CN115584141A - Lithium battery electrolyte-resistant bisphenol high-fluorine fluororubber compound and preparation method thereof - Google Patents
Lithium battery electrolyte-resistant bisphenol high-fluorine fluororubber compound and preparation method thereof Download PDFInfo
- Publication number
- CN115584141A CN115584141A CN202211325898.0A CN202211325898A CN115584141A CN 115584141 A CN115584141 A CN 115584141A CN 202211325898 A CN202211325898 A CN 202211325898A CN 115584141 A CN115584141 A CN 115584141A
- Authority
- CN
- China
- Prior art keywords
- bisphenol
- rubber
- fluorine
- parts
- fluororubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 171
- 239000011737 fluorine Substances 0.000 title claims abstract description 171
- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 122
- 229930185605 Bisphenol Natural products 0.000 title claims abstract description 115
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 150000001875 compounds Chemical class 0.000 title claims abstract description 88
- 239000003792 electrolyte Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 34
- 229920001971 elastomer Polymers 0.000 claims abstract description 268
- 239000005060 rubber Substances 0.000 claims abstract description 268
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000006229 carbon black Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000013538 functional additive Substances 0.000 claims abstract description 12
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 88
- 239000000203 mixture Substances 0.000 claims description 47
- 238000004073 vulcanization Methods 0.000 claims description 46
- 238000006298 dechlorination reaction Methods 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 38
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 claims description 29
- 239000000395 magnesium oxide Substances 0.000 claims description 26
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 26
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 21
- 239000000920 calcium hydroxide Substances 0.000 claims description 21
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 21
- 239000004203 carnauba wax Substances 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 21
- 239000012763 reinforcing filler Substances 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000002250 absorbent Substances 0.000 claims description 5
- 230000002745 absorbent Effects 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000000378 calcium silicate Substances 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims 1
- 239000002516 radical scavenger Substances 0.000 claims 1
- 238000007906 compression Methods 0.000 abstract description 46
- 230000006835 compression Effects 0.000 abstract description 45
- 230000000704 physical effect Effects 0.000 abstract description 17
- 230000000052 comparative effect Effects 0.000 description 74
- 239000006082 mold release agent Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 21
- 239000012752 auxiliary agent Substances 0.000 description 18
- 239000003292 glue Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 150000002978 peroxides Chemical class 0.000 description 13
- 239000003566 sealing material Substances 0.000 description 12
- 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 description 7
- 239000006096 absorbing agent Substances 0.000 description 5
- 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 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- 239000000370 acceptor Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000001180 sulfating effect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920006169 Perfluoroelastomer Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/193—Organic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a lithium battery electrolyte-resistant bisphenol high-fluorine fluororubber compound and a preparation method thereof, belonging to the technical field of fluororubber material preparation, wherein the bisphenol high-fluorine fluororubber is used for reducing the cost and solving the problems of poor demoulding property, large mould pollution, high product reject ratio and the like; the vulcanizing agent of the invention is used to reduce the compression permanent deformation and solve the problem of large compression permanent deformation of bisphenol high fluorine rubber; the compression set is further reduced by using the functional additive N325 carbon black, and the problem of large compression set of the bisphenol high fluorine rubber is solved; the process scheme that the bisphenol high fluorine rubber pre-mixed rubber is firstly manufactured, and then the bisphenol high fluorine rubber mixed rubber is manufactured improves the basic physical properties of the bisphenol high fluorine rubber, and further reduces the compression set; by selecting the bisphenol high fluorine rubber with the fluorine content of 70-71%, the volume expansion rate of the bisphenol high fluorine rubber in the electrolyte is reduced due to the high fluorine content.
Description
Technical Field
The invention belongs to the technical field of preparation of fluororubber materials, and particularly relates to a lithium battery electrolyte-resistant bisphenol high-fluorine fluororubber compound and a preparation method thereof.
Background
With the implementation of the national new energy policy, clean energy becomes a development air port, new energy automobiles and energy storage markets can be rapidly developed, and huge market prospects of automobile power batteries and energy storage batteries are driven. The quality of the battery sealing material directly affects the service life of the battery and is always concerned by the industry. The fluororubber has excellent performances (such as high temperature resistance, oil resistance, corrosion resistance of various strong acids, strong bases and chemical solvents, good electrical performance and the like) which are incomparable with other rubbers, and becomes a preferred material for lithium battery electrolyte sealing materials, wherein the fluororubber is most applied to the high-fluorine fluororubber.
As is well known, high fluorine fluororubbers are classified into peroxy high fluorine fluororubbers and bisphenol high fluorine fluororubbers. The peroxide high fluorine rubber has special properties of low compression permanent deformation, low volume expansion rate in electrolyte, excellent insulating property and the like, and is widely applied to the field of sealing materials of automobile power batteries and energy storage batteries. The traditional bisphenol high fluorine rubber has large compression permanent deformation, and the sealing performance of the traditional bisphenol high fluorine rubber is far lower than that of peroxide high fluorine rubber. However, the existing peroxide high fluorine rubber has high cost which is more than one time higher than that of bisphenol high fluorine rubber, and the existing peroxide high fluorine rubber has poor mold release property, large mold pollution and high product reject ratio; this also limits the use of peroxy perfluoroelastomers to some extent. In order to meet the requirements of sealing performance, reducing cost, improving processability, meeting the requirements of environmental protection, yield and the like, the technical personnel in the field always search for other alternative materials.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a lithium battery electrolyte resistant bisphenol high-fluorine fluororubber rubber compound and a preparation method thereof, and aims to at least solve one of the problems.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of a lithium battery electrolyte-resistant bisphenol high-fluorine fluororubber rubber compound comprises the following steps:
s1, vulcanizing agent preparation:
reacting bisphenol AF with benzyltriphenylphosphonium chloride (BPP) to form bisphenol AF primary salt, and performing dechlorination to form dechlorination type bisphenol AF salt, wherein the dechlorination type bisphenol AF salt is the prepared vulcanizing agent; in the research, the inventors found that the compression set of the dechlorinated bisphenol AF salt sizing material is more excellent compared with the direct use of bisphenol AF or bisphenol AF primary salt through dechlorination reaction to form the dechlorinated bisphenol AF salt;
s2, preparing fluororubber premix rubber:
preparing the fluororubber premix by using raw bisphenol high-fluorine fluororubber, a vulcanization accelerator and the vulcanizing agent prepared in the step S1;
s3, preparing bisphenol high-fluorine fluororubber gross rubber:
and (3) mixing the acid absorbent, the reinforcing filler, the functional assistant and the processing assistant with the fluororubber premix prepared in the step (S2) to obtain the bisphenol high fluororubber mixture.
Optionally, the raw rubber of the bisphenol high fluorine rubber has fluorine content of 70-71% and Mooney viscosity ML1+10 ℃ of 20-60.
Preferably, in step S1, the vulcanizing agent is prepared by the following steps:
s11, mixing bisphenol AF and benzyltriphenylphosphonium chloride, wherein the mixing weight ratio of the bisphenol AF to the benzyltriphenylphosphonium chloride is 3:0.7-2, placing the uniformly mixed mixture into a heating reaction kettle, heating to 200-250 ℃, starting stirring, reacting for 0.5-2h, stopping heating, discharging the product after the reaction, and cooling to room temperature to obtain bisphenol AF primary salt, wherein the preferred mixing weight ratio of the bisphenol AF to the benzyltriphenylphosphonium chloride is 3:1.5;
s12, crushing the bisphenol AF primary salt by a crusher, putting the crushed salt into a stirring kettle, adding dichloromethane, stirring and dissolving, after the dichloromethane is completely dissolved, dropwise adding a 5% sodium bicarbonate solution to generate a large amount of flocculates in the process, continuously stirring for 1h, repeatedly washing the flocculates by deionized water until the chlorine content of the flocculates is lower than 200ppm, and filtering and drying the flocculates to obtain the required dechlorinated bisphenol AF salt, namely the prepared vulcanizing agent.
