CN115594986A - High-conductivity fluororubber sealing ring for lithium battery and preparation method thereof - Google Patents
High-conductivity fluororubber sealing ring for lithium battery and preparation method thereof Download PDFInfo
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- CN115594986A CN115594986A CN202211252486.9A CN202211252486A CN115594986A CN 115594986 A CN115594986 A CN 115594986A CN 202211252486 A CN202211252486 A CN 202211252486A CN 115594986 A CN115594986 A CN 115594986A
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- Prior art keywords
- fluororubber
- sealing ring
- polydopamine
- conductivity
- parts
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- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 91
- 238000007789 sealing Methods 0.000 title claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920001690 polydopamine Polymers 0.000 claims abstract description 57
- 239000003094 microcapsule Substances 0.000 claims abstract description 49
- 229920005610 lignin Polymers 0.000 claims abstract description 48
- 239000003063 flame retardant Substances 0.000 claims abstract description 45
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 73
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 41
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 35
- 239000000047 product Substances 0.000 claims description 33
- 229920001971 elastomer Polymers 0.000 claims description 31
- 239000005060 rubber Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 27
- 238000004073 vulcanization Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 25
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 10
- 239000004203 carnauba wax Substances 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- 229960003638 dopamine Drugs 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 9
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 9
- 238000010074 rubber mixing Methods 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000004513 sizing Methods 0.000 claims description 4
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229920002367 Polyisobutene Polymers 0.000 claims description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 2
- MEBJLVMIIRFIJS-UHFFFAOYSA-N hexanedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)CCCCC(O)=O MEBJLVMIIRFIJS-UHFFFAOYSA-N 0.000 claims description 2
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims description 2
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 238000012695 Interfacial polymerization Methods 0.000 abstract 1
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of fluororubber; in particular to a high-conductivity fluororubber sealing ring for a lithium battery and a preparation method thereof. According to the invention, the lignin-based flame retardant is synthesized firstly, and then polydopamine is loaded on the surface of the lignin flame retardant by an interfacial polymerization method under an alkaline condition to prepare the polydopamine microcapsule, so that the problem of agglomeration generated when the lignin-based flame retardant is directly blended with fluororubber is solved, the flame retardant property of the fluororubber is improved, and the tensile strength of the fluororubber can be enhanced. The polydopamine has a certain conductive capacity, a large number of active groups are rich on the surface of the polydopamine, the polydopamine can adsorb metal ions, the polydopamine can be modified by a hydrothermal method, and metal nano copper with excellent conductive capacity is loaded on the surface of the polydopamine microcapsule. After the modified polydopamine microcapsule and fluororubber are blended, a high-conductivity fluororubber sealing ring with better flame retardance and higher tensile strength can be prepared.
Description
Technical Field
The invention relates to the technical field of fluororubber, in particular to a high-conductivity fluororubber sealing ring for a lithium battery and a preparation method thereof.
Background
The sealing ring is a part for preventing fluid or solid particles from leaking from adjacent joint surfaces and preventing impurities such as external air, dust, moisture and the like from invading the interior of machine equipment, and is widely applied to the fields of chemical industry, agriculture, national defense, aerospace, medical treatment, petroleum, ships and other industries at present.
The sealing ring has various types, and most of the sealing rings belong to rubber materials. Rubber is a high-elasticity polymer material with reversible deformation and is divided into natural rubber and synthetic rubber. Natural rubber is limited by the climate of the producing area, the yield is relatively low and unstable, and synthetic rubber is one of three synthetic materials, which are various, including butyl cyanide rubber, ethylene propylene diene monomer rubber, fluororubber, silica gel and the like, and has the characteristics of wide application, good air tightness, elasticity, cold resistance, heat resistance and the like. Nitrile butadiene rubber, ethylene propylene diene monomer rubber, fluororubber, silica gel and the like. Wherein, the fluorine rubber is a synthetic polymer elastomer containing fluorine atoms on carbon atoms of a main chain or a side chain, and the fluorine atoms have better high temperature resistance, oil resistance and chemical corrosion resistance and can effectively resist most of solutions such as acid, alkali, oil and the like; the fluororubber with high conductivity can lead static out, reduce the harm of the static to the product, and is mainly applied to the fields of liquid crystal semiconductor drying procedures, lithium batteries and the like at present.
The conductive fluororubber is a new material formed by adding conductive substances on the basis of the fluororubber, and the fluororubber with the conductive performance can be obtained by blending the conductive materials and the fluororubber under the normal condition. The conductive capability of the fluororubber is positively correlated with the content of the conductive material, and when a small amount of conductive material is added, the conductive performance of the fluororubber is poor; and because most conductive materials have poor dispersibility in fluororubber, when the content of the conductive materials is high, the fluororubber is difficult to mold. Therefore, the invention of a high-conductivity sealing ring for a lithium battery and a preparation method thereof is needed, which can not only maintain the original performance of a fluororubber material, but also endow the fluororubber material with good conductivity.
Disclosure of Invention
The invention aims to provide a high-conductivity fluororubber sealing ring for a lithium battery and a preparation method thereof, and aims to solve the problems in the background art.
