CN117801446B - High-strength plastic retainer based on polyether-ether-ketone and preparation method thereof - Google Patents
High-strength plastic retainer based on polyether-ether-ketone and preparation method thereof Download PDFInfo
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- CN117801446B CN117801446B CN202410224345.9A CN202410224345A CN117801446B CN 117801446 B CN117801446 B CN 117801446B CN 202410224345 A CN202410224345 A CN 202410224345A CN 117801446 B CN117801446 B CN 117801446B
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- fluorine
- ketone
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- ether
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 50
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 50
- 239000004033 plastic Substances 0.000 title claims abstract description 28
- 229920003023 plastic Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000011737 fluorine Substances 0.000 claims abstract description 84
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 84
- 239000000945 filler Substances 0.000 claims abstract description 75
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 33
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 17
- 239000004917 carbon fiber Substances 0.000 claims abstract description 17
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 96
- 239000000178 monomer Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 43
- 229920006260 polyaryletherketone Polymers 0.000 claims description 38
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 32
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 30
- SXZIXHOMFPUIRK-UHFFFAOYSA-N diphenylmethanimine Chemical compound C=1C=CC=CC=1C(=N)C1=CC=CC=C1 SXZIXHOMFPUIRK-UHFFFAOYSA-N 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 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 16
- 238000001816 cooling Methods 0.000 claims description 16
- 239000002808 molecular sieve Substances 0.000 claims description 16
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- VGENEKMXUVKYGW-UHFFFAOYSA-N C(C)O[Si](C1=C2C(CC2C=C)=CC=C1)(OCC)OCC Chemical compound C(C)O[Si](C1=C2C(CC2C=C)=CC=C1)(OCC)OCC VGENEKMXUVKYGW-UHFFFAOYSA-N 0.000 claims description 11
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 14
- 238000012546 transfer Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 11
- 230000006872 improvement Effects 0.000 abstract description 6
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 3
- OOVQLEHBRDIXDZ-UHFFFAOYSA-N 7-ethenylbicyclo[4.2.0]octa-1,3,5-triene Chemical compound C1=CC=C2C(C=C)CC2=C1 OOVQLEHBRDIXDZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910021389 graphene Inorganic materials 0.000 description 10
- 238000012986 modification Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 7
- 230000009471 action Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 238000005411 Van der Waals force Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical group C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920006361 Polyflon Polymers 0.000 description 2
- 229920004731 VICTREX® PEEK 450PF Polymers 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000006115 defluorination reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000004658 ketimines Chemical group 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- XURVRZSODRHRNK-UHFFFAOYSA-N o-quinodimethane Chemical group C=C1C=CC=CC1=C XURVRZSODRHRNK-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006135 semi-crystalline thermoplastic polymer Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect 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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4031—(I) or (II) containing nitrogen
- C08G65/4037—(I) or (II) containing nitrogen in ring structure, e.g. pyridine group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of high-strength plastic compositions, in particular to a high-strength plastic retainer based on polyether-ether-ketone and a preparation method thereof, and the high-strength plastic retainer comprises the following components in parts by mass: 5 to 20 percent of polyether-ether-ketone, 5 to 20 percent of fluorine-containing polyarylether-ketone, 8.5 to 21 percent of filler and the balance of polytetrafluoroethylene, wherein the fluorine-containing polyarylether-ketone is prepared from diphenol, 4 '-difluorobenzophenone, 2' -bis (trifluoromethyl) diaminobiphenyl and 4-triethoxy silicon-based vinylbenzocyclobutene. According to the invention, through compounding of polyether-ether-ketone, polytetrafluoroethylene, fluorinated graphene and carbon fiber, the prepared composite material has higher strength, the strength of a transfer film generated by friction is improved, simultaneously the tribochemical reaction is promoted, the secondary removal of materials from the transfer film by friction can be effectively prevented, and the formation of a high-quality transfer film and the improvement of the mechanical property and wear resistance of a retainer are promoted.
Description
Technical Field
The invention relates to the technical field of high-strength plastic compositions, in particular to a high-strength plastic retainer based on polyether-ether-ketone and a preparation method thereof.
Background
The cage is a bearing part which partly encloses the rolling elements and moves therewith, and can be used to isolate the rolling elements, and in general also to guide the rolling elements and retain them in the bearing. And when the bearing works, the generated sliding friction can cause the heating and abrasion of the bearing, and particularly when the bearing rotates at a high temperature, the friction, abrasion and heating are aggravated by the inertial centrifugal force, so that the retainer can be burnt, broken and other phenomena, and the normal work of the retainer is influenced. Therefore, we propose a high strength plastic cage based on polyetheretherketone and a method for its preparation.
Disclosure of Invention
The invention aims to provide a high-strength plastic retainer based on polyether-ether-ketone and a preparation method thereof, so as to solve the problems in the background art.
In order to solve the technical problems, the invention provides the following technical scheme: a high-strength plastic retainer based on polyether-ether-ketone comprises the following components in parts by mass: 5 to 15 percent of polyether-ether-ketone, 5 to 15 percent of fluorine-containing polyaryletherketone, 8.5 to 21 percent of filler and the balance of polytetrafluoroethylene;
the fluorine-containing polyaryletherketone is prepared from diphenol, 4 '-difluorobenzophenone, 2' -di (trifluoromethyl) diaminobiphenyl and 4-triethoxysilyl vinylbenzocyclobutene.
