CN115584091B - Ternary fluororubber nanocomposite with diversified performances and preparation method thereof - Google Patents
Ternary fluororubber nanocomposite with diversified performances and preparation method thereof Download PDFInfo
- Publication number
- CN115584091B CN115584091B CN202211176355.7A CN202211176355A CN115584091B CN 115584091 B CN115584091 B CN 115584091B CN 202211176355 A CN202211176355 A CN 202211176355A CN 115584091 B CN115584091 B CN 115584091B
- Authority
- CN
- China
- Prior art keywords
- fluororubber
- mwcnt
- fkm
- parts
- composite material
- 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.)
- Active
Links
- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 108
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 52
- 239000000945 filler Substances 0.000 claims abstract description 43
- 238000004073 vulcanization Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229920001971 elastomer Polymers 0.000 claims description 19
- 239000005060 rubber Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 7
- 239000006096 absorbing agent Substances 0.000 claims description 6
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims 1
- 239000002250 absorbent Substances 0.000 claims 1
- 238000005576 amination reaction Methods 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 43
- 239000003575 carbonaceous material Substances 0.000 abstract description 21
- 239000011159 matrix material Substances 0.000 abstract description 8
- 230000003993 interaction Effects 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 230000035882 stress Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000009977 dual effect Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 3
- 238000010382 chemical cross-linking Methods 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000002679 ablation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 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
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 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 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- JMKJCPUVEMZGEC-UHFFFAOYSA-N methyl 2,2,3,3,3-pentafluoropropanoate Chemical compound COC(=O)C(F)(F)C(F)(F)F JMKJCPUVEMZGEC-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- -1 monomethyl alcohol Chemical compound 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of high polymer material preparation, in particular to a ternary fluororubber nanocomposite with diversified performances and a preparation method thereof, wherein ternary fluororubber is used as a matrix, an aminated multi-walled carbon nanotube (MWCNT-A) and a carboxylated multi-walled carbon nanotube (MWCNT-COOH) are used as fillers, and the ternary fluororubber nanocomposite with diversified performances is prepared through mixing by an open mill, vulcanization and two-stage vulcanization, and the dispersibility of the fillers in the composite is improved due to the hydrogen bond between the MWCNT-COOH and fluororubber and the interaction between the MWCNT-COOH and the MWCNT-A, so that the phenomenon of carbon material agglomeration in fracture surfaces is less from the aspect of appearance; the synergy of the aminated multi-wall carbon nano tube and the carboxylated multi-wall carbon nano tube further increases the tensile strength, 100% stretching stress and hardness of the fluororubber in terms of mechanical properties.
Description
Technical Field
The invention relates to the field of preparation of high polymer materials, in particular to a ternary fluororubber nanocomposite with diversified properties and a preparation method thereof.
Background
The fluororubber is a synthetic polymer rubber (elastomer) containing fluorine atoms on carbon atoms of a main chain or a side chain, and belongs to special fluororubber, compared with other hydrocarbon rubber, the fluororubber has the characteristics of strong electronegativity, fluorine-carbon bond containing high bond energy (bond energy is as high as 465 kj/mol), small Van der Waals bond angle (1.32 angstrom) and the like, and the covalent radius of the fluorine atoms is small (0.64 angstrom, which is only about half of the bond length of a carbon-carbon bond (C-C)), so that the fluorine atoms play a role of shielding the carbon-carbon main chain, thereby protecting the carbon-carbon main chain, ensuring the stability of the carbon-carbon main chain, and the structure endows the fluororubber with good heat resistance, chemical medium aging resistance, good chemical inertness in solvents, hydrocarbons, acids and alkalis, low dielectric constant, low combustibility, low refractive index, low surface energy (oil and water repellency), and low hygroscopicity, and the high energy of the C-F bond is often beneficial to improving oxidation resistance and hydrolysis resistance in all the fluororubber, and the fluororubber is used as a main metal in the harsh synthetic rubber, and is commonly called a very good condition for the most severe synthetic rubber.
The research and development of the fluororubber composite material with diversified performances has profound significance, and the fluororubber performance enhancement method is roughly divided into two types: changing the synthesis process and processing modification. At present, the synthesis technology of fluororubber in China is not generally mastered, and for us, the synthesis technology of breaking fluororubber is difficult, and the improvement of performance by changing the synthesis technology is more difficult. Thus, process modification is an effective way to our reinforced fluororubber. The carbon nano tube has higher length-diameter ratio, mechanical strength and excellent electric conduction and heat conduction properties, can be used as a filler to effectively improve the properties of the fluororubber, but has larger van der Waals force and the existence of C-F bonds in the fluororubber, so that the carbon nano tube cannot be uniformly dispersed in a fluororubber matrix.
