CN114133668B - Ethylene propylene diene monomer with oriented lamellar hybrid network and high sealing resilience and preparation method thereof - Google Patents
Ethylene propylene diene monomer with oriented lamellar hybrid network and high sealing resilience and preparation method thereof Download PDFInfo
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- 238000003756 stirring Methods 0.000 claims description 10
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
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- 238000003825 pressing Methods 0.000 claims description 5
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- 239000007762 w/o emulsion Substances 0.000 claims description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 4
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 4
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 claims description 4
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- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 4
- 229960002447 thiram Drugs 0.000 claims description 4
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 claims description 2
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- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Abstract
The invention discloses Ethylene Propylene Diene Monomer (EPDM) with high sealing resilience and an oriented layered hybrid network and a preparation method thereof, and the EPDM is characterized in that a Pickering emulsion template and a microwave-assisted thermal reduction effect are adopted to regulate and control the surface property of a cellulose nanocrystal/graphene hybrid filler and endow the cellulose nanocrystal/graphene hybrid filler with amphipathy, the cellulose nanocrystal/graphene hybrid filler is distributed at the interface of an EPDM solution and a cellulose nanocrystal/graphene water dispersion under thermodynamic drive to form a water-in-oil stable emulsion system, a water phase and an oil phase are removed through freeze drying to form an EPDM-coated cellulose nanocrystal/graphene three-dimensional hollow spherical shell, and the cellulose nanocrystal/graphene three-dimensional hybrid network is regulated and controlled to be arranged in an oriented layered manner on an EPDM matrix through a cold pressing-hot pressing combination process to realize good dispersion of the hybrid filler, play synergistic enhancement and stabilization functions, endow the EPDM with high enhanced mechanics and sealing resilience and greatly prolong the service life of the EPDM. The EPDM rubber with the oriented laminar hybrid network prepared by the invention has controllable structure and excellent mechanical property and sealing resilience, and can be used in the field of rubber material sealing.
Description
Technical Field
The invention relates to ethylene propylene diene monomer with high sealing resilience and an oriented layered hybrid network and a preparation method thereof, belonging to the field of preparation of high polymer materials.
Background
Ethylene Propylene Diene Monomer (EPDM) is a terpolymer prepared by random copolymerization of ethylene, propylene and a small amount of non-conjugated diene under the action of a Ziegler-Natta catalyst or a metallocene catalyst system, belongs to rubber containing saturated carbon chains, noncrystalline and nonpolar, has excellent compression resilience and chemical stability, and is one of the materials with the largest dosage in the sealing field. However, EPDM is non-self-reinforcing rubber, has low mechanical strength, modulus and toughness, is easy to generate stress relaxation in the service process, has poor high-temperature sealing resilience, and can meet the application requirement only by reinforcing; the main chain of the molecular chain is a completely saturated straight chain structure, the self-adhesion and mutual viscosity are poor, the conventional processing of nano-filler is difficult in material feeding and poor in dispersion, the EPDM does not have a latex form, the nano-composite rubber cannot be prepared by adopting a latex coprecipitation method, the reinforcing effect on the EPDM is limited, and the regulation and control of the filler interface and the network structure form are the key points of the problem.
The cellulose nanocrystal is a nanoparticle with a high crystalline structure formed by closely and orderly arranging cellulose molecular chains by virtue of hydrogen bond action, and has high tensile strength, specific modulus and specific pressure strength. The graphene nanoplatelets are sp 2 The two-dimensional lamellar carbon material with a honeycomb lattice structure, which is formed by closely packing hybridized carbon atoms, can capture free radicals generated by degradation of polymer molecules, and has unique stabilizing effect and anti-aging effect. However, in the processing process, graphene is easily agglomerated due to the high surface energy and the van der waals force between sheets, and the rigid cellulose nanocrystals are more difficult to disperse in the matrix, so that the application of the graphene is limited. The regulation and control of the interface and the network structure are the key points of the nano particles for efficiently reinforcing the rubber elastomer, and at present, two nano fillers with different dimensions are strongly connected to form a hybrid filler network structure, so that the research report for realizing the synergistic effect is lacked. In conclusion, the hybrid filler network is constructed by selecting the cellulose nanocrystals and the graphene, the orientation lamellar arrangement of the hybrid filler network is regulated, and the EPDM has excellent mechanical strength, toughness and high sealing resilience, so that the service life of the EPDM rubber seal is prolonged.