In the technical scheme, the retainer material comprises polyether-ether-ketone and polytetrafluoroethylene. Polytetrafluoroethylene (PTFE) is polymerized from tetrafluoroethylene, the repeat unit of the polymer molecule is-CF 2-, there is no branched structure in the backbone, and the molecular chain is twisted into a helical conformation. The high electronegativity of fluorine, the high bond energy of C-F bond, and the symmetry of tetrafluoroethylene monomer make polytetrafluoroethylene have good chemical inertness and exhibit low surface energy characteristics. The strong electrostatic repulsive force and the large volume effect of fluorine atoms enable polytetrafluoroethylene macromolecular chains to be connected by weak van der Waals force, are easy to separate and slide, enable the friction coefficient of polytetrafluoroethylene to be extremely low, are good self-lubricating materials, and have the characteristics of high lubricating non-viscosity, good chemical stability, corrosion resistance and high and low temperature resistance. However, the chemical structure of the wear-resistant plastic is poor in mechanical property, poor in wear resistance when the wear-resistant plastic is rubbed with hard materials such as metal, larger abrasive dust and a transfer film with poor adhesion can be generated, higher wear is brought, and the wear-resistant plastic has the characteristics of poor wear resistance, low bearing capacity and easiness in creep.
Polyether-ether-ketone is a semi-crystalline thermoplastic polymer material, and the molecular chain of the polyether-ether-ketone is provided with a rigid benzene ring, a compliant ether bond and a carbonyl capable of promoting intermolecular acting force; high mechanical strength, wear resistance, chemical stability, thermal stability and processing plasticity, and good strength and rigidity at high temperature, but limited friction and wear performance at high speed, high temperature and high compounding.
Polytetrafluoroethylene and polyether-ether-ketone are compounded, the polytetrafluoroethylene generates mechanical action and tribochemical reaction in friction, defluorination and adsorption are carried out on the surface of the metal pair to generate metal fluoride, a transfer film is formed, the friction action of the hard metal pair surface on the polytetrafluoroethylene matrix is weakened, the polymer material is in a self-lubricating state, and the wear resistance of the polymer matrix is improved. The molecular chain of the polyether-ether-ketone and the metal friction surface have stronger adsorption strength and are easier to adsorb on the metal dual surface, so that the polyether-ether-ketone in the composite material is preferentially subjected to substance transfer and is firmly adsorbed on the dual friction surface, the transfer film is fixed, and the transfer film which is longer-lasting and has higher viscosity (between the polymer) and strength and wear resistance is generated, so that the sliding friction between the composite material and the metal bearing is promoted; therefore, the heat resistance, the wear resistance, the strength and the hardness of the prepared composite material can be effectively improved, and the mechanical property, the wear resistance and the heat resistance of the prepared retainer are improved.
Further, the filler comprises 3.5-6.0 wt% of fluorinated graphene and 5-15 wt% of carbon fiber.
In the technical scheme, the retainer component is added with a filler, and the filler comprises fluorinated graphene and carbon fibers. The fluorine atoms are introduced into the graphene, new C-F bonds are formed on graphene sheets, the fluorine atoms have strong electronegativity, and strong electrostatic repulsion exists between fluorine atoms of adjacent layers, so that the interlayer spacing of the fluorinated graphene is increased, the interlayer effect is reduced, the sheets are easy to slide, and the surface energy is lower; the layered structure of the graphene is maintained, the graphene has high specific surface area, thermal stability, chemical stability and mechanical property, meanwhile, the adhesive force between friction interfaces is reduced, the durability of the graphene is improved, and the friction coefficient of the composite graphene is reduced. The fluorinated graphene can provide more chemical active sites at the sliding friction interface, reduces the energy barrier of polymer defluorination at the interface of the filler and the polymer, is favorable for the progress of tribochemical reaction, enhances the transfer film and adheres the transfer film to the metal dual surface, thereby improving the wear resistance of the manufactured retainer. Through Van der Waals force and electrostatic acting force on the surface of the graphene fluoride, the graphene fluoride can be bonded and adsorbed on polymer chain segments around the graphene fluoride, so that the stress transmission in the retainer is improved, the interface is reinforced, and the strength of the graphene fluoride is improved. And carbon fiber is used as a filling material, so that the bearing capacity of the composite material and the strength of the transfer film can be improved, and the friction and abrasion are reduced. The composite addition of the fiber and the particle filler forms a synergistic effect, plays a role of reinforcing phase, and is beneficial to the improvement of the mechanical property and the wear resistance of the prepared composite material.
A preparation method of a high-strength plastic retainer based on polyether-ether-ketone comprises the following preparation processes:
Step (1): mixing polytetrafluoroethylene, polyether-ether-ketone, fluorine-containing polyaryletherketone and filler to obtain a mixture;
Step (2): pouring the mixture into a retainer mold, pressing, forming, demolding and sintering to obtain the retainer.
Further, the step (1) comprises the following processes:
Stirring polytetrafluoroethylene at a rotating speed of 10000-120000 r/min for 20-30 s; adding polyether-ether-ketone, fluorine-containing polyaryletherketone and filler, mixing at a rotating speed of 12000-15000 r/min for 60-100 s, and sieving with a 120-mesh sieve to obtain a mixture.
Further, in the step (2), the process conditions of the press forming are as follows: cold pressing at room temperature for 15-25 min under the pressure of 40-50 MPa.
Further, in the step (2), sintering process conditions are as follows: heating to 280-320 ℃ at a heating rate of 1-2 ℃/min, and preserving heat for 60-90 min; heating to 350-360 ℃ at a heating rate of 1-2/min, and preserving heat for 90-120 min; cooling to 290-310 ℃ at the speed of 25-50 ℃/h, and preserving heat for 60-80 min; and (5) furnace cooling.
Further, the fluorine-containing polyaryletherketone is prepared by the following process:
Mixing diphenol, 4' -difluorobenzophenone, fluorine-containing phenylketimine monomer and potassium carbonate in sulfolane, adding toluene, heating to 155-160 ℃ under the protection of nitrogen atmosphere, carrying out reflux reaction for 160-200 min, and discharging water and toluene; heating to 210-215 ℃, and continuing to react for 5-7 h; slowly pouring the mixture into water with the pH of 6.2-6.7, soaking the mixture overnight, taking out the mixture, crushing the mixture, washing the mixture with water, filtering the mixture, and drying the mixture to obtain the fluorine-containing polyaryletherketone.
