Flame-retardant polycarbonate material and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and discloses a flame-retardant polycarbonate material and a preparation method thereof.The flame-retardant polycarbonate material is prepared by adding polycarbonate, sodium sulfonate modified tris (2-acryloyloxyethyl) isocyanurate, sulfur-containing modified bisphenol fluorene and an antioxidant 1068 into a double-screw extruder, extruding and granulating, then putting granules into a press vulcanizer, and carrying out extrusion molding on the granules to obtain the flame-retardant polycarbonate material. And carrying out compression molding to obtain the flame-retardant polycarbonate material. A sulfur element, a phosphorus element, a carbon nano tube structure and a triazine group contained in the sodium sulfonate modified tri (2-acryloyloxyethyl) isocyanurate and the sulfur-containing modified bisphenol fluorene all have better flame-retardant effects and jointly form a flame-retardant system; and the sulfonate group can catalyze isomerization crosslinking carbon formation of polycarbonate, so that the polycarbonate material has higher carbon formation property, and a better flame retardant effect is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to a flame retardant polycarbonate material and a preparation method thereof. Background Art

[0002] Polycarbonate is a biodegradable polymer with the characteristics of high strength, high toughness, high heat resistance, shock resistance, good processing performance, non-toxicity, weather resistance, electrical insulation, etc. It is a thermoplastic engineering plastic with extremely excellent comprehensive performance. Although it has certain flame retardancy, the flame retardant effect is limited, which greatly limits its application. For example, patent CN114790326B discloses a reinforced polycarbonate material and its preparation method and application. The reinforced polycarbonate material of the invention has good toughness and still maintains high strength after multiple bending, but its flame retardant effect is not improved. Summary of the invention

[0003] 1. Technical issues to be resolved In view of the deficiencies of the prior art, the present invention provides a flame retardant polycarbonate material and a preparation method thereof, which has good flame retardant effect.

[0004] (II) Technical solution To achieve the above objectives, the present invention provides the following technical solution: a flame retardant polycarbonate material, comprising the following components by weight: 50-80 parts by weight of polycarbonate, 3-5 parts by weight of sodium sulfonate modified tris(2-acryloyloxyethyl) isocyanurate, 4-6 parts by weight of sulfur-containing modified bisphenol fluorene, and 0.6-0.8 parts by weight of antioxidant 1068.

[0005] Preferably, the preparation method of the sodium sulfonate modified tris(2-acryloyloxyethyl) isocyanurate is: (1) Add tri(2-acryloyloxyethyl)isocyanurate to N,N-dimethylformamide solvent, stir and disperse, then add mercaptoethylamine and benzoin dimethyl ether photoinitiator, irradiate with 365nm ultraviolet light at 25-45°C for 3-6h, centrifuge, wash and dry to obtain intermediate 1; (2) The intermediate 1 and 1,3-propane sultone are dissolved in 1,4-dioxane solvent, and then a sodium hydroxide solution with a mass fraction of 3-5% is added dropwise, and the temperature is raised to 75-90°C for reaction for 6-14 hours. After the reaction, the solvent is removed by vacuum concentration, and the crude product is recrystallized in ethanol to obtain sodium sulfonate modified tri(2-acryloyloxyethyl) isocyanurate.

[0006] Preferably, in step (1), the mass ratio of tri(2-acryloyloxyethyl)isocyanurate, mercaptoethylamine, and benzoin dimethyl ether photoinitiator is 1:2.1-3.4:0.01-0.02.

[0007] Preferably, in step (2), the mass ratio of the intermediate 1 to 1,3-propane sultone is 1.2-1.4:1.