Preferably, the vulcanization accelerator is any one or a mixture of any several of benzyl triphenyl phosphonium chloride (BPP), 8-benzyl-1, 8-diazabicycloundec-7-ene ammonium chloride and tetrabutyl ammonium bromide; benzyltriphenylphosphonium chloride (BPP) is preferred, and is used in an amount of 0.05 to 1.0 part by weight for the purpose of adjusting the vulcanization rate.
Preferably, the acid-absorbing agent is a mixture of magnesium oxide and calcium hydroxide, and the weight parts of the magnesium oxide and the calcium hydroxide are respectively 3-9 parts and 3-6 parts; preferably 3 parts and 6 parts by weight. Wherein the magnesium oxide is high-activity magnesium oxide with an activity value of 150-180.
Preferably, the reinforcing filler is any one or a mixture of any several of carbon black N990, diatomite, calcium silicate, spray carbon black and barium sulfate; preferably, the mixture of the carbon black N990 and the diatomite is used in an amount of 5-20 parts by weight, and the specific amount is determined according to the hardness requirement of the rubber compound.
Preferably, the functional assistant is high heat-resistant carbon black N325, and the using amount is 5-20 parts by weight, preferably 15 parts by weight.
Preferably, the processing aid is any one or a mixture of any several of palm wax, WS280 and erucamide, preferably a mixture of palm wax and WS280, and the mixing ratio is 2:1, the amount is 1 to 3 parts by weight, and 1 to 2 parts by weight is more preferable.
Preferably, the step S2 of preparing the bisphenol high fluorine rubber premix comprises the following steps:
s21, plasticating the raw bisphenol high-fluorine rubber in an internal mixer for 4-10min at the plastication temperature of 80-100 ℃ according to the premixing ratio; preferably, the plastication time is 8-10min, and the plastication temperature is 80-90 ℃;
s22, sequentially adding a vulcanizing agent and a vulcanization accelerator into the internal mixer according to a premixing ratio, fully mixing for 6-10min at the mixing temperature of not more than 110 ℃, discharging, and discharging and cooling by using an open mill to obtain the bisphenol high fluorine rubber premixed rubber; wherein the premixing proportion is as follows: 100 parts of bisphenol high fluorine rubber crude rubber, 2.5-4.0 parts of vulcanizing agent and 0.05-1.0 part of vulcanization accelerator.
Further, the step S3 of preparing the bisphenol high fluorine rubber compound specifically comprises the following steps:
s31, sequentially adding the bisphenol high-fluorine fluororubber premix prepared in the step S2, an acid acceptor, a functional processing aid, a reinforcing filler and a processing aid into an internal mixer according to a mixing ratio, fully mixing for 6-10min at the mixing temperature of not more than 110 ℃, and taking out and cooling;
s32, cooling the rubber material prepared in the step S31 for 24 hours, then thinly passing the rubber material on an open mill for 4-6 times, and then extruding out a filter to obtain a bisphenol high fluorine rubber compound;
wherein the mixing proportion is as follows: 100 parts of bisphenol high fluorine rubber premix, 6-15 parts of acid acceptor, 5-20 parts of reinforcing filler, 5-20 parts of functional assistant and 1-3 parts of processing assistant.
Compared with the prior art, the embodiment of the invention has at least the following advantages or beneficial effects:
(1) According to the lithium battery electrolyte resistant bisphenol high-fluorine fluororubber mixed rubber and the preparation method thereof, low swelling performance in the electrolyte is realized by selecting the fluorine content of raw fluororubber in raw materials; by the selective combination and mutual synergistic effect of the dechlorination type bisphenol AF salt, the functional auxiliary agent and the preparation process, the compression set of the bisphenol high fluorine rubber can be obviously improved;
(2) The bisphenol high fluorine rubber gross rubber prepared by the preparation method provided by the invention is used for a lithium battery electrolyte-resistant sealing material, and has the characteristics of low compression permanent deformation, excellent demoulding performance, high product yield, excellent electrolyte resistance, obvious cost advantage and the like;
(3) The invention provides a lithium battery electrolyte-resistant bisphenol high-fluorine fluororubber rubber compound and a preparation method thereof, which form a complete technical scheme by combining the selection of raw materials, the use amount of the raw materials and the preparation process. Particularly, the bisphenol high-fluorine rubber compound rubber for lithium battery electrolyte prepared by the invention meets the technical requirements of a lithium battery electrolyte sealing material while ensuring excellent physical and mechanical properties, and can effectively replace peroxide high-fluorine rubber in the field of the existing lithium battery electrolyte sealing material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The embodiment provides a preparation method of a lithium battery electrolyte resistant bisphenol high fluorine rubber compound, which comprises the following steps: s1.1, vulcanizing agent preparation:
s1.11, weighing 9Kg of bisphenol AF and 4.5Kg of benzyltriphenylphosphonium chloride (BPP), mixing, placing the uniformly mixed mixture in a 40L heating reaction kettle, heating to 220 ℃, starting stirring, reacting for 1.5h, stopping heating, discharging the product after the reaction, and cooling to room temperature to obtain bisphenol AF primary salt;
s1.12, crushing the bisphenol AF primary salt by a crusher, putting the crushed salt into a 100L stirring kettle, adding 20L dichloromethane, stirring and dissolving, after the dichloromethane is completely dissolved, continuously stirring and simultaneously dropwise adding 30L of 5% sodium bicarbonate solution, generating a large amount of flocculate in the process, continuously stirring for 1h, repeatedly washing the flocculate by deionized water until the chlorine content of the flocculate is lower than 200ppm, filtering and drying the flocculate to obtain the required dechlorinated bisphenol AF salt, namely the prepared vulcanizing agent;
s1.2, preparing fluororubber premix rubber:
s1.21, taking raw bisphenol high-fluorine rubber, the dechlorination type bisphenol AF salt prepared in the step S1.1 and a vulcanization accelerator BPP for later use, wherein the raw materials are prepared according to a first formula in parts by weight for later use, and the first formula comprises the following components in parts by weight: 100 parts of raw bisphenol high fluorine rubber, 3.45 parts of dechlorination type bisphenol AF salt and 0.2 part of vulcanization accelerator BPP, wherein the dosage of the dechlorination type bisphenol AF salt is calculated by 2.5 parts by weight of bisphenol AF contained in the raw rubber; in the embodiment, the raw rubber of bisphenol high-fluorine rubber has fluorine content of 70.2%, mooney viscosity ML121 ℃ (1 + 10) of 30 and weight of 20Kg;
s1.22, according to a formula I, putting raw bisphenol high-fluorine fluororubber into a 25L internal mixer for plastication, wherein the plastication temperature is 85 ℃; plasticating time is 10min;
s1.23, sequentially adding a vulcanizing agent and a vulcanization accelerator into an internal mixer according to a formula, fully mixing for 8min at the mixing temperature of not more than 110 ℃, discharging, taking out a sheet by using an open mill, and cooling to obtain a fluororubber premix, wherein the fluororubber premix is marked as example premix I;
s1.3, preparing a fluororubber compound:
s1.31, preparing the first premixed glue prepared in the step S1.2 according to a second formula for later use, wherein the second formula comprises the following components in parts by weight: example one 100 parts of premix rubber, 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 5 parts of N990 carbon black, 15 parts of diatomite, 0.5 part of WS280 fluororubber internal mold release agent and 1 part of palm wax; in this example, 20Kg of the pre-mixed glue in the example is taken; wherein, the acid absorbent of the embodiment is formed by mixing magnesium oxide and calcium hydroxide, the reinforcing filler of the embodiment is formed by mixing N990 carbon black and diatomite, and the processing aid of the embodiment is formed by mixing WS280 fluororubber internal mold release agent and palm wax;
s1.32, sequentially adding premixed rubber, namely the premixed rubber I, an acid absorbing agent, a reinforcing filler and a processing aid in the embodiment into a two-way 25L internal mixer according to a formula, fully mixing for 8min at the mixing temperature of not more than 110 ℃, and discharging and cooling;
s1.33, cooling the rubber material prepared in the step S1.32 for 24 hours, then thinly passing the rubber material on an open mill for 5 times, and then extruding a filter to obtain a sheet to obtain a fluororubber gross rubber which is marked as the first gross rubber of the embodiment;
the prepared first rubber compound of the example is prepared into a standard test piece for testing, and the vulcanization conditions are one-stage vulcanization: 180 ℃ for @5min, and post-vulcanization at 230 ℃ for @24h, and the physical properties are shown in Table 1 below.