Further, the diphenol is the mixture of 4,4' -biphenol and hexafluorobisphenol A, the mol ratio is1 (0.5-1.0);
the molar ratio of diphenol to 4,4' -difluorobenzophenone to fluorine-containing benzophenone imine monomer is 10 (2-5) (5-8);
The mass ratio of the 4,4' -biphenol to the potassium carbonate is 10 (8.9-9.1);
the ratio of 4,4' -biphenol, toluene and sulfolane is 17g (12-15 mL:100mL.
Further, the fluorine-containing benzophenone imine monomer is prepared by the following process:
Mixing 2,2' -di (trifluoromethyl) diaminobiphenyl and 4-triethoxysilyl vinylbenzocyclobutene, adding a catalyst, heating to 50-55 ℃ and reacting for 4-8 hours; washing and drying to obtain an aniline compound;
mixing 4,4' -difluorobenzophenone, an aniline compound, toluene and a molecular sieve, heating to 111-115 ℃ under the protection of nitrogen atmosphere, and carrying out reflux reaction for 24 hours; cooling to room temperature, filtering to remove molecular sieve, rotary evaporating, recrystallizing with methanol, and drying to obtain the fluorine-containing benzophenone imine monomer.
Further, the molar ratio of the 2,2' -bis (trifluoromethyl) diaminobiphenyl to the 4-triethoxysilyl vinylbenzocyclobutene is 1:1;
the catalyst is one of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD) and 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (MTBD), and the dosage is 1 weight percent of the total mass of 2,2' -bis (trifluoromethyl) diaminobiphenyl and 4-triethoxysilyl vinylbenzocyclobutene.
Further, the mass ratio of the 4,4' -difluorobenzophenone and the aniline compound is 10 (39.2 to 42.0);
The proportion of 4,4' -difluorobenzophenone, molecular sieve and toluene is 27g (58.6-62.5 g) to 100mL.
In the technical scheme, 2 '-di (trifluoromethyl) diaminobiphenyl and 4-triethoxy silicon-based vinylbenzocyclobutene are added and then are dehydrated and condensed with 4,4' -difluorobenzophenone to form a ketimine structure, so as to generate the fluorine-containing ketimine monomer. 4,4 '-biphenol and hexafluorobisphenol A are used as diphenol, nucleophilic polycondensation is carried out on the diphenol, 4' -difluorobenzophenone and fluorine-containing benzophenone imine monomers in a solvent under the action of salt forming agent potassium carbonate and water-carrying agent toluene to form a linear molecular chain of polyaryletherketone, and then the linear molecular chain is solidified and soaked in acidic water, so that silicon-oxygen bonds in the system structure are hydrolyzed and crosslinked, the heat resistance and mechanical property of the prepared fluorine-containing polyaryletherketone are improved, and the mechanical strength and wear resistance of the fluorine-containing polyaryletherketone are improved. The molecular structure system of the fluorine-containing polyaryletherketone contains biphenyl and aryl Schiff base side groups, so that the fluorine-containing polyaryletherketone has higher rigidity, the internal rotation of a molecular chain segment is blocked, and the toughness of a polymer is improved; the fluorine-containing groups introduced by the polymerization monomers can increase the free volume among polymer molecules and further improve the rigidity of the prepared polymer molecular chain; the high bond energy of the C-F bond helps to improve the thermal stability of the polymer. The fluorine-containing polyaryletherketone is introduced into a polytetrafluoroethylene/polyether ether ketone/filler composite system, under the action of high temperature, a four-membered ring in a benzocyclobutene structure is opened, a o-quinodimethane structure is formed between the four-membered ring and adjacent benzocyclobutene, and a crosslinked network is formed in the composite material structure, so that the hardness, the strength and the thermal stability of the fluorine-containing polyaryletherketone are further improved, the thermal expansion coefficient of the fluorine-containing polyaryletherketone is reduced, and the mechanical property, the wear resistance and the heat resistance of the retainer are improved.
Further, the filler is modified by a modification process specifically comprising:
Mixing absolute ethyl alcohol and deionized water, adding fluorine-containing phenylketonurine monomer and filler, and ball milling for 8-10 h at a rotating speed of 400-500 rpm; filtering, washing and vacuum drying at 120 deg.c for 4-6 hr.
Further, the volume ratio of the absolute ethyl alcohol to the deionized water is 1:1;
the proportion of the filler, the fluorine-containing phenylketimine monomer and the deionized water is (40-50) g (2-3) g:100mL.
Polytetrafluoroethylene (PTFE): POLYFLON PTFE M-18F, density 2.14-2.20 g/cm 3, average particle size 38-40 μm, from Japanese big gold industry Co Ltd;
Polyetheretherketone (PEEK): victrex PEEK 450 PF, density 1.30-1.35 g/cm 3, average particle size < 75 μm, from Wiggs Co., UK;
Fluorinated graphene: XF096, fluorine content 47% -55%, sheet diameter 0.4-5 μm, comes from Jiangsu Xianfeng nano material science and technology Co., ltd;
Carbon Fiber (CF): ZL-CF200, fiber length 3mm, diameter 7 μm, from New Material technology Co., ltd;
the molecular sieve is 4A and is derived from national pharmaceutical group chemical reagent Co.
In the technical scheme, in the alcohol aqueous solution, the filler and the fluorine-containing benzophenone imine monomer are blended and modified, so that the aggregation phenomenon among the fillers can be relieved, the dispersibility of the prepared modified filler in the composite material is improved, and the full play of the performance of the modified filler in the retainer material is promoted. The modified filler has coulomb force and Van der Waals force between surface molecules and polymer molecules, can enhance the adsorption effect on the polymer, and improves the mechanical property and wear resistance of the retainer.