Patent CN202210723245.1 discloses a method for preparing fluororubber with higher retention rate of performance at high temperature. The preparation method of the fluororubber with higher performance retention rate at high temperature is simple and easy to operate, and low in cost, and the prepared fluororubber has higher performance retention rate at high temperature and good processability, and can be widely applied to the technical fields of aerospace, military industry, national defense, automobiles, petrochemical industry and the like. However, the preparation method involves the use of solution, is easy to cause environmental pollution, contains vacuum environment and gas protection in the process, has very strict control on experimental conditions, and is easy to cause errors.
Patent CN202210467957.1 discloses a preparation method of low-compression stress relaxation fluororubber for battery sealing parts. Fluororubber with low compression stress relaxation, excellent high temperature resistance, electrolyte resistance, acid and alkali resistance and chemical corrosion resistance is prepared through simple mechanical blending, and the sealing element prepared from the fluororubber has the advantages of high temperature resistance, electrolyte resistance, acid and alkali resistance, chemical corrosion resistance, good sealing reliability, long service life and the like. But has lower hardness and wear resistance, and is easy to wear in the use process of the sealing element, thereby shortening the service life.
Patent CN202210683998.4 provides a preparation method of a fluororubber composite material, and by combining wollastonite with a needle structure and magnesium hydroxide with a sheet structure, continuous filling of fluororubber can be realized, and the heat conducting property of fluororubber is further improved. However, the secondary mixing process involves drying of water, and a few dryness will be incomplete, which will generate bubbles during vulcanization, thereby affecting the properties of the composite material, and the tensile strength of the composite material after combining the two inorganic fillers is lower.
Patent CN202111417540.6 discloses a conductive fluororubber for oil seal. The modified ternary fluororubber raw rubber, the carbon nano tube, the conductive carbon black, the magnetic powder, the graphite and the dioctyl sebacate are mixed with the acid absorber, the release agent and the dispersing agent to be mixed in the internal mixer, so that the novel conductive fluororubber material for the oil seal is prepared. However, the method of mixing in an internal mixer cannot uniformly disperse various fillers such as carbon nanotubes, so that the fillers are agglomerated in a fluororubber matrix to influence the performance of fluororubber.
Patent CN202110800238.2 discloses a method for preparing low-resistivity fluororubber for automobile fuel pipeline system. After kneading and generating heat in an internal mixer, adding N990 carbon black, active magnesium oxide, carbon nano tubes, nano-scale surface silver-plated glass beads, calcium hydroxide and a release agent, and stirring and kneading; turning to an open mill for turning, thinning out the sheet, taking out and standing; then putting the mixture into an open mill again for mixing, adding bisphenol AF and a vulcanization accelerator, and discharging the sheet after open mixing to obtain a mixed rubber; and (3) after the rubber compound is preformed, placing the rubber compound into a mould for moulding, and finally, carrying out secondary vulcanization. However, the fluororubber composite material added with various fillers has relatively reduced tensile strength and compression set, which is unfavorable for application in sealing elements.
The patent CN201710620527.8 provides an automobile cooling pipe, which is modified by adding nano simple substance tungsten, nano graphite fiber and nano potassium feldspar on the basis of the original material of the automobile cooling pipe, so that the heat transfer effect of the automobile cooling pipe is improved. Although the heat transfer effect of the fluororubber is greatly improved by adding various fillers, the use amount of the fillers is too large and the economic benefit is not high.
Patent CN202210388971.2 discloses a preparation method of a silicone filler modified fluororubber master batch. Dispersing micro-nano silicon filler in a mixed solution of absolute ethyl alcohol and deionized water, regulating the PH value after ultrasonic mixing, adding a modifier to realize organic bridging of the silicon filler and fluororubber, washing a reaction product, centrifuging and drying to obtain a modified silicon filler; the modified silicon filler and the fluororubber are mixed and then are mixed, lump materials are segmented after mixing to form particles, and the silicon filler modified fluororubber master batch is obtained, so that the master batch can not only overcome the problem of uneven dispersion of common fillers in rubber, but also improve the low temperature resistance and mechanical property, and has the advantages of simple production process, low cost and easy industrial production. However, in the preparation process, an organic solvent is required, so that the environment is easily polluted, the environment-friendly requirement cannot be met, and a large amount of deionized water solution is used, so that bubbles are easily formed in the fluororubber under the high-temperature condition, and the performance and quality of the fluororubber are affected.
