving a flame-retardant effect.

Description

Technical Field

[0001] The present invention relates to the technical field of formaldehyde-free boards, in particular to a flame-retardant activated carbon formaldehyde-free board and a preparation method thereof. Background Art

[0002] Activated carbon formaldehyde-free board is an environmentally friendly artificial board produced without the addition of formaldehyde-containing additives. With the rapid development of the construction industry, the use of these boards has increased significantly. However, fires can cause these boards to become unusable, making them difficult to use. Therefore, preventing this issue is crucial. For example, patent CN117106315A discloses an environmentally friendly artificial board and its preparation method. This invention incorporates a specific formaldehyde-removing and odor-removing additive, directly mixing it with wood and adhesive before laminating. While the resulting artificial board retains formaldehyde-removing properties, its flame retardancy remains unchanged. Summary of the Invention

[0003] (1) Technical problems solved

[0004] In view of the deficiencies in the prior art, the present invention provides a flame-retardant activated carbon formaldehyde-free board and a preparation method thereof, which has good flame-retardant effect.

[0005] (2) Technical solution

[0006] To achieve the above-mentioned purpose, the present invention provides the following technical solution: a flame-retardant activated carbon formaldehyde-free board, comprising the following components by weight: 2-6 parts by weight of sodium sulfonate-modified boric acid, 3-5 parts by weight of modified bentonite, 10-14 parts by weight of activated carbon, 60-120 parts by weight of wood powder, 1-2 parts by weight of cerium oxide, and 4-8 parts by weight of animal protein glue.

[0007] Preferably, the preparation method of the sodium sulfonate modified boric acid is:

[0008] (1) 4-10 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and xylene solvent were added to a stirrer, mechanically stirred, nitrogen was introduced for protection, and the temperature was raised to 75-90°C. After the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was completely dissolved, 8-15 parts by weight of chloroethanol was added thereto, and the reaction was continued for 5-7 hours. After the reaction was completed, the mixture was cooled to room temperature, the white solid product was removed, and the mixture was filtered under normal pressure and washed to obtain intermediate 1;

[0009] (2) Add 2,2-bis(bromomethyl)-1,3-propanediol and intermediate 1 to acetone solvent, stir evenly, then continue to add 3-6 mol / L sodium hydroxide aqueous solution, react at 65-80 ° C for 4-8 hours. After the reaction is completed, neutralize, concentrate, filter, wash and dry to obtain intermediate 2;

[0010] (3) Add 4-aminophenylboronic acid and intermediate 2 to N,N-dimethylformamide solvent, introduce nitrogen protection, stir evenly, react at 70-90°C for 4-7 hours, cool to room temperature, filter, wash and dry to obtain phosphorus-modified boronic acid;

[0011] (4) Dissolve the phosphorus-modified boronic acid and 1,3-propane sultone in acetone solvent, then add 3-5% by mass of sodium hydroxide solution dropwise, heat to 65-80°C and react for 6-12 hours. After the reaction, add dropwise vacuum concentration to remove the solvent, and recrystallize the crude product in ethanol to obtain sodium sulfonate-modified boronic acid.

[0012] Preferably, the mass ratio of 2,2-bis(bromomethyl)-1,3-propanediol to intermediate 1 in (2) is 1:1.4-1.6.

[0013] Preferably, the mass ratio of 4-aminophenylboronic acid to intermediate 2 in (3) is 0.8-1.2:1.

[0014] Preferably, the mass ratio of phosphorus-modified boronic acid to 1,3-propane sultone in (4) is 1:1.4-1.6.

[0015] Preferably, the preparation method of the modified bentonite is:

[0016] S1. 7-15 parts by weight of γ- glycidyloxypropyltrimethoxysilane-modified bentonite was added to a 2-4% sulfuric acid solution, stirred at 50-75 ° C for 16-20h, and after completion, filtered, washed and dried to obtain hydroxylated bentonite;

[0017] S2. Add hydroxylated bentonite and phosphorus-modified boric acid to N,N-dimethylformamide solvent, stir and dissolve, continue to add dichloroacetyl chloride and triethylamine catalyst, react at 75-90°C for 6-12 hours, and then distill under reduced pressure, wash, and dry to obtain modified bentonite.

