CN114621557A - Composite material based on modified polyether-ether-ketone and preparation method thereof - Google Patents
Composite material based on modified polyether-ether-ketone and preparation method thereof Download PDFInfo
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- CN114621557A CN114621557A CN202210338625.3A CN202210338625A CN114621557A CN 114621557 A CN114621557 A CN 114621557A CN 202210338625 A CN202210338625 A CN 202210338625A CN 114621557 A CN114621557 A CN 114621557A
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- 239000002131 composite material Substances 0.000 title claims abstract description 94
- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 64
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000835 fiber Substances 0.000 claims abstract description 60
- 239000004094 surface-active agent Substances 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 20
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 20
- 239000002608 ionic liquid Substances 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 12
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 230000008961 swelling Effects 0.000 claims abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- CKHQKWRHPZIGTM-UHFFFAOYSA-N 1-bromo-2-methylhexane Chemical compound CCCCC(C)CBr CKHQKWRHPZIGTM-UHFFFAOYSA-N 0.000 claims description 4
- XHYRIXNUUUUPAL-UHFFFAOYSA-N 1-bromo-2-methyloctane Chemical compound CCCCCCC(C)CBr XHYRIXNUUUUPAL-UHFFFAOYSA-N 0.000 claims description 4
- BFYPQDKZLOZOLQ-UHFFFAOYSA-N 1-bromo-6-methylheptane Chemical compound CC(C)CCCCCBr BFYPQDKZLOZOLQ-UHFFFAOYSA-N 0.000 claims description 4
- AHTKGFIYHBHGAM-UHFFFAOYSA-N 4-ethenyl-2,6-dimethylpyridine Chemical compound CC1=CC(C=C)=CC(C)=N1 AHTKGFIYHBHGAM-UHFFFAOYSA-N 0.000 claims description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 4
- KSHXKHLVWCSOJZ-UHFFFAOYSA-N 4-pent-1-en-3-ylpyridine Chemical compound CCC(C=C)C1=CC=NC=C1 KSHXKHLVWCSOJZ-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 2
- HDTCUJLOLXSFQE-UHFFFAOYSA-N [dimethoxy(methyl)silyl]oxymethyl prop-2-enoate Chemical compound CO[Si](C)(OC)OCOC(=O)C=C HDTCUJLOLXSFQE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims 1
- 229920006351 engineering plastic Polymers 0.000 abstract description 7
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical class N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
-
- 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
Abstract
The invention discloses a preparation method of a composite material based on modified polyether-ether-ketone, which comprises the following steps of S1: swelling the composite fiber in a supercritical state; adding potassium permanganate and ionic liquid, and maintaining the supercritical state again; s2: dispersing the modified composite fiber into a reactive surfactant, adding a mixed solution compounded by an acrylate monomer, a fluorine-silicon additive and an initiator, and reacting to obtain the modified composite fiber; s3: mixing the mixture with polytetrafluoroethylene resin and polyether-ether-ketone; s4: and (3) melting and extruding the mixed material, cooling and granulating to obtain the modified polyether-ether-ketone-based composite material. The composite material prepared by the invention not only improves the comprehensive performance of the polyetheretherketone engineering plastic, widens the application range of the polyetheretherketone material, but also reduces the use cost of the polyetheretherketone engineering plastic.
Description
Technical Field
The invention relates to the technical field of polyether-ether-ketone engineering plastics, in particular to a composite material based on modified polyether-ether-ketone and a preparation method thereof.