Patent CN202210376077.3 discloses an oil resistant and processable fluoroelastomer composition. The poly (hexafluoropropylene oxide) methyl pentafluoropropionate is obtained through reflux esterification dehydration reaction of poly (hexafluoropropylene oxide) monomethyl alcohol and pentafluoropropionic acid for 3-4 hours under the action of catalyst phosphoric acid. According to the invention, the fluororubber is softened by adding the high-fluoroalkyl ester with medium and low molecular weight into the fluororubber, so that the fluidity, the demolding property and the roll-off property of the fluororubber are improved. The fluorine-containing elastomer has good solvent resistance, processing manufacturability, high temperature resistance, corrosion resistance and good mechanical strength. However, the preparation process is complex, the requirement on the process is high, and a large amount of organic solvents are used, so that the preparation process is easy to cause harm to human bodies and pollute the environment.
Patent CN202210705213.9 provides a preparation process of high-temperature-resistant special fluororubber. The high-temperature resistant fluororubber composite material is obtained through simple mechanical blending, the problem that fluororubber has poor low-temperature performance due to poor molecular chain flexibility and higher glass transition temperature of fluororubber is solved, but a large amount of powder and organic solvent are added, so that the environment is easily polluted in the processing process, the health of operators is endangered, and the value for improving the tensile property is low.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings of the prior art and provide a ternary fluororubber nanocomposite with diversified performances and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a preparation method of ternary fluororubber nanocomposite with diversified properties comprises the following steps:
(1) Weighing the following raw materials in parts by mass:
100 parts of ternary fluororubber;
1-5 parts of acid absorber;
1-5 parts of a promoter;
0.5-5 parts of octadecylamine;
1-10 parts of carboxylated multiwall carbon nanotubes;
1-10 parts of aminated multi-wall carbon nano tube;
1-5 parts of vulcanizing agent;
(2) Setting the roller temperature of an open mill to be 45-55 ℃, putting fluororubber into the open mill, adding a premixed acid absorber and an accelerator into the open mill for uniform mixing, and finally adding octadecylamine, carboxylated multiwall carbon nanotubes, aminated multiwall carbon nanotubes and a vulcanizing agent into the open mill for uniform mixing;
(3) After the composite material refined in the step (2) is cooled for a period of time, pressing the composite material into a rubber sheet by a flat vulcanizing machine;
(4) And (3) placing the rubber sheet prepared in the step (3) into an oven for secondary vulcanization to prepare the ternary fluororubber nanocomposite with the double-filler system.
Preferably, the acid absorber is zinc oxide, the accelerator is triallyl isocyanurate, and the vulcanizing agent is 2, 5-dimethyl-2, 5-bishexane.
Preferably, in the step (3), the vulcanization pressure is 8-10MPa, the vulcanization temperature is 175-180 ℃, and the vulcanization time is 6-8 min.
Preferably, in the step (4), the secondary vulcanization temperature is 230-234 ℃ and the time is 1-3 h.
Preferably, the carboxylated multi-wall carbon nanotubes are 1-5 parts by mass.
Preferably, the mass fraction of the aminated multi-wall carbon nano tube is 1-5.
The ternary fluororubber nanocomposite with diversified properties prepared by the preparation method is also provided.
The beneficial effects of the invention are as follows: the ternary fluororubber nanocomposite with the dual-filler system is prepared by taking ternary fluororubber as a matrix, and taking an aminated multi-wall carbon nano tube (MWCNT-A) and a carboxylated multi-wall carbon nano tube (MWCNT-COOH) as fillers, and the phenomenon of carbon material agglomeration in a fracture surface is less from the aspect of appearance, so that the dispersibility of the carbon material in the dual-filler system is improved; from the mechanical property, due to the hydrogen bond between the MWCNT-COOH and the FKM and the interaction between the MWCNT-COOH and the MWCNT-A, the dispersibility of the filler in the composite material is improved, so that the tensile strength, 100% stretching stress and hardness of the fluororubber are further increased, and the degree of reduction of the elongation at break of the composite material is reduced although the elongation at break of the composite material is still reduced; the conductivity of the composite material containing the double-filler system is improved by 9 orders of magnitude in conductivity, which is attributed to the good conductivity of the multi-walled carbon nanotubes and the more perfect conductive path formed inside the polymer; compared with a composite material without any carbon nano material, the double-filler system of MWCNT-COOH and MWCNT-A can improve the heat conductivity coefficient and carbon residue rate of the composite material in terms of heat conductivity.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that it is within the scope of the invention to one skilled in the art to obtain other drawings from these drawings without inventive faculty.