Comparative example 1:
in this comparative example, two comparison groups, a comparison group one and a comparison group two, are provided.
In contrast to example 1, in comparative group one, the preparation of pre-mixes and mixes was carried out using bisphenol AF primary salt as vulcanizing agent, in particular:
when the fluororubber premix is prepared, 20Kg of raw bisphenol high fluororubber with 70.2% of fluorine and 30 Mooney viscosity ML121 ℃ (1 + 10) is taken, and the bisphenol AF primary salt prepared in the curing agent preparation step (S1.1) in example 1 is taken, and all the raw materials are prepared according to the third formula for standby, wherein the third formula is as follows: 100 parts of raw bisphenol high-fluorine rubber, 3.75 parts of bisphenol AF primary salt and 0.2 part of vulcanization accelerator BPP, wherein the using amount of the bisphenol AF primary salt is calculated by 2.5 parts by weight of bisphenol AF contained in the raw bisphenol high-fluorine rubber; then preparing the fluororubber premix marked as the premix rubber one of the comparative example according to the preparation steps (S1.22-S1.23, formula one is replaced by formula three) of the fluororubber premix rubber in the example 1;
and then, preparing a rubber compound, namely taking 20Kg of the prepared premix rubber of the comparative example, and preparing the premix rubber according to a formula IV (the raw materials are calculated according to parts by weight) for later use, wherein the formula IV comprises the following components: comparative example one 100 parts of premix rubber, 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 5 parts of N990 carbon black, 15 parts of diatomaceous earth, 0.5 part of WS280 fluororubber internal mold release agent and 1 part of palm wax; then, a fluororubber mix, which was designated as comparative example mix one, was prepared according to the procedure for preparing a fluororubber mix in example 1 described above (comparative example mix one instead of example mix one).
In contrast to example 1, in the comparative group two, the preparation of the rubber mixtures was carried out directly with bisphenol AF, in particular: firstly, preparing 20Kg of raw bisphenol high-fluorine fluororubber rubber with fluorine content of 70.2 percent and Mooney viscosity ML121 ℃ (1 + 10) of 30 according to a fifth formula (the raw materials are calculated by weight parts) for standby, wherein the fifth formula is as follows: 100 parts of raw bisphenol high fluorine rubber, 100 parts of bisphenol AF, 0.8 part of vulcanization accelerator BPP, 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 5 parts of N990 carbon black, 15 parts of diatomite, 0.5 part of WS280 fluorine rubber internal mold release agent and 1 part of palm wax;
a fluororubber compound was prepared as follows:
firstly, according to a fifth formula, raw bisphenol high-fluorine fluororubber is plasticated in a 25L internal mixer at the temperature of 85 ℃; plasticating time is 10min; then, according to the fifth formula, adding an acid-absorbing agent, a work reinforcing filler and a processing aid into a 25L internal mixer in sequence, then fully mixing for 8min at the mixing temperature of not more than 110 ℃, and carrying out plate-out cooling (wherein the acid-absorbing agent, the work reinforcing filler and the processing aid are defined as in the example 1);
then, the rubber material prepared in the previous step is cooled for 24 hours and then thinly passed on an open mill for 5 times, and then a sheet is extruded from an extrusion filter to obtain a fluororubber gross rubber which is marked as a second comparative gross rubber;
the prepared first and second rubber compounds of the comparative example are prepared into standard test pieces for testing, and the vulcanization conditions are primary vulcanization: 180 ℃ for 5min and secondary vulcanization for 230 ℃ for 24h, and the physical properties are shown in Table 1 below.
The test results of example 1 and comparative example 1 are shown in table 1:
table 1 table of physical properties (example 1 and comparative example 1).
Example 2
The embodiment provides a preparation method of a lithium battery electrolyte-resistant bisphenol high-fluorine fluororubber rubber compound, which comprises the following steps: s2.1, preparing a vulcanizing agent:
taking three parts of dechlorinated bisphenol AF salt prepared according to the preparation step (S1.1) of the vulcanizing agent in the embodiment 1 for standby;
s2.2, preparing the fluororubber premix:
weighing three parts of raw bisphenol high-fluorine fluororubber with 70.2 percent of fluorine content and 30 Mooney viscosity ML121 ℃ (1 + 10), wherein each part is 20Kg, and preparing three parts of dechlorinated bisphenol AF salt prepared by S2.1 according to the formula I in the embodiment 1 (the raw materials are calculated according to the parts by weight) to prepare the raw rubber for standby; then, preparing the fluororubber premix according to the preparation steps (S1.22-S1.23) of the fluororubber premix in the embodiment 1, wherein the prepared fluororubber premix is marked as embodiment premix II, embodiment premix III and embodiment premix IV;
s2.3, preparing fluororubber gross rubber:
s2.31, respectively taking 20Kg of the second embodiment premixed glue, the third embodiment premixed glue and the fourth embodiment premixed glue prepared in the step S2.2, and preparing the second embodiment premixed glue, the third embodiment premixed glue and the fourth embodiment premixed glue according to a formula six, a formula seven and a formula eight (all raw materials are calculated according to parts by weight) for later use; wherein the sixth formula comprises: example two 100 parts of premixed rubber, 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 5 parts of N990 carbon black, 10 parts of diatomite, 5 parts of N325 high-heat-resistant carbon black serving as a functional assistant, 0.5 part of WS280 fluororubber internal mold release agent and 1 part of palm wax; the seventh formula comprises: the preparation method comprises the following steps of (1) preparing three 100 parts of premixed rubber, 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 5 parts of N990 carbon black, 5 parts of kieselguhr, 10 parts of N325 high-heat-resistance carbon black serving as a functional assistant, 0.5 part of WS280 fluororubber internal mold release agent and 1 part of palm wax; the eight formula comprises: example four 100 parts of premixed rubber, 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 2 parts of N990 carbon black, 5 parts of kieselguhr, 15 parts of functional assistant N325 high-heat-resistance carbon black, 0.5 part of WS280 fluororubber internal mold release agent and 1 part of palm wax;
s2.32, sequentially adding premix rubber (namely, premix rubber II, premix rubber III or premix rubber IV, acid acceptor, functional additive, reinforcing filler and processing additive in the embodiment) into a 25L internal mixer according to the sixth, seventh and eighth formulas, fully mixing for 8min, wherein the mixing temperature is not more than 110 ℃, and taking out and cooling; wherein the acid acceptor, reinforcing filler and processing aid in this example are defined as in example 1; s2.33, cooling the rubber compound prepared in the step S2.32 for 24 hours, then thinly passing the rubber compound on an open mill for 5 times, and then extruding a filter to obtain fluororubber mixed rubber, wherein the fluororubber mixed rubber is marked as example mixed rubber II, example mixed rubber III and example mixed rubber IV respectively;
and (3) respectively preparing two to four prepared example rubber mixtures into standard test pieces for testing, wherein the vulcanization conditions are one-stage vulcanization: @ 180 ℃ for 5min; post-vulcanization at 230 ℃ and @24H, the physical properties of which are shown in Table 2 below.
