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CN-118852797-B - Modified graphene reinforced ethylene propylene diene monomer rubber composite material and preparation method

CN118852797BCN 118852797 BCN118852797 BCN 118852797BCN-118852797-B

Abstract

The invention relates to the technical field of ethylene propylene diene monomer rubber, and discloses a modified graphene reinforced ethylene propylene diene monomer rubber composite material and a preparation method thereof, wherein the modified graphene reinforced ethylene propylene diene monomer rubber composite material comprises, by weight, 100 parts of ethylene propylene diene monomer rubber, 1-1.4 parts of anti-aging agent, 2-3 parts of sulfur, 1-1.5 parts of accelerator, 0.5-5 parts of flame retardant modified graphene and 0.15-2 parts of compatilizer ethylene-vinyl acetate copolymer. The ethylene-vinyl acetate copolymer can be used as a compatilizer to enhance the compatibility between the flame retardant modified graphene and ethylene propylene diene monomer, so that the graphene plays a better role in reinforcing, and the mechanical properties such as hardness of the material are obviously improved. The polymer containing a large amount of diphenyl diphosphate flame retardant groups in the flame retardant modified graphene is used as a phosphorus-containing flame retardant, so that the composite material has better flame retardant performance and shows higher limiting oxygen index.

Inventors

  • WANG FANGMIN

Assignees

  • 株洲泰信电子科技有限公司

Dates

Publication Date
20260505
Application Date
20240710

Claims (8)

  1. 1. The modified graphene reinforced ethylene propylene diene monomer composite material is characterized by comprising 100 parts by weight of ethylene propylene diene monomer, 1-1.4 parts by weight of an anti-aging agent, 2-3 parts by weight of sulfur, 1-1.5 parts by weight of an accelerator, 1-2 parts by weight of stearic acid, 6-12 parts by weight of zinc oxide, 0.5-5 parts by weight of flame retardant modified graphene and 0.15-2 parts by weight of compatilizer ethylene-vinyl acetate copolymer; Adding KH570 modified graphene into toluene, adding a vinyl acetate flame retardant after ultrasonic dispersion, introducing nitrogen, adding an initiator, concentrating the solution after reaction, washing with ethanol, and drying to obtain the flame retardant modified graphene; The structural formula of the vinyl acetate flame retardant is shown in the formula (I): Formula (I); The KH570 modified graphene is 100 parts by weight, the vinyl acetate flame retardant is 500-1500 parts by weight, and the initiator is 4.4-16 parts by weight.
  2. 2. The modified graphene reinforced ethylene propylene diene monomer composite material according to claim 1, wherein the initiator is azobisisobutyronitrile or dibenzoyl peroxide.
  3. 3. The modified graphene reinforced ethylene propylene diene monomer composite material according to claim 1, wherein the reaction is carried out for 8-12 hours at 75-85 ℃.
  4. 4. The modified graphene reinforced ethylene propylene diene monomer composite material according to claim 1, wherein the preparation method of the vinyl acetate flame retardant is as follows: Step (1), adding 2- (3, 5-dihydroxyphenyl) acetic acid, vinyl acetate and mercury acetate into tetrahydrofuran, dropwise adding concentrated sulfuric acid, adding sodium acetate after reaction, stirring, concentrating the solution, adding water and ethyl acetate, carrying out oscillation extraction, standing for layering, drying an ethyl acetate phase, and concentrating to obtain 2- (3, 5-dihydroxyphenyl) vinyl acetate; And (2) adding 2- (3, 5-dihydroxyphenyl) vinyl acetate, diphenyl chlorophosphate and triethylamine into toluene under ice water bath, then reacting for 18-24h at 30-45 ℃, concentrating the solution, washing with methanol, and recrystallizing with ethyl acetate to obtain the vinyl acetate flame retardant.
  5. 5. The modified graphene reinforced ethylene propylene diene monomer rubber composite material according to claim 4, wherein in the step (1), the amount of 2- (3, 5-dihydroxyphenyl) acetic acid is 100 parts by weight, the amount of vinyl acetate is 650-720 parts by weight, the amount of mercury acetate is 3.6-4.4 parts by weight, and the amount of concentrated sulfuric acid is 1.2-1.5 parts by weight.
  6. 6. The modified graphene reinforced ethylene propylene diene monomer composite material according to claim 4, wherein in the step (1), the reaction is performed at 60-65 ℃ for 6-10 hours.
  7. 7. The modified graphene reinforced ethylene propylene diene monomer rubber composite material according to claim 4, wherein in the step (2), the amount of 2- (3, 5-dihydroxyphenyl) vinyl acetate is 100 parts by weight, diphenyl chlorophosphate is 280-310 parts by weight, and triethylamine is 200-225 parts by weight.
  8. 8. A preparation method of the modified graphene reinforced ethylene propylene diene monomer composite material according to any one of claims 1-7 is characterized by comprising the steps of banburying ethylene propylene diene monomer in an internal mixer for 3-4min at a roll temperature of 120-125 ℃, adding zinc oxide, flame retardant modified graphene, compatilizer ethylene-vinyl acetate copolymer and stearic acid, discharging rubber at 100-110 ℃ to obtain master batch, performing triangular package, thin pass and lower piece mixing for 10-15min in a double-roll open mill, cooling, and finally vulcanizing in a plate vulcanizing agent at 160-170 ℃ under a pressure of 8-10MPa to obtain the modified graphene reinforced ethylene propylene diene monomer composite material.