[0018] Preferably, the weight ratio of hydroxylated bentonite, phosphorus-modified boric acid, dichloroacetyl chloride and triethylamine catalyst in S2 is 1.1-1.3:1:1.2-1.5:0.01-0.03.

[0019] Preferably, the preparation method of the flame-retardant activated carbon formaldehyde-free board is: sodium sulfonate-modified boric acid, modified bentonite, activated carbon, wood powder, cerium oxide, and animal protein glue are added to a blender, stirred and mixed, and then laminated at 80-160°C and a pressure of 1-5Mpa to obtain a plain board, and then the plain board is cut and placed for curing, and then surface polished to obtain a flame-retardant activated carbon formaldehyde-free board.

[0020] (3) Beneficial technical effects

[0021] The flame retardant activated carbon formaldehyde-free board is obtained by adding sodium sulfonate-modified boric acid, modified bentonite, activated carbon, wood powder, cerium oxide and animal protein glue into a blender, stirring and mixing, and then laminating to obtain a plain board. The plain board is then cut and placed for curing, and then surface polished to obtain a flame retardant activated carbon formaldehyde-free board.

[0022] The phosphorus, boron, sodium sulfonate groups, and bentonite in sodium sulfonate-modified boric acid and modified bentonite all have flame retardant properties, forming a flame retardant system. The phosphorus contained in the bentonite can be heated to produce phosphoric acid and metaphosphoric acid, highly dehydrating substances that promote the dehydration of the material into carbon, thus achieving a flame retardant effect. Under high temperature conditions, the boron element can release bound water, a process that absorbs a large amount of heat, helping to lower the material's temperature and slow the combustion rate, thus achieving a flame retardant effect. The sodium sulfonate group can promote the release of carbon dioxide and water at high temperatures, thereby achieving a flame retardant effect. Bentonite itself has good flame retardancy, and the reaction between 2,2-bis(bromomethyl)-1,3-propanediol and intermediate 1 increases the degree of substitution of the phosphorus element. The reaction between the hydroxylated bentonite and the phosphorus-modified boric acid increases the degree of substitution of the phosphorus and boron elements, further enhancing its flame retardant effect. DETAILED DESCRIPTION

[0023] γ-glycidyloxypropyltrimethoxysilane modified bentonite was prepared according to the literature "Adsorption Performance of Tetraethylenepentamine Grafted Bentonite on Acid Red GR" (Chemical Industry Progress, Vol. 40, No. 5, 2021):

[0024] Add 2 g of bentonite to 100 mL of 7% hydrochloric acid solution, heat under reflux at 80°C for acidification, filter, wash with deionized water, and dry to obtain acid-modified bentonite. Disperse 2 g of the acid-modified bentonite in 150 mL of ethanol, add 8 g of γ-glycidyloxypropyltrimethoxysilane, and stir under reflux at 90°C under nitrogen for 24 hours. Filter, wash, and dry to obtain γ-glycidyloxypropyltrimethoxysilane-modified bentonite.

[0025] Example 1

[0026] (1) 4 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and xylene solvent were added to a stirrer, mechanically stirred, nitrogen was introduced for protection, and the temperature was raised to 75°C. After the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was completely dissolved, 8 parts by weight of chloroethanol was added thereto, and the reaction was continued for 5 hours. After the reaction was completed, the mixture was cooled to room temperature, the white solid product was removed, and the mixture was filtered under normal pressure and washed to obtain intermediate 1;

[0027] (2) Add 2,2-bis(bromomethyl)-1,3-propylene glycol and intermediate 1 to acetone solvent, wherein the mass ratio of 2,2-bis(bromomethyl)-1,3-propylene glycol to intermediate 1 is 1:1.4, stir evenly, then continue to add 3 mol / L sodium hydroxide aqueous solution, react at 65°C for 4 hours, and after the reaction is completed, neutralize, concentrate, filter, wash and dry to obtain intermediate 2;

[0028] (3) Add 4-aminophenylboronic acid and intermediate 2 to N,N-dimethylformamide solvent, wherein the mass ratio of 4-aminophenylboronic acid to intermediate 2 is 0.8:1, introduce nitrogen protection, stir evenly, react at 70°C for 4 hours, cool to room temperature after completion, filter, wash and dry to obtain phosphorus-modified boronic acid;

[0029] (4) Dissolve the phosphorus-modified boronic acid and 1,3-propane sultone in acetone solvent, wherein the mass ratio of the phosphorus-modified boronic acid to 1,3-propane sultone is 1:1.4, then add a 3% sodium hydroxide solution dropwise, heat to 65°C and react for 6 hours, then add dropwise to remove the solvent by vacuum concentration, and recrystallize the crude product in ethanol to obtain sodium sulfonate-modified boronic acid;

[0030] (5) 7 parts by weight of γ-glycidyloxypropyltrimethoxysilane-modified bentonite was added to a 2% sulfuric acid solution, and the mixture was stirred at 50°C for 16 hours. After the reaction, the mixture was filtered, washed, and dried to obtain hydroxylated bentonite.