Comparative example 2:
the physical properties of the example compound one prepared in example 1, which was taken as a comparative example compound three, are shown in Table 2 below.
The test results of example 2 and comparative example 2 are shown in table 2:
table 2 physical properties table (example 2 and comparative example 2).
Example 3:
the embodiment provides a preparation method of a lithium battery electrolyte resistant bisphenol high fluorine rubber compound, which comprises the following steps: s3.1 vulcanizing agent preparation:
the dechlorinated bisphenol AF salt prepared in the step of preparing the sulfating agent (S1.1) in example 1 was taken for future use;
s3.2 preparation of fluororubber compound:
s3.21, taking 20Kg of bisphenol high fluorine rubber raw rubber with fluorine content of 70.2 percent and Mooney viscosity ML121 ℃ (1 + 10) of 30, taking dechlorinated bisphenol AF salt prepared by S3.1, and preparing the raw rubber according to the formula nine (the raw materials are calculated according to parts by weight) for later use; the formula nine is as follows: 100 parts of raw bisphenol high fluorine rubber, 3.45 parts of dechlorination type bisphenol AF salt, 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 5 parts of N990 carbon black, 15 parts of diatomite, 0.5 part of WS280 fluorine rubber internal mold release agent and 1 part of palm wax;
and the number of the first and second groups,
taking 20Kg of raw bisphenol high-fluorine fluororubber rubber with fluorine content of 70.2% and Mooney viscosity ML121 ℃ (1 + 10) of 30, taking dechlorinated bisphenol AF salt prepared by S3.1, and preparing the raw bisphenol high-fluorine fluororubber rubber according to a formula ten (the raw materials are calculated by weight parts) for later use; wherein the formula ten is as follows: 100 parts of raw bisphenol high fluorine rubber, 3.45 parts of dechlorination type bisphenol AF salt, 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 2 parts of N990 carbon black, 5 parts of diatomite, 15 parts of functional assistant N325 high heat-resistant carbon black, 0.5 part of WS280 fluorine rubber internal mold release agent and 1 part of palm wax;
fluororubber mixes, designated example mix five and example mix six, were prepared as follows:
s3.22, placing the corresponding crude rubber into a 25L internal mixer for plastication according to the ninth formula or the tenth formula, wherein the plastication temperature is 85 ℃, and the plastication time is 10min; then, sequentially adding an acid absorbent, a reinforcing filler and a processing aid into a 25L internal mixer according to the ninth formula, fully mixing for 8min at the mixing temperature of not more than 110 ℃, and discharging and cooling; sequentially adding an acid absorbing agent, a functional additive, a reinforcing filler and a processing aid into a 25L internal mixer according to a formula ten, fully mixing for 8min at the mixing temperature of not more than 110 ℃, and taking out and cooling; wherein the acid acceptor, reinforcing filler and processing aid in this example are defined as in example 1; s3.23, respectively cooling the rubber materials prepared according to the formula nine and the formula ten in the step S3.22 for 24 hours, then thinly passing the rubber materials on an open mill for 5 times, and then extruding a filter to obtain fluororubber rubber mixtures, namely embodiment rubber mixtures five and embodiment rubber mixtures six; the prepared fifth and sixth example rubber mixtures were prepared into standard test pieces and tested, and the vulcanization conditions were one-stage vulcanization: @ 180 ℃ for 5min; post-vulcanization at 230 ℃ and @24H, the physical properties of which are shown in Table 3 below.
Comparative example 3:
example compound four, prepared in example 2, was taken as comparative example compound four and its physical properties are shown in table 3 below.
The test results of example 3 and comparative example 3 are shown in table 3:
table 3 physical properties table (example 3 and comparative example 3).
Example 4:
the embodiment provides a preparation method of a lithium battery electrolyte-resistant bisphenol high-fluorine fluororubber rubber compound, which comprises the following steps: s4.1 vulcanizing agent preparation:
the dechlorinated bisphenol AF salt prepared in the step (S1.1) of preparing the sulfating agent in example 1 is taken for standby;
s4.2, preparing the fluororubber premix:
respectively taking 20Kg of raw bisphenol high-fluorine rubber with 70 percent of fluorine content, 70.5 percent of fluorine content, 71 percent of fluorine content and 30 Mooney viscosity ML121 ℃ (1 + 10), and respectively preparing dechlorinated bisphenol AF salt prepared by S4.1 according to a formula eleven, a formula twelve and a formula thirteen (calculated by the weight parts of all raw materials) for standby; wherein,
the formula eleven comprises the following components: 100 parts of bisphenol high fluorine rubber crude rubber (fluorine content is 70%), 3.45 parts of dechlorination type bisphenol AF salt and 0.2 part of vulcanization accelerator BPP;
the formula is twelve: 100 parts of raw bisphenol high-fluorine rubber (fluorine content is 70.5%), 3.45 parts of dechlorination type bisphenol AF salt and 0.2 part of vulcanization accelerator BPP;
the thirteen formula comprises: 100 parts of raw bisphenol high-fluorine rubber (with fluorine content of 71%), 3.45 parts of dechlorination type bisphenol AF salt and 0.2 part of vulcanization accelerator BPP;
in formulas eleven to thirteen, the amount of the dechlorinated bisphenol AF salt is calculated by 2.5 parts by weight of bisphenol AF contained therein;
then, preparing the fluororubber premix according to the preparation steps (S1.22-S1.23, and corresponding formula conversion) of the fluororubber premix in example 1, wherein the preparation steps are marked as example premix fifth, example premix sixth and example premix seventh;
s4.3 preparation of fluororubber compound:
taking 20Kg of each of the prepared fifth example premixed glue, sixth example premixed glue and seventh example premixed glue, and preparing the mixed glue according to fourteen, fifteen and sixty formulas (the raw materials are calculated according to parts by weight) for later use; wherein,
the fourteen formula comprises: example five 100 parts of premixed rubber, 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 5 parts of N990 carbon black, 15 parts of diatomite, 0.5 part of WS280 fluororubber internal mold release agent and 1 part of palm wax;
fifteen of the formula is as follows: example six 100 parts of premix rubber, 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 5 parts of N990 carbon black, 15 parts of diatomite, 0.5 part of WS280 fluororubber internal mold release agent and 1 part of palm wax;
the sixteen formula is as follows: example premix gum seven 100 parts, magnesium oxide 3 parts, calcium hydroxide 6 parts, N990 carbon black 5 parts, diatomaceous earth 15 parts, WS280 fluororubber internal mold release agent 0.5 parts and palm wax 1 parts;
then, fluororubber mixes were prepared in the steps for preparing the fluororubber mixes of example 1 (S1.32 to S1.33, with the formulations being changed accordingly), and were designated as example mix seven, example mix eight, and example mix nine;
the prepared example compound seven, example compound eight and example compound nine are respectively prepared into a standard test piece for testing, and the vulcanization conditions are one-stage vulcanization: @ 180 ℃ for 5min; post-vulcanization at 230 ℃ and @24H, the physical properties of which are shown in Table 4 below.