[0008] Preferably, the preparation method of the sulfur-containing modified bisphenol fluorene is: S1. Under a nitrogen atmosphere, 5-10 parts by weight of bisphenol fluorene and 0.02-0.07 parts by weight of triethylamine are added to a dichloromethane solvent, stirred at 8-12 ° C until fully dissolved, and then 4-9 parts by weight of phenylphosphoryl dichloride are added thereto, and the reaction is continued to be stirred for 10-14h, and then dried to obtain an intermediate 2; S2. Add itaconic acid to N,N-dimethylformamide solvent, stir evenly, continue to add intermediate 2 and p-toluenesulfonic acid catalyst, react at 70-85°C for 6-10h, and then distill under reduced pressure, wash and dry to obtain bisphenol fluorene-modified itaconic acid; S3. Add sodium dodecyl sulfate emulsifier and vinyl carbon nanotubes into deionized water, disperse them evenly, add bisphenol fluorene-modified itaconic acid and 1,3,5-triacryloylhexahydro-1,3,5-triazine, introduce nitrogen protection, and then continue to add azobisisobutyronitrile initiator, react at 80-110°C for 3-5h, wash with deionized water and ethanol in turn, and dry to obtain sulfur-modified bisphenol fluorene.

[0009] Preferably, the mass ratio of itaconic acid, intermediate 2, and p-toluenesulfonic acid catalyst in S2 is 1:1.2-1.5:0.02-0.04.

[0010] Preferably, the mass ratio of sodium dodecyl sulfate emulsifier, vinyl carbon nanotubes, bisphenol fluorene-modified itaconic acid, 1,3,5-triacryloylhexahydro-1,3,5-triazine, and azobisisobutyronitrile initiator in S3 is 0.02-0.03:0.9-1.1:1:0.4-0.8:0.01-0.03.

[0011] Preferably, the preparation method of the flame-retardant polycarbonate material is: adding polycarbonate, sodium sulfonate-modified tri(2-acryloyloxyethyl) isocyanurate, sulfur-modified bisphenol fluorene, and antioxidant 1068 into a twin-screw extruder, extruding and granulating at 170-180°C, and then molding the pellets in a flat vulcanizer at a pressure of 10-12MPa and 175-180°C to obtain a flame-retardant polycarbonate material.

[0012] 3. Beneficial technical effects The invention provides a flame retardant polycarbonate material by adding polycarbonate, sodium sulfonate modified tris(2-acryloyloxyethyl) isocyanurate, sulfur-containing modified bisphenol fluorene and antioxidant 1068 into a twin-screw extruder, extruding and granulating the granules, and then molding the granules in a flat vulcanizer.

[0013] The alkenyl group in tris(2-acryloyloxyethyl)isocyanurate and the mercapto group in mercaptoethylamine are subjected to addition reaction to introduce an amine group to obtain intermediate 1, and the amine group in intermediate 1 is reacted with 1,3-propane sultone to obtain sodium sulfonate-modified tris(2-acryloyloxyethyl)isocyanurate; the phenolic hydroxyl group in bisphenol fluorene is reacted with chlorine in phenylphosphoryl dichloride to obtain intermediate 2, itaconic acid is reacted with the phenolic hydroxyl group of intermediate 2 to introduce an alkenyl group to obtain bisphenol fluorene-modified itaconic acid, and vinyl carbon nanotubes, bisphenol fluorene-modified itaconic acid, and 1,3,5-triacryloylhexahydro-1,3,5-triazine are subjected to polymerization reaction to obtain sulfur-containing modified bisphenol fluorene, and at the same time, the substitution degree of carbon nanotubes is increased to make the flame retardant effect better.

[0014] The sulfur element, phosphorus element, carbon nanotube structure and triazine group contained in sodium sulfonate modified tri(2-acryloyloxyethyl) isocyanurate and sulfur-containing modified bisphenol fluorene all have good flame retardant effects and together constitute a flame retardant system; and the sulfonate groups therein can catalyze the isomerization and cross-linking of polycarbonate into carbon, thereby making the polycarbonate material have higher carbon forming properties and achieving better flame retardant effects. DETAILED DESCRIPTION

