Flame-retardant buckle applied to lion head and preparation method of flame-retardant buckle

Abstract

The invention relates to the technical field of materials, and discloses a flame-retardant buckle applied to a lion head and a preparation method of the flame-retardant buckle applied to the lion head. Polycarbonate, quaternary ammonium salt modified sodium sulfonate chitosan and an antioxidant 1076 are blended in a torque rheometer; and performing hot pressing on the material in a press vulcanizer to obtain the flame-retardant buckle applied to the lion head. Silicon elements, phosphorus elements and nitrogen elements contained in quaternary ammonium salt modified sodium sulfonate chitosan have good flame-retardant effects, quaternary ammonium salt groups and chitosan in the quaternary ammonium salt modified sodium sulfonate chitosan have good antibacterial effects, and the flame-retardant and antibacterial effects of the quaternary ammonium salt modified sodium sulfonate chitosan are improved when the quaternary ammonium salt modified sodium sulfonate chitosan is applied to buckles of lion heads.

Description

Technical Field

[0001] The invention relates to the field of material technology, and in particular to a flame retardant buckle applied to a lion head and a preparation method thereof. Background Art

[0002] The lion head buckle is a buckle with the shape of a lion's head. It is generally used as a decorative buckle on clothing. It is made of plastic, resin and other materials. It plays the role of embellishing and fixing clothes, and can also show personality and fashion sense. However, it will be flammable when it encounters flames and is eroded by bacteria during use, which makes its quality poor and will cause it to be unable to be used normally. Therefore, how to avoid this phenomenon is the key to solving the problem. For example, patent CN109265960A discloses a halogen-free flame retardant polycarbonate and its preparation method. The mechanical properties, halogen-free flame retardancy and impact resistance of the halogen-free flame retardant polycarbonate are good, but its antibacterial properties are not improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides a flame retardant buckle for lion heads and a preparation method thereof, which has good flame retardant and antibacterial effects.

[0005] (II) Technical solution

[0006] To achieve the above objectives, the present invention provides the following technical solutions: A flame retardant buckle applied to a lion head, comprising the following components by weight: 80-95 parts by weight of polycarbonate, 0.4-0.6 parts by weight of quaternary ammonium salt modified sodium sulfonate chitosan, and 0.01-0.02 parts by weight of antioxidant 1076.

[0007] Preferably, the preparation method of the quaternary ammonium salt modified phosphorus-containing chitosan is:

[0008] (1) adding 4-(2-methylpropenyl)carbonyloxyphenylboronic acid and hexachlorocyclotriphosphazene to an acetone solvent, stirring and dissolving, introducing nitrogen protection, reacting at 70-85° C. for 2-4 hours, and after the reaction is completed, rotary evaporation is performed to obtain boron-modified hexachlorocyclotriphosphazene;

[0009] (2) adding boron-modified hexachlorocyclotriphosphazene and hexamethyldisilazane to an ethanol solvent, stirring and dispersing, and continuously adding chloroplatinic acid catalyst thereto, reacting at 65-82° C. for 4-5 hours, and then distilling, washing and drying to obtain a tertiary amino phosphorus-containing silane;

[0010] (3) dissolving the double-terminal epoxy silicone oil in a reaction kettle filled with isopropanol solvent, adding tertiary amino phosphorus-containing silane thereto, stirring and reacting at 60-70° C. for 6-8 hours, concentrating the solution after the reaction, washing, and obtaining quaternary ammonium salt-modified phosphorus-containing silane;

[0011] (4) adding quaternary ammonium salt-modified phosphorus-containing silane, adipoyl chloride, and hydroxypropanesulfonic acid-modified chitosan to N,N-dimethylformamide solvent, stirring to dissolve, then adding pyridine catalyst, reacting at 76-83° C., and then distilling under reduced pressure and washing to obtain quaternary ammonium salt-modified sodium sulfonate chitosan.

[0012] In the above reaction process, the boric acid group in 4-(2-methylpropylene)carbonyloxyphenylboronic acid reacts with the chlorine in hexachlorocyclotriphosphazene to introduce an olefin group, thereby obtaining boron-modified hexachlorocyclotriphosphazene; the addition reaction is continued with the silicon-hydrogen bond in hexamethyldisilazane (amine) to introduce a tertiary amine group, thereby obtaining a tertiary amine phosphorus-containing silane, and then the ring-opening reaction is carried out with the epoxy group in the double-terminal epoxy silicone oil to generate a quaternary ammonium salt group, and a hydroxyl group is introduced at the same time, thereby obtaining a quaternary ammonium salt-modified phosphorus-containing silane; the hydroxyl group in the quaternary ammonium salt-modified phosphorus-containing silane, the hydroxyl group in the hydroxypropanesulfonic acid-modified chitosan and the acyl chloride group in the adipoyl chloride are subjected to an esterification reaction, thereby obtaining a quaternary ammonium salt-modified sodium sulfonate chitosan.