FIG. 1 is a SEM photograph of (a) FKM/C-1, (b) FKM/C-4, (C) FKM/C-5, and (d) FKM/C-8;
FIG. 2 is a FTIR spectrum of comparative example 1 (FKM/C-1), comparative example 2 (FKM/C-4), comparative example 3 (FKM/C-5) and example 1 (FKM/C-8);
FIG. 3 shows (a) tensile strength, (b) elongation at break, (c) 100% tensile stress, and (d) hardness of comparative examples 1-3 and example 1;
FIG. 4 is the bulk attrition rates of comparative examples 1-3 and example 1;
FIG. 5 is the electrical conductivities of comparative examples 1-3 and example 1;
FIG. 6 shows the thermal conductivity (a), (b) thermogravimetric analysis (TG), (c) thermogravimetric analysis (DTG), and (d) carbon residue of comparative examples 1-3 and example 1.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
Comparative examples 1-3 and example 1:
the samples were prepared according to the formulation of table 1, the preparation method was: setting the roller temperature to 50 ℃, taking the ternary fluororubber raw rubber, putting the ternary fluororubber raw rubber into an open mill, then sequentially and uniformly adding the premixed zinc oxide (ZnO) and triallyl isocyanurate (TAIC), and triangulating for 3 times. Then octadecylamine, carboxylated multi-walled carbon nanotube (MWCNT-COOH), aminated multi-walled carbon nanotube (MWCNT-A) and 2, 5-dimethyl-2, 5-double hexane (biwu) are respectively added in sequence, triangulated for 6 times, and refined to be uniform. Samples of comparative examples 1-3 and example 1 were numbered sequentially as FKM/C-1, FKM/C-4, FKM/C-5, FKM/C-8 and left at room temperature for 24h.
Pressing the prepared sample into a rubber sheet by using a flat vulcanizing machine, wherein the vulcanizing pressure is 10MPa, the vulcanizing temperature and time are 177 ℃, the temperature is 7 minutes, and then, the rubber sheet is put into an oven for secondary vulcanization, and the vulcanizing temperature and time are 232 ℃ and 2 h.
Performance testing
1. Morphology of composite material
A scanning electron microscope image of several composite materials is shown in fig. 1. Fig. (a) shows the fracture surface of the fluororubber not filled with the carbon material (comparative example 1), which was smooth and clean with zinc oxide particles clearly visible. Graphs (b) and (C) are fracture planes of composites containing MWCNT-COOH (comparative example 2) and MWCNT-A (comparative example 3), respectively, red circles marked in the graph are MWCNT-COOH and MWCNT-A pulled out when composites FKM/C-4 and FKM/C-5 fracture, respectively, and red boxes are aggregates of MWCNT-COOH and MWCNT-A in the composites, respectively. Since both MWCNT-COOH and MWCT-a are multi-walled carbon nanotubes in nature, the surface of the composite containing both carbon materials has lamellar folds, and in addition to this, both composites have some pinholes. Panel (d) is the microscopic morphology of a composite containing both MWCNT-COOH and MWCNT-A (example 1), which is relatively similar to panels (b) and (C), the fracture surface of composite FKM/C-8 has distinct lamellar folds accompanied by Xu Xiaokong, except that the carbon material in the fracture surface of composite FKM/C-8 agglomerates less, which may benefit from filler-to-filler, filler-to-rubber interactions.
2. Infrared analysis
The infrared spectra of the four composite materials are shown in fig. 2. As can be seen from the figure, the infrared spectra of the four composites are not too different, probably because of the wide variety of adjuvants in the fluororubber, the complex mechanism at vulcanization and the covering effect of the Jiang Kuan peak on the nearby weak peak in the spectra. As indicated in FIG. 2, the four composites are mostly 893 cm -1 ，1127 cm -1 ，1393 cm -1 And 1692 cm -1 Has more obvious absorption peaks corresponding to fluorine respectively-CF in rubber Structure 3 radicals-CF 2 -a group and-a CF-group, a non-conjugated carbon-carbon double bond (c=c bond) generated upon vulcanization. Composite FKM/C-4 and FKM/C-8 containing MWCNT-COOH at 2963 cm -1 There is no obvious-C-H-absorption peak, but-C-H-absorption peaks appear in FKM/C-1 and FKM/C-5 of composite materials without MWCNT-COOH, so that the existence of carboxylated carbon nano-tubes has a certain influence on the structural composition of the composite materials in the vulcanization process of fluororubber. 1259 and cm in the IR spectrum -1 The infrared absorption peak appearing at this point is a characteristic peak of a single carbon-carbon bond (C-C bond), but since there is a very strong absorption peak in the vicinity of this peak (1127 cm) -1 ) Therefore, the characteristic peak is easily affected by nearby strong peaks.
3. Tensile Properties
The tensile strength, elongation at break, 100% tensile stress and hardness of the four composite materials are shown in FIGS. 3 (a) - (d), respectively. It can be seen from the figure that the dual filler system of MWCNT-COOH and MWCNT-a is capable of significantly increasing the tensile strength, 100% tensile stress and hardness of the fluororubber, but the elongation at break of the composite is still reduced. From experimental data, the rigidity of the composite material is obviously increased after two carbon materials are added, and the flexibility of the composite material is obviously reduced.