In order to solve the technical problems, the invention provides the following technical scheme: a high-conductivity fluororubber sealing ring for a lithium battery and a preparation method thereof are disclosed, which comprises the following steps:
step 1: preparing modified polydopamine microcapsules:
s1: preparing a lignin-based flame retardant:
a. dissolving anhydrous piperazine (PIP), carbon tetrachloride and triethylamine in dichloromethane, dropwise adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) in a nitrogen environment, reacting for 8 hours at room temperature, washing and drying to obtain a product A;
b. mixing lignin and the product A, dissolving in dimethylformamide, heating in a water bath to 75 ℃, adding formaldehyde, carrying out condensation reflux reaction for 3 hours, adding ionized water to obtain a precipitate, washing with ethanol, and drying to obtain a product B;
c. dispersing the product B, triethylamine and DOPO in dimethylformamide, adding carbon tetrachloride in the nitrogen atmosphere, reacting at room temperature for 8h, and adding excessive deionized water to obtain a precipitate; washing with ethanol, and drying to obtain lignin-based flame retardant;
s2: adding the lignin-based flame retardant into a dimethylformamide solution, and performing ultrasonic treatment for 30min to uniformly disperse to obtain a mixed solution; adding dopamine into the mixed solution under the water bath condition of 30-40 ℃, rotating at 300-500 rpm, and stirring for 10-20 min; then adding trihydroxymethyl aminomethane for reaction for 0.5-1 h, after the reaction is finished, performing suction filtration to obtain a filter cake, dispersing the filter cake in an acetone solution, washing to remove impurities, and then washing, filtering and drying by using deionized water to obtain polydopamine microcapsules;
s3: dispersing polydopamine microcapsules into deionized water, adding dopamine hydrochloride solution, stirring for 30min, adding copper sulfate solution, and continuously stirring; and dropwise adding a sodium hydroxide solution to adjust the pH value to 4-5, then continuously stirring, transferring into a high-pressure kettle, heating to 120-140 ℃, reacting for 10-12 h, centrifuging, filtering, washing and drying to obtain the modified polydopamine microcapsule.
Step 2: adding the raw fluororubber, the modified polydopamine microcapsules, the antioxidant and the plasticizer into an internal mixer together, controlling the temperature to be 130-180 ℃, fully mixing, extruding, bracing and granulating by a double-screw extruder at 150-190 ℃ to obtain raw fluororubber mixing rubber material;
and step 3: and (3) adding a vulcanizing agent and the raw rubber mixed rubber material prepared in the step (2) into an internal mixer by adopting a two-stage vulcanization method for uniform dispersion, and performing a hot press molding process to obtain the fluororubber sealing ring.
Furthermore, the molar ratio of the triethylamine, the carbon tetrachloride, the DOPO and the PIP in the step a is 1 to (1-1.2) to (0.8-1.1) to (2.8-3.2).
Further, the content of each component in the b is 8-10 parts of lignin, 15-20 parts of product A and 18-22 parts of formaldehyde by weight.
Furthermore, the content of each component in c is 2-3 parts of product B, 2-3 parts of triethylamine, 4-4.5 parts of DOPO and 2.8-3.3 parts of carbon tetrachloride by weight.
Further, in S1, the water bath temperature is 60-75 ℃, and the acid treatment time is 2-3 h.
Further, the S2 comprises 0.5-1 part of lignin-based flame retardant, 3-5 parts of dimethylformamide solution, 0.1-0.25 part of dopamine, 0.01-0.02 part of tris (hydroxymethyl) aminomethane and 2-3 parts of acetone solution by weight.
Further, the dosage of each component in S3 is, by weight, 1-2 parts of polydopamine microcapsule, 2-3 parts of deionized water, 0.5-0.6 part of dopamine hydrochloride solution and 0.6-0.8 part of copper sulfate solution.
Further, in the step 2, the raw rubber mixing sizing material comprises, by weight, 110-145 parts of raw fluororubber, 0.4-0.6 part of modified polydopamine microcapsule, 0.1-0.5 part of antioxidant, 0.1-0.3 part of plasticizer and 0.1-0.3 part of flame retardant.
Further, in the step 2, the crude fluororubber is any one of vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer and vinylidene fluoride-hexafluoropropylene copolymer; the antioxidant is one or more of 1010, 168, 1076, 626 and 1790; the plasticizer is one or more of dioctyl adipate, epoxy butyl oleate, dioctyl sebacate, propylene glycol adipate, polyisobutylene and palm wax.
Further, in the step 3, the contents of the components are 0.4-1.3 parts by weight of vulcanizing agent and 115-135 parts by weight of raw rubber mixing rubber material.
Further, in step 3, the vulcanizing agent is any one of sulfur, benzoyl peroxide and 2, 4-dichlorobenzoyl peroxide.