[0015] The preparation process of vinyl carbon nanotubes refers to the journal "Materials Science and Engineering Plastics", Volume 23, Issue 4, "Surface Vinyl Functionalization of Multi-walled Carbon Nanotubes": 0.3g of multi-walled carbon nanotubes were added to 30mL of 98% concentrated sulfuric acid and 10mL of 70% concentrated nitric acid, refluxed at 140°C for 1h, filtered, and washed. 0.1g of the acidified carbon nanotubes obtained were weighed and dispersed in 15mL of acetone and 15mL of chloroform, 2mL of triethylamine and 5mL of acryloyl chloride were added, and the reaction was carried out at 40°C for 24h. Then 10mL of ethanol was added and stirred for 2h, filtered, and washed to obtain vinyl carbon nanotubes. Example 1

[0016] (1) tri(2-acryloyloxyethyl) isocyanurate is added to N,N-dimethylformamide solvent, and the mixture is stirred and dispersed. Then, mercaptoethylamine and benzoin dimethyl ether photoinitiator are added thereto, wherein the mass ratio of tri(2-acryloyloxyethyl) isocyanurate, mercaptoethylamine and benzoin dimethyl ether photoinitiator is 1:2.1:0.01. The mixture is irradiated with ultraviolet light of 365 nm at 25° C. for 3 h. After the irradiation, the mixture is centrifuged, washed and dried to obtain intermediate 1. (2) Dissolving the intermediate 1 and 1,3-propane sultone in a 1,4-dioxane solvent, wherein the mass ratio of the intermediate 1 to 1,3-propane sultone is 1.2:1, then dropping a 3% sodium hydroxide solution, heating to 75°C to react for 6 hours, dropping and concentrating under reduced pressure to remove the solvent after the reaction, and recrystallizing the crude product in ethanol to obtain sodium sulfonate modified tris(2-acryloyloxyethyl) isocyanurate; (3) Under a nitrogen atmosphere, 5 parts by weight of bisphenol fluorene and 0.02 parts by weight of triethylamine were added to a dichloromethane solvent and stirred at 8°C until fully dissolved. Then, 4 parts by weight of phenylphosphoryl dichloride was added thereto and the reaction was continued with stirring for 10 hours. After completion, the reaction was dried to obtain an intermediate 2. (4) adding itaconic acid to N,N-dimethylformamide solvent, stirring evenly, and continuously adding intermediate 2 and p-toluenesulfonic acid catalyst thereto, wherein the mass ratio of itaconic acid, intermediate 2, and p-toluenesulfonic acid catalyst is 1:1.2:0.02, reacting at 70°C for 6h, and then distilling under reduced pressure, washing and drying to obtain bisphenol fluorene-modified itaconic acid; (5) adding sodium dodecyl sulfate emulsifier and vinyl carbon nanotubes into deionized water, and adding bisphenol fluorene modified itaconic acid and 1,3,5-triacryloyl hexahydro-1,3,5-triazine after uniform dispersion, introducing nitrogen protection, and then continuing to add azobisisobutyronitrile initiator, wherein the mass ratio of sodium dodecyl sulfate emulsifier, vinyl carbon nanotubes, bisphenol fluorene modified itaconic acid, 1,3,5-triacryloyl hexahydro-1,3,5-triazine, and azobisisobutyronitrile initiator is 0.02:0.9:1:0.4:0.01, reacting at 80°C for 3h, washing with deionized water and ethanol in turn, and drying to obtain sulfur-modified bisphenol fluorene; (6) 50 parts by weight of polycarbonate, 3 parts by weight of sodium sulfonate-modified tri(2-acryloyloxyethyl) isocyanurate, 4 parts by weight of sulfur-modified bisphenol A, and 0.6 parts by weight of antioxidant 1068 were added into a twin-screw extruder, extruded into pellets at 170°C, and then the pellets were compression molded in a flat vulcanizer at a pressure of 10 MPa and 175°C to obtain a flame-retardant polycarbonate material. Example 2

