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CN-122011606-A - Synergistically modified ethylene propylene diene monomer glove material with high chemical medium permeation resistance and preparation method thereof

CN122011606ACN 122011606 ACN122011606 ACN 122011606ACN-122011606-A

Abstract

The invention relates to the technical field of rubber protective materials, and discloses a synergistic modified ethylene propylene diene monomer rubber glove material with high chemical medium permeation resistance and a preparation method thereof. The glove material comprises a synergistically modified ethylene propylene diene monomer, zinc oxide, dicumyl peroxide, sulfur, an accelerator, an anti-aging agent, carbon black, a silane coupling agent and an organic solvent, wherein the synergistically modified ethylene propylene diene monomer is used for synergistically constructing a multiple crosslinking system by introducing a hydrazone dynamic covalent network, a coordination structure and an organic-inorganic hybridization structure. The preparation method comprises the steps of preparing the synergistic modified ethylene propylene diene monomer, preparing the rubber compound and the rubber cement, and performing dip molding by a mold to form the glove material with the multilayer compact structure. The invention obviously improves the chemical medium permeation resistance, air tightness, mechanical property and ageing resistance of the material through multi-scale cooperative modification, has simple preparation process and is suitable for the field of high-end dry box protection.

Inventors

  • Luo Pingchang
  • XUE FULI
  • LIU HUAN
  • ZHAO LIJIE
  • ZHANG LILI

Assignees

  • 北京瑞京乳胶制品有限公司

Dates

Publication Date
20260512
Application Date
20260410

Claims (8)

  1. 1. The glove material is characterized by comprising, by weight, 60-120 parts of synergistically modified ethylene propylene diene monomer rubber, 5-12 parts of zinc oxide, 3-6 parts of dicumyl peroxide, 0.5-3 parts of sulfur, 2-5 parts of accelerator A, 1-4 parts of accelerator B, 1-5 parts of anti-aging agent, 10-30 parts of carbon black, 1-5 parts of silane coupling agent and 60-100 parts of organic solvent, wherein the synergistically modified ethylene propylene diene monomer rubber is formed by constructing a hydrazone dynamic covalent network by condensation reaction of ethylene propylene diene monomer rubber, 2-acetyl pyridine and terephthaloyl dihydrazide, forming a coordination structure with ferulic acid and lanthanum chloride, and introducing organic-inorganic hybrid structure through hydrolytic polycondensation of vinyl trimethoxy silane to perform synergistic modification.
  2. 2. The synergistic modified ethylene propylene diene monomer glove material with high chemical medium permeation resistance according to claim 1 is characterized by comprising, by weight, 50-100 parts of ethylene propylene diene monomer, 0.5-5 parts of 2-acetylpyridine, 0.5-6 parts of terephthaloyl dihydrazide, 0.5-5 parts of ferulic acid, 0.1-2 parts of lanthanum chloride and 1-6 parts of vinyl trimethoxysilane.
  3. 3. The synergistic modified ethylene propylene diene monomer glove material with high chemical medium permeation resistance according to claim 1 or 2, wherein the preparation method of the synergistic modified ethylene propylene diene monomer glove material comprises the following steps: (1) After plasticating ethylene propylene diene monomer, mixing the ethylene propylene diene monomer with 2-acetyl pyridine, heating and stirring the mixture to uniformly disperse the mixture in a rubber matrix to obtain a pre-modified rubber intermediate; (2) Adding terephthaloyl dihydrazide into the pre-modified rubber intermediate for reaction to form a hydrazone dynamic covalent network structure, and simultaneously adding ferulic acid and lanthanum chloride for complex reaction to construct a coordination crosslinking structure to obtain a synergistic network rubber intermediate; (3) And adding vinyl trimethoxy silane into the synergistic network rubber intermediate and performing hydrolysis polycondensation reaction to form an organic-inorganic hybrid network structure in a rubber matrix to obtain the synergistic modified ethylene propylene diene monomer.
  4. 4. The synergistic modified ethylene propylene diene monomer glove material with high chemical medium permeation resistance according to claim 3, wherein the reaction condition of the step (1) is plasticating temperature of 60-100 ℃, mixing temperature of 50-80 ℃ and stirring time of 20-60 min.
  5. 5. The synergistic modified ethylene propylene diene monomer glove material with high chemical medium permeation resistance according to claim 3, wherein the reaction condition of the step (2) is that the reaction temperature is 60-120 ℃ and the reaction time is 1-4 h.
  6. 6. The synergistic modified ethylene propylene diene monomer glove material with high chemical medium permeation resistance according to claim 3, wherein the reaction condition of the step (3) is that the hydrolysis polycondensation temperature is 50-90 ℃, the reaction time is 1-3 h, and the pH is 4-6.
  7. 7. The synergistic modified ethylene propylene diene monomer glove material with high chemical medium permeation resistance according to claim 1 is characterized in that an accelerator A is formed by mixing an accelerator dibenzothiazyl and an accelerator 2-mercaptobenzothiazole according to a mass ratio of (1-3): 1-2, an accelerator B is formed by mixing an accelerator tetramethyl thiuram disulfide and an accelerator dipentyl thiuram tetrasulfide according to a mass ratio of (1-2): 1-1.5, and an antioxidant is formed by mixing 2, 6-di-tert-butyl-p-cresol and an antioxidant diphenylamine antioxidant according to a mass ratio of (1-2): 1-1.5.
  8. 8. The preparation method of the synergetic modified ethylene propylene diene monomer glove material with high chemical medium permeation resistance is characterized by comprising the following steps of: (1) Uniformly mixing zinc oxide, an accelerator A, an accelerator B, an anti-aging agent, carbon black and a silane coupling agent according to parts by weight, stirring for 10-30 min, then adding the mixture and the synergistic modified ethylene propylene diene monomer after plasticating treatment into a rubber mixing mill for mixing until materials are uniformly dispersed and powder is not scattered, and finally adding dicumyl peroxide and sulfur for continuous mixing to obtain the rubber mixture; (2) Preparing mucilage, namely cutting the rubber compound, then adding the rubber compound into an organic solvent which is being stirred for dissolution and dispersion, and continuously stirring until uniform and stable mucilage is formed; (3) The mold treatment, namely cleaning and drying a forming mold, wherein the mold is a ceramic hand mold, a stainless steel hand mold or a gypsum hand mold, and cooling to normal temperature for standby after drying; (4) Positioning a mold above the adhesive cement through equipment, fully immersing the mold in the adhesive cement through vertical movement to enable the adhesive cement to be uniformly adhered to the surface of the mold, lifting the mold and separating the mold from the adhesive cement, enabling the adhered adhesive cement to form a wet film on the surface of the mold and performing primary solidification to obtain a single-layer adhesive film; (5) Immersing the die with the single-layer adhesive film into the adhesive cement through vertical movement again, enabling the new adhesive cement to cover the surface of the formed adhesive film, lifting the die and solidifying the die to enable the newly formed adhesive film to be combined with the former adhesive film, and repeating the immersing, lifting and solidifying processes for 2-10 times to form a multi-layer adhesive film, wherein the thickness of each layer is 0.03-0.06 mm, and the total thickness is 0.4-0.8 mm; (6) And demolding and forming, namely removing the adhesive film subjected to multi-layer impregnation and curing from the mold to obtain the synergistic modified ethylene propylene diene monomer rubber glove material consistent with the surface structure of the mold.