Background
Polyether-ether-ketone (PEEK) is a special engineering plastic with ultrahigh performance developed in the last 80 th century, and the PEEK belongs to an aromatic crystalline thermoplastic polymer material, has a melting point of 334 ℃ and excellent comprehensive performance, can replace traditional materials such as metal and ceramic in a plurality of special fields, becomes one of the hottest high-performance engineering plastics at present, and is widely applied to the fields of aerospace, automobile industry, energy nuclear power, electronics, electrical and medical machinery and the like. However, the PEEK raw material unit price is high, and with the development of large-size products of projects, the PEEK material is only used for application, so that the manufacturing cost and the cost of the projects are greatly increased. The performance of the pure PEEK material is difficult to meet different requirements in different industry fields, so that the PEEK needs to be modified in a special working environment, and the main means of the PEEK modification method comprises the technologies of blending modification, copolymerization modification, composite reinforcement modification, filling modification, nano modification, surface modification and the like. The application aims to obtain the modified polyether-ether-ketone composite material with excellent comprehensive performance by the mixed modification treatment of the composite fiber and the polytetrafluoroethylene, thereby widening the application range of the polyether-ether-ketone material and reducing the use cost of the material.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a composite material based on modified polyetheretherketone, which aims to solve the problem that the performance of a pure polyetheretherketone material is difficult to meet the requirement of long-term continuous and stable use under severe working conditions.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:
a preparation method of a composite material based on modified polyetheretherketone comprises the following steps:
s1: placing the composite fiber into a high-pressure kettle, introducing carbon dioxide into the high-pressure kettle, heating and boosting the pressure to keep the composite fiber in a supercritical state for 5-10 min, and swelling; after pressure relief, adding a solution compounded by potassium permanganate and ionic liquid, introducing carbon dioxide again, heating and boosting the pressure to keep the pressure in a supercritical state for 1-5 min; after pressure relief, washing the mixture for multiple times by using absolute ethyl alcohol until the mixture is neutral, and drying the mixture until the weight is constant for later use; the mass ratio of the potassium permanganate to the ionic liquid to the composite fiber is 1-3: 20: 10-15; according to the invention, the composite fiber is swelled by supercritical carbon dioxide, then the composite fiber is further softened under the strong oxidation action of potassium permanganate, and the hydrophilic modification and ionization treatment are carried out on the surface and the interior of the composite fiber under the action of the supercritical carbon dioxide in combination with the strong dissolving capacity of the ionic liquid. The composite fiber treated in step S1 is more easily dispersed in the reactive surfactant in step S2, and the modification reaction treatment can be efficiently performed on the surface and inside of the fiber.
S2: uniformly dispersing the composite fiber treated in the step S1 in a reactive surfactant, adding a mixed solution compounded by an acrylate monomer, a fluorine-silicon additive and an initiator, heating to 120-160 ℃, and reacting to obtain a modified composite fiber; the mass ratio of the composite fiber to the reactive surfactant is 15-25: 7-13; the molar ratio of the reactive surfactant to the acrylate monomer to the fluorosilicone additive is 1-5: 1-2: 1; adding a proper amount of the initiator;
s3: putting the modified composite fiber obtained in the step S2, polytetrafluoroethylene resin and polyether-ether-ketone powder into a high-speed mixer for mixing; the mass ratio of the modified composite fibers to the polytetrafluoroethylene resin to the polyether-ether-ketone is (3-5): 4-10: 20;
s4: and (5) melting and extruding the material mixed in the step (S3), cooling and granulating to obtain the modified polyether-ether-ketone-based composite material.
Preferably, the composite fiber is prepared by mixing, by mass, 1-5: 1 ceramic fibers and glass fibers.
Preferably, the ionic liquid is at least one of pyridine ionic liquid, carboxylic acid ionic liquid or imidazole ionic liquid.
Preferably, the reactive surfactant is prepared by mixing the following components in a molar ratio of 1: 1, reacting with bromoalkane, then adding an aqueous solution of sodium fluoborate to precipitate the solution, filtering the precipitate, and recrystallizing the filter cake to obtain the sodium fluoborate-containing aqueous solution. According to the reactive surfactant, firstly, bromine atoms on brominated alkanes and nitrogen atoms in pyridine rings are subjected to substitution reaction to obtain pyridinium grafted with alkane branched chains, and further, the ionic exchange effect of bromine ions and fluoroborate is utilized to obtain the reactive surfactant with ionization. The ionization reaction type surfactant promotes the uniform dispersion effect of the composite fiber treated in the step S1, and ensures the high temperature resistance, chemical resistance and other performances of the modified polyether-ether-ketone composite material.
Preferably, the pyridine compound is at least one of 4-vinylpyridine, 4- (1-penten-3-yl) pyridine and 2, 6-dimethyl-4-vinylpyridine. The method selects the pyridine compound with unsaturated double bonds to synthesize the reactive surfactant, and the reactive surfactant, the acrylate monomer and the fluorine-silicon additive are subjected to three-dimensional crosslinking reaction on the surface and the inner pore canal of the composite fiber in a chemical bond combination mode, so that the comprehensive mechanical property and the peeling resistance of the composite material are improved, and the performances of high temperature resistance, corrosion resistance, impact resistance, self-lubricating property and the like of the composite material are improved.
