CN116426074B - Preparation method of double-crosslinked-network-enhanced stabilized ethylene propylene diene monomer rubber - Google Patents
Preparation method of double-crosslinked-network-enhanced stabilized ethylene propylene diene monomer rubber Download PDFInfo
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- 229920002943 EPDM rubber Polymers 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 36
- 229920001971 elastomer Polymers 0.000 claims abstract description 29
- 239000000945 filler Substances 0.000 claims abstract description 26
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 24
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 24
- 229920002258 tannic acid Polymers 0.000 claims abstract description 24
- 229940033123 tannic acid Drugs 0.000 claims abstract description 24
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002121 nanofiber Substances 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000007547 defect Effects 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000007731 hot pressing Methods 0.000 claims abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 238000010008 shearing Methods 0.000 claims abstract description 7
- 238000010128 melt processing Methods 0.000 claims abstract description 6
- 238000009826 distribution Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 230000003712 anti-aging effect Effects 0.000 claims description 11
- 230000001276 controlling effect Effects 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 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 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 230000008439 repair process Effects 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 5
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 5
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 235000013922 glutamic acid Nutrition 0.000 claims description 5
- 239000004220 glutamic acid Substances 0.000 claims description 5
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 5
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-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
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-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
- 238000000034 method Methods 0.000 claims description 4
- KPNYFXUDBVQRNK-UHFFFAOYSA-N 1-(4-anilinophenyl)pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1NC1=CC=CC=C1 KPNYFXUDBVQRNK-UHFFFAOYSA-N 0.000 claims description 3
- 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
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000846 In alloy Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- JJZFJUJKZUIFKN-UHFFFAOYSA-N 1,2-ditert-butyl-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(C(C)(C)C)=C1C(C)(C)C JJZFJUJKZUIFKN-UHFFFAOYSA-N 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- 238000010074 rubber mixing Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 18
- 229910021389 graphene Inorganic materials 0.000 abstract description 17
- 230000032683 aging Effects 0.000 abstract description 10
- 230000003014 reinforcing effect Effects 0.000 abstract description 9
- 230000000087 stabilizing effect Effects 0.000 abstract description 7
- 239000007790 solid phase Substances 0.000 abstract description 6
- 230000009471 action Effects 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920001872 Spider silk Polymers 0.000 description 1
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 1
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a preparation method of a double-crosslinked-network-enhanced stabilized Ethylene Propylene Diene Monomer (EPDM), which is characterized in that a macromolecular reactive melt processing is utilized to graft a carboxylic acid functional compound on an EPDM molecular chain, a carboxyl reactive active site with adjustable interface action is constructed, tannic Acid (TA) is used for repairing the defect of Graphene (GNs) sheets, liquid Metal (LM) is fixed on the surface of silicon nano fibers/graphene (SiNF/GNs) through mechanical shearing, and is induced to be uniformly distributed to form SiNF/GNs-LM hybrid filler, the SiNF/GNs-LM hybrid filler is dispersed on an EPDM rubber matrix through mixing, and covalent and coordination double-crosslinked-network-enhanced EPDM composite rubber is prepared through hot pressing; the carboxyl groups of the EPDM molecular chains and the LM form coordination crosslinking effect, solid-phase stretching-high-temperature exchange is adopted to induce the EPDM molecular chains and SiNF/GNs-LM orientation, the high temperature is adopted to trigger coordination bond exchange reaction, external force is released by cooling at room temperature, siNF/GNs-LM orientation is fixed, the orientation distribution of the hybrid filler in the EPDM matrix is realized, meanwhile, the coordination crosslinking preferentially breaks down covalent crosslinking bonds, energy is dissipated, covalent crosslinking is protected, and the reinforcing and stabilizing effects of the double-crosslinking network are exerted. The dual-crosslinked-network-reinforced stabilized EPDM rubber prepared by the invention has the advantages of simple and convenient preparation process and excellent mechanical property and ageing resistance, and can be used in the field of ageing-resistant rubber products.
Description
Technical Field
The invention relates to a preparation method of a double-crosslinked-network-reinforced stabilized ethylene propylene diene monomer rubber, and belongs to the field of rubber material preparation.