The tensile strengths of the four composites shown in FIG. 3 (a) were 8.2 MPa,11.7 MPa,12.1 MPa and 17.4 MPa, respectively. It is known that the multi-walled carbon nanotubes are elongated and tubular and have ultra-high strength, so that the mechanical strength of fluororubber can be effectively improved after fluororubber is added. Wherein the tensile strength of the composite material FKM/C-4 containing the carboxylated multi-wall carbon nano-tube is improved by 42.7%, and the tensile strength of the composite material FKM/C-5 containing the aminated multi-wall carbon nano-tube is improved by 47.6%, so that the aminated modified multi-wall carbon nano-tube can improve the tensile strength of fluororubber more than the carboxylated multi-wall carbon nano-tube, and the composite material FKM/C-5 has higher tensile strength than the composite material FKM/C-4 due to the chemical crosslinking between the MWCNT-A and the fluororubber molecular chain. While a composite material containing both MWCNT-COOH and MWCNT-AThe tensile strength of FKM/C-8 is improved by 112.2%, which is far greater than the sum of FKM/C-4 and FKM/C-5 (42.7% + 47.6% = 90.3%) of a composite material added with only one carbon nanomaterial, and is not only an improvement effect caused by superposition of two carbon materials, but also beneficial to hydrogen bonds between MWCNT-COOH and FKM and interactions between MWCNT-COOH and MWCNT-A. But due to-COOH groups and-NH groups in both carbon materials 2 The content of the groups is small, although the two react with each other in the vulcanization process, the peak is hard to be displayed in an infrared spectrum, so that the interaction between the two is more improved in the dispersibility of the carbon material, which is shown in an SEM image of the composite material FKM/C-8.
FIG. 3 (b) shows elongation at break of 344.0%,200.0%,218.0% and 154.0%, respectively, for four composites. The elongation at break of the fluororubber is reduced to various degrees due to the addition of the high-strength multi-walled carbon nanotubes. Wherein the elongation at break of the composite material FKM/C-4 containing carboxylated multi-walled carbon nanotubes is reduced by 41.9%, and the elongation at break of the composite material FKM/C-5 containing aminated multi-walled carbon nanotubes is reduced by 36.6%, probably because the MWCNT-A and FKM woven cross-linked network receives a part of stress when being pulled by external force, thereby converging the reduction of the elongation at break of the composite material FKM/C-5. At this time, the elongation at break of the composite FKM/C-8 containing both the MWCNT-COOH and the MWCNT-A double filler was reduced by only 55.2%, which is far smaller than the sum of the composite FKM/C-4 and the composite FKM/C-5 (41.9% + 36.6% = 78.5%). Thus, the combination of MWCNT-COOH and MWCNT-A can not only improve the tensile strength of the fluororubber, but also reduce the degree of decrease in elongation at break.
FIG. 3 (c) is a graph of 100% elongation stress of several composite materials, in which we can more clearly see the superiority of dual filler incorporation. The 100% elongation stress of the composite FKM/C-4, FKM/C-5 and FKM/C-8 was increased by 212.2%,195.1% and 573.2%, respectively, compared with the composite FKM/C-1 without carbon material, wherein the increase rate (573.2%) of the composite FKM/C-8 was 165.9% higher than the sum of the increase rates (212.2% +195.1% = 407.3%) of the composite FKM/C-4 and FKM/C-5. From this data, the performance enhancement effect brought by the combination of two carbon materials is extremely remarkable, which is related to the reinforcing effect of the carbon materials themselves and the compatibility and dispersibility of the double filler inside the fluororubber matrix.
The hardness of the four composites is shown in fig. 3 (d). Wherein, the hardness of the MWCNT-COOH and the MWCNT-A on the fluororubber is slightly different, and after the two materials form a double-filler system, compared with the composite material FKM/C-1 without adding carbon material, the hardness of the composite material FKM/C-8 is improved by 44.2%; the hardness of the composite FKM/C-8 was increased by 15.8% compared to the composite FKM/C-5 containing MWCNT. That is, the synergistic effect of MWCNT-COOH and MWCNT-A in the composite FKM/C-8 is remarkably represented in tensile strength, elongation at break and 100% elongation stress, but the strong lifting effect is not remarkably represented in hardness.