Further, the first stage vulcanization conditions are as follows: the pressure is 8-10 MPa, the temperature is 150-180 ℃, and the time is 10-15 min; the secondary vulcanization conditions are as follows: the temperature is 200-230 ℃, and the time is 2-4 h; the temperature is controlled at 170-230 ℃ in the molding process, the pressure is 1-3 MPa, and the molding time is 0.5-2 h.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, the lignin-based flame retardant is synthesized, and then polydopamine is loaded on the surface of the lignin flame retardant under an alkaline condition by an interface polymerization method, so that the polydopamine microcapsule is prepared. The polydopamine microcapsule can be better blended with the fluororubber, so that the flame retardant is uniformly dispersed in the fluororubber, the problem of the performance reduction of the fluororubber caused by the agglomeration of the flame retardant is solved, the flame retardant property of the fluororubber is improved, and the tensile strength of the fluororubber can be enhanced. The polydopamine has a certain conductive capability, a large number of active groups are rich on the surface of the polydopamine, the polydopamine can adsorb metal ions, metal nano-copper with excellent conductive capability can be loaded on the surface of a polydopamine microcapsule by a hydrothermal method to modify the polydopamine microcapsule, and after the modified dopamine microcapsule is blended with fluororubber, the conductive performance is remarkably improved, so that the high-conductive fluororubber sealing ring with better flame retardance and higher tensile strength is prepared.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the following examples, the main material sources are as follows: lignin comes from saikogaku science, CAS No.: 9005-53-2, average molecular weight 509, purity 98%; triethylamine from mcoline, CAS number: 121-44-8, dichloromethane from lixin chemical, CAS number: 75-09-2; carbon tetrachloride is available from mclin, CAS No.: 56-23-5; PIP from mcelin, CAS number: 110-85-0, DOPO from mclin, CAS No.: 35948-25-5, wherein the crude fluororubber is a copolymer of vinylidene fluoride and chlorotrifluoroethylene, and is from Jiangsu Zhongyu rubber and plastic science and technology Co.Ltd; carbon black is from New Dilute Metallurgical chemical Co., ltd, guangzhou; nitric acid from tengsheng chemistry, CAS number: 9697-37-2; dopamine hydrochloride comes from cameisu biotechnology, CAS number: 62-31-7; copper sulfate was from mingxin chemical, CAS number: 7758-98-7; sodium hydroxide was from the hainakawa chemical industry, CAS No.: 1310-73-2; acetone is from mclin, CAS No.: 67-64-1; n, N-dimethylformamide was obtained from xinsheng chemical, CAS No.: 68-12-2; dopamine is from shanxi hana biotechnology ltd, CAS number: 51-61-6; antioxidant 1010 is from Shanghai peacui chemical Co., ltd; the palm wax is from Shanghai Yiba chemical industry Co., ltd; 2,4, 6-tribromophenol from a prothallium organism, CAS No.: 106-40-2;2, 4-Dichlorobenzoyl peroxide was obtained from Jiangsu pexing chemical Co., ltd, CAS No.: 133-14-2; the carbon nanotube is from Shenzhen Tuling evolutionary technology, inc.; the carbon fiber is from silk-resistant carbon fiber technology limited of Dongguan.
Example 1:
step 1: preparing modified polydopamine microcapsules:
s1: preparing a lignin-based flame retardant:
a. dissolving 1mol of triethylamine, 1mol of carbon tetrachloride and 2.8mol of PIP in dichloromethane, adding 0.8mol of DOPO in a nitrogen environment, reacting for 8 hours at room temperature, washing and drying to obtain a product A;
b. mixing 0.8kg of lignin and 1.5kg of the product A, dissolving in dimethylformamide, heating in a water bath to 75 ℃, adding 1.8kg of formaldehyde, carrying out condensation reflux reaction for 3 hours, adding ionized water to obtain a precipitate, washing with ethanol, and drying to obtain a product B;
c. dispersing 2kg of the product B, 2kg of triethylamine and 4kg of DOPO in dimethylformamide, adding 2.8kg of carbon tetrachloride in the nitrogen atmosphere, reacting at room temperature for 8h, and adding excessive deionized water to obtain a precipitate; washing with ethanol, and drying to obtain lignin-based flame retardant;
s2: adding 0.5kg of lignin-based flame retardant into 3kg of dimethylformamide solution, and performing ultrasonic treatment for 30min to uniformly disperse to obtain mixed solution; adding 0.1kg of dopamine into the mixed solution under the condition of water bath at the temperature of 30 ℃, rotating at 300rpm, and stirring for 10min; then adding 0.01kg of tris (hydroxymethyl) aminomethane for reaction for 0.5h, after the reaction is finished, performing suction filtration to obtain a filter cake, dispersing the filter cake in 2kg of acetone solution, washing to remove impurities, washing with deionized water, filtering, and drying to obtain polydopamine microcapsules;
s3: dispersing 1kg of polydopamine microcapsules into 2kg of deionized water, adding 0.5kg of dopamine hydrochloride solution, stirring for 30min, adding 0.6kg of copper sulfate solution, and continuously stirring; dropwise adding a sodium hydroxide solution to adjust the pH value to 4, then continuously stirring, transferring into an autoclave, heating to 120 ℃, reacting for 10 hours, and then centrifuging, filtering, washing and drying to obtain modified polydopamine microcapsules;
step 2: adding 110kg of fluororubber raw rubber, 0.4kg of modified polydopamine microcapsules, 0.1kg of antioxidant 1010 and 0.1kg of palm wax into an internal mixer, controlling the temperature to be 130 ℃ for full mixing, extruding, bracing and granulating by a double-screw extruder at 150 ℃ to obtain fluororubber raw rubber mixing rubber material;
and step 3: adding 0.4kg of 2, 4-dichlorobenzoyl peroxide and 115kg of the fluororubber raw rubber mixed rubber material prepared in the step 2 into an internal mixer by adopting a two-stage vulcanization method for uniform dispersion, wherein the one-stage vulcanization condition is as follows: the pressure is 8MPa, the temperature is 150 ℃, and the time is 10min; the secondary vulcanization conditions are as follows: the temperature is 200 ℃, and the time is 2h; and in the hot-press forming process, the temperature is controlled at 170 ℃, the pressure is 1MPa, and the forming time is 0.5h to obtain the fluororubber sealing ring.