Preferably, the brominated alkane is at least one of 1-bromo-2-methylhexane, 1-bromo-6-methylheptane, 1-bromooctane and 1-bromo-2-methyl-octane. According to the preparation method, long-chain alkane is preferably grafted on a pyridine compound, and the performance requirements of the composite fiber such as impact resistance, peeling resistance and the like are further improved through the molecular winding effect of the long-chain alkane.
Preferably, the acrylate monomer is at least one of butyl acrylate, ethyl acrylate, methyl methacrylate and butyl methacrylate.
Preferably, the preparation method of the fluorosilicone additive comprises the following steps: dissolving 3,3, 3-trifluoropropyltrimethoxysilane 20-30 g in a dichloromethane solvent 250mL, adding 3-7 mL of dilute hydrochloric acid for hydrolysis reaction to obtain a cage-type polysilsesquioxane intermediate, adding a triethylamine solution of acryloyloxy methyl trimethoxysilane with the mass concentration of 20-40%, and performing ring closing reaction to obtain the fluorine silicon additive. Wherein, the triethylamine solution of the acryloxymethyltrimethoxysilane is prepared by mixing the acryloxymethyltrimethoxysilane and the cage-type polysilsesquioxane intermediate in a molar ratio of 1: 1 addition.
The fluorine-silicon additive is POSS (also called cage polysilsesquioxane) with a cage-type framework structure, and the general formula of the fluorine-silicon additive is (RSiO)3/2) n, wherein R is a group to which eight apical Si atoms are attached. In the invention, the intermediate of the cage type polysilsesquioxane, namely seven vertex angles are connected with fluorine-containing groups, and the other vertex angle is not closed and is respectively provided with three hydroxyl groups; further, by reacting with acryloxymethyltrimethoxysilane, the remaining one vertex angle from which POSS is obtained contains the reactive functional group acryloxy. The acryloxy active functional group can perform cross-linking polymerization reaction with a reactive surfactant and an acrylate monomer, a layer of compact functional coating is formed on the surface of the composite fiber, and the functional coating is grafted with a fluorine-containing group and a nano POSS group, so that the modified polyether-ether-ketone composite material has the corrosion resistance, weather resistance, self-lubrication of the fluorine-containing group and the small-size effect of nano particles of the POSS group, the comprehensive performance of the polyether-ether-ketone composite material is remarkably improved, and the impact resistance, high temperature resistance, corrosion resistance, wear resistance and the like of the composite material are synergistically improved.
Preferably, the initiator is at least one of an azo-type initiator or a peroxide-type initiator.
The invention also provides a composite material based on modified polyetheretherketone, which is prepared by the preparation method of the composite material based on modified polyetheretherketone.
The invention has the beneficial effects that:
the composite material based on the modified polyether-ether-ketone prepared by the invention has good comprehensive mechanical property and environmental property, has excellent high-temperature resistance, corrosion resistance, stripping resistance and wear resistance, has excellent self-lubricating property, flame retardance and impact resistance, and can meet the high-performance requirement of long-term continuous stable use under severe working conditions.
The composite material based on the modified polyether-ether-ketone prepared by the invention not only improves the comprehensive performance of the polyether-ether-ketone engineering plastic, widens the application range of the polyether-ether-ketone material, but also reduces the use cost of the polyether-ether-ketone engineering plastic.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
Example 1
The preparation method of the composite material based on modified polyetheretherketone of the embodiment comprises the following steps:
s1: mixing the components in a mass ratio of 1: 1, placing the composite fiber consisting of the ceramic fiber and the glass fiber in a high-pressure kettle, introducing carbon dioxide into the high-pressure kettle, heating and boosting the pressure to keep the composite fiber in a supercritical state for 5min, and swelling; after pressure relief, adding a solution compounded by potassium permanganate and 1-butyl-3-methylimidazolium chloride ionic liquid, introducing carbon dioxide again, heating and boosting pressure to keep the mixture in a supercritical state for 1 min; after pressure relief, washing the mixture for many times by absolute ethyl alcohol until the mixture is neutral, and drying the mixture until the weight is constant for later use; the mass ratio of the potassium permanganate to the ionic liquid to the composite fiber is 1: 20: 10;
s2: uniformly dispersing the composite fiber treated in the step S1 in a reactive surfactant, adding a mixed solution compounded by a butyl acrylate monomer, a fluorine-silicon additive and an initiator azo-bis-iso-butyl amidine hydrochloride, heating to 130 ℃, and reacting to obtain a modified composite fiber; the mass ratio of the composite fiber to the reactive surfactant is 15: 7; the molar ratio of the reactive surfactant to the butyl acrylate monomer to the fluorine-silicon additive is 2: 1: 1; adding a catalytic amount of the initiator;
s3: putting the modified composite fiber obtained in the step S2, polytetrafluoroethylene resin and polyether-ether-ketone powder into a high-speed mixer for mixing; the mass ratio of the modified composite fiber to the polytetrafluoroethylene resin to the polyether-ether-ketone is 3: 4: 20;
s4: and (5) melting and extruding the material mixed in the step (S3), cooling and cutting into granules, wherein the melting and extruding temperature is 350 ℃, and obtaining the modified polyether-ether-ketone-based composite material.