[0013] Preferably, the mass ratio of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid to hexachlorocyclotriphosphazene in (1) is 3.1-3.4 g:1-1.1 g.

[0014] Preferably, the mass ratio of the boron-modified hexachlorocyclotriphosphazene, hexamethyldisilazane, and chloroplatinic acid catalyst in (2) is 2.6-2.8 g: 2.36-2.44 g: 0.01-0.02 g.

[0015] Preferably, the mass ratio of the double-terminal epoxy silicone oil to the tertiary amino phosphorus-containing silane in (3) is 1.36-1.84 g:2.3-2.7 g.

[0016] Preferably, the mass ratio of the quaternary ammonium salt-modified phosphorus-containing silane, adipoyl chloride, hydroxypropanesulfonic acid-modified chitosan, and pyridine catalyst in (4) is 1.7-1.82 g: 1.31-1.42 g: 1.64-1.9 g: 0.02-0.023 g.

[0017] Preferably, the reaction time in (4) is 4-6 hours.

[0018] Preferably, the preparation method of the flame-retardant buckle applied to the lion head comprises the following steps: polycarbonate, quaternary ammonium salt modified sodium sulfonate chitosan, and antioxidant 1076 are first blended in a torque rheometer at 200-220°C for 10-15 minutes; then the materials are hot-pressed in a flat vulcanizer at 200-210°C under a pressure of 11-12MPa for 2-3 minutes to obtain the flame-retardant buckle applied to the lion head.

[0019] (III) Beneficial technical effects

[0020] The invention prepares a flame retardant buckle for lion head by first blending polycarbonate, quaternary ammonium salt modified sodium sulfonate chitosan and antioxidant 1076 in a torque rheometer and then hot pressing the materials in a flat vulcanizer.

[0021] The silicon, phosphorus and nitrogen elements contained in the quaternary ammonium salt modified sodium sulfonate chitosan have good flame retardant effect. The quaternary ammonium salt group and chitosan have good antibacterial effect, and the sodium sulfonate group contained therein has good compatibility with polycarbonate. When burning, the sulfonate group can catalyze the cross-linking of polycarbonate into carbon, which has a good flame retardant effect. When the silicon element is heated, it can produce a glass-like substance on the surface of the material, isolating the material transport and energy transfer, and achieving the purpose of flame retardancy; when burning, the phosphorus element can generate polyphosphoric acid and metaphosphoric acid with strong dehydration. Since polyphosphoric acid and metaphosphoric acid are not easy to volatilize, they can form a dense protective layer on the surface of the coating, thereby achieving a flame retardant effect; when heated, the nitrogen element can produce a flame-retardant gas, which can not only dilute the concentration of the flammable gas, but also take away some heat, further limiting the combustion of the substance. In addition, quaternary ammonium salt-modified sodium sulfonate chitosan uses boron-modified hexachlorocyclotriphosphazene as a matrix and introduces quaternary ammonium salt, silicon element, phosphorus element, and nitrogen element, all of which increase its degree of substitution and make its antibacterial and flame retardant effects better. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is the flame retardant clip limiting oxygen index test. DETAILED DESCRIPTION

[0023] Add 12.8 g of octamethylcyclotetrasiloxane and 1 g of 1,3-diglycidyloxypropyl-1,1,3,3-tetramethyldisiloxane to the reactor, introduce nitrogen protection, and then continue to add 11 mg of tetramethylammonium hydroxide catalyst, heat to 110°C and react for 4 hours, then heat to 140°C and react for 1 hour. After the reaction, cool and discharge the material to obtain double-terminal epoxy silicone oil.

[0024] The preparation method of DOPO-based chitosan is as follows: add 6.09g of vanillin and 40ml of anhydrous ethanol to a three-necked flask connected with a reflux tube and mechanical stirring, stir at room temperature until the vanillin is dissolved, then add 5g of chitosan, heat to 80°C for reaction for 12h, filter while hot after the reaction, and wash with industrial alcohol for several times to remove excess vanillin to obtain yellow powder; second step, add 8.33g of DOPO and 40ml of anhydrous ethanol to a three-necked flask connected with a reflux tube and mechanical stirring, wait for DOPO to be stirred and dissolved, add the yellow powder obtained in the first step, heat to 80°C, continue to react for 12h, cool after the reaction, filter, and wash the filtered product with anhydrous ethanol for several times to remove excess DOPO. Then put it in a 65°C vacuum oven for 24h to dry, and obtain DOPO-based chitosan.