Compared with the prior art, the invention has the following beneficial effects:
1. According to the high-strength plastic retainer based on polyether-ether-ketone, through compounding of polyether-ether-ketone, polytetrafluoroethylene, fluorinated graphene and carbon fibers, the prepared composite material has high strength, the strength of a transfer film generated by friction is improved, a friction chemical reaction is promoted, the friction can be effectively prevented from removing materials from the transfer film for the second time, and the formation of a high-quality transfer film and the improvement of the mechanical property and the wear resistance of the retainer are promoted.
2. The invention describes a high-strength plastic retainer based on polyether-ether-ketone, which is formed by adding 2,2 '-di (trifluoromethyl) diaminobiphenyl and 4-triethoxysilyl vinylbenzocyclobutene, dehydrating and condensing 4,4' -difluorobenzophenone to form a fluorine-containing benzophenone imine monomer, carrying out nucleophilic polycondensation on the fluorine-containing benzophenone imine monomer and 4,4 '-biphenol, hexafluorobisphenol A and 4,4' -difluorobenzophenone to form a polyaryletherketone linear molecular chain, then solidifying the polyaryletherketone linear molecular chain in acidic water, hydrolyzing and crosslinking a silicon-oxygen bond in a system structure to generate fluorine-containing polyaryletherketone with higher heat resistance, mechanical property and wear resistance, introducing the fluorine-containing polyaryletherketone into a composite system, and forming a o-quinodimethane structure at high temperature by a four-membered ring of benzocyclobutene to form a crosslinked network, so that the hardness, strength and thermal stability of the material are further improved, and the mechanical property, wear resistance and heat resistance of the retainer are improved.
3. According to the high-strength plastic retainer based on polyether-ether-ketone, disclosed by the invention, the aggregation phenomenon among fillers is relieved by blending and modifying the fillers and the fluorine-containing benzophenone imine monomer, the dispersibility of the fillers in a composite material is improved, and the full play of the performance of the fillers in a retainer material is promoted. The modified filler has coulomb force and Van der Waals force between surface molecules and polymer molecules, can enhance the adsorption effect on the polymer, and improves the mechanical property and wear resistance of the retainer.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following description of the embodiments of the present invention,
Polytetrafluoroethylene (PTFE): POLYFLON PTFE M-18F, density 2.17g/cm 3, average particle size 38 μm, from Japanese Dajinyu Co Ltd;
Polyetheretherketone (PEEK): victrex PEEK 450 PF, density 1.32g/cm 3, average particle size 60 μm, from Wiggs Co., UK;
Fluorinated graphene: XF096, fluorine content 52%, sheet diameter 5 μm, from Jiangsu Xianfeng nanomaterial technologies Co., ltd;
Carbon Fiber (CF): ZL-CF200, fiber length 3mm, diameter 7 μm, from New Material technology Co., ltd;
the molecular sieve is 4A and is derived from national pharmaceutical group chemical reagent Co.
Example 1: a preparation method of a high-strength plastic retainer based on polyether-ether-ketone comprises the following preparation processes:
Preparing a mixture in the step (1):
1.1. 2,2' -bis (trifluoromethyl) diaminobiphenyl and 4-triethoxysilyl vinylbenzocyclobutene with equal molar weight are mixed, 1 weight percent of catalyst 1,5, 7-triazabicyclo [4.4.0] dec-5-ene is added, the temperature is raised to 55 ℃, and the reaction is carried out for 4 hours; washing and drying to obtain an aniline compound;
10g of 4,4' -difluorobenzophenone, 39.2g of aniline compound, 37mL of toluene and 21.7g of molecular sieve are mixed, heated to 111 ℃ under the protection of nitrogen atmosphere and subjected to reflux reaction for 24 hours; cooling to room temperature, filtering to remove a molecular sieve, performing rotary evaporation, recrystallizing with methanol, and drying to obtain a fluorine-containing phenylketimine monomer;
1.2. Mixing 4,4 '-biphenol, hexafluorobisphenol A, 4' -difluorobenzophenone, fluorine-containing benzophenone imine monomer and potassium carbonate in sulfolane, adding toluene, heating to 155 ℃ under the protection of nitrogen atmosphere, and carrying out reflux reaction for 200min to release water and toluene; heating to 210 ℃, and continuing to react for 7h; slowly pouring into water with pH of 6.5, soaking overnight, pulverizing, washing with water, filtering, and drying to obtain fluorine-containing polyaryletherketone; the molar ratio of 4,4 '-biphenol, hexafluorobisphenol A, 4' -difluorobenzophenone and the fluorine-containing benzophenone imine monomer (relative molecular weight 811) is 1:1:1:1; the mass ratio of the 4,4' -biphenol to the potassium carbonate is 10:8.9; the ratio of 4,4' -biphenol, toluene and sulfolane is 17g:12mL:100mL;
1.3. Modification of filler: mixing absolute ethyl alcohol with equal volume and deionized water, adding fluorine-containing benzophenone imine monomer and filler, and ball milling for 8 hours at a rotating speed of 400 rpm; filtering, washing, and vacuum drying at 120 ℃ for 4 hours to obtain modified filler; the filler comprises 5wt% of fluorinated graphene and 10wt% of carbon fiber; the proportion of the filler, the fluorine-containing phenylketimine monomer and the deionized water is 40g:2g:100mL;
1.4. Stirring polytetrafluoroethylene at a rotating speed of 10000r/min for 20s; adding polyether-ether-ketone, fluorine-containing polyaryletherketone and modified filler, mixing at a rotating speed of 12000r/min for 60s, and sieving with a 120-mesh sieve to obtain a mixture; the mixture comprises the following components in parts by mass: 15% of polyether-ether-ketone, 5% of fluorine-containing polyaryletherketone, 15% of filler and the balance of polytetrafluoroethylene;
And (2) preparing a retainer: pouring the mixture into a retainer die, cold pressing at a pressure of 40MPa at room temperature for 25min, demoulding, sintering, wherein the technological conditions of sintering are as follows: heating to 280 ℃ at a heating rate of 1 ℃/min, and preserving heat for 60min; heating to 350 ℃ at a heating rate of 1/min, and preserving heat for 90min; cooling to 290 ℃ at a speed of 25 ℃/h, and preserving heat for 80min; and cooling the furnace to obtain the retainer.