[0017] (1) tri(2-acryloyloxyethyl) isocyanurate is added to N,N-dimethylformamide solvent, stirred and dispersed, and then mercaptoethylamine and benzoin dimethyl ether photoinitiator are added thereto, wherein the mass ratio of tri(2-acryloyloxyethyl) isocyanurate, mercaptoethylamine, and benzoin dimethyl ether photoinitiator is 1:3.4:0.02, and irradiated with 365 nm ultraviolet light at 45°C for 6 h. After the irradiation, centrifugation is performed, washing and drying are performed to obtain intermediate 1; (2) Dissolving intermediate 1 and 1,3-propane sultone in 1,4-dioxane solvent, wherein the mass ratio of intermediate 1 to 1,3-propane sultone is 1.4:1, then dropping a 5% by mass sodium hydroxide solution, heating to 90°C to react for 14 hours, dropping and concentrating under reduced pressure to remove the solvent after the reaction, and the crude product is recrystallized in ethanol to obtain sodium sulfonate modified tris(2-acryloyloxyethyl) isocyanurate; (3) Under a nitrogen atmosphere, 10 parts by weight of bisphenol fluorene and 0.07 parts by weight of triethylamine were added to a dichloromethane solvent and stirred at 12° C. until fully dissolved. Then, 9 parts by weight of phenylphosphoryl dichloride was added thereto and the reaction was continued with stirring for 14 hours. After completion, the reaction was dried to obtain an intermediate 2. (4) adding itaconic acid to N,N-dimethylformamide solvent, stirring evenly, and continuously adding intermediate 2 and p-toluenesulfonic acid catalyst thereto, wherein the mass ratio of itaconic acid, intermediate 2, and p-toluenesulfonic acid catalyst is 1:1.5:0.04, reacting at 85°C for 10 hours, and then distilling under reduced pressure, washing and drying to obtain bisphenol fluorene-modified itaconic acid; (5) adding sodium dodecyl sulfate emulsifier and vinyl carbon nanotubes into deionized water, and adding bisphenol fluorene modified itaconic acid and 1,3,5-triacryloyl hexahydro-1,3,5-triazine after uniform dispersion, introducing nitrogen protection, and then continuing to add azobisisobutyronitrile initiator, wherein the mass ratio of sodium dodecyl sulfate emulsifier, vinyl carbon nanotubes, bisphenol fluorene modified itaconic acid, 1,3,5-triacryloyl hexahydro-1,3,5-triazine, and azobisisobutyronitrile initiator is 0.03:1.1:1:0.8:0.03, reacting at 110°C for 5h, washing with deionized water and ethanol in turn, and drying to obtain sulfur-modified bisphenol fluorene; (6) 80 parts by weight of polycarbonate, 5 parts by weight of sodium sulfonate-modified tri(2-acryloyloxyethyl) isocyanurate, 6 parts by weight of sulfur-modified bisphenol A, and 0.8 parts by weight of antioxidant 1068 were added into a twin-screw extruder, extruded into pellets at 180°C, and then the pellets were compression molded in a flat vulcanizer at a pressure of 12 MPa and 180°C to obtain a flame-retardant polycarbonate material. Example 3