Example 2:
step 1: preparing modified polydopamine microcapsules:
s1: preparing a lignin-based flame retardant:
a. dissolving 1mol of triethylamine, 1.1mol of carbon tetrachloride and 3mol of PIP in dichloromethane, adding 1mol of DOPO in a nitrogen environment, reacting for 8 hours at room temperature, washing and drying to obtain a product A;
b. mixing 0.9kg of lignin and 1.8kg of the product A, dissolving in dimethylformamide, heating in a water bath to 75 ℃, adding 2kg of formaldehyde, carrying out condensation reflux reaction for 3 hours, adding ionized water to obtain a precipitate, washing with ethanol, and drying to obtain a product B;
c. dispersing 2.3kg of the product B, 2.6kg of triethylamine and 4.2kg of DOPO in dimethylformamide, adding 3kg of carbon tetrachloride in the nitrogen atmosphere, reacting at room temperature for 8 hours, and adding excessive deionized water to obtain a precipitate; washing with ethanol, and drying to obtain lignin-based flame retardant;
s2: adding 0.6kg of lignin-based flame retardant into 3.8kg of dimethylformamide solution, and performing ultrasonic treatment for 30min to uniformly disperse to obtain mixed solution; adding 0.15kg of dopamine into the mixed solution under the condition of 35 ℃ water bath, rotating at 400rpm, and stirring for 15min; then adding 0.015kg of tris (hydroxymethyl) aminomethane for reaction for 0.75h, after the reaction is finished, performing suction filtration to obtain a filter cake, dispersing the filter cake in 2.3kg of acetone solution, washing to remove impurities, washing with deionized water, filtering, and drying to obtain polydopamine microcapsules;
s3: dispersing 1.2kg of polydopamine microcapsules into 2.4kg of deionized water, adding 0.54kg of dopamine hydrochloride solution, stirring for 30min, adding 0.65kg of copper sulfate solution, and continuously stirring; dropwise adding a sodium hydroxide solution to adjust the pH value to 4.5, then continuously stirring, transferring into an autoclave, heating to 120 ℃, reacting for 11 hours, and then centrifuging, filtering, washing and drying to obtain modified polydopamine microcapsules;
step 2: adding 125kg of raw fluororubber, 0.54kg of modified polydopamine microcapsules, 0.3kg of antioxidant 1010 and 0.2kg of palm wax into an internal mixer, controlling the temperature to be 150 ℃, fully mixing, extruding, bracing and granulating by a double-screw extruder at 170 ℃ to obtain raw fluororubber mixed rubber material;
and 3, step 3: adding 0.7kg of 2, 4-dichlorobenzoyl peroxide and 120kg of the fluororubber raw rubber mixed sizing material prepared in the step 2 into an internal mixer by adopting a two-stage vulcanization method for uniform dispersion, wherein the one-stage vulcanization condition is as follows: the pressure is 8.5MPa, the temperature is 160 ℃, and the time is 10min; the secondary vulcanization conditions are as follows: the temperature is 210 ℃, and the time is 2.5h; and in the hot-press forming process, the temperature is controlled at 190 ℃, the pressure is 2MPa, and the forming time is 1h to obtain the fluororubber sealing ring.