Example 2: a preparation method of a high-strength plastic retainer based on polyether-ether-ketone comprises the following preparation processes:
Preparing a mixture in the step (1):
1.1. 2,2' -bis (trifluoromethyl) diaminobiphenyl and 4-triethoxysilyl vinylbenzocyclobutene with equal molar weight are mixed, 1 weight percent of 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene serving as a catalyst is added, the temperature is raised to 52 ℃, and the reaction is carried out for 6 hours; washing and drying to obtain an aniline compound;
10g of 4,4' -difluorobenzophenone, 40.6g of aniline compound, 37mL of toluene and 22.4g of molecular sieve are mixed, heated to 113 ℃ under the protection of nitrogen atmosphere and subjected to reflux reaction for 24 hours; cooling to room temperature, filtering to remove a molecular sieve, performing rotary evaporation, recrystallizing with methanol, and drying to obtain a fluorine-containing phenylketimine monomer;
1.2. Mixing 4,4 '-biphenol, hexafluorobisphenol A, 4' -difluorobenzophenone, fluorine-containing benzophenone imine monomer and potassium carbonate in sulfolane, adding toluene, heating to 158 ℃ under the protection of nitrogen atmosphere, and carrying out reflux reaction for 180min to discharge water and toluene; heating to 212 ℃, and continuing to react for 6 hours; slowly pouring into water with pH of 6.5, soaking overnight, pulverizing, washing with water, filtering, and drying to obtain fluorine-containing polyaryletherketone; the molar ratio of the 4,4 '-biphenol to the hexafluorobisphenol A to the 4,4' -difluorobenzophenone to the fluorine-containing benzophenone imine monomer is 5:5:3:7; the mass ratio of the 4,4' -biphenol to the potassium carbonate is 10:9; the ratio of 4,4' -biphenol, toluene and sulfolane is 17g to 13mL to 100mL;
1.3. Modification of filler: mixing absolute ethyl alcohol with equal volume and deionized water, adding fluorine-containing benzophenone imine monomer and filler, and ball milling for 9 hours at the rotating speed of 450 rpm; filtering, washing, and vacuum drying at 120 ℃ for 5 hours to obtain modified filler; the filler comprises 5wt% of fluorinated graphene and 10wt% of carbon fiber; the proportion of the filler, the fluorine-containing phenylketimine monomer and the deionized water is 45g:2.5g:100mL;
1.4. Polytetrafluoroethylene is mixed and stirred for 25 seconds at the rotating speed of 110000 r/min; adding polyether-ether-ketone, fluorine-containing polyaryletherketone and modified filler, mixing at a rotating speed of 13500r/min for 80s, and sieving with a 120-mesh sieve to obtain a mixture; the mixture comprises the following components in parts by mass: 10% of polyether-ether-ketone, 10% of fluorine-containing polyaryletherketone, 15% of filler and the balance of polytetrafluoroethylene;
And (2) preparing a retainer: pouring the mixture into a retainer die, cold pressing at a pressure of 45MPa at room temperature for 20min, demoulding, sintering, wherein the technological conditions of sintering are as follows: heating to 3000 ℃ at a heating rate of 1.5 ℃/min, and preserving heat for 75min; heating to 355 ℃ at a heating rate of 1.5/min, and preserving heat for 105min; cooling to 300 ℃ at a speed of 35 ℃/h, and preserving heat for 70min; and cooling the furnace to obtain the retainer.
Example 3: a preparation method of a high-strength plastic retainer based on polyether-ether-ketone comprises the following preparation processes:
Preparing a mixture in the step (1):
1.1. 2,2' -bis (trifluoromethyl) diaminobiphenyl and 4-triethoxysilyl vinylbenzocyclobutene with equal molar weight are mixed, 1 weight percent of catalyst 1,5, 7-triazabicyclo [4.4.0] dec-5-ene is added, the temperature is raised to 55 ℃, and the reaction is carried out for 4 hours; washing and drying to obtain an aniline compound;
10g of 4,4' -difluorobenzophenone, 42.0g of aniline compound, 37mL of toluene and 23.1g of molecular sieve are mixed, heated to 115 ℃ under the protection of nitrogen atmosphere, and subjected to reflux reaction for 24 hours; cooling to room temperature, filtering to remove a molecular sieve, performing rotary evaporation, recrystallizing with methanol, and drying to obtain a fluorine-containing phenylketimine monomer;
1.2. mixing 4,4 '-biphenol, hexafluorobisphenol A, 4' -difluorobenzophenone, fluorine-containing benzophenone imine monomer and potassium carbonate in sulfolane, adding toluene, heating to 160 ℃ under the protection of nitrogen atmosphere, and carrying out reflux reaction for 160min to discharge water and toluene; heating to 215 ℃, and continuing to react for 5 hours; slowly pouring into water with pH of 6.5, soaking overnight, pulverizing, washing with water, filtering, and drying to obtain fluorine-containing polyaryletherketone; the molar ratio of the 4,4 '-biphenol to the hexafluorobisphenol A to the 4,4' -difluorobenzophenone to the fluorine-containing benzophenone imine monomer is 5:5:2:8; the mass ratio of the 4,4' -biphenol to the potassium carbonate is 10:9.1; the ratio of 4,4' -biphenol, toluene and sulfolane is 17g:15mL:100mL;
1.3. Modification of filler: mixing absolute ethyl alcohol with equal volume and deionized water, adding fluorine-containing benzophenone imine monomer and filler, and ball milling for 8 hours at a rotating speed of 500 rpm; filtering, washing, and vacuum drying at 120 ℃ for 6 hours to obtain modified filler; the filler comprises 5wt% of fluorinated graphene and 10wt% of carbon fiber; the proportion of the filler, the fluorine-containing phenylketimine monomer and the deionized water is 50g:3g:100mL;
1.4. Polytetrafluoroethylene is mixed and stirred for 30s at the rotating speed of 120000 r/min; adding polyether-ether-ketone, fluorine-containing polyaryletherketone and modified filler, mixing at a rotating speed of 15000r/min for 100s, and sieving with a 120-mesh sieve to obtain a mixture; the mixture comprises the following components in parts by mass: 5% of polyether-ether-ketone, 15% of fluorine-containing polyaryletherketone, 15% of filler and the balance of polytetrafluoroethylene;
and (2) preparing a retainer: pouring the mixture into a retainer die, cold pressing at a pressure of 50MPa at room temperature for 15min, demoulding, sintering, wherein the technological conditions of sintering are as follows: heating to 320 ℃ at a heating rate of 2 ℃/min, and preserving heat for 90min; heating to 360 ℃ at a heating rate of 2/min, and preserving heat for 120min; cooling to 310 ℃ at a speed of 50 ℃/h, and preserving heat for 90min; and cooling the furnace to obtain the retainer.