[0018] (1) tri(2-acryloyloxyethyl) isocyanurate is added to N,N-dimethylformamide solvent, and the mixture is stirred and dispersed. Then, mercaptoethylamine and benzoin dimethyl ether photoinitiator are added thereto, wherein the mass ratio of tri(2-acryloyloxyethyl) isocyanurate, mercaptoethylamine and benzoin dimethyl ether photoinitiator is 1:2.63:0.015. The mixture is irradiated with 365 nm ultraviolet light at 32° C. for 4 h. After the irradiation, the mixture is centrifuged, washed and dried to obtain intermediate 1. (2) Dissolving intermediate 1 and 1,3-propane sultone in 1,4-dioxane solvent, wherein the mass ratio of intermediate 1 to 1,3-propane sultone is 1.3:1, then dropping a 4% sodium hydroxide solution, heating to 82°C to react for 10 hours, dropping and concentrating under reduced pressure to remove the solvent after the reaction, and recrystallizing the crude product in ethanol to obtain sodium sulfonate modified tri(2-acryloyloxyethyl) isocyanurate; (3) Under a nitrogen atmosphere, 7.5 parts by weight of bisphenol fluorene and 0.05 parts by weight of triethylamine were added to a dichloromethane solvent and stirred at 10° C. until fully dissolved. Then, 6 parts by weight of phenylphosphoryl dichloride were added thereto and the reaction was continued with stirring for 12 hours. After completion, the reaction was dried to obtain an intermediate 2. (4) adding itaconic acid to N,N-dimethylformamide solvent, stirring evenly, and continuously adding intermediate 2 and p-toluenesulfonic acid catalyst thereto, wherein the mass ratio of itaconic acid, intermediate 2, and p-toluenesulfonic acid catalyst is 1:1.35:0.03, reacting at 80°C for 8h, and then distilling under reduced pressure, washing and drying to obtain bisphenol fluorene-modified itaconic acid; (5) adding sodium dodecyl sulfate emulsifier and vinyl carbon nanotubes into deionized water, and adding bisphenol fluorene modified itaconic acid and 1,3,5-triacryloyl hexahydro-1,3,5-triazine after uniform dispersion, introducing nitrogen protection, and then continuing to add azobisisobutyronitrile initiator, wherein the mass ratio of sodium dodecyl sulfate emulsifier, vinyl carbon nanotubes, bisphenol fluorene modified itaconic acid, 1,3,5-triacryloyl hexahydro-1,3,5-triazine, and azobisisobutyronitrile initiator is 0.025:0.9:1:0.6:0.02, reacting at 90°C for 4h, washing with deionized water and ethanol in turn, and drying to obtain sulfur-modified bisphenol fluorene; (6) 65 parts by weight of polycarbonate, 4 parts by weight of sodium sulfonate-modified tri(2-acryloyloxyethyl) isocyanurate, 5 parts by weight of sulfur-modified bisphenol A, and 0.7 parts by weight of antioxidant 1068 were added into a twin-screw extruder, extruded into pellets at 175°C, and then the pellets were compression molded in a flat vulcanizer at a pressure of 11 MPa and 178°C to obtain a flame-retardant polycarbonate material.

[0019] Comparative Example 1 65 parts by weight of polycarbonate, 5 parts by weight of sulfur-modified bisphenol A and 0.7 parts by weight of antioxidant 1068 were added into a twin-screw extruder, extruded into granules at 175°C, and then the granules were compression molded in a flat vulcanizer at a pressure of 11 MPa and 178°C to obtain a flame-retardant polycarbonate material.

[0020] Comparative Example 2 65 parts by weight of polycarbonate, 4 parts by weight of sodium sulfonate modified tri(2-acryloxyethyl) isocyanurate, and 0.7 parts by weight of antioxidant 1068 are added into a twin-screw extruder, extruded into granules at 175°C, and then the granules are compression molded in a flat vulcanizer at a pressure of 11 MPa and 178°C to obtain a flame-retardant polycarbonate material.

[0021] Use an oxygen index meter to test the limiting oxygen index of flame-retardant polycarbonate materials; use horizontal and vertical combustion The instrument tests the combustion grade of flame retardant polycarbonate materials.

[0022] Table 1: Tests of flame retardancy.

[0023] project Limiting oxygen index (%) Combustion level Example 1 32 V-0 Example 2 34 V-0 Example 3 31 V-0 Comparative Example 1 28 V-1 Comparative Example 2 27 V-1 It can be seen from Table 1 that the flame-retardant polycarbonate materials prepared in Examples 1-3 of the present invention have better flame-retardant effects than those prepared in Comparative Examples 1-2.

[0024] 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 polycarbonate material, characterized in that: The invention comprises the following components by weight: 50-80 parts by weight of polycarbonate, 3-5 parts by weight of sodium sulfonate modified tris(2-acryloyloxyethyl) isocyanurate, 4-6 parts by weight of sulfur-containing modified bisphenol fluorene, and 0.6-0.8 parts by weight of antioxidant 1068.