Example 3:
step 1: preparing modified polydopamine microcapsules:
s1: preparing a lignin-based flame retardant:
a. dissolving 1mol of triethylamine, 1.2mol of carbon tetrachloride and 3.2mol of PIP in dichloromethane, adding 1.1mol of DOPO in a nitrogen environment, reacting for 8 hours at room temperature, washing and drying to obtain a product A;
b. mixing 1kg of lignin and 2kg of the product A, dissolving in dimethylformamide, heating in water bath to 75 ℃, adding 2.2kg of formaldehyde, carrying out condensation reflux reaction for 3 hours, adding ionized water to obtain a precipitate, washing with ethanol, and drying to obtain a product B;
c. dispersing 3kg of the product B, 3kg of triethylamine and 4.5kg of DOPO in dimethylformamide, adding 3.3kg of carbon tetrachloride in the nitrogen atmosphere, reacting at room temperature for 8h, and adding excessive deionized water to obtain a precipitate; washing with ethanol, and drying to obtain lignin-based flame retardant;
s2: adding 1kg of lignin-based flame retardant into 5kg of dimethylformamide solution, and performing ultrasonic treatment for 30min to uniformly disperse the lignin-based flame retardant to obtain a mixed solution; adding 0.25kg of dopamine into the mixed solution under the condition of water bath at 40 ℃, rotating at 500rpm, and stirring for 20min; then adding 0.02kg of tris (hydroxymethyl) aminomethane for reaction for 1h, performing suction filtration after the reaction is finished to obtain a filter cake, dispersing the filter cake in 3kg of acetone solution, washing to remove impurities, washing with deionized water, filtering, and drying to obtain polydopamine microcapsules;
s3: dispersing 2kg of polydopamine microcapsules into 3kg of deionized water, adding 0.6kg of dopamine hydrochloride solution, stirring for 30min, adding 0.8kg of copper sulfate solution, and continuously stirring; dropwise adding a sodium hydroxide solution to adjust the pH value to 5, then continuously stirring, transferring into a high-pressure kettle, heating to 140 ℃, reacting for 12 hours, and then centrifuging, filtering, washing and drying to obtain modified polydopamine microcapsules;
step 2: adding 145kg of raw fluororubber, 0.6kg of modified polydopamine microcapsules, 0.5kg of antioxidant 1010 and 0.3kg of palm wax into an internal mixer, controlling the temperature to be 180 ℃, fully mixing, extruding, bracing and granulating at 190 ℃ through a double-screw extruder to obtain raw fluororubber mixed rubber material;
and step 3: 1.3kg of 2, 4-dichlorobenzoyl peroxide and 135kg of the raw rubber mixing rubber material prepared in the step 2 are added into an internal mixer to be uniformly dispersed by adopting a two-stage vulcanization method, wherein the one-stage vulcanization condition is as follows: the pressure is 10MPa, the temperature is 180 ℃, and the time is 15min; the secondary vulcanization conditions are as follows: the temperature is 230 ℃, and the time is 4h; and in the hot-press forming process, the temperature is controlled at 230 ℃, the pressure is 3MPa, and the forming time is 2 hours to obtain the fluororubber sealing ring.
Comparative example 1:
lignin was used instead of lignin-based flame retardants.
Step 1: preparing modified polydopamine microcapsules:
s1: adding 0.5kg of lignin into 3kg of dimethylformamide solution, and performing ultrasonic treatment for 30min to uniformly disperse the lignin so as to obtain a mixed solution; adding 0.1kg of dopamine into the mixed solution under the condition of water bath at 30 ℃, rotating at 300rpm, and stirring for 10min; then adding 0.01kg of tris (hydroxymethyl) aminomethane for reaction for 0.5h, performing suction filtration after the reaction is finished to obtain a filter cake, dispersing the filter cake in 2kg of acetone solution, washing to remove impurities, washing with deionized water, filtering, and drying to obtain polydopamine microcapsules;
s2: dispersing 1kg of polydopamine microcapsules into 2kg of deionized water, adding 0.5kg of dopamine hydrochloride solution, stirring for 30min, adding 0.6kg of copper sulfate solution, and continuously stirring; dropwise adding a sodium hydroxide solution to adjust the pH value to 4, then continuously stirring, transferring into an autoclave, heating to 120 ℃, reacting for 10 hours, and then centrifuging, filtering, washing and drying to obtain modified polydopamine microcapsules;
step 2: adding 110kg of raw fluororubber, 0.4kg of modified polydopamine microcapsules, 0.1kg of antioxidant 1010 and 0.1kg of palm wax into an internal mixer, controlling the temperature to be 130 ℃ for full mixing, extruding, bracing and granulating at 150 ℃ through a double-screw extruder to obtain raw fluororubber mixed rubber material;
and step 3: adding 0.4kg of 2, 4-dichlorobenzoyl peroxide and 115kg of the fluororubber raw rubber mixing material prepared in the step 2 into an internal mixer for uniform dispersion by adopting a two-stage vulcanization method, wherein the one-stage vulcanization condition is as follows: the pressure is 8MPa, the temperature is 150 ℃, and the time is 10min; the secondary vulcanization conditions are as follows: the temperature is 200 ℃, and the time is 2h; and in the hot-press forming process, the temperature is controlled at 170 ℃, the pressure is 1MPa, and the forming time is 0.5h to obtain the fluororubber sealing ring.