[0031] (6) Add hydroxylated bentonite and phosphorus-modified boric acid to N,N-dimethylformamide solvent, stir and dissolve, continue to add dichloroacetyl chloride and triethylamine catalyst, wherein the weight ratio of hydroxylated bentonite, phosphorus-modified boric acid, dichloroacetyl chloride, and triethylamine catalyst is 1.1:1:1.2:0.01, react at 75°C for 6h, and then distill under reduced pressure, wash, and dry to obtain modified bentonite;

[0032] (7) Add 2 parts by weight of sodium sulfonate modified boric acid, 3 parts by weight of modified bentonite, 10 parts by weight of activated carbon, 60 parts by weight of wood powder, 1 part by weight of cerium oxide, and 4 parts by weight of animal protein glue into a blender, stir and mix, and then laminate at 80°C and a pressure of 1 MPa to obtain a plain board. Then, cut the plain board into pieces and place it for curing, and then polish the surface to obtain a flame-retardant activated carbon formaldehyde-free board.

[0033] Example 2

[0034] (1) 10 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and xylene solvent were added to a stirrer, mechanically stirred, nitrogen was introduced for protection, and the temperature was raised to 90°C. After the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was completely dissolved, 15 parts by weight of chloroethanol was added thereto, and the reaction was continued for 7 hours. After the reaction was completed, the mixture was cooled to room temperature, the white solid product was removed, and the mixture was filtered under normal pressure and washed to obtain intermediate 1;

[0035] (2) Add 2,2-bis(bromomethyl)-1,3-propylene glycol and intermediate 1 to acetone solvent, wherein the mass ratio of 2,2-bis(bromomethyl)-1,3-propylene glycol to intermediate 1 is 1:1.6, stir evenly, then continue to add 6 mol / L sodium hydroxide aqueous solution, react at 80°C for 8 hours, after the reaction is completed, neutralize, concentrate, filter, wash and dry to obtain intermediate 2;

[0036] (3) Add 4-aminophenylboronic acid and intermediate 2 to N,N-dimethylformamide solvent, wherein the mass ratio of 4-aminophenylboronic acid to intermediate 2 is 1.2:1, introduce nitrogen protection, stir evenly, react at 90°C for 7 hours, cool to room temperature after completion, filter, wash and dry to obtain phosphorus-modified boronic acid;

[0037] (4) Phosphorus-modified boronic acid and 1,3-propane sultone were dissolved in acetone solvent, wherein the mass ratio of phosphorus-modified boronic acid to 1,3-propane sultone was 1:1.6, and then a 5% sodium hydroxide solution was added dropwise, and the temperature was raised to 80°C for 12 hours. After the reaction, the solvent was removed by dropwise concentration under reduced pressure, and the crude product was recrystallized in ethanol to obtain sodium sulfonate-modified boronic acid;

[0038] (5) 15 parts by weight of γ-glycidyloxypropyltrimethoxysilane-modified bentonite was added to a 4% sulfuric acid solution, and the mixture was stirred at 75°C for 20 hours. After the reaction, the mixture was filtered, washed, and dried to obtain hydroxylated bentonite.

[0039] (6) Add hydroxylated bentonite and phosphorus-modified boric acid to N,N-dimethylformamide solvent, stir and dissolve, continue to add dichloroacetyl chloride and triethylamine catalyst, wherein the weight ratio of hydroxylated bentonite, phosphorus-modified boric acid, dichloroacetyl chloride, and triethylamine catalyst is 1.3:1:1.5:0.03, react at 90°C for 12h, and then distill under reduced pressure, wash, and dry to obtain modified bentonite;

[0040] (7) 6 parts by weight of sodium sulfonate-modified boric acid, 5 parts by weight of modified bentonite, 14 parts by weight of activated carbon, 120 parts by weight of wood flour, 2 parts by weight of cerium oxide, and 8 parts by weight of animal protein glue were added into a blender and stirred to mix. The mixture was then laminated at 160°C and a pressure of 5 MPa to obtain a plain board. The plain board was then cut and cured, and then surface polished to obtain a flame-retardant activated carbon formaldehyde-free board.