The preparation method of the reactive surfactant comprises the following steps: 10g of 4-vinylpyridine was dissolved in tetrahydrofuran and reacted by adding 1-bromo-2-methylhexane in a molar ratio of 4-vinylpyridine to 1-bromo-2-methylhexane of 1: 1, then adding an excessive sodium fluoroborate aqueous solution to precipitate the solution, filtering the precipitate and recrystallizing a filter cake to obtain the sodium fluoroborate aqueous solution.
The preparation method of the fluorine-silicon additive comprises the following steps: dissolving 3 g, 3, 3-trifluoropropyltrimethoxysilane in 250mL of dichloromethane solvent, adding 3mL of dilute hydrochloric acid (with the concentration of 10 wt%, the same below) for hydrolysis reaction to obtain a polyhedral oligomeric silsesquioxane intermediate, then adding 20% by mass of a triethylamine solution of acryloyloxymethyl trimethoxysilane for ring closing reaction to obtain the fluorosilicone additive. Wherein, the triethylamine solution of the acryloxymethyltrimethoxysilane is prepared by mixing the acryloxymethyltrimethoxysilane and the cage-type polysilsesquioxane intermediate in a molar ratio of 1: 1 addition.
Example 2
The preparation method of the composite material based on modified polyetheretherketone of the embodiment comprises the following steps:
s1: and (3) mixing the following components in percentage by mass: 1, placing the composite fiber consisting of the ceramic fiber and the glass fiber in a high-pressure kettle, introducing carbon dioxide into the high-pressure kettle, heating and boosting the pressure to keep the composite fiber in a supercritical state for 7min, and swelling; after pressure relief, adding a solution compounded by potassium permanganate and 1-butyl-3-methylimidazolium chloride ionic liquid, introducing carbon dioxide again, heating and boosting pressure to keep the mixture in a supercritical state for 3 min; after pressure relief, washing the mixture for many times by absolute ethyl alcohol until the mixture is neutral, and drying the mixture until the weight is constant for later use; the mass ratio of the potassium permanganate, the ionic liquid and the composite fiber is 2: 20: 13;
s2: uniformly dispersing the composite fiber treated in the step S1 in a reactive surfactant, adding a mixed solution compounded by an ethyl acrylate monomer, a fluorosilicone additive and an initiator azodiisobutymidine hydrochloride, heating to 150 ℃, and reacting to obtain a modified composite fiber; the mass ratio of the composite fiber to the reactive surfactant is 20: 13; the molar ratio of the reactive surfactant to the ethyl acrylate monomer and the fluorosilicone additive is 3: 2: 1; adding a catalytic amount of the initiator;
s3: putting the modified composite fiber obtained in the step S2, polytetrafluoroethylene resin and polyether-ether-ketone powder into a high-speed mixer for mixing; the mass ratio of the modified composite fiber to the polytetrafluoroethylene resin to the polyether-ether-ketone is 4: 7: 20;
s4: and (5) melting and extruding the material mixed in the step (S3), cooling and cutting into granules, wherein the melting and extruding temperature is 350 ℃, and obtaining the modified polyether-ether-ketone-based composite material.
The preparation method of the reactive surfactant comprises the following steps: 10g of 4- (1-penten-3-yl) pyridine was dissolved in tetrahydrofuran and reacted by adding 1-bromo-6-methylheptane in a molar ratio of 4- (1-penten-3-yl) pyridine to 1-bromo-6-methylheptane of 1: 1, adding an excessive sodium fluoborate aqueous solution, completely precipitating the solution, filtering the precipitate and recrystallizing a filter cake to obtain the sodium fluoborate aqueous solution.
The preparation method of the fluorosilicone additive is the same as that of example 1.