[0025] The preparation method of hydroxypropanesulfonic acid modified chitosan is as follows: add 4.5g of DOPO-based chitosan and 7.3g of sodium 3-chloro-2-hydroxypropanesulfonate to 25ml of N,N-dimethylformamide solvent, stir and disperse, react at 75°C for 6h, and then perform reduced pressure distillation and filtration to obtain hydroxypropanesulfonic acid modified chitosan.

[0026] Example 1

[0027] (1) 3.1 g of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid and 1 g of hexachlorocyclotriphosphazene were added to 30 mL of acetone solvent, stirred to dissolve, nitrogen was introduced for protection, and the mixture was reacted at 70° C. for 2 h. After the reaction was completed, rotary evaporation was performed to obtain boron-modified hexachlorocyclotriphosphazene;

[0028] (2) Add 2.6 g of boron-modified hexachlorocyclotriphosphazene and 2.36 g of hexamethyldisilazane to 25 mL of ethanol solvent, stir and disperse, continue to add 0.01 g of chloroplatinic acid catalyst, react at 65° C. for 4 h, distill after completion, wash and dry to obtain tertiary amino phosphorus silane;

[0029] (3) 1.36 g of double-terminal epoxy silicone oil was dissolved in a reaction kettle containing 20 mL of isopropanol solvent, and 2.3 g of tertiary amino phosphorus-containing silane was added thereto, and the mixture was stirred at 60° C. for 6 h. After the reaction, the solution was concentrated and washed to obtain quaternary ammonium salt-modified phosphorus-containing silane;

[0030] (4) Add 1.7 g of quaternary ammonium salt-modified phosphorus-containing silane, 1.31 g of adipoyl chloride, and 1.64 g of hydroxypropanesulfonic acid-modified chitosan to 24 mL of N,N-dimethylformamide solvent, stir to dissolve, then add 0.02 g of pyridine catalyst, react at 76 ° C for 4 h, and then perform reduced pressure distillation and washing to obtain quaternary ammonium salt-modified sodium sulfonate chitosan;

[0031] (5) 80 parts by weight of polycarbonate, 0.4 parts by weight of quaternary ammonium salt-modified sodium sulfonate chitosan, and 0.01 parts by weight of antioxidant 1076 were first blended in a torque rheometer at 200°C for 10 minutes; then the materials were hot-pressed in a flat vulcanizer at 200°C for 2 minutes at a pressure of 11 MPa to obtain a flame-retardant buckle for use in a lion head.

[0032] Example 2

[0033] (1) 3.4 g of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid and 1.1 g of hexachlorocyclotriphosphazene were added to 40 mL of acetone solvent, stirred to dissolve, nitrogen was introduced for protection, and the mixture was reacted at 85° C. for 4 h. After the reaction was completed, rotary evaporation was performed to obtain boron-modified hexachlorocyclotriphosphazene;

[0034] (2) Add 2.8 g of boron-modified hexachlorocyclotriphosphazene and 2.44 g of hexamethyldisilazane to 50 mL of ethanol solvent, stir and disperse, continue to add 0.02 g of chloroplatinic acid catalyst, react at 82° C. for 5 h, distill after completion, wash and dry to obtain tertiary amino phosphorus silane;

[0035] (3) 1.84 g of double-terminal epoxy silicone oil was dissolved in a reaction kettle containing 35 mL of isopropanol solvent, and 2.7 g of tertiary amino phosphorus-containing silane was added thereto, and the mixture was stirred at 70° C. for 8 h. After the reaction, the solution was concentrated and washed to obtain quaternary ammonium salt-modified phosphorus-containing silane;

[0036] (4) Add 1.82 g of quaternary ammonium salt-modified phosphorus-containing silane, 1.42 g of adipoyl chloride, and 1.9 g of hydroxypropanesulfonic acid-modified chitosan to 40 mL of N,N-dimethylformamide solvent, stir to dissolve, then add 0.023 g of pyridine catalyst, react at 83 ° C for 6 h, and then perform reduced pressure distillation and washing to obtain quaternary ammonium salt-modified sodium sulfonate chitosan;

[0037] (5) 95 parts by weight of polycarbonate, 0.6 parts by weight of quaternary ammonium salt-modified sodium sulfonate chitosan, and 0.02 parts by weight of antioxidant 1076 were first blended in a torque rheometer at 220° C. for 15 min; then the materials were hot-pressed in a flat vulcanizer at 210° C. for 3 min at a pressure of 12 MPa to obtain a flame-retardant buckle for use in a lion head.