4. Wear resistance
The volume attrition amounts of composite FKM/C-1 without carbon material, composite FKM/C-4 with MWCNT-COOH, composite FKM/C-5 with MWCNT-A, and composite FKM/C-8 with double fillers (MWCNT-COOH and MWCNT-A) are shown in FIG. 4 below, respectively. After the test of the abrasion resistance instrument, the volume abrasion amounts of the four composite materials are 124.1 and mm in sequence 3 ，93.2 mm 3 ，93.1 mm 3 And 87.0. 87.0 mm 3 . According to experimental data, the carboxylated multi-wall carbon nano-tube and the aminated multi-wall carbon nano-tube have little difference in the help of the abrasion resistance of the fluororubber, and the surface of the MWCNT-A is presumed to be rough compared with the MWCNT-COOH and is easier to fall off under the action force of rolling friction, but the condition that the MWCNT-A is tightly crosslinked with FKM molecular chains exists at the same time, while the MWCNT-COOH has weaker hydrogen bonds formed between the MWCNT-COOH and the FKM matrix in spite of the smoother surface, so that the enhancement effect of the abrasion resistance of the two carbon materials on the fluororubber is almost consistent. The compatibility among MWCNT-COOH, MWCNT-A and fluororubber in the composite material FKM/C-8 is good and has interaction force, so that the volume abrasion of the composite material FKM/C-8 containing the double-filler system is reduced by 6.1 mm on the basis of the composite material added with only one carbon material 3 。
5. Conductivity of conductive material
The conductivities of the composite FKM/C-1, FKM/C-4, FKM/C-5 and FKM/C-8 are shown in the sequence as shown in FIG. 5. It can be seen from the graph that after addition of MWCNT-COOH and MWCNT-A, the conductivity of the fluororubber is improved by 5 orders of magnitude and 6 orders of magnitude, respectively. According to the self-properties of the multi-wall carbon nano tube, the conductivity of the modified multi-wall carbon nano tube is relatively reduced, while the MWCNT-A is secondarily modified on the basis of the MWCNT-COOH, the conductivity is lower, but chemical crosslinking exists between the MWCNT-A and the fluororubber matrix, so that the assistance is provided for the formation of conductive paths in the polymer, and therefore, the conductivity of the composite FKM/C-5 is slightly higher than that of the composite FKM/C-4. However, when two multi-walled carbon nanotubes are added to fluororubber at the same time, the good conductivity of the composite material FKM/C-8 is improved by 9 orders of magnitude (compared with an unfilled system) due to the good conductivity of the composite material FKM/C-8 and the more perfect conductive path inside the polymer.
6. Thermal performance
The effect of the dual filler system of MWCNT-COOH and MWCNT-a on the thermal properties of the composite was investigated by four aspects of thermal conductivity, TG, DTG and char yield of the composite. The thermal conductivities of the four composites are shown below in FIG. 6 (a), 0.1941W/(mK), 0.2369W/(mK), 0.2385W/(mK) and 0.2660W/(mK), respectively. From experimental results, it can be obtained that the addition of the carboxylated multi-wall carbon nanotubes and the aminated multi-wall carbon nanotubes can effectively improve the heat conductivity coefficient of the fluororubber, and respectively improve the heat conductivity coefficient by 22.1% and 22.9%, which indicates that the two multi-wall carbon nanotubes do not greatly differ from each other in the help provided by the enhancement of the heat conductivity of the fluororubber. However, in the composite FKM/C-8, the synergistic effect of the double fillers of the MWCNT-COOH and the MWCNT-A is not reflected, which shows that the mixed filler system has enhanced heat conduction performance of fluororubber, but the enhancement effect still needs to be improved.
FIGS. 6 (b) and (c) are, respectively, the percent mass change of a composite sample over a temperature range of 40℃to 600℃and the corresponding first derivative change with increasing temperature. From these two figures we can see that the initial decomposition temperatures of the four composites are 437.6 ℃,444.3 ℃,442.8 ℃ and 435.6 ℃, respectively. The multi-wall carbon nanotubes themselves have high thermal stability and can not be thermally decomposed within 600 ℃, so that the thermal stability of FKM can be improved after the composite material is added, which is needless to say. However, at the same time, the multi-wall carbon nano tube can also form a good heat conduction network inside the polymer by virtue of the excellent heat conduction property, so that the external heat is quickly transferred into the polymer, and the structure of the polymer is collapsed in advance. The MWCNT-A and the fluororubber have the same effect of accelerating heat transfer after forming a second cross-linked network, so that the initial decomposition temperature of the composite FKM/C-5 is lower than that of the composite FKM/C-4. The two properties of the multi-wall carbon nano tube are similar to a double-edged sword in the thermal property enhancement of the composite material, and when a heat conduction network formed by the multi-wall carbon nano tube is advantageous, the thermal property of the composite material is affected and reduced; when the thermal stability of the multiwall carbon nanotubes is advantageous, the thermal properties of the composite are improved. The composite material FKM/C-8 contains 5 parts of carboxylated multi-wall carbon nanotubes and 5 parts of aminated multi-wall carbon nanotubes, but hydrogen bonds exist between the carboxylated multi-wall carbon nanotubes and the FKM, and chemical cross-linking exists between the aminated multi-wall carbon nanotubes and the FKM, so that a heat conduction network formed by the two carbon nano materials in the composite material is in a dominant position, and the initial decomposition temperature of the composite material FKM/C-8 is reduced.