Disclosure of Invention
The invention aims to provide a preparation method of ethylene propylene diene monomer rubber with high sealing resilience of an oriented layered hybrid network, which is characterized in that a Pickering emulsion template and a microwave-assisted thermal reduction effect are adopted to regulate and control the surface property of a cellulose nanocrystal/graphene hybrid filler and endow the cellulose nanocrystal/graphene hybrid filler with amphipathy, the cellulose nanocrystal/graphene hybrid filler is distributed at the interface of an EPDM solution and the cellulose nanocrystal/graphene water dispersion under the driving of thermodynamics to form a water-in-oil stable emulsion system, a water phase and an oil phase are removed through freeze drying to form an EPDM-coated cellulose nanocrystal/graphene three-dimensional hollow spherical shell, the cellulose nanocrystal/graphene three-dimensional hybrid network is regulated and controlled to be oriented and layered in an EPDM matrix through a cold pressing-hot pressing combination process, the good dispersion, the synergistic enhancement and the stabilization of the hybrid filler are realized, the high-enhanced mechanics and sealing resilience of EPDM are endowed, and the service life of the EPDM is greatly prolonged.
The invention provides ethylene propylene diene monomer rubber with high sealing resilience and oriented layered hybrid network, which comprises the following components in parts by mass:
EPDM 100 parts
0.5 to 5 portions of zinc oxide
0.2-4 parts of stearic acid
0.4 to 3 portions of anti-aging agent
0.3 to 4 portions of vulcanization accelerator
0.5 to 6 portions of vulcanizing agent
2-15 parts of cellulose nanocrystal
2-15 parts of graphene oxide
Wherein the anti-aging agent is any one of 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 2-Mercaptobenzimidazole (MB), N-cyclohexyl-N '-phenyl-p-phenylenediamine (4010), N-phenyl-2-naphthylamine (D) and N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (6 PPD);
the vulcanization accelerator is any one of sulfur (S), triallyl isocyanurate (TAIC), 2-Mercaptobenzothiazole (MBT), tetramethylthiuram disulfide (TMTD), zinc dibutyl dithiocarbamate (BZ) and N-cyclohexyl-2-benzothiazole sulfonamide (CZ);
the vulcanizing agent is any one of dicumyl peroxide (DCP), sulfur (S) and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane (AD).
The invention provides a preparation method of ethylene propylene diene monomer with high sealing resilience and oriented layered hybrid network, which is characterized by comprising the following steps:
(1) Preparation of amphiphilic cellulose nanocrystal/graphene hybrid aqueous dispersion
Extracting cellulose nanocrystals from plants such as cotton, wood, bamboo, sisal and the like and ascidians by a sulfuric acid hydrolysis method, dispersing 2-15 parts of the cellulose nanocrystals in 200-400 parts of deionized water, adding 2-15 parts of graphene oxide, uniformly stirring at 60 ℃, ultrasonically dispersing for 30-150 min, keeping the temperature at 60 ℃ unchanged, then putting the mixed dispersion liquid into a microwave oven, controlling the temperature of the microwave oven to be 120 ℃, reacting for 20-90 s, and thermally reducing the graphene oxide by microwave radiation to obtain amphiphilic cellulose nanocrystal/graphene water dispersion liquid;
(2) Construction of cellulose nanocrystalline/graphene oriented layered hybrid network
Completely dissolving 100 parts of EPDM in 300-1000 parts of cyclohexane, adding the prepared amphiphilic cellulose nanocrystal/graphene aqueous dispersion into an EPDM solution, stirring for 30-60 min by strong magnetic force, stably distributing the cellulose nanocrystal/graphene at a water-cyclohexane interface to form a stable water-in-oil emulsion system, removing a water phase and a cyclohexane phase by freeze drying to obtain an EPDM-coated cellulose nanocrystal/graphene three-dimensional hollow spherical shell, regulating and controlling the orientation and lamellar arrangement of a cellulose nanocrystal/graphene hybridization network in an EPDM matrix by cold pressing for 2 min at the room temperature of 3-6 MPa, and obtaining unvulcanized EPDM/cellulose nanocrystal/graphene composite adhesive;
(3) Preparation of oriented layered hybrid network EPDM rubber with high sealing resilience
Plasticating the prepared unvulcanized EPDM/cellulose nanocrystal/graphene composite rubber on an open mill at room temperature in a vertical roller direction, sequentially adding 0.5-5 parts of zinc oxide, 0.2-4 parts of stearic acid and 0.4-3 parts of an anti-aging agent, uniformly mixing, then adding 0.3-4 parts of a vulcanization accelerator and 0.5-6 parts of a vulcanizing agent, and mixing uniformly in a fixed direction to obtain an EPDM/cellulose nanocrystal/graphene mixed rubber; placing 24 h, hot-pressing and vulcanizing at 150-180 ℃ and 10-20 MPa for 3-18 min to obtain the EPDM/cellulose nanocrystalline/graphene nano composite rubber with the oriented laminar hybrid network.