Background
Ethylene Propylene Diene Monomer (EPDM) has excellent compression rebound, electrical insulation, chemical stability and ageing resistance, and has wide application in the fields of automobile industry, building industry, electronic devices and the like, and especially has the largest consumption in the sealing field. However, unlike natural rubber, EPDM rubber has non-self-reinforcing property, and has application value because of the necessity of filler reinforcement, and is generally reinforced by a manner of filling a large amount of conventional fillers such as carbon black, white carbon black and montmorillonite or novel nanofillers such as graphene, carbon nanotubes and nanofibers, so that the mechanical strength and ageing resistance of the EPDM rubber are improved to meet the actual application requirements, but the EPDM rubber generally has the problems of large addition amount, interface effect regulation and control, filler dispersibility and the like. The adoption of the novel reinforcing and stabilizing preparation method for improving the comprehensive performance of the EPDM rubber has important significance.
The natural world such as spider silks, mussel foot silks, bones and the like have extremely excellent toughness, experiments and theories prove that hydrogen bonds, ionic bonds, coordination bonds and the like exist in the materials, the energy dissipation effect is achieved when the materials are subjected to external force, and the mechanical toughness of the materials can be remarkably improved. Tu et al Nature Communication, 2021, 12, 2916 introduce zinc ion coordination bond at lignin and EPDM phase interface, and then through repeated mechanical training, orientation of rubber molecular chain is realized, and functional rubber material with self-reinforcing property is prepared. The Chinese patent CN201910065140.X discloses a reversible crosslinking ethylene propylene diene monomer and a preparation method thereof, wherein a reversible crosslinking system is constructed by utilizing the crosslinking reaction of a D-A reactive group and bismaleimide contained on the side group of EPDM, so that the mechanical property of the reversible crosslinking system is improved. Zhang Ganggang et al, polymer materials science and engineering, 2021, 37 (01), prepared epoxidized ethylene propylene diene monomer, then adopted biobased sebacic acid as a crosslinking agent, and utilized the reaction between epoxy groups and carboxyl groups to construct a dynamic covalent crosslinking network containing beta-hydroxyl ester bonds, which shows excellent mechanical properties. The above reports focus on the study of EPDM mechanical properties, while the study of dynamic cross-linked networks on EPDM aging resistance involves less. At present, the construction of the double cross-linked network is still carried out by adopting a complex polymerization reaction method or taking an organic solvent as a medium, so that the industrialized application is greatly limited, and the research of constructing the double cross-linked network structure aiming at the EPDM rubber system and improving the density and ageing resistance of the EPDM rubber system is lacking. The dynamic cross-linked network is easy to break under the action of external force, the bond energy of the dynamic cross-linked network is lower than that of the covalent cross-linked network, and how to improve the stability of the EPDM rubber in the construction of the dynamic cross-linked system is very important.
The one-dimensional silicon nanofiber has larger length-diameter ratio, high mechanical strength and modulus and obvious reinforcing effect on rubber. The two-dimensional graphene has excellent mechanical strength, and meanwhile, the lamellar structure of the graphene can separate heat and oxygen, has reinforcing and stabilizing effects on high polymer materials such as rubber, has defects, influences the performance of the graphene, and can repair the structural defects of the graphene by utilizing pi-pi conjugation between tannic acid and graphene. The one-dimensional silicon nanofiber and the two-dimensional graphene are hybridized, the reinforcement and stabilization functions of the two are cooperatively exerted, and the reinforcement and stabilization of the EPDM rubber are expected to be realized. Meanwhile, research on realizing the enhancement and stabilization effect of the network structure by regulating and controlling the processing means by utilizing the characteristics of exchangeable reaction and energy dissipation of reversible crosslinking bonds is not reported yet. Therefore, the invention adopts macromolecule reactive melt processing to prepare a double-crosslinked network and utilizes solid-phase stretching-high-temperature exchange to regulate and control a crosslinked network structure, thereby endowing EPDM rubber with high reinforcing and stabilizing effects.