Comparative example 1: a preparation method of a high-strength plastic retainer based on polyether-ether-ketone comprises the following preparation processes:
Preparing a mixture in the step (1):
1.1. 2,2' -bis (trifluoromethyl) diaminobiphenyl and equimolar vinyl trimethoxy silane are mixed, 1wt% of catalyst 1,5, 7-triazabicyclo [4.4.0] dec-5-ene is added, the temperature is raised to 55 ℃, and the reaction is carried out for 4 hours; washing and drying to obtain an aniline compound;
10g of 4,4' -difluorobenzophenone, 30.0g of aniline compound, 37mL of toluene and 21.7g of molecular sieve are mixed, heated to 111 ℃ under the protection of nitrogen atmosphere and subjected to reflux reaction for 24 hours; cooling to room temperature, filtering to remove a molecular sieve, performing rotary evaporation, recrystallizing with methanol, and drying to obtain a fluorine-containing phenylketimine monomer;
1.2. Mixing 4,4 '-biphenol, hexafluorobisphenol A, 4' -difluorobenzophenone, fluorine-containing benzophenone imine monomer and potassium carbonate in sulfolane, adding toluene, heating to 155 ℃ under the protection of nitrogen atmosphere, and carrying out reflux reaction for 200min to release water and toluene; heating to 210 ℃, and continuing to react for 7h; slowly pouring into water with pH of 6.5, soaking overnight, pulverizing, washing with water, filtering, and drying to obtain fluorine-containing polyaryletherketone; the molar ratio of the 4,4 '-biphenol to the hexafluorobisphenol A to the 4,4' -difluorobenzophenone to the fluorine-containing benzophenone imine monomer (relative molecular weight 669) is 1:1:1:1; the mass ratio of the 4,4' -biphenol to the potassium carbonate is 10:8.9; the ratio of 4,4' -biphenol, toluene and sulfolane is 17g:12mL:100mL;
1.3. Modification of filler: mixing absolute ethyl alcohol with equal volume and deionized water, adding fluorine-containing benzophenone imine monomer and filler, and ball milling for 8 hours at a rotating speed of 400 rpm; filtering, washing, and vacuum drying at 120 ℃ for 4 hours to obtain modified filler; the filler comprises 5wt% of fluorinated graphene and 10wt% of carbon fiber; the proportion of the filler, the fluorine-containing phenylketimine monomer and the deionized water is 40g:2g:100mL;
step 1.4, (2) was the same as in example 1, to obtain a cage.
Comparative example 2: a preparation method of a high-strength plastic retainer based on polyether-ether-ketone comprises the following preparation processes:
Preparing a mixture in the step (1):
1.1. 10g of 4,4' -difluorobenzophenone, 6g of aniline, 37mL of toluene and 21.7g of molecular sieve are mixed, heated to 111 ℃ under the protection of nitrogen atmosphere and subjected to reflux reaction for 24 hours; cooling to room temperature, filtering to remove a molecular sieve, performing rotary evaporation, recrystallizing with methanol, and drying to obtain a fluorine-containing phenylketimine monomer;
1.2. Mixing 4,4 '-biphenol, hexafluorobisphenol A, 4' -difluorobenzophenone, fluorine-containing benzophenone imine monomer and potassium carbonate in sulfolane, adding toluene, heating to 155 ℃ under the protection of nitrogen atmosphere, and carrying out reflux reaction for 200min to release water and toluene; heating to 210 ℃, and continuing to react for 7h; slowly pouring into water with pH of 6.5, soaking overnight, pulverizing, washing with water, filtering, and drying to obtain fluorine-containing polyaryletherketone; the molar ratio of the 4,4 '-biphenol, the hexafluorobisphenol A, the 4,4' -difluorobenzophenone and the fluorine-containing benzophenone imine monomer (relative molecular weight 293) is 1:1:1:1; the mass ratio of the 4,4' -biphenol to the potassium carbonate is 10:8.9; the ratio of 4,4' -biphenol, toluene and sulfolane is 17g:12mL:100mL;
1.3. Modification of filler: mixing absolute ethyl alcohol with equal volume and deionized water, adding fluorine-containing benzophenone imine monomer and filler, and ball milling for 8 hours at a rotating speed of 400 rpm; filtering, washing, and vacuum drying at 120 ℃ for 4 hours to obtain modified filler; the filler comprises 5wt% of fluorinated graphene and 10wt% of carbon fiber; the proportion of the filler, the fluorine-containing phenylketimine monomer and the deionized water is 40g:2g:100mL;
step 1.4, (2) was the same as in example 1, to obtain a cage.