Comparative example 4:
in this comparative example, when the fluororubber premix is prepared, 20Kg of raw ternary bisphenol fluororubber having a fluorine content of 68.5% and a Mooney viscosity ML121 ℃ (1 + 10) of 30, 20Kg of raw binary bisphenol fluororubber having a fluorine content of 66% and a Mooney viscosity ML121 ℃ (1 + 10) of 30, and 20Kg of raw bisphenol AF primary salt prepared by the preparation procedure of example 1 are prepared according to seventeen and eighteen (in parts by weight) formulas; wherein the seventeenth formula is: 100 parts of ternary bisphenol fluororubber raw rubber, 3.45 parts of dechlorination type bisphenol AF salt and 0.2 part of vulcanization accelerator BPP; the formula is eighteen: 100 parts of raw binary bisphenol fluororubber, 3.45 parts of dechlorinated bisphenol AF salt and 0.2 part of vulcanization accelerator BPP; wherein the dosage of the dechlorination type bisphenol AF salt is calculated by 2.5 parts by weight of bisphenol AF contained in the dechlorination type bisphenol AF salt; then, the fluororubber premix is prepared according to the preparation steps (S1.22-S1.23, corresponding formula transformation) of the fluororubber premix in the embodiment 1, and marked as a second comparative premix and a third comparative premix;
then, 20Kg of the prepared premixed glue II in the comparative example and 20Kg of the prepared premixed glue III in the comparative example are prepared according to the formula nineteen and the formula twenty (the raw materials are calculated according to the parts by weight) respectively for later use; wherein,
the formula is nineteen: comparative example premix rubber two 100 parts, magnesium oxide 3 parts, calcium hydroxide 6 parts, N990 carbon black 5 parts, diatomaceous earth 15 parts, WS280 fluororubber internal mold release agent 0.5 parts, and palm wax 1 part;
the twenty formula is as follows: comparative example three 100 parts of premix rubber, 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 5 parts of N990 carbon black, 15 parts of diatomite, 0.5 part of WS280 fluororubber internal mold release agent and 1 part of palm wax;
then, fluororubber mixes were prepared as in the fluororubber mix preparation steps (S1.32 to S1.33, with the formulations being changed accordingly) of example 1, and were respectively labeled as comparative example mix five and comparative example mix six;
and testing the prepared fifth and sixth rubber compounds of the comparative examples by using standard test pieces under the following one-stage vulcanization conditions: 180 ℃ for @5min, and post-vulcanization at 230 ℃ for @24h, and the physical properties are shown in Table 4 below.
The test results of example 4 and comparative example 4 are shown in table 4:
table 4 table of physical properties (example 4 and comparative example 4).
Example 5:
the embodiment provides a preparation method of a lithium battery electrolyte resistant bisphenol high fluorine rubber compound, which comprises the following steps: s5.1 vulcanizing agent preparation:
the dechlorinated bisphenol AF salt prepared in the step of preparing the sulfating agent (S1.1) in example 1 was taken for future use;
s5.2 preparing the fluororubber premix:
respectively taking 20Kg of raw bisphenol high-fluorine fluororubber with 70 percent of fluorine content, 70.5 percent of fluorine content, 71 percent of fluorine content and 30 Mooney viscosity ML121 ℃ (1 + 10), and respectively preparing dechlorinated bisphenol AF salt prepared by S5.1 according to a formula twenty-one, a formula twenty-two and a formula twenty-three (the raw materials are calculated according to parts by weight) for standby; wherein,
the twenty-one formula is as follows: 100 parts of raw bisphenol high-fluorine rubber (fluorine content is 70%), 3.45 parts of dechlorination type bisphenol AF salt and 0.2 part of vulcanization accelerator BPP;
the formula twenty-two is as follows: 100 parts of bisphenol high fluorine rubber crude rubber (fluorine content is 70.5%), 3.45 parts of dechlorination type bisphenol AF salt and 0.2 part of vulcanization accelerator BPP;
the formula twenty-three is as follows: 100 parts of raw bisphenol high-fluorine fluororubber (fluorine content 71%), 3.45 parts of dechlorinated bisphenol AF salt and 0.2 part of vulcanization accelerator BPP;
in formulas twenty one to twenty three, the dosage of the dechlorination type bisphenol AF salt is calculated by 2.5 parts by weight of bisphenol AF contained in the dechlorination type bisphenol AF salt; then, the fluororubber premix is prepared according to the preparation steps (S1.22-S1.23, and the formula is correspondingly changed) of the fluororubber premix in example 1, and the prepared fluororubber premix is marked as example premix eight, example premix nine and example premix ten;
s5.3 preparation of fluororubber compound:
taking eight to ten 20Kg of the prepared premixed glue of the embodiment, and preparing the premixed glue according to twenty-four formulas, twenty-five formulas and twenty-six formulas (the weight parts of the raw materials are calculated) for later use; wherein,
twenty-four of the formula are: eight 100 parts of premixed rubber, 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 2 parts of N990 carbon black, 5 parts of diatomite, 15 parts of N325 high-heat-resistance carbon black serving as a functional assistant, 0.5 part of WS280 fluororubber internal mold release agent and 1 part of palm wax;
the twenty-five formula is as follows: nine 100 parts of premixed rubber, 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 2 parts of N990 carbon black, 5 parts of kieselguhr, 15 parts of functional assistant N325 high-heat-resistance carbon black, 0.5 part of WS280 fluororubber internal mold release agent and 1 part of palm wax;
the twenty-six formula is as follows: the preparation method comprises the following steps of taking ten 100 parts of premixed rubber, 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 2 parts of N990 carbon black, 5 parts of diatomite, 15 parts of N325 high-heat-resistance carbon black serving as a functional additive, 0.5 part of WS280 fluororubber internal mold release agent and 1 part of palm wax;
then, fluororubber mixes were prepared in the steps for preparing the fluororubber mixes of example 1 (S1.32 to S1.33, with the formulations changed accordingly), and were designated as example mix ten, example mix eleven, and example mix twelve, respectively;
the prepared example rubber mixtures ten to twelve of the example rubber mixtures are prepared into standard test pieces for testing, and the vulcanization conditions are one-stage vulcanization: 180 ℃ for @5min, and post-vulcanization at 230 ℃ for @24h, and the physical properties are shown in Table 5 below.
Comparative example 5:
taking 20Kg of peroxide high fluorine rubber crude rubber (Kemu GF200S, general specification of lithium battery sealing material) with fluorine content of 70.3% and Mooney viscosity ML121 ℃ (1 + 10) of 25; taking fluorine content as 70.1% and Mooney viscosity ML121 ℃ (1 + 10) as 220Kg of peroxide high fluorine rubber crude rubber (3M FPO 3820, general specification of lithium battery sealing material); respectively preparing according to twenty-seven and twenty-eight (in parts by weight) formulas for standby; wherein the twenty-seven formula is as follows: 100 parts of peroxide high-fluorine rubber crude rubber (Kemu GF 200S), 20 parts of N990 carbon black, TAIC (triallyl isocyanurate,
TAIC 75%), bis 2,5 (Luperox 101XL 45) 3, HT290 internal mold release agent 0.5 and WS280 fluororubber internal mold release agent 0.5;
twenty-eight of the formula is: 100 parts of peroxide high fluorine rubber crude rubber (3M FPO 3820), 20 parts of N990 carbon black, TAIC (triallyl isocyanurate,
TAIC 75%), bis 2,5 (Luperox 101XL 45) 3, HT290 internal mold release agent 0.5 and WS280 fluororubber internal mold release agent 0.5;
the fluororubber premix was prepared according to the following procedure, labeled as comparative example mix seven and comparative example mix eight:
firstly, plasticating corresponding crude rubber (peroxide high fluorine rubber crude rubber) in a 25L internal mixer according to a formula twenty-seven or a formula twenty-eight, wherein the plasticating temperature is 85 ℃, and the plasticating time is 3min; then, sequentially adding bis 2,5 (Luperox 101XL 45), N990 carbon black, TAIC, HT290 internal mold release agent and WS280 fluororubber internal mold release agent into a 25L internal mixer according to a formula twenty seven or a formula twenty eight, fully mixing for 8min, wherein the mixing temperature is not more than 110 ℃, and taking out and cooling;
then, cooling the rubber material prepared by cooling the sheet discharged from the previous step for 24 hours, then thinly passing the rubber material on an open mill for 5 times, and then extruding the sheet from the extrusion filter to obtain fluororubber mixed rubber, wherein the fluororubber mixed rubber comprises seven mixed rubber in comparative example and eight mixed rubber in comparative example;
the prepared rubber materials of the seventh rubber compound and the eighth rubber compound of the comparative example are prepared into standard test pieces for testing, and the vulcanization conditions are one-stage vulcanization: 180 ℃ for @5min, and post-vulcanization at 230 ℃ for @4H, and the physical properties are shown in Table 5 below.