Step 1: adding 110kg of fluororubber raw rubber, 0.4kg of lignin, 0.1kg of antioxidant 1010 and 0.1kg of palm wax into an internal mixer together, controlling the temperature to be 130 ℃ for full mixing, extruding, bracing and granulating at 150 ℃ by a double-screw extruder to obtain fluororubber raw rubber mixing rubber material;
step 2: adding 0.4kg of 2, 4-dichlorobenzoyl peroxide and 115kg of the fluororubber raw rubber mixed rubber material prepared in the step 2 into an internal mixer by adopting a two-stage vulcanization method for uniform dispersion, wherein the one-stage vulcanization condition is as follows: the pressure is 8MPa, the temperature is 150 ℃, and the time is 10min; the secondary vulcanization conditions are as follows: the temperature is 200 ℃, and the time is 2h; and in the hot-press forming process, the temperature is controlled at 170 ℃, the pressure is 1MPa, and the forming time is 0.5h to obtain the fluororubber sealing ring.
Comparative example 2:
the lignin-based flame retardant is directly blended with the fluororubber.
Step 1: preparing a lignin-based flame retardant:
a. dissolving 1mol of triethylamine, 1.1mol of carbon tetrachloride and 3mol of PIP in dichloromethane, adding 1mol of DOPO in a nitrogen environment, reacting for 8 hours at room temperature, washing and drying to obtain a product A;
b. mixing 0.9kg of lignin and 1.8kg of the product A, dissolving in dimethylformamide, heating in a water bath to 75 ℃, adding 2kg of formaldehyde, carrying out condensation reflux reaction for 3 hours, adding ionized water to obtain a precipitate, washing with ethanol, and drying to obtain a product B;
c. dispersing 2.3kg of the product B, 2.6kg of triethylamine and 4.2kg of DOPO in dimethylformamide, adding 3kg of carbon tetrachloride in the nitrogen atmosphere, reacting at room temperature for 8 hours, and adding excessive deionized water to obtain a precipitate; washing with ethanol, and drying to obtain lignin-based flame retardant;
and 2, step: adding 125kg of raw fluororubber, 0.54kg of lignin-based flame retardant, 0.3kg of antioxidant 1010 and 0.2kg of palm wax into an internal mixer, controlling the temperature to be 150 ℃, fully mixing, extruding, bracing and granulating at 170 ℃ by using a double-screw extruder to obtain raw fluororubber mixed rubber material;
and step 3: adding 0.7kg of 2, 4-dichlorobenzoyl peroxide and 120kg of the fluororubber raw rubber mixed sizing material prepared in the step 2 into an internal mixer by adopting a two-stage vulcanization method for uniform dispersion, wherein the one-stage vulcanization condition is as follows: the pressure is 8.5MPa, the temperature is 160 ℃, and the time is 10min; the secondary vulcanization conditions are as follows: the temperature is 210 ℃, and the time is 2.5h; and in the hot-press forming process, the temperature is controlled at 190 ℃, the pressure is 2MPa, and the forming time is 1h to obtain the fluororubber sealing ring.
Comparative example 3:
the polydopamine microcapsule is not modified by nano copper.
Step 1: preparing polydopamine microcapsules:
s1: preparing a lignin-based flame retardant:
a. dissolving 1mol of triethylamine, 1.2mol of carbon tetrachloride and 3.2mol of PIP in dichloromethane, adding 1.1mol of DOPO in a nitrogen environment, reacting for 8 hours at room temperature, washing and drying to obtain a product A;
b. mixing 1kg of lignin and 2kg of the product A, dissolving in dimethylformamide, heating in a water bath to 75 ℃, adding 2.2kg of formaldehyde, carrying out condensation reflux reaction for 3 hours, adding ionized water to obtain a precipitate, washing with ethanol, and drying to obtain a product B;
c. dispersing 3kg of the product B, 3kg of triethylamine and 4.5kg of DOPO in dimethylformamide, adding 3.3kg of carbon tetrachloride in the nitrogen atmosphere, reacting at room temperature for 8h, and adding excessive deionized water to obtain a precipitate; washing with ethanol, and drying to obtain lignin-based flame retardant;
s2: adding 1kg of lignin-based flame retardant into 5kg of dimethylformamide solution, and performing ultrasonic treatment for 30min to uniformly disperse the lignin-based flame retardant to obtain a mixed solution; adding 0.25kg of dopamine into the mixed solution under the condition of water bath at 40 ℃, rotating at 500rpm, and stirring for 20min; then adding 0.02kg of tris (hydroxymethyl) aminomethane for reaction for 1h, after the reaction is finished, performing suction filtration to obtain a filter cake, dispersing the filter cake in 3kg of acetone solution, washing to remove impurities, washing with deionized water, filtering, and drying to obtain polydopamine microcapsules;
and 2, step: adding 145kg of raw fluororubber, 0.6kg of polydopamine microcapsules, 0.5kg of antioxidant 1010 and 0.3kg of palm wax into an internal mixer, controlling the temperature to be 180 ℃, fully mixing, extruding, bracing and granulating at 190 ℃ through a double-screw extruder to obtain raw fluororubber mixed rubber material;
and step 3: 1.3kg of 2, 4-dichlorobenzoyl peroxide and 135kg of the raw rubber mixing rubber material prepared in the step 2 are added into an internal mixer to be uniformly dispersed by adopting a two-stage vulcanization method, wherein the one-stage vulcanization condition is as follows: the pressure is 10MPa, the temperature is 180 ℃, and the time is 15min; the secondary vulcanization conditions are as follows: the temperature is 230 ℃, and the time is 4h; and in the hot-press forming process, the temperature is controlled at 230 ℃, the pressure is 3MPa, and the forming time is 2h to obtain the fluororubber sealing ring.