The invention has the following advantages: the prepared high-sealing-resilience ethylene propylene diene monomer rubber with the oriented laminar hybrid network breaks through the conventional blending method, the oriented laminar nano hybrid network is constructed, the synergistic enhancement and stabilization effects of the one-dimensional cellulose nanocrystals and the two-dimensional graphene are exerted, the mechanical strength and the sealing resilience of the EPDM composite rubber are greatly improved, the compression permanent deformation and the stress relaxation of the EPDM are effectively reduced, and the service life of the EPDM seal is obviously prolonged.
Drawings
Fig. 1 is a schematic diagram of an oriented layered cellulose nanocrystal/graphene hybrid network.
Detailed Description
The present invention is further described in the following by the following specific embodiments and the attached fig. 1, it should be noted that the embodiments are only used for further illustration of the present invention, and should not be construed as limiting the scope of the present invention, and the skilled person in the art can make non-essential modifications to the present invention based on the above disclosure.
Example 1
Dispersing 10 parts of cellulose nanocrystals in 400 parts of deionized water, adding 15 parts of graphene oxide, uniformly stirring at 60 ℃, ultrasonically dispersing for 100 min, keeping the temperature at 60 ℃, then putting the mixed dispersion liquid into a microwave oven, controlling the temperature of the microwave oven to be 120 ℃, reacting for 90 s, and thermally reducing the graphene oxide through microwave radiation to obtain amphiphilic cellulose nanocrystal/graphene water dispersion liquid;
completely dissolving 100 parts of EPDM in 1000 parts of cyclohexane, adding the prepared amphiphilic cellulose nanocrystal/graphene aqueous dispersion into an EPDM solution, stirring for 60 min by strong magnetic force, stably distributing cellulose nanocrystals/graphene at a water-cyclohexane interface to form a stable water-in-oil emulsion system, removing a water phase and a cyclohexane phase by freeze drying to obtain an EPDM-coated cellulose nanocrystal/graphene three-dimensional hollow spherical shell, cold pressing at the room temperature of 5 MPa pressure for 2 min to regulate the orientation and lamellar arrangement of a cellulose nanocrystal/graphene hybrid network in an EPDM matrix, and obtaining the unvulcanized EPDM/cellulose nanocrystal/graphene composite adhesive;
plasticating the prepared unvulcanized EPDM/cellulose nanocrystal/graphene composite rubber on an open mill at room temperature in a vertical roller direction, sequentially adding 3 parts of zinc oxide, 1.5 parts of stearic acid and 3 parts of an anti-aging agent, uniformly mixing, then adding 2 parts of a vulcanization accelerator and 2 parts of a vulcanizing agent, and uniformly mixing in a fixed direction to obtain an EPDM/cellulose nanocrystal/graphene composite rubber; after 24 h is parked, hot-pressing vulcanization is carried out for 13 min at 165 ℃ and 15 MPa, and the EPDM/cellulose nanocrystal/graphene nano composite rubber with the oriented layered hybrid network is obtained. Under the aging condition of 120 ℃ '25% strain' 168 h, the compression permanent deformation is 17%, the stress relaxation coefficient is 0.87, and the tensile strength retention rate is 88%.