FIG. 6 (d) shows that the carbon residue at 600℃of the samples of four kinds of composite materials, after the addition of the carbon material, the carbon residue of the composite material was greatly improved, wherein the carbon residue of FKM/C-4 of the composite material containing MWCNT-COOH was improved by 223.9% and the carbon residue of FKM/C-5 of the composite material containing MWCNT-A was improved by 210.9% as compared with the FKM/C-1 of the system without carbon material, and the carbon residue of FKM/C-8 of the composite material containing both MWCNT-COOH and MWCNT-A was improved by 293.5%. In combination with the conclusion about heat conduction and heat stability, even though the heat conduction performance and the heat stability of the composite material FKM/C-5 containing the MWCNT-A are higher than those of the composite material FKM/C-4, the carboxyl groups (-COOH) of the carboxylated multi-wall carbon nano tubes in the composite material FKM/C-4 can react with Hydrogen Fluoride (HF) generated when fluororubber is defluorinated at high temperature, so that the carbon forming process is accelerated, a compact carbon layer is formed on the surface of a sample faster than that of the composite material FKM/C-5, and the ablation resistance of the fluororubber is improved. The FKM/C-8 of the composite material has higher heat conduction performance than the composite material of a single filler system due to the existence of a double filler system, so that a carbon layer can be rapidly formed and the carbon residue rate can be improved. This indicates that MWCNT-COOH is suitable for forming a dual filler system with MWCNT-A to improve the ablation resistance of the fluororubber.
In summary, in the dual-filler system fluororubber nanocomposite prepared by taking ternary fluororubber as a matrix and taking aminated multi-wall carbon nanotubes (MWCNT-A) and carboxylated multi-wall carbon nanotubes (MWCNT-COOH) as fillers, the phenomenon of agglomeration of carbon materials in fracture surfaces is less from the aspect of appearance, which indicates that the dispersibility of the carbon materials in the dual-filler system is improved; from the mechanical property, due to the hydrogen bond between the MWCNT-COOH and the FKM and the interaction between the MWCNT-COOH and the MWCNT-A, the dispersibility of the filler in the composite material is improved, so that the tensile strength, 100% stretching stress and hardness of the fluororubber are further increased, and the degree of reduction of the elongation at break of the composite material is reduced although the elongation at break of the composite material is still reduced; in terms of conductivity, although the conductivity of the composite material containing the double-filler system has no synergistic assistance, the conductivity is still improved by 9 orders of magnitude due to the good conductivity of the multi-walled carbon nanotubes and the more perfect conductive path formed inside the polymer; compared with a composite material without any carbon nano material, the double-filler system of MWCNT-COOH and MWCNT-A can improve the heat conductivity coefficient and carbon residue rate of the composite material in terms of heat conductivity.
The foregoing disclosure is illustrative of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (2)
1. The preparation method of the ternary fluororubber nanocomposite with diversified properties is characterized by comprising the following steps:
(1) Weighing the following raw materials in parts by mass:
100 parts of ternary fluororubber;
1-5 parts of acid absorber;
1-5 parts of a promoter;
0.5-5 parts of octadecylamine;
1-10 parts of carboxylated multiwall carbon nanotubes;
1-10 parts of aminated multi-wall carbon nano tube;
1-5 parts of vulcanizing agent;
(2) Setting the roller temperature of an open mill to be 45-55 ℃, putting ternary fluororubber into the open mill, adding a premixed acid absorbent and an accelerant into the open mill for uniform mixing, and finally adding octadecylamine, carboxylated multiwall carbon nanotubes, aminated multiwall carbon nanotubes and a vulcanizing agent into the open mill for uniform mixing;
(3) After the composite material refined in the step (2) is cooled for a period of time, pressing the composite material into a rubber sheet by a flat vulcanizing machine;
(4) Putting the rubber sheet prepared in the step (3) into an oven for secondary vulcanization to prepare a double-filler system ternary fluororubber nanocomposite;
the acid absorber is zinc oxide, the accelerator is triallyl isocyanurate, and the vulcanizing agent is 2, 5-dimethyl-2, 5-bishexane;
in the step (3), the vulcanization pressure is 8-10MPa, the vulcanization temperature is 175-180 ℃, and the vulcanization time is 6-8 min;
in the step (4), the second-stage vulcanization temperature is 230-234 ℃ and the time is 1-3 h;
the carboxylated multiwall carbon nanotubes comprise 1-5 parts by mass;
the mass portion of the amination multiwall carbon nanotube is 1-5 portions.