Example 3
The preparation method of the composite material based on modified polyetheretherketone in the embodiment comprises the following steps:
s1: and (2) mixing the components in a mass ratio of 5: 1, placing the composite fiber consisting of the ceramic fiber and the glass fiber in a high-pressure kettle, introducing carbon dioxide into the high-pressure kettle, heating and boosting the pressure to keep the composite fiber in a supercritical state for 10min, and swelling; after pressure relief, adding a solution compounded by potassium permanganate and 1-butyl-3-methylimidazolium chloride ionic liquid, introducing carbon dioxide again, heating and boosting pressure to keep the mixture in a supercritical state for 5 min; after pressure relief, washing the mixture for multiple times by using absolute ethyl alcohol until the mixture is neutral, and drying the mixture until the weight is constant for later use; the mass ratio of the potassium permanganate to the ionic liquid to the composite fiber is 3: 20: 15;
s2: uniformly dispersing the composite fiber treated in the step S1 in a reactive surfactant, adding a mixed solution compounded by a methyl methacrylate monomer, a fluorosilicone additive and an initiator azodiisobutymidine hydrochloride, heating to 160 ℃, and reacting to obtain a modified composite fiber; the mass ratio of the composite fiber to the reactive surfactant is 25: 13; the molar ratio of the reactive surfactant to the methyl methacrylate monomer and the fluorosilicone additive is 5: 2: 1; adding a catalytic amount of the initiator;
s3: putting the modified composite fiber obtained in the step S2, polytetrafluoroethylene resin and polyether-ether-ketone powder into a high-speed mixer for mixing; the mass ratio of the modified composite fiber to the polytetrafluoroethylene resin to the polyether-ether-ketone is (5): 10: 20;
s4: and (5) melting and extruding the material mixed in the step (S3), cooling and cutting into granules, wherein the melting and extruding temperature is 350 ℃, and obtaining the modified polyether-ether-ketone-based composite material.
The preparation method of the reactive surfactant comprises the following steps: dissolving 2, 6-dimethyl-4-vinylpyridine 10g in tetrahydrofuran, adding 1-bromo-2-methyl-octane to react, wherein the molar ratio of 2, 6-dimethyl-4-vinylpyridine to 1-bromo-2-methyl-octane is 1: 1, adding an excessive sodium fluoborate aqueous solution, completely precipitating the solution, filtering the precipitate and recrystallizing a filter cake to obtain the sodium fluoborate aqueous solution.
The preparation method of the fluorosilicone additive is the same as that of example 1.
Comparative example 1
This comparative example was a preparation method of a modified polyetheretherketone-based composite material, which was substantially the same as in example 1, except that the composite fiber was not treated in step S1.
Comparative example 2
This comparative example was a preparation method of a modified polyetheretherketone-based composite material, which was substantially the same as in example 1, except that 4-methylpyridine, which is the raw material in the reactive surfactant preparation method of step S2, was replaced with 4-methylpyridine.
Comparative example 3
The comparative example preparation method of the modified polyetheretherketone-based composite material was substantially the same as in example 1, except that no fluorosilicone additive was added in step S2.
The composite materials based on modified polyether-ether-ketone prepared in the embodiments 1 to 3 and the comparative examples 1 to 3 are prepared into polyether-ether-ketone composite fiber yarns under the same process conditions, the polyether-ether-ketone composite fiber yarns are woven into plain fabrics (both the warp density and the weft density are 32 yarns/cm), then corresponding performance tests are carried out, and the performance results are shown in table 1:
wherein, the cantilever beam impact strength is tested according to ISO 180/A; tensile strength and elongation at break were tested according to ISO 527; limiting oxygen index test: the test was performed with reference to the national standard GB/T2406. And (3) testing the wear resistance: the test was carried out in accordance with the standard GB/T13775 (test conditions: weight 395g, sample size 100mm diameter circular fabric, covering the surface of a wear-resistant instrument for friction test, and measuring the amount of fabric wear after 5 ten thousand rubs). Testing the thermal expansion coefficient: the test was carried out with reference to ISO 11359.
And (3) corrosion resistance testing: 3 parts of the samples prepared in examples 1 to 3 and comparative examples 1 to 3 were immersed in 10 wt% hydrochloric acid, sodium hydroxide and sodium chloride solutions for 72 hours, and the surface change was observed.