The test results of example 5 and comparative example 5 are shown in table 5:
table 5 tables of physical properties (example 5 and comparative example 5).
In addition, in the embodiments of the present application, the vulcanization accelerator may be selected from 8-benzyl-1, 8-diazabicycloundecen-7-ene ammonium chloride, and/or tetrabutyl ammonium bromide, in addition to benzyltriphenyl phosphonium chloride (BPP); the reinforcing filler is any one or a mixture of any more of carbon black N990, diatomite, calcium silicate, spray carbon black and barium sulfate; the processing aid is any one or a mixture of any several of palm wax, WS280 and erucamide.
Next, the above examples 1 to 5 and comparative examples 1 to 5 were analyzed as follows:
(1) Example 1 and comparative example 1 show that: in the rubber compound of the embodiment 1, the dechlorination type bisphenol AF salt is adopted, the process of firstly preparing the pre-mixed rubber and then preparing the rubber compound is adopted, and no functional auxiliary agent is used; the rubber compound of the comparative example 1 adopts bisphenol AF primary salt, adopts the process of firstly preparing pre-rubber and then preparing rubber compound, and has no functional auxiliary agent; in comparative example II of comparative example 1, bisphenol AF was used as it was, and a rubber compound having no functional assistant was prepared. The compression set of the first mixed rubber of the embodiment is 25 percent, the compression set of the first mixed rubber of the comparative embodiment is 28 percent, and the compression set of the second mixed rubber of the comparative embodiment is 34 percent, which are compared with the compression set of the first mixed rubber of the comparative embodiment, so that the dechlorination type bisphenol AF salt prepared by the invention effectively reduces the compression set of the bisphenol high fluorine-containing rubber;
(2) Example 2 and comparative example 2 show that: in the second rubber compound in the embodiment 2, the dechlorination type bisphenol AF salt is adopted, 5 parts of the functional auxiliary agent N325 is added, and the process of firstly preparing the pre-mixed rubber and then preparing the rubber compound is adopted; in the third rubber compound in the embodiment 2, the dechlorination type bisphenol AF salt is adopted, 10 parts of functional auxiliary agents are added, and the process of firstly preparing pre-rubber compound and then preparing rubber compound is adopted; in the embodiment 2, the mixed rubber IV adopts the dechlorination type bisphenol AF salt, 15 parts of functional auxiliary agents are added, and the process of firstly preparing pre-mixed rubber and then preparing mixed rubber is adopted; comparative example 3 in comparative example 2 the dechlorinated bisphenol AF salt of the invention was used in a process of preparing a pre-mix and then a mix, without a functional aid. The compression set of the second rubber compound of the embodiment is 24 percent, the compression set of the third rubber compound of the embodiment is 22 percent, the compression set of the fourth rubber compound of the embodiment is 20 percent and the compression set of the third rubber compound of the comparative example is 25 percent, which shows that the compression set of the rubber compound is gradually reduced along with the proper increase of the use amount of the functional additive, and the functional additive used in the invention effectively reduces the compression set of the bisphenol high fluorine rubber;
(3) Example 3 and comparative example 3 show that: in the embodiment 3, the mixed rubber V is prepared by directly using the dechlorination type bisphenol AF salt and the non-functional auxiliary agent; in the embodiment of the embodiment 3, the dechlorination type bisphenol AF salt is adopted, 15 parts of functional auxiliary agents are added, and the mixed rubber is directly prepared; in the fourth comparative example of the 3, the dechlorination type bisphenol AF salt is adopted, 15 parts of functional auxiliary agents are added, and the process of firstly preparing premixed rubber and then preparing rubber compound is adopted; the five compression set of the example compound was 27%, the six compression set of the example compound was 22%, and the four compression set of the comparative example compound was 20%; the method shows that the compression set of the bisphenol high fluorine rubber can be effectively reduced by adopting the process of firstly preparing the pre-mixed rubber and then preparing the mixed rubber, and simultaneously, the compression set of the bisphenol high fluorine rubber can be effectively reduced by using a proper amount of functional additives;
(4) Example 4 and comparative example 4 show that: the mixed rubber seven in the embodiment of the embodiment 4 is prepared by selecting raw bisphenol high-fluorine fluororubber with 70 percent of fluorine content, adopting the dechlorination type bisphenol AF salt and no functional auxiliary agent, and adopting the process of firstly preparing premixed rubber and then preparing mixed rubber; the octa-selected raw rubber of bisphenol high fluorine fluororubber with fluorine content of 70.5 percent in the mixed rubber of the embodiment 4 adopts the dechlorination type bisphenol AF salt and no functional auxiliary agent, and adopts the process of firstly preparing pre-mixed rubber and then preparing mixed rubber; in the embodiment 4, the mixed rubber nine selects raw bisphenol high-fluorine fluororubber with the fluorine content of 71 percent, adopts the dechlorination type bisphenol AF salt and the non-functional auxiliary agent, and adopts the process of firstly preparing the pre-mixed rubber and then preparing the mixed rubber; the compound rubber V of the comparative example in the comparative example 4 is prepared by selecting ternary bisphenol fluororubber raw rubber with fluorine content of 68.5%, adopting dechlorination type bisphenol AF salt and a non-functional auxiliary agent, and adopting a process of firstly preparing pre-mixed rubber and then preparing mixed rubber; in the comparative example of the compound of comparative example 4, raw binary bisphenol fluororubber with 66% of fluorine content is selected, the dechlorination type bisphenol AF salt and the non-functional auxiliary agent are adopted, and the process of preparing pre-mixed rubber and then preparing the compound rubber is adopted. Seven compression set of the example compound was 24%, eight compression set of the example compound was 26%, nine compression set of the example compound was 28%, five compression set of the comparative example compound was 19%, and six compression set of the comparative example compound was 11%. The electrolyte volume expansion resistance of seven of the mixed rubber in the example is +30.7%, the electrolyte volume expansion resistance of eight of the mixed rubber in the example is +26.3%, the electrolyte volume expansion resistance of nine of the mixed rubber in the example is +24.6%, the electrolyte volume expansion resistance of five of the mixed rubber in the comparative example is 78.3%, and the electrolyte volume expansion resistance of six of the mixed rubber in the comparative example is 112.7%, which shows that the higher the fluorine content is, the larger the compression set is, and the higher the fluorine content is, the lower the electrolyte volume expansion resistance is;
(5) Example 5 and comparative example 5 show that: the rubber compound in the embodiment of the embodiment 5 is prepared by selecting raw bisphenol high-fluorine fluororubber with 70% of fluorine content, adding 15 parts of functional auxiliary agent into dechlorinated bisphenol AF salt, and adopting a process of firstly preparing pre-rubber compound and then preparing rubber compound; the eleventh embodiment of the mixed rubber in the embodiment 5 selects raw bisphenol high fluorine rubber with fluorine content of 70.5 percent, adopts dechlorination type bisphenol AF salt of the invention, adds 15 parts of functional auxiliary agents, adopts the process of firstly preparing pre-mixed rubber and then preparing mixed rubber; the raw rubber of the bisphenol high-fluorine fluororubber with the fluorine content of 71 percent is selected in the mixed rubber of the embodiment 5, the dechlorination type bisphenol AF salt is adopted, 15 parts of functional auxiliary agents are added, and the process of firstly preparing the pre-mixed rubber and then preparing the mixed rubber is adopted; the compound rubber seven in the comparative example 5 is prepared by directly selecting peroxide high fluorine rubber raw rubber (electrolyte resistant common specification) with fluorine content of 70.3 percent; eighthly, in the compound of comparative example 5, raw rubber of peroxide high fluorine rubber (electrolyte resistant general specification) with fluorine content of 70.1% was selected to directly prepare the compound. The ten compression set of the example compound was 19%, the eleven compression set of the example compound was 21%, the twelve compression set of the example compound was 24%, the seven compression set of the comparative example compound was 23%, and the eight compression set of the comparative example compound was 21%. The electrolyte volume expansion resistance of the mixed rubber in the embodiment is +29.1 percent, the electrolyte volume expansion resistance of the mixed rubber in the embodiment is +25.2 percent, the electrolyte volume expansion resistance of the mixed rubber in the embodiment is +22.0 percent, the electrolyte volume expansion resistance of the mixed rubber in the comparative example is 27.3 percent, and the electrolyte volume expansion resistance of the mixed rubber in the comparative example is 28.2 percent, which indicates that the bisphenol high fluorine rubber with 70 to 71 percent of fluorine content passes through the selection of a vulcanizing agent, the selection of a functional assistant and the optimization of a processing process, and the prepared bisphenol high fluorine rubber mixed rubber has excellent low-compression permanent deformation performance, excellent electrolyte resistance performance and excellent electrical performance and meets the technical requirements of the electrolyte sealing material of a lithium battery;
(6) Examples 1-5 and comparative examples 1-5 show that: when the lithium battery electrolyte-resistant bisphenol high-fluorine fluororubber rubber compound is prepared: selecting bisphenol high fluorine fluororubber raw rubber with fluorine content of 70-71% to realize low volume expansion rate performance required in electrolyte resistance; the dechlorination type bisphenol AF salt prepared by the invention is used as a vulcanizing agent, the high heat resistance type carbon black N325 is used as a functional auxiliary agent, the process of preparing the pre-mixed rubber and then preparing the mixed rubber is adopted, and the low compression permanent deformation performance required by the electrolyte-resistant sealing material is realized through the cooperation of the materials, the formula and the process; meanwhile, through the selection of materials and formulas, the electrical property requirement required by the electrolyte-resistant sealing material is met, and the requirements of excellent demolding property, good mold pollution, high product yield and the like are met.