2. The ternary fluororubber nanocomposite with diversified performances prepared by the preparation method of the ternary fluororubber nanocomposite with diversified performances of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211176355.7A CN115584091B (en) | 2022-09-26 | 2022-09-26 | Ternary fluororubber nanocomposite with diversified performances and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211176355.7A CN115584091B (en) | 2022-09-26 | 2022-09-26 | Ternary fluororubber nanocomposite with diversified performances and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115584091A CN115584091A (en) | 2023-01-10 |
| CN115584091B true CN115584091B (en) | 2024-02-13 |
Family
ID=84773294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211176355.7A Active CN115584091B (en) | 2022-09-26 | 2022-09-26 | Ternary fluororubber nanocomposite with diversified performances and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115584091B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080050735A (en) * | 2006-12-04 | 2008-06-10 | 인하대학교 산학협력단 | A method for preparation of silicone rubber/carbon nanotube composites with electrical insulating properties |
| CN108203522A (en) * | 2016-12-20 | 2018-06-26 | 东洋橡胶工业株式会社 | Rubber masterbatch and its manufacturing method, the rubber composition obtained by the rubber masterbatch |
| CN112662095A (en) * | 2020-11-17 | 2021-04-16 | 温州大学 | Ternary fluororubber nanocomposite with three-crosslinking-network structure and preparation method thereof |
-
2022
- 2022-09-26 CN CN202211176355.7A patent/CN115584091B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080050735A (en) * | 2006-12-04 | 2008-06-10 | 인하대학교 산학협력단 | A method for preparation of silicone rubber/carbon nanotube composites with electrical insulating properties |
| CN108203522A (en) * | 2016-12-20 | 2018-06-26 | 东洋橡胶工业株式会社 | Rubber masterbatch and its manufacturing method, the rubber composition obtained by the rubber masterbatch |
| CN112662095A (en) * | 2020-11-17 | 2021-04-16 | 温州大学 | Ternary fluororubber nanocomposite with three-crosslinking-network structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115584091A (en) | 2023-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102585349B (en) | Antistatic material, preparation method and applications of antistatic material | |
| CN108641150B (en) | Rubber material capable of being repeatedly processed and preparation method thereof | |
| WO2014040397A1 (en) | Fluoro-rubber compound and preparation method therefor | |
| CN113105703B (en) | Modified conductive fluororubber, preparation method and conductive medium-resistant fluororubber sealing ring | |
| CN103613883A (en) | Wear-resistant hard composite material using graphene as filler and preparation method thereof | |
| Fan et al. | Thermal conductivity and mechanical properties of high density polyethylene composites filled with silicon carbide whiskers modified by cross-linked poly (vinyl alcohol) | |
| CN112210130A (en) | Semi-steel base rubber material using carbon nanotube composite masterbatch and preparation method thereof | |
| Li et al. | Enhancing mechanical property and thermal conductivity of fluororubber by the synergistic effect of CNT and BN | |
| Basha et al. | Cure and degradation kinetics of sulfur cured nanocomposites of EPDM-NBR rubber blends | |
| CN115584091B (en) | Ternary fluororubber nanocomposite with diversified performances and preparation method thereof | |
| CN112662095B (en) | Ternary fluororubber nanocomposite with three-crosslinking-network structure and preparation method thereof | |
| CN113429712A (en) | Low-resistivity fluororubber for automobile fuel pipeline system and preparation method thereof | |
| Xu et al. | Green fabrication of high-performance, lignosulfonate-functionalized, and reduced-graphene oxide styrene–butadiene rubber composites | |
| CN115627039B (en) | Ternary fluororubber nanocomposite material with double filler systems and preparation method thereof | |
| CZ5999A3 (en) | Composition and articles produced from this composition | |
| CN110734593A (en) | Method for preparing emulsion polymerized styrene butadiene rubber from modified graphene | |
| KR20190087232A (en) | Polyketone-hybrid carbon filler based composite with enhanced mechanical properties and thermal stability and process of preparing the same | |
| CN111303500B (en) | Preparation method of graphene oxide/butyronitrile latex nanocomposite | |
| CN110240805B (en) | Graphene modified polyphenylene sulfide material, preparation method thereof and heat-conducting plastic pipe | |
| CN110607014A (en) | Preparation method of high-strength high-toughness electromagnetic shielding composite material | |
| CN111187449A (en) | Carbon nanotube functional modification method suitable for composite rubber system | |
| Jafari et al. | Cured Poly (ethylene-g-maleic anhydride)/Graphene Nanocomposite: Properties and Characterization | |
| CN115926344B (en) | Modified fluororubber compound and preparation method thereof | |
| CN114230863B (en) | Graphene and carbon black compound reinforced heat conduction filler and application thereof in preparation of high-strength high-elasticity heat conduction styrene butadiene rubber composite material | |
| CN109206814A (en) | A kind of 150 DEG C of interior thermoplastic elastomer (TPE)s of grade oxytolerant oil resistant automobile engine of heatproof 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 |