Example 2
Dispersing 5 parts of cellulose nanocrystals in 300 parts of deionized water, adding 12 parts of graphene oxide, uniformly stirring at 60 ℃, ultrasonically dispersing for 80 min, keeping the temperature at 60 ℃, then placing the mixed dispersion liquid into a microwave oven, controlling the temperature of the microwave oven to be 120 ℃, reacting for 70 s, and thermally reducing the graphene oxide through microwave radiation to obtain amphiphilic cellulose nanocrystal/graphene water dispersion liquid;
completely dissolving 100 parts of EPDM in 1000 parts of cyclohexane, adding the prepared amphiphilic cellulose nanocrystal/graphene aqueous dispersion into an EPDM solution, stirring for 45 min by strong magnetic force, stably distributing cellulose nanocrystals/graphene at a water-cyclohexane interface to form a stable water-in-oil emulsion system, removing a water phase and a cyclohexane phase by freeze drying to obtain an EPDM-coated cellulose nanocrystal/graphene three-dimensional hollow spherical shell, cold pressing for 2 min at the room temperature under the pressure of 6 MPa to regulate the orientation and lamellar arrangement of a cellulose nanocrystal/graphene hybrid network in an EPDM matrix, and obtaining the unvulcanized EPDM/cellulose nanocrystal/graphene composite adhesive;
plasticating the prepared unvulcanized EPDM/cellulose nanocrystal/graphene composite rubber on an open mill at room temperature in a vertical roller direction, sequentially adding 5 parts of zinc oxide, 2 parts of stearic acid and 3 parts of an anti-aging agent, uniformly mixing, then adding 0.5 part of a vulcanization accelerator and 2.5 parts of a vulcanizing agent, and uniformly mixing in a fixed direction to obtain an EPDM/cellulose nanocrystal/graphene composite rubber; placing 24 h, hot-pressing and vulcanizing at 175 ℃ and 12 MPa for 6 min to obtain the EPDM/cellulose nanocrystal/graphene nano composite rubber with the oriented layered hybrid network. Under the aging condition of 120 ℃ '25% strain' 168 h, the compression permanent deformation is 22%, the stress relaxation coefficient is 0.84, and the tensile strength retention rate is 83%.
Example 3
Dispersing 3 parts of cellulose nanocrystals in 200 parts of deionized water, adding 8 parts of graphene oxide, uniformly stirring at 60 ℃, ultrasonically dispersing for 60 min, keeping the temperature at 60 ℃, then placing the mixed dispersion liquid into a microwave oven, controlling the temperature of the microwave oven to be 120 ℃, reacting for 20 s, and thermally reducing the graphene oxide through microwave radiation to obtain amphiphilic cellulose nanocrystal/graphene water dispersion liquid;
completely dissolving 100 parts of EPDM in 800 parts of cyclohexane, adding the prepared amphiphilic cellulose nanocrystal/graphene aqueous dispersion into an EPDM solution, stirring for 35 min by strong magnetic force, stably distributing the cellulose nanocrystal/graphene at a water-cyclohexane interface to form a stable water-in-oil emulsion system, removing a water phase and a cyclohexane phase by freeze drying to obtain an EPDM-coated cellulose nanocrystal/graphene three-dimensional hollow spherical shell, cold pressing for 2 min at room temperature under the pressure of 3 MPa to regulate the orientation and lamellar arrangement of a cellulose nanocrystal/graphene hybrid network in an EPDM matrix, and obtaining the unvulcanized EPDM/cellulose nanocrystal/graphene composite adhesive;
plasticating the prepared unvulcanized EPDM/cellulose nanocrystal/graphene composite rubber on an open mill at room temperature in a vertical roller direction, sequentially adding 2 parts of zinc oxide, 1 part of stearic acid and 1.5 parts of an anti-aging agent, uniformly mixing, then adding 1 part of a vulcanization accelerator and 3 parts of a vulcanizing agent, and uniformly mixing in a fixed direction to obtain an EPDM/cellulose nanocrystal/graphene composite rubber; after 24 h is parked, hot pressing vulcanization is carried out for 8 min at 170 ℃ and 15 MPa, and the EPDM/cellulose nanocrystal/graphene nano composite rubber with the oriented layered hybrid network is obtained. Under the aging condition of 120 ℃ '25% strain' 168 h, the compression permanent deformation is 28%, the stress relaxation coefficient is 0.79, and the tensile strength retention rate is 81%.