TABLE 1
The foregoing shows and describes the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a composite material based on modified polyether-ether-ketone is characterized by comprising the following steps:
s1: placing the composite fiber into a high-pressure kettle, introducing carbon dioxide into the high-pressure kettle, heating and boosting the pressure to keep the composite fiber in a supercritical state for 5-10 min, and swelling; after pressure relief, adding a solution compounded by potassium permanganate and ionic liquid, introducing carbon dioxide again, heating and boosting the pressure to keep the pressure in a supercritical state for 1-5 min; after pressure relief, washing the mixture for multiple times by using absolute ethyl alcohol until the mixture is neutral, and drying the mixture until the weight is constant for later use;
s2: uniformly dispersing the composite fiber treated in the step S1 in a reactive surfactant, adding a mixed solution compounded by an acrylate monomer, a fluorine-silicon additive and an initiator, heating to 120-160 ℃, and reacting to obtain a modified composite fiber;
s3: putting the modified composite fiber obtained in the step S2, polytetrafluoroethylene resin and polyether-ether-ketone powder into a high-speed mixer for mixing;
s4: and (5) melting and extruding the material mixed in the step (S3), cooling and granulating to obtain the modified polyether-ether-ketone-based composite material.
2. The preparation method of the modified polyetheretherketone-based composite material of claim 1, wherein the composite fiber is prepared by mixing the following components in a mass ratio of 1-5: 1 ceramic fibers and glass fibers.
3. The method for preparing the modified polyetheretherketone-based composite material of claim 1, wherein the ionic liquid is at least one of a pyridine ionic liquid, a carboxylic acid ionic liquid or an imidazole ionic liquid.
4. The method for preparing the modified polyetheretherketone-based composite material of claim 1, wherein the reactive surfactant is prepared by first reacting a mixture of the following components in a molar ratio of 1: 1, reacting with bromoalkane, then adding an aqueous solution of sodium fluoborate to precipitate the solution, filtering the precipitate, and recrystallizing the filter cake to obtain the sodium fluoborate-containing aqueous solution.
5. The method according to claim 4, wherein the pyridine compound is at least one selected from the group consisting of 4-vinylpyridine, 4- (1-penten-3-yl) pyridine, and 2, 6-dimethyl-4-vinylpyridine.
6. The method of claim 4, wherein the brominated alkane is at least one of 1-bromo-2-methylhexane, 1-bromo-6-methylheptane, 1-bromooctane, and 1-bromo-2-methyl-octane.
7. The method of claim 1, wherein the acrylate monomer is at least one of butyl acrylate, ethyl acrylate, methyl methacrylate, and butyl methacrylate.
8. The method for preparing the modified polyetheretherketone-based composite material of claim 1, wherein the fluorosilicone additive is prepared by the following steps: dissolving 3,3, 3-trifluoropropyltrimethoxysilane 20-30 g in a dichloromethane solvent 250mL, adding 3-7 mL of dilute hydrochloric acid for hydrolysis reaction to obtain a cage-type polysilsesquioxane intermediate, adding a triethylamine solution of acryloyloxy methyl trimethoxysilane with the mass concentration of 20-40%, and performing ring closing reaction to obtain the fluorine silicon additive.
9. The method for preparing a modified polyetheretherketone-based composite material according to claim 1, wherein the initiator is at least one of an azo initiator or a peroxide initiator.
10. The composite material based on the modified polyetheretherketone is characterized by being prepared by the preparation method of the composite material based on the modified polyetheretherketone according to any one of claims 1 to 9.
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| CN107057276A (en) * | 2017-05-16 | 2017-08-18 | 广东盟信塑胶实业有限公司 | A kind of glass-fiber reinforced antistatic polyether-ether-ketone composite material and preparation method |
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| US20210179805A1 (en) * | 2019-12-11 | 2021-06-17 | Changsha University Of Science And Technology | Polyetheretherketone composite and method of preparing same |
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| CN107057276A (en) * | 2017-05-16 | 2017-08-18 | 广东盟信塑胶实业有限公司 | A kind of glass-fiber reinforced antistatic polyether-ether-ketone composite material and preparation method |
| US20210179805A1 (en) * | 2019-12-11 | 2021-06-17 | Changsha University Of Science And Technology | Polyetheretherketone composite and method of preparing same |
| CN112778560A (en) * | 2020-11-24 | 2021-05-11 | 宁波康加分电器科技有限公司 | Easily-cleaned filter element composite material for juicer and preparation method thereof |
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