The test result shows that the lithium battery electrolyte resistant bisphenol high-fluorine rubber compound prepared by the invention obviously improves the compression permanent deformation of the high-fluorine rubber, meets the requirements of low compression permanent deformation performance and electrical performance required by electrolyte resistant sealing materials, has the same technical effect as peroxide high-fluorine rubber when used as a lithium battery electrolyte resistant material, greatly reduces the cost, and completely realizes the aim of the invention. The invention achieves the purposes of reducing the cost by using the bisphenol high fluorine rubber and solving the problems of poor demoulding property, large mould pollution, high reject ratio of products and the like; the vulcanizing agent of the invention is used to reduce the compression permanent deformation and solve the problem of large compression permanent deformation of bisphenol high fluorine rubber; the compression permanent deformation is further reduced by using the functional additive N325 carbon black, and the problem of large compression permanent deformation of the bisphenol high fluorine rubber is solved; the process scheme that the bisphenol high fluorine rubber pre-mixed rubber is firstly manufactured, and then the bisphenol high fluorine rubber mixed rubber is manufactured improves the basic physical properties of the bisphenol high fluorine rubber, and further reduces the compression set; by selecting the bisphenol high fluorine rubber with fluorine content of 70-71%, the volume expansion rate of the bisphenol high fluorine rubber in the electrolyte is reduced due to the high fluorine content.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention.
Claims (10)
1. A preparation method of a lithium battery electrolyte resistant bisphenol high fluorine rubber compound is characterized by comprising the following steps:
s1, preparing a vulcanizing agent:
reacting bisphenol AF with benzyltriphenylphosphonium chloride to form bisphenol AF primary salt, and performing dechlorination to form dechlorination type bisphenol AF salt, wherein the dechlorination type bisphenol AF salt is the prepared vulcanizing agent;
s2, preparing the fluororubber premix:
preparing the fluororubber premix by using raw bisphenol high-fluorine fluororubber, a vulcanization accelerator and the vulcanizing agent prepared in the step S1;
s3, preparing a bisphenol high fluorine rubber compound:
and (3) mixing the acid absorbent, the reinforcing filler, the functional additive and the processing additive with the fluororubber premix prepared in the step (S2) to obtain the bisphenol high-fluorine fluororubber rubber compound.
2. The method for preparing the bisphenol high-fluorine fluororubber compound which is resistant to the lithium battery electrolyte according to claim 1, wherein in step S1, the vulcanizing agent is prepared by the following steps:
s11, mixing bisphenol AF and benzyltriphenylphosphonium chloride, wherein the mixing weight ratio of the bisphenol AF to the benzyltriphenylphosphonium chloride is 3:0.7-2, placing the uniformly mixed mixture in a heating reaction kettle, heating to 200-250 ℃, starting stirring, reacting for 0.5-2h, stopping heating, discharging the product after the reaction, and cooling to room temperature to obtain bisphenol AF primary salt;
and S12, crushing the bisphenol AF primary salt prepared in the step S11 by a crusher, putting the crushed bisphenol AF primary salt into a stirring kettle, adding dichloromethane, stirring and dissolving, dropwise adding a 5% sodium bicarbonate solution after complete dissolution to generate a large amount of flocculates, continuously stirring for 1h, repeatedly washing the flocculates by deionized water until the chlorine content of the flocculates is lower than 200ppm, and filtering and drying the flocculates to obtain the required dechlorinated bisphenol AF salt, namely the prepared vulcanizing agent.
3. The method for preparing the bisphenol high-fluorine rubber compound capable of resisting the lithium battery electrolyte as claimed in claim 1 or 2, wherein the step S2 of preparing the bisphenol high-fluorine rubber pre-mixed rubber specifically comprises the following steps:
s21, plasticating the raw bisphenol high-fluorine rubber in an internal mixer for 4-10min at the plastication temperature of 80-100 ℃ according to the premixing ratio;
s22, sequentially adding a vulcanizing agent and a vulcanization accelerator into the internal mixer according to a premixing ratio, fully mixing for 6-10min at the mixing temperature of not more than 110 ℃, discharging, and discharging and cooling by using an open mill to obtain the bisphenol high fluorine rubber premixed rubber;
wherein the premixing proportion is as follows: 100 parts of raw bisphenol high fluorine rubber, 2.5-4.0 parts of vulcanizing agent and 0.05-1.0 part of vulcanization accelerator.
4. The method for preparing the lithium battery electrolyte resistant bisphenol high-fluorine rubber compound as claimed in claim 3, wherein the fluorine content of the raw bisphenol high-fluorine rubber is 70% -71%, the Mooney viscosity ML121 ℃ is 1+10 is 20-60; and/or the vulcanization accelerator is any one or a mixture of any several of benzyl triphenyl phosphonium chloride, 8-benzyl-1, 8-diazabicycloundec-7-ene ammonium chloride and tetrabutyl ammonium bromide.
5. The preparation method of the bisphenol high-fluorine fluororubber gross rubber with lithium battery electrolyte resistance as claimed in claim 1, characterized in that the step S3 of preparing the bisphenol high-fluorine fluororubber gross rubber comprises the following steps:
s31, sequentially adding the bisphenol high-fluorine fluororubber premix prepared in the step S2, an acid acceptor, a functional assistant, a reinforcing filler and a processing assistant into an internal mixer according to a mixing ratio, fully mixing for 6-10min at the mixing temperature of not more than 110 ℃, and taking out of a sheet for cooling;
s32, cooling the rubber material prepared in the step S31 for 24 hours, then thinly passing the rubber material on an open mill for 4-6 times, and then extruding out a filter to obtain a bisphenol high fluorine rubber compound;
wherein the mixing proportion is as follows: 100 parts of bisphenol high fluorine rubber premix, 6-15 parts of acid absorbent, 5-20 parts of reinforcing filler, 5-20 parts of functional additive and 1-3 parts of processing additive, wherein the functional additive is high heat-resistant carbon black N325, and the dosage of the functional additive is 5-20 parts by weight.