Disclosure of Invention
The invention aims to provide a preparation method of a double-crosslinked-network-enhanced stabilized Ethylene Propylene Diene Monomer (EPDM) rubber, aiming at the defects of the prior art, and the preparation method is characterized in that a carboxylic acid functional compound is grafted with an EPDM molecular chain by utilizing macromolecule reactive melt processing, a carboxyl reaction active site with adjustable interface action is constructed, a Graphene (GNs) lamellar defect is repaired by Tannic Acid (TA), liquid Metal (LM) is fixed on the surface of silicon nanofiber/graphene (SiNF/GNs) through mechanical shearing, and is induced to be uniformly distributed to form SiNF/GNs-LM hybrid filler, the SiNF/GNs-LM hybrid filler is dispersed in an EPDM rubber matrix through mixing, and covalent and coordination double-crosslinked-network-enhanced EPDM composite rubber is prepared through hot pressing; the carboxyl groups of the EPDM molecular chains and the LM form coordination crosslinking effect, solid-phase stretching-high-temperature exchange is adopted to induce the EPDM molecular chains and SiNF/GNs-LM orientation, the coordination bond exchange reaction is triggered at high temperature, the network rearrangement enables the EPDM molecular chains to recover the thermodynamically stable random conformation, the external force is released after cooling at room temperature, siNF/GNs-LM orientation is fixed, the oriented distribution of the hybrid filler in the EPDM matrix is realized, meanwhile, the coordination crosslinking preferentially covalent crosslinking bonds are dissociated and destroyed, the energy is dissipated, the covalent crosslinking is protected, and the reinforcing and stabilizing effects of the double crosslinking network are exerted.
The dual-crosslinked-network-reinforced stabilized ethylene propylene diene monomer rubber is characterized by comprising the following main raw materials in parts by weight:
100 parts of EPDM
0.5-10 Parts of carboxylic acid functional compound
0.2-2 Parts of Liquid Metal (LM)
2-8 Parts of silicon nanofiber (SiNF)
1-12 Parts of Graphene (GNs)
1-5 Parts of anti-aging agent
0.8-5 Parts of vulcanizing agent
0.2-3 Parts of vulcanization accelerator
Wherein the carboxyl functional compound is any one of glutamic acid, maleamic acid and histidine;
The Liquid Metal (LM) is gallium indium alloy Ga65-In35;
the anti-aging agent is any one of N-phenyl-alpha naphthylamine (anti-aging agent A), N-phenyl-2-naphthylamine (anti-aging agent D), 2-Mercaptobenzimidazole (MB) and N- (4-anilinophenyl) Maleimide (MC);
the vulcanizing agent is one of bis (tert-butyl) peroxyisopropyl benzene (BIPB), dicumyl peroxide (DCP) and 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane (bis 25).
The vulcanization accelerator is one of triallyl isocyanurate (TAIC) and zinc methacrylate (ZDMA);
The preparation method of the double-crosslinked-network-enhanced stabilized ethylene propylene diene monomer rubber comprises the following steps:
(1) Preparation of carboxyl functional grafted EPDM rubber
100 Parts of EPDM rubber is added into an internal mixer to be melted at 170 ℃ for 1 min by adopting a macromolecular reactive melt processing method, 0.5 to 10 parts of carboxylic acid functional compound is added for shearing reaction at 50 r/min for 5 to 15 min, and rubber is discharged, so that the carboxyl functional grafted EPDM rubber is prepared.
(2) Preparation of silicon nanofiber/graphene-liquid metal (SiNF/GNs-LM) hybrid filler
1-12 Parts of Graphene (GNs) powder is ultrasonically dispersed in 100-1200 parts of deionized water to form uniform dispersion, 0.1-1.2 parts of Tannic Acid (TA) is added to continue ultrasonic treatment for 1-10 min parts, pi-pi stacking of TA and GNs is promoted to repair the defects of the GNs sheets, then 0.2-2 parts of Liquid Metal (LM) is added to ultrasonically disperse for 20min parts, mechanical stirring for 10 min parts is carried out to promote coordination of TA hydroxyl and LM, then 2-8 parts of silicon nanofiber (SiNF) is added to ultrasonically disperse for 10-120 min parts, after the reaction is finished, suction filtration and deionized water washing are carried out for 3 times, and vacuum drying is carried out at 50 ℃ to obtain the silicon nanofiber/graphene-liquid metal (SiNF/GNs-LM) hybrid filler.