2. The flame retardant polycarbonate material according to claim 1, characterized in that: The preparation method of the sodium sulfonate modified tri(2-acryloyloxyethyl) isocyanurate is as follows: (1) Add tri(2-acryloyloxyethyl)isocyanurate to N,N-dimethylformamide solvent, stir and disperse, then add mercaptoethylamine and benzoin dimethyl ether photoinitiator, irradiate with 365nm ultraviolet light at 25-45°C for 3-6h, centrifuge, wash and dry to obtain intermediate 1; (2) The intermediate 1 and 1,3-propane sultone are dissolved in 1,4-dioxane solvent, and then a sodium hydroxide solution with a mass fraction of 3-5% is added dropwise, and the temperature is raised to 75-90°C for reaction for 6-14 hours. After the reaction, the solvent is removed by vacuum concentration, and the crude product is recrystallized in ethanol to obtain sodium sulfonate modified tri(2-acryloyloxyethyl) isocyanurate.

3. The flame retardant polycarbonate material according to claim 2, characterized in that: In the step (1), the mass ratio of tri(2-acryloyloxyethyl)isocyanurate, mercaptoethylamine and benzoin dimethyl ether photoinitiator is 1:2.1-3.4:0.01-0.

02.

4. The flame retardant polycarbonate material according to claim 2, characterized in that: In the step (2), the mass ratio of the intermediate 1 to 1,3-propane sultone is 1.2-1.4:

1.

5. The flame retardant polycarbonate material according to claim 1, characterized in that: The preparation method of the sulfur-containing modified bisphenol fluorene is: S1. Under a nitrogen atmosphere, 5-10 parts by weight of bisphenol fluorene and 0.02-0.07 parts by weight of triethylamine are added to a dichloromethane solvent, stirred at 8-12 ° C until fully dissolved, and then 4-9 parts by weight of phenylphosphoryl dichloride are added thereto, and the reaction is continued to be stirred for 10-14h, and then dried to obtain an intermediate 2; S2. Add itaconic acid to N,N-dimethylformamide solvent, stir evenly, continue to add intermediate 2 and p-toluenesulfonic acid catalyst, react at 70-85°C for 6-10h, and then distill under reduced pressure, wash and dry to obtain bisphenol fluorene-modified itaconic acid; S3. Add sodium dodecyl sulfate emulsifier and vinyl carbon nanotubes into deionized water, disperse them evenly, add bisphenol fluorene-modified itaconic acid and 1,3,5-triacryloylhexahydro-1,3,5-triazine, introduce nitrogen protection, and then continue to add azobisisobutyronitrile initiator, react at 80-110°C for 3-5h, wash with deionized water and ethanol in turn, and dry to obtain sulfur-modified bisphenol fluorene.

6. The flame retardant polycarbonate material according to claim 5, characterized in that: The mass ratio of itaconic acid, intermediate 2 and p-toluenesulfonic acid catalyst in S2 is 1:1.2-1.5:0.02-0.

04.

7. The flame retardant polycarbonate material according to claim 5, characterized in that: The mass ratio of sodium dodecyl sulfate emulsifier, vinyl carbon nanotubes, bisphenol fluorene-modified itaconic acid, 1,3,5-triacryloylhexahydro-1,3,5-triazine, and azobisisobutyronitrile initiator in S3 is 0.02-0.03:0.9-1.1:1:0.4-0.8:0.01-0.

03.

8. A method for preparing a flame retardant polycarbonate material according to any one of claims 1 to 7, characterized in that: The preparation method of the flame-retardant polycarbonate material comprises the following steps: adding polycarbonate, sodium sulfonate-modified tris(2-acryloyloxyethyl) isocyanurate, sulfur-modified bisphenol fluorene and antioxidant 1068 into a twin-screw extruder, extruding and granulating the polycarbonate at 170-180° C., and then molding the polycarbonate in a flat vulcanizer at 175-180° C. under a pressure of 10-12 MPa to obtain the flame-retardant polycarbonate material.