6. The method for preparing the bisphenol high-fluorine fluororubber compound which is resistant to lithium battery electrolyte according to claim 5, wherein the acid scavenger is a mixture of magnesium oxide and calcium hydroxide, the weight portions of the magnesium oxide and the calcium hydroxide are respectively 3-9 parts and 3-6 parts, wherein the magnesium oxide is high-activity magnesium oxide, and the activity value of the magnesium oxide is 150-180; and/or the reinforcing filler is any one or a mixture of any several of N990 carbon black, diatomite, calcium silicate, spray carbon black and barium sulfate.
7. The method for preparing the bisphenol high-fluorine fluororubber compound which is resistant to lithium battery electrolytes according to claim 6, wherein the reinforcing filler is a mixture of N990 carbon black and diatomite.
8. The method for preparing the lithium battery electrolyte resistant bisphenol high-fluorine rubber compound as claimed in claim 5, 6 or 7, wherein the processing aid is any one or a mixture of any several of palm wax, WS280 fluorine rubber internal release agent and erucamide.
9. The lithium battery electrolyte-resistant bisphenol high-fluorine rubber compound prepared by the preparation method of any one of claims 1 to 8.
10. A fluororubber product produced by using the lithium battery electrolyte resistant bisphenol high-fluorine fluororubber compound according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211325898.0A CN115584141B (en) | 2022-10-27 | 2022-10-27 | Bisphenol high-fluorine rubber compound for lithium-resistant battery electrolyte and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211325898.0A CN115584141B (en) | 2022-10-27 | 2022-10-27 | Bisphenol high-fluorine rubber compound for lithium-resistant battery electrolyte and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115584141A true CN115584141A (en) | 2023-01-10 |
| CN115584141B CN115584141B (en) | 2023-07-18 |
Family
ID=84781800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211325898.0A Active CN115584141B (en) | 2022-10-27 | 2022-10-27 | Bisphenol high-fluorine rubber compound for lithium-resistant battery electrolyte and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115584141B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001192482A (en) * | 2000-01-13 | 2001-07-17 | Nok Corp | Method for producing vulcanized molded product of fluororubber |
| CN101875750A (en) * | 2010-07-27 | 2010-11-03 | 中昊晨光化工研究院 | Low compression and permanent deformation fluororubber compounded rubber and preparation method thereof |
| CN102875937A (en) * | 2012-09-12 | 2013-01-16 | 中昊晨光化工研究院有限公司 | Fluororubber rubber compound and preparation method thereof |
| CN104479265A (en) * | 2014-12-31 | 2015-04-01 | 山东华夏神舟新材料有限公司 | Low-compression-deformation fluororubber premix and preparation method thereof |
| CN111087650A (en) * | 2019-12-25 | 2020-05-01 | 浙江加诚新材料有限公司 | Vulcanizing agent system for fluororubber, fluororubber compound and application |
| CN115109357A (en) * | 2022-07-01 | 2022-09-27 | 江苏中煜橡塑科技有限公司 | Fluororubber sealing nail material for power battery plugging liquid and preparation method thereof |
-
2022
- 2022-10-27 CN CN202211325898.0A patent/CN115584141B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001192482A (en) * | 2000-01-13 | 2001-07-17 | Nok Corp | Method for producing vulcanized molded product of fluororubber |
| CN101875750A (en) * | 2010-07-27 | 2010-11-03 | 中昊晨光化工研究院 | Low compression and permanent deformation fluororubber compounded rubber and preparation method thereof |
| CN102875937A (en) * | 2012-09-12 | 2013-01-16 | 中昊晨光化工研究院有限公司 | Fluororubber rubber compound and preparation method thereof |
| CN104479265A (en) * | 2014-12-31 | 2015-04-01 | 山东华夏神舟新材料有限公司 | Low-compression-deformation fluororubber premix and preparation method thereof |
| CN111087650A (en) * | 2019-12-25 | 2020-05-01 | 浙江加诚新材料有限公司 | Vulcanizing agent system for fluororubber, fluororubber compound and application |
| CN115109357A (en) * | 2022-07-01 | 2022-09-27 | 江苏中煜橡塑科技有限公司 | Fluororubber sealing nail material for power battery plugging liquid and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 洪江永;孟庆文;王京辉;余考明;陈伟峰;: "三元氟橡胶硫化时硫化剂和促进剂的配方优化", 化工生产与技术, no. 05 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115584141B (en) | 2023-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105061829A (en) | Method for preparing aluminum hydroxide flame-retardant adhesive | |
| CN108485013A (en) | A kind of fire-retardant ozone-resistant rubbber of oil resistant and preparation method thereof | |
| CN115895266B (en) | Low-smoke flame-retardant cable material and preparation method thereof | |
| CN110577706A (en) | Halogen-free flame-retardant ethylene propylene diene monomer rubber for sealing strip and preparation method thereof | |
| CN111675858A (en) | Formula and preparation method of corrosion-resistant rubber material | |
| CN108276704A (en) | Flame-retardant cable protective sleeve and preparation method thereof | |
| CN101570611A (en) | Nuclear power 1E-level K3-type thermal shrinkage material and preparation process | |
| CN102643489B (en) | Flame-retarding toughening polystyrene master batch and preparation method thereof | |
| CN111087650A (en) | Vulcanizing agent system for fluororubber, fluororubber compound and application | |
| CN115584141A (en) | Lithium battery electrolyte-resistant bisphenol high-fluorine fluororubber compound and preparation method thereof | |
| CN109912885A (en) | PP composite material and its preparation method and application, automobile component, automobile | |
| CN110964240B (en) | Wear-resistant flame-retardant foam material for shoes and preparation method thereof | |
| CN110577695A (en) | material formula and manufacturing process of flame-retardant high-polymer heat-shrinkable high-voltage insulating sleeve | |
| CN1746214A (en) | Fire-retardant rubber contactor under high-temperature | |
| CN102977479A (en) | Preparation method for dynamic cross-linking flame retardant chlorinated polyethylene thermoplastic elastomer | |
| CN102295797B (en) | Zero-halogen flame-retardant polyolefin material and preparation method as well as application thereof | |
| CN111073082A (en) | Plastic and rubber composite material and preparation method thereof | |
| CN115304836B (en) | Low-sulfur rubber-plastic sponge product and preparation method thereof | |
| CN106751007A (en) | A kind of high-strength low-density thermoplastic vulcanizate material and preparation method thereof | |
| CN110885504A (en) | Sealing strip suitable for glass curtain wall frame and production process thereof | |
| CN101699635B (en) | Insulating back panel of solar photovoltaic cell and preparation method thereof | |
| CN105273223B (en) | Hydroxo complex heat stabilizer, composite thermal stabilizer and poly (vinyl chloride) resin composition and preparation method | |
| CN108530786A (en) | A kind of ageing-resistant HIPS foamed plastics and preparation method thereof | |
| CN106560487A (en) | Halogen-free flame-retardant polypropylene compound and preparation method thereof | |
| CN103059436A (en) | Polymer alloy material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No. 4 Yufeng Road, Shangyi Town, Dongpo District, Meishan City, Sichuan Province, 620000 yuan Patentee after: Sichuan Daohong New Materials Co.,Ltd. Country or region after: China Address before: 620000 Jinxiang Chemical Industrial Park, Dongpo District, Meishan City, Sichuan Province Patentee before: SICHUAN DAOHONG NEW MATERIALS Co.,Ltd. Country or region before: China |