(3) Preparation of dual-crosslinked-network-enhanced stabilized ethylene propylene diene monomer rubber
Mixing the carboxyl functional grafted EPDM rubber prepared in the step (1) and SiNF/GNs-LM hybrid filler prepared in the step (2) on an open mill, sequentially adding 1-5 parts of an anti-aging agent, 0.8-5 parts of a vulcanizing agent and 0.2-3 parts of a vulcanization accelerator, uniformly mixing, and hot-pressing and vulcanizing at 160 ℃ and 15 MPa for 5-20 min to obtain EPDM composite rubber with a double cross-linked network; and placing the EPDM composite rubber in a high-temperature environment box, controlling the temperature to be 50-120 ℃, regulating and controlling the tensile strain to be 30-300%, triggering the coordination bond exchange reaction at high temperature, and then releasing the strain after cooling at room temperature to realize the oriented distribution of the hybrid filler in the EPDM matrix, thereby obtaining the double-crosslinked reinforced stabilized EPDM rubber.
The invention has the following advantages: a macromolecular reactive melt processing method is adopted to introduce carboxyl reaction sites into EPDM molecular chains, tannic Acid (TA) is used for repairing defects of Graphene (GNs) sheets, silicon nanofiber/graphene-liquid metal (SiNF/GNs-LM) hybrid filler is prepared through mechanical shearing, EPDM composite rubber with covalent and coordination double-crosslinking networks is prepared through mixing and hot pressing, the reinforcing effect is exerted, the carboxyl groups of the EPDM molecular chains and the LM form the coordination crosslinking effect, solid-phase stretching-high-temperature exchange is adopted to induce the EPDM molecular chains and SiNF/GNs-LM orientation, the high-temperature trigger coordination bond exchange reaction is adopted, external force is released through cooling at room temperature, siNF/GNs-LM orientation is fixed, the orientation distribution of the hybrid filler in an EPDM matrix is realized, the coordination crosslinking preferential covalent crosslinking bonds are dissociated and destroyed under the action of the external force, the energy is dissipated, so that the covalent crosslinking network is protected, and the reinforcing and stabilizing effects of the double-crosslinking network are exerted.
Drawings
FIG. 1 is a schematic illustration of a silicon nanofiber/graphene-liquid metal (SiNF/GNs-LM) hybrid filler and solid phase stretching-high temperature exchange.
Detailed Description
The present invention is further described with reference to specific examples and fig. 1, where it is to be understood that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, since other modifications can be made by those skilled in the art to which the invention pertains.
Examples
100 Parts of EPDM rubber is added into an internal mixer to be melted at 170 ℃ for 1min, 2 parts of glutamic acid is added for shearing reaction at 50 r/min for 7 min, and rubber is discharged, so that the glutamic acid grafted EPDM rubber is prepared.
5 Parts of Graphene (GNs) powder is ultrasonically dispersed in 500 parts of deionized water to form a uniform dispersion, 0.6 part of Tannic Acid (TA) is added to continue ultrasonic treatment for 10 min parts, pi-pi stacking effect of TA and GNs is promoted to repair GNs lamellar defects, then 1 part of Liquid Metal (LM) is added to ultrasonically disperse 20min parts, mechanical stirring is carried out for 10 min parts to promote coordination of TA hydroxyl and LM, 3 parts of silicon nanofiber (SiNF) is added to ultrasonically disperse 30 min parts, after the reaction is finished, suction filtration and deionized water washing are carried out for 3 times, and then the silicon nanofiber/graphene-liquid metal (SiNF/GNs-LM) hybrid filler is obtained through vacuum drying at 50 ℃.
Mixing the prepared glutamic acid grafted EPDM rubber and SiNF/GNs-LM hybrid filler on an open mill, sequentially adding 2 parts of an anti-aging agent MB, 3 parts of DCP and1 part of TAIC, uniformly mixing, and hot-pressing and vulcanizing at 160 ℃ and 15: 15 MPa for 10 min to obtain EPDM composite rubber with a double cross-linked network; and (3) placing the EPDM composite rubber in a high-temperature environment box, controlling the temperature to be 70 ℃, regulating and controlling the tensile strain to be 100%, and then cooling at room temperature and then releasing the strain to obtain the double-crosslinked-network reinforced stabilized EPDM rubber. The tensile strength of the EPDM composite rubber is 8.52 MPa, and the elongation at break is 466%; under the aging condition of 100 ℃ 1.2 MPa' 96 h, the stress relaxation coefficient is 0.82, the tensile strength retention rate is 86%, and the elongation at break retention rate is 83%.