Description

Modified graphene reinforced ethylene propylene diene monomer rubber composite material and preparation method Technical Field The invention relates to the technical field of ethylene propylene diene monomer rubber, in particular to a modified graphene reinforced ethylene propylene diene monomer rubber composite material and a preparation method thereof. Background The ethylene propylene diene monomer rubber has good heat resistance, weather resistance, aging resistance and other properties, and is widely applied to the aspects of wires and cables, household appliances, building pavement materials and the like. Improving the mechanical strength, flame retardance and other properties of ethylene propylene diene monomer rubber is a research hot spot. The ethylene propylene diene monomer rubber is reinforced by adopting the inorganic nano particles such as graphene, titanium dioxide and the like, so that the method is an effective method for improving the mechanical properties and the like of the ethylene propylene diene monomer rubber. The graphene has the advantages of high mechanical strength, high temperature resistance, certain flame retardant effect and wide application. Chinese patent CN107236199B discloses a modified ethylene propylene diene monomer and a preparation method, wherein hyperbranched phosphoramide is synthesized in situ on the surface of graphene oxide, so that the mechanical property, flame retardant property and heat conducting property of ethylene propylene diene monomer can be improved. The compatibility between the graphene and the ethylene propylene diene monomer is improved, so that the graphene can play a better reinforcing role, and the mechanical property of the ethylene propylene diene monomer is enhanced. Disclosure of Invention The invention solves the problems of poor compatibility of graphene and ethylene propylene diene monomer and poor flame retardance of ethylene propylene diene monomer. The technical scheme provided by the invention is as follows: The modified graphene reinforced ethylene propylene diene monomer composite material comprises 100 parts by weight of ethylene propylene diene monomer, 1-1.4 parts by weight of an anti-aging agent, 2-3 parts by weight of sulfur, 1-1.5 parts by weight of an accelerator, 1-2 parts by weight of stearic acid, 6-12 parts by weight of zinc oxide, 0.5-5 parts by weight of flame retardant modified graphene and 0.15-2 parts by weight of a compatilizer ethylene-vinyl acetate copolymer. Adding KH570 modified graphene into toluene, adding a vinyl acetate flame retardant after ultrasonic dispersion, introducing nitrogen, adding an initiator, concentrating the solution after reaction, washing with ethanol, and drying to obtain the flame retardant modified graphene. The structural formula of the vinyl acetate flame retardant is shown as formula (I): Formula (I). Wherein the dosage of KH570 modified graphene is 100 weight parts, the dosage of vinyl acetate flame retardant is 500-1500 weight parts, and the dosage of initiator is 4.4-16 weight parts. Wherein the initiator is azobisisobutyronitrile or dibenzoyl peroxide. Wherein the reaction is carried out at 75-85 ℃ for 8-12h. The preparation method of the vinyl acetate flame retardant comprises the following steps: Step (1), adding 100 parts by weight of 2- (3, 5-dihydroxyphenyl) acetic acid (CAS accession number 4670-09-1), 650-720 parts by weight of vinyl acetate (CAS accession number 108-05-4) and 3.6-4.4 parts by weight of mercury acetate into tetrahydrofuran, dropwise adding 1.2-1.5 parts by weight of concentrated sulfuric acid (mass fraction 98%), reacting for 6-10h at 60-65 ℃, carrying out condensation reflux during the reaction, adding sodium acetate after the reaction, concentrating the solution after stirring, adding water and ethyl acetate, oscillating for extraction, standing for layering, drying the ethyl acetate phase, and concentrating to obtain 2- (3, 5-dihydroxyphenyl) vinyl acetate. The reaction formula is as follows: Step (2), adding 100 parts by weight of 2- (3, 5-dihydroxyphenyl) vinyl acetate, 280-310 parts by weight of diphenyl chlorophosphate (CAS accession number 2524-64-3) and 200-225 parts by weight of triethylamine into toluene under ice water bath, then reacting for 18-24 hours at 30-45 ℃, concentrating the solution, washing with methanol, and recrystallizing with ethyl acetate to obtain the vinyl acetate flame retardant. The reaction formula is: The preparation method of the modified graphene reinforced ethylene propylene diene monomer composite material comprises the steps of banburying ethylene propylene diene monomer in an internal mixer for 3-4min, wherein the roll temperature is 120-125 ℃, then adding zinc oxide, flame retardant modified graphene, compatilizer ethylene-vinyl acetate copolymer and stearic acid, discharging rubber at 100-110 ℃ to obtain master batch, then carrying out triangular package, thin pass and lower piece mixing for 10-15min on the maste