Comparative example 3: a preparation method of a high-strength plastic retainer based on polyether-ether-ketone comprises the following preparation processes:
Preparing a mixture in the step (1):
1.1. Mixing 4,4 '-biphenol, hexafluorobisphenol A, 4' -difluorobenzophenone and potassium carbonate in sulfolane, adding toluene, heating to 155 ℃ under the protection of nitrogen atmosphere, and carrying out reflux reaction for 200min to discharge water and toluene; heating to 210 ℃, and continuing to react for 7h; slowly pouring into water with pH of 6.5, soaking overnight, pulverizing, washing with water, filtering, and drying to obtain fluorine-containing polyaryletherketone; the molar ratio of the 4,4 '-biphenol to the hexafluorobisphenol A to the 4,4' -difluorobenzophenone is 1:1:2; the mass ratio of the 4,4' -biphenol to the potassium carbonate is 10:8.9; the ratio of 4,4' -biphenol, toluene and sulfolane is 17g:12mL:100mL;
1.3. modification of filler: mixing absolute ethyl alcohol with equal volume and deionized water, adding a coupling agent KH550 and a filler, and ball milling for 8 hours at a rotating speed of 400 rpm; filtering, washing, and vacuum drying at 120 ℃ for 4 hours to obtain modified filler; the filler comprises 5wt% of fluorinated graphene and 10wt% of carbon fiber; the ratio of filler, coupling agent KH550 and deionized water is 40g:2g:100mL;
step 1.3 was the same as step 1.4 in example 1, and step (2) was the same as step (2) in example 1, to obtain a cage.
Comparative example 4: a preparation method of a high-strength plastic retainer based on polyether-ether-ketone comprises the following preparation processes:
Preparing a mixture in the step (1):
Mixing absolute ethyl alcohol with equal volume and deionized water, adding a coupling agent KH550 and a filler, and ball milling for 8 hours at a rotating speed of 400 rpm; filtering, washing, and vacuum drying at 120 ℃ for 4 hours to obtain modified filler; the filler comprises 5wt% of fluorinated graphene and 10wt% of carbon fiber; the ratio of filler, coupling agent KH550 and deionized water is 40g:2g:100mL;
Stirring polytetrafluoroethylene at a rotating speed of 10000r/min for 20s; adding polyether-ether-ketone and filler, mixing at 12000r/min for 60s, and sieving with 120 mesh sieve to obtain mixture; the mixture comprises the following components in parts by mass: 15% of polyether-ether-ketone, 5% of fluorine-containing polyaryletherketone, 15% of filler and the balance of polytetrafluoroethylene;
Step (2) was the same as in example 1, to obtain a cage.
Experiment: the holders obtained in examples 1 to 3 and comparative examples 1 to 4 were used to prepare samples, and the properties were measured and the measurement results were recorded:
Tribological properties: taking ASTM G133 as a reference standard, adopting a frictional wear testing machine to scan the abrasion marks after test of the samples, wherein the abrasion rate (average sectional area of the abrasion marks multiplied by the length of the abrasion marks/(load multiplied by the sliding distance)) of the samples is used as a performance index, and the linear reciprocating linear motion, the reciprocating stroke of the frictional wear testing machine is 8mm, the load of the frictional wear testing machine is 10N, the reciprocating motion speed is 0.075m/s, and the sliding distance of the frictional wear testing machine is 500 m; the upper test piece is a GCr15 bearing steel ball (diameter 6mm, hardness 63HRC, average surface roughness 0.02 μm), the lower test piece is a retainer sample (20 mm×12mm×4 mm), the experimental condition is 22 ℃, and the relative humidity is 40%; before the experiment, the surface of the sample is sequentially polished by 1000 meshes, 1500 meshes and 2000 meshes of silicon carbide abrasive paper, and the upper test piece and the lower test piece are ultrasonically cleaned by absolute ethyl alcohol and dried for 30min at 100 ℃;
mechanical property test: using GB/T1040.2 as a reference standard, and adopting an electronic universal testing machine to test the tensile property of the sample, wherein the tensile rate is 1mm/min;
Using GB/T1041 as a reference standard, adopting an electronic universal testing machine to test the compression performance of a sample for a second time, wherein the compression rate is 1mm/min, and the shape of the sample is a cylinder with the diameter of 10mm and the thickness of 4 mm;
Thermal stability performance test: and (3) carrying out thermogravimetric test on the sample by adopting a synchronous thermal analyzer, wherein the mass of the sample is 10mg, the argon flow is 20mL/min under the argon atmosphere, the temperature is increased to 800 ℃ at the heating rate of 10 ℃/min, the sample is cooled along with the furnace, and the thermal decomposition temperature of the sample is used as a performance index.
From the data in the above table, the following conclusions can be clearly drawn:
The retainers obtained in examples 1 to 3 were compared with the retainers obtained in comparative examples 1 to 4, and it was found that the results of the detection,
The retainers obtained in examples 1-3 had higher tensile strength, compressive strength and thermal decomposition temperature data, and lower wear rate data than the comparative examples. This fully demonstrates that the present invention achieves improvements in strength, wear resistance and thermal stability of the resulting cage.