Examples
100 Parts of EPDM rubber is added into an internal mixer to be melted at 170 ℃ for 1 min parts of maleamic acid is added into the internal mixer to be sheared for 10 min at 50r/min, and rubber is discharged, so that the maleamic acid grafted EPDM rubber is prepared.
8 Parts of Graphene (GNs) powder is ultrasonically dispersed in 800 parts of deionized water to form a uniform dispersion, 1 part of Tannic Acid (TA) is added to continue ultrasonic treatment for 10 min parts, pi-pi stacking effect of TA and GNs is promoted to repair the defects of GNs sheets, then 1.2 parts of Liquid Metal (LM) is added to ultrasonically disperse 20min parts, mechanical stirring is carried out for 10 min parts to promote coordination of TA hydroxyl and LM, then 5 parts of silicon nanofiber (SiNF) is added to ultrasonically disperse 30 min parts, after the reaction is finished, suction filtration and deionized water washing are carried out for 3 times, and then the silicon nanofiber/graphene-liquid metal (SiNF/GNs-LM) hybridized filler is obtained through vacuum drying at 50 ℃.
Mixing the prepared maleamic acid grafted EPDM rubber and SiNF/GNs-LM hybrid filler on an open mill, sequentially adding 2.5 parts of anti-aging agent D, 2.5 parts of BIPB and 1.5 parts of TAIC, uniformly mixing, and hot-pressing and vulcanizing at 160 ℃ and 15 MPa for 15 min to obtain EPDM composite rubber with a double cross-linked network; and (3) placing the EPDM composite rubber in a high-temperature environment box, controlling the temperature to 90 ℃, regulating and controlling the tensile strain to 200%, and then cooling at room temperature to release the strain to obtain the double-crosslinked reinforced stabilized EPDM rubber. The tensile strength of the EPDM composite rubber is 11.36 MPa, and the elongation at break is 519%; the stress relaxation coefficient of the alloy is 0.87, the tensile strength retention rate is 89% and the elongation at break retention rate is 86% under the aging condition of 100 ℃ 1.2 MPa' 96 h.
Examples
100 Parts of EPDM rubber is added into an internal mixer to be melted at 170 ℃ for 1 min, 7 parts of histidine is added for shearing reaction at 50 r/min for 12 min, and rubber is discharged, so that the histidine grafted EPDM rubber is prepared.
10 Parts of Graphene (GNs) powder is ultrasonically dispersed in 1000 parts of deionized water to form a uniform dispersion, 1.2 parts of Tannic Acid (TA) is added for continuously carrying out ultrasonic treatment for 10 min, pi-pi stacking of TA and GNs is promoted to repair GNs lamellar defects, then 2 parts of Liquid Metal (LM) is added for ultrasonic dispersion for 20 min, mechanical stirring for 10 min is adopted for promoting TA hydroxyl and LM coordination, then 6 parts of silicon nanofiber (SiNF) is added for ultrasonic dispersion for 30 min, after the reaction is finished, suction filtration and deionized water washing are carried out for 3 times, and then the silicon nanofiber/graphene-liquid metal (SiNF/GNs-LM) hybrid filler is obtained through vacuum drying at 50 ℃.
Mixing the prepared histidine grafted EPDM rubber and SiNF/GNs-LM hybrid filler on an open mill, sequentially adding 3 parts of anti-aging agent MC, 2 parts of double 25 and 2 parts of ZDMA, uniformly mixing, and hot-pressing and vulcanizing at 160 ℃ and 15: 15 MPa for 20: 20 min to obtain EPDM composite rubber with a double cross-linked network; and (3) placing the EPDM composite rubber in a high-temperature environment box, controlling the temperature to be 100 ℃, regulating and controlling the tensile strain to be 300%, and then cooling at room temperature and then releasing the strain to obtain the double-crosslinked-network reinforced stabilized EPDM rubber. The tensile strength of the EPDM composite rubber is 12.41 MPa, and the elongation at break is 602%; under the aging condition of 100 ℃ 1.2 MPa' 96 h, the stress relaxation coefficient is 0.91, the tensile strength retention rate is 90%, and the elongation at break retention rate is 85%.