Experiment: the fluororubber seal rings prepared in examples 1 to 5 and comparative examples 1 to 5 were subjected to the relevant performance tests. And testing the tensile property by adopting an HY-5080 universal tensile testing machine according to GB/T528-2009. The volume resistivity was measured using a resistance meter RM 3548. According to UL94 flame retardant rating test, the generation condition of the molten drops is inspected, if no molten drops are generated, the flame retardant property is good, and the flame retardant property is poor in an irregular mode.
| Examples | Tensile strength/MPa | Resistivity/(Ω cm) | Flame retardancy |
| Example 1 | 6.62 | 2.87 | Good effect |
| Example 2 | 6.38 | 2.96 | Good effect |
| Example 3 | 6.45 | 3.05 | Good effect |
| Comparative example 1 | 5.97 | 2.85 | Difference (D) |
| Comparative example 2 | 4.92 | 10.64 | Difference (D) |
| Comparative example 3 | 6.19 | 6.45 | Good effect |
And (4) conclusion: as shown in the table, the data of examples 1-3 show that the fluororubbers prepared by using the invention have excellent properties. The data of comparative example 1, with reference to example 1, show that the flame retardant performance of the fluororubber is improved after the lignin-based flame retardant is added. By taking the example 2 as a reference, the data of the comparative example 2 show that the polydopamine microcapsule has better dispersibility, and can be uniformly dispersed in the fluororubber after being blended with the fluororubber, so that the effect of the lignin-based flame retardant is exerted, the flame resistance is improved, and the tensile strength of the fluororubber is increased. By taking the example 3 as a reference, the data of the comparative example 3 show that the polydopamine microcapsule has strong adsorption capacity on copper ions, and the conductivity of the polydopamine microcapsule loaded with nano copper particles can be remarkably improved, so that the high-conductivity fluororubber is prepared.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-conductivity fluororubber sealing ring for a lithium battery is characterized by comprising the following steps: the method comprises the following steps:
step 1: preparing modified polydopamine microcapsules:
s1: preparing a lignin-based flame retardant:
a. dissolving anhydrous piperazine (PIP), carbon tetrachloride and triethylamine in dichloromethane, dropwise adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) in a nitrogen environment, stirring for reaction, washing and drying to obtain a product A;
b. mixing lignin and the product A, dissolving the mixture in dimethylformamide, heating in a water bath, adding formaldehyde for reaction, adding ionized water to obtain a precipitate, washing with ethanol, and drying to obtain a product B;
c. dispersing the product B, triethylamine and DOPO in dimethylformamide, adding carbon tetrachloride in nitrogen atmosphere for reaction, and adding excessive deionized water to obtain a precipitate; washing with ethanol, and drying to obtain lignin-based flame retardant;
s2: dispersing the lignin-based flame retardant in a dimethylformamide solution to obtain a mixed solution; adding dopamine into the mixed solution and uniformly stirring; then adding trihydroxymethyl aminomethane for reaction for 0.5-1 h, performing suction filtration after the reaction is finished to obtain a filter cake, dispersing the filter cake in an acetone solution, washing to remove impurities, and then washing, filtering and drying to obtain a polydopamine microcapsule;
s3: dispersing polydopamine microcapsules into water, adding dopamine hydrochloride solution, stirring for 30min, adding copper sulfate solution, and continuously stirring; and dropwise adding a sodium hydroxide solution to adjust the pH value to 4-5, then continuously stirring, transferring into a high-pressure kettle, heating for reaction, centrifuging, filtering, washing and drying to obtain the modified polydopamine microcapsule.
Step 2: mixing raw fluororubber, modified polydopamine microcapsules, an antioxidant, a plasticizer and a flame retardant at 130-180 ℃, and then extruding, bracing and granulating at 150-190 ℃ to obtain raw fluororubber mixed rubber material;
and step 3: vulcanizing the raw fluororubber mixed rubber material prepared in the step 2 with a vulcanizing agent by adopting a two-stage vulcanization method, and then performing hot press molding to obtain the fluororubber sealing ring.
2. The method for preparing the high-conductivity fluororubber sealing ring for the lithium battery according to claim 1, wherein the method comprises the following steps: in a, the molar ratio of the triethylamine to the carbon tetrachloride to the DOPO to the PIP is 1 to (1-1.2) to (0.8-1.1) to (2.8-3.2); the content of each component in b is 8-10 parts of lignin, 15-20 parts of product A and 18-22 parts of formaldehyde by weight; the contents of the components in c are, by weight, 2-3 parts of the product B, 2-3 parts of triethylamine, 4-4.5 parts of DOPO and 2.8-3.3 parts of carbon tetrachloride.