[0038] Example 3

[0039] (1) 3.2 g of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid and 1.1 g of hexachlorocyclotriphosphazene were added to 35 mL of acetone solvent, stirred to dissolve, nitrogen was introduced for protection, and the mixture was reacted at 72° C. for 3 h. After the reaction was completed, rotary evaporation was performed to obtain boron-modified hexachlorocyclotriphosphazene;

[0040] (2) Add 2.7 g of boron-modified hexachlorocyclotriphosphazene and 2.42 g of hexamethyldisilazane to 40 mL of ethanol solvent, stir and disperse, continue to add 0.01 g of chloroplatinic acid catalyst, react at 70° C. for 5 h, distill after completion, wash and dry to obtain tertiary amino phosphorus silane;

[0041] (3) 1.57 g of double-terminal epoxy silicone oil was dissolved in a reaction kettle containing 30 mL of isopropanol solvent, and 2.5 g of tertiary amino phosphorus-containing silane was added thereto. The mixture was stirred at 65° C. for 7 h. After the reaction, the solution was concentrated and washed to obtain quaternary ammonium salt-modified phosphorus-containing silane;

[0042] (4) Add 1.81 g of quaternary ammonium salt-modified phosphorus-containing silane, 1.36 g of adipoyl chloride, and 1.7 g of hydroxypropanesulfonic acid-modified chitosan to 30 mL of N,N-dimethylformamide solvent, stir to dissolve, then add 0.023 g of pyridine catalyst, react at 80° C. for 5 h, and then perform vacuum distillation and washing to obtain quaternary ammonium salt-modified sodium sulfonate chitosan;

[0043] (5) 85 parts by weight of polycarbonate, 0.5 parts by weight of quaternary ammonium salt-modified sodium sulfonate chitosan, and 0.01 parts by weight of antioxidant 1076 were first blended in a torque rheometer at 210° C. for 12 min; then the materials were hot-pressed in a flat vulcanizer at 205° C. for 3 min at a pressure of 12 MPa to obtain a flame-retardant buckle for use in a lion head.

[0044] Example 4

[0045] (1) 3.1 g of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid and 1 g of hexachlorocyclotriphosphazene were added to 30 mL of acetone solvent, stirred to dissolve, nitrogen was introduced for protection, and the mixture was reacted at 70° C. for 2 h. After the reaction was completed, rotary evaporation was performed to obtain boron-modified hexachlorocyclotriphosphazene;

[0046] (2) Add 2.6 g of boron-modified hexachlorocyclotriphosphazene and 2.36 g of hexamethyldisilazane to 25 mL of ethanol solvent, stir and disperse, continue to add 0.01 g of chloroplatinic acid catalyst, react at 65° C. for 4 h, distill after completion, wash and dry to obtain tertiary amino phosphorus silane;

[0047] (3) 1.84 g of double-terminal epoxy silicone oil was dissolved in a reaction kettle containing 35 mL of isopropanol solvent, and 2.7 g of tertiary amino phosphorus-containing silane was added thereto, and the mixture was stirred at 70° C. for 8 h. After the reaction, the solution was concentrated and washed to obtain quaternary ammonium salt-modified phosphorus-containing silane;

[0048] (4) Add 1.82 g of quaternary ammonium salt-modified phosphorus-containing silane, 1.42 g of adipoyl chloride, and 1.9 g of hydroxypropanesulfonic acid-modified chitosan to 40 mL of N,N-dimethylformamide solvent, stir to dissolve, then add 0.023 g of pyridine catalyst, react at 83 ° C for 6 h, and then perform reduced pressure distillation and washing to obtain quaternary ammonium salt-modified sodium sulfonate chitosan;

[0049] (5) 85 parts by weight of polycarbonate, 0.5 parts by weight of quaternary ammonium salt-modified sodium sulfonate chitosan, and 0.01 parts by weight of antioxidant 1076 were first blended in a torque rheometer at 210° C. for 12 min; then the materials were hot-pressed in a flat vulcanizer at 205° C. for 3 min at a pressure of 12 MPa to obtain a flame-retardant buckle for use in a lion head.

[0050] Comparative Example 1

[0051] Compared with Example 4, this comparative example uses chitosan instead of quaternary ammonium salt to modify the phosphorus-containing chitosan.

[0052] Comparative Example 2

[0053] Compared with Example 4, this comparative example uses quaternary ammonium salt-modified phosphorus-containing silane instead of quaternary ammonium salt-modified phosphorus-containing chitosan.

[0054] Depend on Figure 1 It can be seen that Examples 1-4 of the present invention have better flame retardant effects than Comparative Examples 1-2.