Description

Synergistically modified ethylene propylene diene monomer glove material with high chemical medium permeation resistance and preparation method thereof Technical Field The invention relates to the technical field of rubber protective products and high polymer materials, in particular to a synergistic modified ethylene propylene diene monomer rubber glove material with high chemical medium permeation resistance and a preparation method thereof. Background The dry box glove is also called as an operation box glove, is usually arranged on a closed isolation box body and is used for operating in an ultrapure environment such as no water, no oxygen, no dust and the like, and is widely applied to the fields of medicine, biotechnology, biosafety, electronic semiconductors, nuclear power, precision manufacturing and the like. According to different use environments and performance requirements, the existing glove materials for the dry box mainly comprise natural latex, nitrile rubber, ethylene propylene diene monomer rubber, chlorosulfonated polyethylene, butyl rubber and the like. The ethylene propylene diene monomer has excellent ozone resistance, heat resistance and weather resistance because the molecular main chain of the ethylene propylene diene monomer is of a saturated hydrocarbon structure and contains a small amount of unsaturated double bonds on the side chain, and the ethylene propylene diene monomer has good stability in severe environments such as strong oxidation, acid and alkali, and the like, so the ethylene propylene diene monomer is one of important materials of high-end dry box gloves. In the prior art, ethylene propylene diene monomer rubber gloves are generally prepared into rubber cement through mixing and dissolving, then a rubber film is formed layer by layer on the surface of a die through an impregnation forming process, and a glove product is obtained through vulcanization and solidification. The method can realize uniform glove thickness and compact surface to a certain extent, but has the defects that on one hand, the traditional ethylene propylene diene monomer rubber system mainly depends on a filler and a vulcanization system to improve performance, the internal structure of the material is relatively single, the permeation barrier performance of the traditional ethylene propylene diene monomer rubber system still has a room for improvement when facing organic solvents, small molecular chemical media and complex corrosive environments, and on the other hand, the traditional formula system is easy to have the problems of insufficient flowability, untight bonding of adhesive layers, bubbling and the like in the adhesive layer forming process, and the air tightness and long-term use stability of the glove are affected. At present, the production formula and the process of the high-performance dry box glove are still mainly mastered in the hands of foreign enterprises, and the material system and the forming process with independent intellectual property rights are still lacking in the field of high-end chemical medium permeation resistant rubber gloves in China. Therefore, on the basis of the existing ethylene propylene diene monomer rubber system, from the aspects of material structural design and process optimization, a rubber glove material with better barrier property, ageing resistance and processability and a preparation method thereof are required to be developed so as to meet the requirements of the high-end application field. Disclosure of Invention In order to overcome the problems of insufficient chemical medium blocking performance, single material structure and poor compactness and bonding property of a rubber layer in the dip forming process of the ethylene propylene diene monomer glove in the background art, the invention aims to provide the high chemical medium permeation resistant synergistically modified ethylene propylene diene monomer glove material and the preparation method thereof, and the method is characterized in that a dynamic covalent bond, a coordination structure and an organic-inorganic hybridization structure are introduced into an ethylene propylene diene monomer rubber matrix to construct a multiple synergistic network, and a dip forming process is combined to form a multilayer compact structure, so that the gas-liquid blocking performance and the structural stability of the material are obviously improved, and the beneficial effects of obviously improving the chemical medium permeation resistant performance and the comprehensive use performance are brought. The aim of the invention can be achieved by the following technical scheme: The glove material comprises, by weight, 60-120 parts of synergistically modified ethylene propylene diene monomer rubber, 5-12 parts of zinc oxide, 3-6 parts of dicumyl peroxide, 0.5-3 parts of sulfur, 2-5 parts of accelerator A, 1-4 parts of accelerator B, 1-5 parts of anti-aging agent, 10-30 parts of carbon black, 1-5 pa