In comparative example 1, the modified component of the filler was changed by replacing 4-triethoxysilyl vinylbenzocyclobutene with an equimolar amount of vinyltrimethoxysilane as compared with example 1; comparative example 2 the modified component of the filler was changed by substituting aniline compound with aniline; comparative example 3 the fluorine-containing benzophenone imine monomer in the fluorine-containing polyaryletherketone preparation component was deleted and the filler was modified by the coupling agent KH 550; the mixture of comparative example 4 was not added with fluorine-containing polyaryletherketone, and the filler was modified with a coupling agent KH 550. The wear rate, tensile strength, compressive strength, and thermal decomposition temperature data of the retainers obtained in comparative examples 1 to 4 were deteriorated, and it was found that the arrangement of the components of the retainer and the preparation process thereof according to the present invention can promote improvement of mechanical properties, wear resistance and thermal stability.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A high strength plastic cage based on polyetheretherketone, characterized in that: comprises the following components in mass percent: 5 to 15 percent of polyether-ether-ketone, 5 to 15 percent of fluorine-containing polyaryletherketone, 8.5 to 21 percent of filler and the balance of polytetrafluoroethylene;
the fluorine-containing polyaryletherketone is prepared by the following process:
Mixing diphenol, 4' -difluorobenzophenone, fluorine-containing phenylketimine monomer and potassium carbonate in sulfolane, adding toluene, heating to 155-160 ℃ under the protection of nitrogen atmosphere, carrying out reflux reaction for 160-200 min, and discharging water and toluene; heating to 210-215 ℃, and continuing to react for 5-7 h; slowly pouring the mixture into water with the pH of 6.2-6.7, soaking the mixture overnight, taking out the mixture, crushing the mixture, washing the mixture with water, filtering the mixture, and drying the mixture to obtain fluorine-containing polyaryletherketone;
the diphenol is the mixture of 4,4' -biphenol and hexafluorobisphenol A, the mol ratio is 1 (0.5-1.0); the molar ratio of diphenol to 4,4' -difluorobenzophenone to fluorine-containing benzophenone imine monomer is 10 (2-5) (5-8);
The fluorine-containing benzophenone imine monomer is prepared by the following process:
mixing 2,2' -di (trifluoromethyl) diaminobiphenyl and 4-triethoxysilyl vinylbenzocyclobutene, adding a catalyst, heating to 50-55 ℃, and reacting for 4-8 hours to obtain an aniline compound;
Mixing 4,4' -difluorobenzophenone, an aniline compound, toluene and a molecular sieve, heating to 111-115 ℃ under the protection of nitrogen atmosphere, and carrying out reflux reaction for 24 hours to obtain a fluorine-containing phenylketimine monomer;
The molar ratio of the 2,2' -bis (trifluoromethyl) diaminobiphenyl to the 4-triethoxysilyl vinylbenzocyclobutene is 1:1; the mass ratio of the 4,4' -difluorobenzophenone and the aniline compound is 10 (39.2 to 42.0);
the filler comprises 3.5-6.0 wt% of fluorinated graphene and 5-15 wt% of carbon fiber;
the filler is modified by the following specific steps:
Mixing absolute ethyl alcohol and deionized water, adding fluorine-containing phenylketonurine monomer and filler, and ball milling for 8-10 h at a rotating speed of 400-500 rpm; filtering, washing and vacuum drying at 120 deg.c for 4-6 hr.
2. The method for preparing the high-strength plastic retainer based on polyether-ether-ketone as claimed in claim 1, which is characterized by comprising the following steps: the preparation method comprises the following preparation processes:
Step (1): mixing polytetrafluoroethylene, polyether-ether-ketone, fluorine-containing polyaryletherketone and filler to obtain a mixture;
Step (2): pouring the mixture into a retainer mold, pressing, forming, demolding and sintering to obtain the retainer.
3. The method for preparing the high-strength plastic retainer based on polyether-ether-ketone as claimed in claim 2, which is characterized in that: the step (1) comprises the following processes:
Stirring polytetrafluoroethylene at a rotating speed of 10000-120000 r/min for 20-30 s; adding polyether-ether-ketone, fluorine-containing polyaryletherketone and filler, mixing at a rotating speed of 12000-15000 r/min for 60-100 s, and sieving with a 120-mesh sieve to obtain a mixture.
4. The method for preparing the high-strength plastic retainer based on polyether-ether-ketone as claimed in claim 2, which is characterized in that: in the step (2), the sintering process conditions are as follows: heating to 280-320 ℃ at a heating rate of 1-2 ℃/min, and preserving heat for 60-90 min; heating to 350-360 ℃ at a heating rate of 1-2/min, and preserving heat for 90-120 min; cooling to 290-310 ℃ at the speed of 25-50 ℃/h, and preserving heat for 60-80 min; and (5) furnace cooling.
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| JP2001181502A (en) * | 1999-12-28 | 2001-07-03 | Tosoh Corp | Polyphenylene sulfide resin composition |
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| CN106633034A (en) * | 2017-01-06 | 2017-05-10 | 北京奥精医药科技有限公司 | Preparation method of polyether-ether-ketone resin and prepared polyether-ether-ketone resin |
| CN108384193A (en) * | 2018-03-13 | 2018-08-10 | 如皋市非标轴承有限公司 | A kind of high molecular material bearing and preparation method thereof |
| CN109749076A (en) * | 2019-01-25 | 2019-05-14 | 吉林大学 | A kind of crystal type poly(aryl ether ketone) and preparation method thereof |
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| US20220135740A1 (en) * | 2020-11-05 | 2022-05-05 | The Texas A&M University System | Poly(aryl ether ketone) compositions containing carbon-based nanomaterials |
| US20230051959A1 (en) * | 2021-07-30 | 2023-02-16 | Agilent Technologies, Inc. | Methods of making monodisperse populations of polyarylketone or polyarylthioetherketone particles |
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| JP2001181502A (en) * | 1999-12-28 | 2001-07-03 | Tosoh Corp | Polyphenylene sulfide resin composition |
| CN103242641A (en) * | 2013-05-30 | 2013-08-14 | 吉林大学 | Polyaryletherketone-based abrasion-resistant composite material and preparation method thereof |
| CN105936724A (en) * | 2016-06-22 | 2016-09-14 | 芜湖市长江起重设备制造有限公司 | Polyether-ether-ketone modified polytetrafluoroethylene material and preparation method thereof |
| CN106633034A (en) * | 2017-01-06 | 2017-05-10 | 北京奥精医药科技有限公司 | Preparation method of polyether-ether-ketone resin and prepared polyether-ether-ketone resin |
| CN108384193A (en) * | 2018-03-13 | 2018-08-10 | 如皋市非标轴承有限公司 | A kind of high molecular material bearing and preparation method thereof |
| CN109749076A (en) * | 2019-01-25 | 2019-05-14 | 吉林大学 | A kind of crystal type poly(aryl ether ketone) and preparation method thereof |
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