[0041] Example 3

[0042] (1) 7 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and xylene solvent were added to a stirrer, mechanically stirred, nitrogen was introduced for protection, and the temperature was raised to 80°C. After the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was completely dissolved, 13 parts by weight of chloroethanol was added thereto, and the reaction was continued for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, the white solid product was removed, and the mixture was filtered under normal pressure and washed to obtain intermediate 1;

[0043] (2) Add 2,2-bis(bromomethyl)-1,3-propylene glycol and intermediate 1 to acetone solvent, wherein the mass ratio of 2,2-bis(bromomethyl)-1,3-propylene glycol to intermediate 1 is 1:1.5, stir evenly, then continue to add 4.5 mol / L sodium hydroxide aqueous solution, react at 72°C for 6 hours, and after the reaction is completed, neutralize, concentrate, filter, wash and dry to obtain intermediate 2;

[0044] (3) Add 4-aminophenylboronic acid and intermediate 2 to N,N-dimethylformamide solvent, wherein the mass ratio of 4-aminophenylboronic acid to intermediate 2 is 1.0:1, introduce nitrogen protection, stir evenly, react at 80°C for 5.5h, cool to room temperature after reaction, filter, wash and dry to obtain phosphorus-modified boronic acid;

[0045] (4) Phosphorus-modified boronic acid and 1,3-propane sultone were dissolved in acetone solvent, wherein the mass ratio of phosphorus-modified boronic acid to 1,3-propane sultone was 1:1.5, and then a 4% sodium hydroxide solution was added dropwise, and the temperature was raised to 70°C for reaction for 9 hours. After the reaction, the solvent was removed by dropwise concentration under reduced pressure, and the crude product was recrystallized in ethanol to obtain sodium sulfonate-modified boronic acid;

[0046] (5) 12 parts by weight of γ-glycidyloxypropyltrimethoxysilane-modified bentonite was added to a 3% sulfuric acid solution, and the mixture was stirred at 62°C for 18 hours. After the reaction, the mixture was filtered, washed, and dried to obtain hydroxylated bentonite.

[0047] (6) Add hydroxylated bentonite and phosphorus-modified boric acid to N,N-dimethylformamide solvent, stir and dissolve, continue to add dichloroacetyl chloride and triethylamine catalyst, wherein the weight ratio of hydroxylated bentonite, phosphorus-modified boric acid, dichloroacetyl chloride, and triethylamine catalyst is 1.2:1:1.35:0.02, react at 82°C for 9h, and then distill under reduced pressure, wash, and dry to obtain modified bentonite;

[0048] (7) 4 parts by weight of sodium sulfonate-modified boric acid, 4 parts by weight of modified bentonite, 12 parts by weight of activated carbon, 90 parts by weight of wood flour, 1.5 parts by weight of cerium oxide, and 6 parts by weight of animal protein glue were added into a blender and stirred to mix. The mixture was then laminated at 120°C and a pressure of 3 MPa to obtain a plain board. The plain board was then cut and cured, and then surface polished to obtain a flame-retardant activated carbon formaldehyde-free board.

[0049] Comparative Example 1

[0050] This comparative example is different from Example 3 in that sodium sulfonate is not added to modify the boric acid.

[0051] Comparative Example 2

[0052] This comparative example is different from Example 3 in that no modified bentonite is added.

[0053] Use an oxygen index meter to test the limiting oxygen index of water-based paint; use a horizontal and vertical combustion instrument to test the combustion level of water-based paint.

[0054] Table 1: Flame retardancy test.

[0055] project Limiting oxygen index (%) Combustion level Example 1 30 V-0 Example 2 33 V-0 Example 3 32 V-0 Comparative Example 1 22 V-1 Comparative Example 1 20 V-1

[0056] As can be seen from Table 1, Examples 1-3 have better flame retardant effects than Comparative Examples 1-2, indicating that the flame retardant activated carbon formaldehyde-free board prepared by the present invention has good flame retardant effect.