In summary, the EPDM composite rubber material with high reinforcing and stabilizing effects is obtained by a solid-phase stretching-high-temperature exchange preparation method based on the preparation of EPDM rubber with double cross-linked networks, and can be used in the field of aging-resistant rubber products.
Claims (1)
1. The dual-crosslinked-network-reinforced stabilized ethylene propylene diene monomer rubber is characterized by comprising the following main raw materials in parts by weight:
100 parts of EPDM
0.5-10 Parts of carboxylic acid functional compound
Liquid metal LM 0.2-2 parts
Silicon nanofiber SiNF-8 parts
GNs 1-12 parts
1-5 Parts of anti-aging agent
0.8-5 Parts of vulcanizing agent
0.2-3 Parts of vulcanization accelerator;
Wherein the carboxylic acid functional compound is any one of glutamic acid, maleamic acid and histidine;
The liquid metal LM is gallium indium alloy Ga65-In35;
The anti-aging agent is any one of N-phenyl-alpha naphthylamine, N-phenyl-2-naphthylamine, 2-mercaptobenzimidazole MB and N- (4-anilinophenyl) maleimide MC;
the vulcanizing agent is one of di-tert-butyl isopropyl benzene BIPB peroxide, dicumyl peroxide DCP and 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane;
The vulcanization accelerator is one of triallyl isocyanurate TAIC and zinc methacrylate ZDMA;
The preparation method of the double-crosslinked-network-enhanced stabilized ethylene propylene diene monomer rubber comprises the following steps:
(1) Preparation of carboxyl functional grafted EPDM rubber
Adding 100 parts of EPDM rubber into an internal mixer to melt at 170 ℃ for 1 min by adopting a macromolecular reactive melt processing method, adding 0.5-10 parts of carboxylic acid functional compound, carrying out shearing reaction at 50 r/min for 5-15 min, and discharging rubber to prepare carboxyl functional grafted EPDM rubber;
(2) Preparation of silicon nanofiber/GNs-liquid metal hybrid filler
1-12 Parts of GNs powder is ultrasonically dispersed in 100-1200 parts of deionized water to form uniform dispersion, 0.1-1.2 parts of tannic acid TA is added to continue ultrasonic treatment for 1-10 min, pi-pi stacking effect of TA and GNs is promoted to repair the defects of GNs sheets, then 0.2-2 parts of liquid metal LM is added to ultrasonically disperse 20min, mechanical stirring is carried out for 10 min to promote coordination of TA hydroxyl and LM, 2-8 parts of silicon nanofiber SiNF is added to ultrasonically disperse 10-120 min, after the reaction is finished, suction filtration and deionized water washing are carried out for 3 times, and vacuum drying is carried out at 50 ℃ to obtain the silicon nanofiber/GNs-liquid metal hybrid filler;
(3) Preparation of dual-crosslinked-network-enhanced stabilized ethylene propylene diene monomer rubber
Mixing the carboxyl functional grafted EPDM rubber prepared in the step (1) and the silicon nanofiber/GNs-liquid metal hybrid filler prepared in the step (2) on an open mill, sequentially adding 1-5 parts of an anti-aging agent, 0.8-5 parts of a vulcanizing agent and 0.2-3 parts of a vulcanization accelerator, uniformly mixing, and hot-pressing and vulcanizing at 160 ℃ and 15 MPa to 20min to obtain EPDM composite rubber with a double cross-linked network; and placing the EPDM composite rubber in a high-temperature environment box, controlling the temperature to be 50-120 ℃, regulating and controlling the tensile strain to be 30-300%, triggering the coordination bond exchange reaction at high temperature, and then releasing the strain after cooling at room temperature to realize the oriented distribution of the hybrid filler in the EPDM matrix, thereby obtaining the double-crosslinked reinforced stabilized EPDM rubber.
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