3. The high-conductivity fluororubber sealing ring for lithium batteries and the preparation method thereof according to claim 1, wherein the sealing ring comprises: the S2 comprises 0.5-1 part of lignin-based flame retardant, 3-5 parts of dimethylformamide solution, 0.1-0.25 part of dopamine, 0.01-0.02 part of tris (hydroxymethyl) aminomethane and 2-3 parts of acetone solution by weight.
4. The high-conductivity fluororubber sealing ring for the lithium battery and the preparation method thereof according to claim 1, wherein the high-conductivity fluororubber sealing ring comprises: the dosage of each component in S3 is 1-2 parts of polydopamine microcapsule, 2-3 parts of water, 0.5-0.6 part of dopamine hydrochloride solution and 0.6-0.8 part of copper sulfate solution by weight.
5. The high-conductivity fluororubber sealing ring for the lithium battery and the preparation method thereof according to claim 1, wherein the high-conductivity fluororubber sealing ring comprises: the heating reaction temperature in the S3 is 120-140 ℃, and the heating reaction time is 10-12 h.
6. The method for preparing the high-conductivity fluororubber sealing ring for the lithium battery according to claim 1, wherein the method comprises the following steps: in the step 2, the raw rubber mixing sizing material comprises, by weight, 110-145 parts of fluororubber raw rubber, 0.4-0.6 part of modified polydopamine microcapsule, 0.1-0.5 part of antioxidant, 0.1-0.3 part of plasticizer and 0.1-0.3 part of flame retardant.
7. The method for preparing the high-conductivity fluororubber sealing ring for the lithium battery according to claim 1, wherein the method comprises the following steps: in the step 2, the crude fluororubber is any one of vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer and vinylidene fluoride-hexafluoropropylene copolymer; the antioxidant is one or more of 1010, 168, 1076, 626 and 1790; the plasticizer is one or more of dioctyl adipate, epoxy butyl oleate, dioctyl sebacate, propylene glycol adipate, polyisobutylene and palm wax.
8. The method for preparing the high-conductivity fluororubber sealing ring for the lithium battery according to claim 1, wherein the method comprises the following steps: in the step 3, the contents of the components are 0.4 to 1.3 parts by weight of vulcanizing agent and 115 to 135 parts by weight of raw rubber mixing rubber material.
9. The method for preparing the high-conductivity fluororubber sealing ring for the lithium battery according to claim 1, wherein the method comprises the following steps: the first stage vulcanization conditions are as follows: the pressure is 8-10 MPa, the temperature is 150-180 ℃, and the time is 10-15 min; the secondary vulcanization conditions are as follows: the temperature is 200-230 ℃, and the time is 2-4 h; the temperature is controlled at 170-230 ℃ in the molding process, the pressure is 1-3 MPa, and the molding time is 0.5-2 h.
10. The highly conductive fluororubber sealing ring for lithium battery prepared by the method according to any one of claims 1 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245138A (en) * | 2017-06-12 | 2017-10-13 | 长春工业大学 | A kind of preparation of lignin-base fire retardant and its application process |
| CN108997617A (en) * | 2018-09-01 | 2018-12-14 | 华北科技学院 | A kind of preparation and its application method of poly-dopamine encapsulated red phosphorus microcapsule flame retardant |
| CN109957114A (en) * | 2019-04-09 | 2019-07-02 | 南京林业大学 | A kind of lignin expansion type flame retardant and preparation method thereof |
| CN113292737A (en) * | 2021-05-31 | 2021-08-24 | 青岛科技大学 | N, P, Si type synergistic lignin-based flame retardant and preparation method and application thereof |
| CN114395173A (en) * | 2021-12-13 | 2022-04-26 | 东莞市瑞拓五金橡塑有限公司 | Formula and preparation method of high-temperature-resistant rubber sealing ring |
-
2022
- 2022-10-13 CN CN202211252486.9A patent/CN115594986B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245138A (en) * | 2017-06-12 | 2017-10-13 | 长春工业大学 | A kind of preparation of lignin-base fire retardant and its application process |
| CN108997617A (en) * | 2018-09-01 | 2018-12-14 | 华北科技学院 | A kind of preparation and its application method of poly-dopamine encapsulated red phosphorus microcapsule flame retardant |
| CN109957114A (en) * | 2019-04-09 | 2019-07-02 | 南京林业大学 | A kind of lignin expansion type flame retardant and preparation method thereof |
| CN113292737A (en) * | 2021-05-31 | 2021-08-24 | 青岛科技大学 | N, P, Si type synergistic lignin-based flame retardant and preparation method and application thereof |
| CN114395173A (en) * | 2021-12-13 | 2022-04-26 | 东莞市瑞拓五金橡塑有限公司 | Formula and preparation method of high-temperature-resistant rubber sealing ring |
Non-Patent Citations (2)
| Title |
|---|
| XINYU LU等: "Pyrolysis mechanism and kinetics of high-performance modified lignin-based epoxy resin", 《JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS》, vol. 154, pages 1 - 11 * |
| 梁孟珂 等: "木质素基膨胀型阻燃剂的制备及其应用", 林产化学与工业, vol. 41, no. 04, pages 10 - 16 * |
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