[0057] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to the specific embodiments described. Obviously, many modifications and variations are possible based on the content of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A flame retardant activated carbon formaldehyde-free board, characterized in that: The invention comprises the following components by weight: 2-6 parts by weight of sodium sulfonate modified boric acid, 3-5 parts by weight of modified bentonite, 10-14 parts by weight of activated carbon, 60-120 parts by weight of wood powder, 1-2 parts by weight of cerium oxide, and 4-8 parts by weight of animal protein glue; The preparation method of the sodium sulfonate modified boric acid is as follows: (1) 4-10 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and xylene solvent were added to a stirrer, mechanically stirred, nitrogen was introduced for protection, and the temperature was raised to 75-90°C. After the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was completely dissolved, 8-15 parts by weight of chloroethanol was added thereto, and the reaction was continued for 5-7 hours. After the reaction was completed, the mixture was cooled to room temperature, the white solid product was removed, and the mixture was filtered under normal pressure and washed to obtain intermediate 1; (2) Add 2,2-bis(bromomethyl)-1,3-propanediol and intermediate 1 to acetone solvent, stir evenly, then continue to add 3-6 mol / L sodium hydroxide aqueous solution, react at 65-80 ° C for 4-8 hours. After the reaction is completed, neutralize, concentrate, filter, wash and dry to obtain intermediate 2; (3) Add 4-aminophenylboronic acid and intermediate 2 to N,N-dimethylformamide solvent, introduce nitrogen protection, stir evenly, react at 70-90°C for 4-7 hours, cool to room temperature, filter, wash and dry to obtain phosphorus-modified boronic acid; (4) Dissolve the phosphorus-modified boronic acid and 1,3-propane sultone in acetone solvent, then add 3-5% by mass of sodium hydroxide solution dropwise, heat to 65-80°C and react for 6-12 hours. After the reaction, add dropwise vacuum concentration to remove the solvent, and recrystallize the crude product in ethanol to obtain sodium sulfonate-modified boronic acid.

2. The flame-retardant activated carbon formaldehyde-free board according to claim 1, characterized in that: The mass ratio of 2,2-bis(bromomethyl)-1,3-propanediol to intermediate 1 in (2) is 1:1.4-1.

6.

3. The flame-retardant activated carbon formaldehyde-free board according to claim 1, characterized in that: The mass ratio of 4-aminophenylboronic acid to intermediate 2 in (3) is 0.8-1.2:

1.

4. The flame-retardant activated carbon formaldehyde-free board according to claim 1, characterized in that: The mass ratio of phosphorus-modified boronic acid to 1,3-propane sultone in (4) is 1:1.4-1.

6.

5. The flame-retardant activated carbon formaldehyde-free board according to claim 1, characterized in that: The preparation method of the modified bentonite is: S1. 7-15 parts by weight of γ- glycidyloxypropyltrimethoxysilane-modified bentonite was added to a 2-4% sulfuric acid solution, stirred at 50-75 ° C for 16-20h, and after completion, filtered, washed and dried to obtain hydroxylated bentonite; S2. Add hydroxylated bentonite and phosphorus-modified boric acid to N,N-dimethylformamide solvent, stir and dissolve, continue to add dichloroacetyl chloride and triethylamine catalyst, react at 75-90°C for 6-12 hours, and then distill under reduced pressure, wash, and dry to obtain modified bentonite.

6. The flame-retardant activated carbon formaldehyde-free board according to claim 5, characterized in that: The weight ratio of hydroxylated bentonite, phosphorus-modified boric acid, dichloroacetyl chloride and triethylamine catalyst in S2 is 1.1-1.3:1:1.2-1.5:0.01-0.

03.

7. A method for preparing a flame-retardant activated carbon formaldehyde-free board according to any one of claims 1 to 6, characterized in that: The preparation method of the flame-retardant activated carbon formaldehyde-free board comprises the following steps: adding sodium sulfonate-modified boric acid, modified bentonite, activated carbon, wood powder, cerium oxide, and animal protein glue into a blender, stirring and mixing, and then laminating at 80-160° C. and a pressure of 1-5 MPa to obtain a plain board; then cutting the plain board, curing and placing it, and then polishing the surface to obtain the flame-retardant activated carbon formaldehyde-free board.