[0055] A Staphylococcus aureus liquid with a concentration of 2×108 CFU / mL was added to a sterilized culture dish as a test strain, and then a solid agar medium was added and dissolved, cooled to 45°C, and then poured into a culture dish, 20 mL was poured into each plate with an inner diameter of 10 cm, and then the buckles of the embodiments of the present invention and the comparative example (with a diameter of 3 cm and a thickness of 1 mm) were placed on the culture plate, and cultured in a constant temperature incubator for 12 hours at a temperature of 37°C. After culture, the diameter of the inhibition zone was measured. The test results are shown in Table 1.

[0056] Table 1: Antimicrobial testing.

[0057]

[0058]

[0059] It can be seen from Table 1 that Examples 1-4 of the present invention have better antibacterial effects than Comparative Examples 1-2.

[0060] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A flame retardant buckle used for a lion head, characterized in that: The invention comprises the following components by weight: 80-95 parts by weight of polycarbonate, 0.4-0.6 parts by weight of quaternary ammonium salt modified sodium sulfonate chitosan, and 0.01-0.02 parts by weight of antioxidant 1076.

2. The flame retardant buckle applied to the lion head according to claim 1 is characterized in that: The preparation method of the quaternary ammonium salt modified sodium sulfonate chitosan is: (1) adding 4-(2-methylpropenyl)carbonyloxyphenylboronic acid and hexachlorocyclotriphosphazene to an acetone solvent, stirring and dissolving, introducing nitrogen protection, reacting at 70-85° C. for 2-4 hours, and after the reaction is completed, rotary evaporation is performed to obtain boron-modified hexachlorocyclotriphosphazene; (2) adding boron-modified hexachlorocyclotriphosphazene and hexamethyldisilazane to an ethanol solvent, stirring and dispersing, and continuously adding chloroplatinic acid catalyst thereto, reacting at 65-82° C. for 4-5 hours, and then distilling, washing and drying to obtain a tertiary amino phosphorus-containing silane; (3) dissolving the double-terminal epoxy silicone oil in a reaction kettle filled with isopropanol solvent, adding tertiary amino phosphorus-containing silane thereto, stirring and reacting at 60-70° C. for 6-8 hours, concentrating the solution after the reaction, washing, and obtaining quaternary ammonium salt-modified phosphorus-containing silane; (4) adding quaternary ammonium salt-modified phosphorus-containing silane, adipoyl chloride, and hydroxypropanesulfonic acid-modified chitosan to N,N-dimethylformamide solvent, stirring to dissolve, then adding pyridine catalyst, reacting at 76-83° C., and then distilling under reduced pressure and washing to obtain quaternary ammonium salt-modified sodium sulfonate chitosan.

3. The flame retardant buckle applied to the lion head according to claim 2 is characterized in that: The mass ratio of 4-(2-methylpropenyl)carbonyloxyphenylboronic acid to hexachlorocyclotriphosphazene in (1) is 3.1-3.4 g:1-1.1 g.

4. The flame retardant buckle applied to the lion head according to claim 2 is characterized in that: The mass ratio of the boron-modified hexachlorocyclotriphosphazene, hexamethyldisilazane, and chloroplatinic acid catalyst in (2) is 2.6-2.8g:2.36-2.44g:0.01-0.02g.

5. The flame retardant buckle applied to the lion head according to claim 2 is characterized in that: The mass ratio of the double-terminal epoxy silicone oil to the tertiary amino phosphorus-containing silane in (3) is 1.36-1.84g:2.3-2.7g.

6. The flame retardant buckle applied to the lion head according to claim 2, characterized in that: The mass ratio of the quaternary ammonium salt modified phosphorus-containing silane, adipoyl chloride, hydroxypropanesulfonic acid modified chitosan, and pyridine catalyst in (4) is 1.7-1.82 g: 1.31-1.42 g: 1.64-1.9 g: 0.02-0.023 g.

7. The flame retardant buckle applied to the lion head according to claim 2, characterized in that: The reaction time in (4) is 4-6 hours.

8. A method for preparing a flame retardant buckle for a lion head as claimed in any one of claims 1 to 7, characterized in that: The preparation method of the flame-retardant buckle applied to the lion head comprises the following steps: polycarbonate, quaternary ammonium salt modified sodium sulfonate chitosan, and antioxidant 1076 are first blended in a torque rheometer at 200-220° C. for 10-15 minutes; and then the materials are hot-pressed in a flat vulcanizer at 200-210° C. for 2-3 minutes at a pressure of 11-12 MPa to obtain the flame-retardant buckle applied to the lion head.

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