Claims (1)
1. The ethylene propylene diene monomer with high sealing resilience and oriented laminar hybrid network is characterized in that the main raw material of the ethylene propylene diene monomer is composed of the following components in parts by mass:
EPDM 100 parts
0.5 to 5 portions of zinc oxide
0.2-4 parts of stearic acid
0.4 to 3 portions of anti-aging agent
0.3-4 parts of vulcanization accelerator
0.5 to 6 portions of vulcanizing agent
2-15 parts of cellulose nanocrystal
2-15 parts of graphene oxide
Wherein the anti-aging agent is any one of 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 2-Mercaptobenzimidazole (MB), N-cyclohexyl-N '-phenyl-p-phenylenediamine (4010), N-phenyl-2-naphthylamine (D) and N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (6 PPD);
the vulcanization accelerator is any one of sulfur (S), triallyl isocyanurate (TAIC), 2-Mercaptobenzothiazole (MBT), tetramethylthiuram disulfide (TMTD), zinc dibutyl dithiocarbamate (BZ) and N-cyclohexyl-2-benzothiazole sulfonamide (CZ);
the vulcanizing agent is any one of dicumyl peroxide (DCP), sulfur (S) and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane (AD);
the preparation method of the ethylene propylene diene monomer rubber with high sealing resilience and oriented layered hybrid network comprises the following steps:
(1) Preparation of amphiphilic cellulose nanocrystal/graphene hybrid aqueous dispersion:
extracting cellulose nanocrystals from cotton, wood, bamboo, sisal plant and sea squirt by a sulfuric acid hydrolysis method, dispersing 2-15 parts of the cellulose nanocrystals in 200-400 parts of deionized water, adding 2-15 parts of graphene oxide, uniformly stirring at 60 ℃, ultrasonically dispersing for 30-150 min, keeping the temperature at 60 ℃ unchanged, then putting the mixed dispersion liquid into a microwave oven, controlling the temperature of the microwave oven to be 120 ℃, reacting for 20-90 s, and thermally reducing the graphene oxide by microwave radiation to obtain amphiphilic cellulose nanocrystal/graphene water dispersion liquid;
(2) Constructing a cellulose nanocrystal/graphene oriented layered hybrid network:
completely dissolving 100 parts of EPDM in 300-1000 parts of cyclohexane, adding the amphiphilic cellulose nanocrystal/graphene aqueous dispersion prepared in the step (1) into an EPDM solution, stirring for 30-60 min by strong magnetic force, stably distributing the cellulose nanocrystal/graphene at a water-cyclohexane interface to form a stable water-in-oil emulsion system, removing a water phase and a cyclohexane phase by freeze drying to obtain an EPDM-coated cellulose nanocrystal/graphene three-dimensional hollow spherical shell, regulating and controlling the orientation and lamellar arrangement of a cellulose nanocrystal/graphene hybridization network in an EPDM matrix at room temperature under the pressure of 3-6 MPa by cold pressing for 2 min, and obtaining the unvulcanized EPDM/cellulose nanocrystal/graphene composite adhesive;
(3) Preparation of oriented layered hybrid network high seal resilience EPDM rubber:
plasticating the unvulcanized EPDM/cellulose nanocrystal/graphene composite rubber prepared in the step (2) on an open mill at room temperature in a direction vertical to a roller, sequentially adding 0.5-5 parts of zinc oxide, 0.2-4 parts of stearic acid and 0.4-3 parts of an anti-aging agent, uniformly mixing, then adding 0.3-4 parts of a vulcanization accelerator and 0.5-6 parts of a vulcanizing agent, and uniformly mixing in a fixed direction to obtain EPDM/cellulose nanocrystal/graphene mixed rubber; placing 24 h, hot-pressing and vulcanizing at 150-180 ℃ and 10-20 MPa for 3-18 min to obtain the EPDM/cellulose nanocrystalline/graphene nano composite rubber with the oriented laminar hybrid network.
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