CN114621557B - 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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- 239000002131 composite material Substances 0.000 title claims abstract description 89
- 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 22
- 239000000835 fiber Substances 0.000 claims abstract description 53
- 239000004094 surface-active agent Substances 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- -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
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 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
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000919 ceramic Substances 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
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium 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
- 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
- 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 4
- 150000001335 aliphatic alkanes Chemical class 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 229920006351 engineering plastic Polymers 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 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
- 238000005299 abrasion Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 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
- 239000000155 melt Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical group CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 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
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000005056 compaction 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group 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
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a preparation method of a modified polyether-ether-ketone based composite material, which comprises the following steps of S1: swelling the composite fiber in a supercritical state; adding potassium permanganate and ionic liquid, and keeping the supercritical state again; s2: dispersing the modified composite fiber in a reactive surfactant, and then adding a mixed solution compounded by acrylate monomers, a fluorosilicone additive and an initiator to react to obtain the modified composite fiber; s3: mixing the mixture with polytetrafluoroethylene resin and polyether-ether-ketone; s4: and (3) carrying out melt extrusion on 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 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.
Description
Technical Field
The invention relates to the technical field of polyether-ether-ketone engineering plastics, in particular to a modified polyether-ether-ketone based composite material and a preparation method thereof.
Background
Polyether-ether-ketone (PEEK) is an ultra-high performance special engineering plastic developed in the 80 th century, and has excellent comprehensive performance because PEEK belongs to an aromatic crystalline thermoplastic polymer material, the melting point of PEEK is 334 ℃, and the PEEK can replace traditional materials such as metal, ceramic and the like in a plurality of special fields, so that PEEK becomes one of the most popular high performance engineering plastics at present and is widely applied to the fields of aerospace, automobile industry, energy nuclear power, electronics, electric and medical machinery and the like. However, the PEEK raw material unit price is high, and along with the development of large-size products of the project, the PEEK raw material is only used for application, so that the manufacturing cost and the cost of the project are greatly improved. The performance of the PEEK pure material is difficult to meet different requirements in different industries, so the PEEK needs to be modified in special working environments, and the main means of the PEEK pure material comprise blending modification, copolymerization modification, composite reinforcement modification, compaction modification, nano modification, surface modification and other technologies. The application aims to obtain the modified polyether-ether-ketone composite material with excellent comprehensive performance through the mixed modification treatment of the composite fiber and the polytetrafluoroethylene, so that the application range of the polyether-ether-ketone material is widened, and the use cost of the material is reduced.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a modified polyether-ether-ketone-based composite material to solve the problem that the performance of the pure polyether-ether-ketone material is difficult to meet the requirement of continuous and stable use for a long time under severe working conditions.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing a modified polyetheretherketone-based composite material, the method comprising the steps of:
S1: putting the composite fiber into an autoclave, introducing carbon dioxide into the autoclave, heating and boosting the pressure to keep the 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 pressure to keep the supercritical state for 1-5 min; after pressure relief, washing for many times by using absolute ethyl alcohol to be neutral, and drying to constant weight for standby; the mass ratio of the potassium permanganate, the ionic liquid and the composite fiber is 1-3: 20:10 to 15 percent; the invention firstly swells the composite fiber by supercritical carbon dioxide, then further softens the composite fiber under the strong oxidation action of potassium permanganate, combines the strong dissolution capability of ionic liquid, and makes the surface and the inside of the composite fiber carry out hydrophilic modification and ionization treatment under the action of supercritical carbon dioxide. The composite fiber treated in the step S1 is easier to disperse in the reactive surfactant in the step S2, so that the modification reaction treatment can be efficiently performed on the surface and the 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 acrylate monomers, a fluorosilicone 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 mol ratio of the reactive surfactant to the acrylic ester monomer to the fluorosilicone additive is 1-5: 1-2: 1, a step of; the initiator is added with a proper amount;
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 3-5: 4-10: 20, a step of;
S4: and (3) carrying out melt extrusion on the materials mixed in the step (S3), cooling and granulating to obtain the modified polyether-ether-ketone-based composite material.
Preferably, the composite fiber consists of the following components in percentage by mass of 1-5: 1 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 the following steps of: 1, then adding aqueous solution of sodium fluoborate to precipitate the solution, filtering the precipitate, and recrystallizing the filter cake. The reactive surfactant of the application firstly carries out substitution reaction on bromine atoms on bromoalkane and nitrogen atoms in pyridine ring to obtain pyridine salt grafted with alkane branched chains, and further carries out ion exchange action of bromide ions and fluoroborate to obtain the ionic reactive surfactant. The ionization reaction type surfactant promotes the uniform dispersion effect of the composite fiber treated in the step S1, and simultaneously 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, 2, 6-dimethyl-4-vinylpyridine. The application selects the pyridine compound with unsaturated double bond for synthesizing the reactive surfactant, and makes the pyridine compound with unsaturated double bond and the acrylic ester monomer and the fluorosilicone additive perform three-dimensional crosslinking reaction on the surface and the internal 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 bromoalkane is at least one of 1-bromo-2-methylhexane, 1-bromo-6-methylheptane, 1-bromooctane, 1-bromo-2-methyl-octane. The application preferably grafts long-chain alkane on pyridine compound, and further improves the performance requirements of impact resistance, peeling resistance and the like of the composite fiber through the molecular winding action 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 20-30 g of 3, 3-trifluoro propyl trimethoxy silane in 250mL of dichloromethane solvent, adding 3-7 mL of dilute hydrochloric acid for hydrolysis reaction to obtain a cage polysilsesquioxane intermediate, and then adding a triethylamine solution of 20-40% of acryloyloxy methyl trimethoxy silane for ring closure reaction to obtain the fluorosilicone additive. Wherein, the molar ratio of the acryloxymethyl trimethoxysilane to the cage polysilsesquioxane intermediate is 1: 1.
The fluorosilicone additive is POSS with a cage-shaped framework structure (also called cage-shaped polysilsesquioxane), and the general formula of the fluorosilicone additive is (RSiO 3/2) n, wherein R is a group connected with eight top angle Si atoms. In the application, the cage polysilsesquioxane intermediate, namely seven vertex angles are connected with fluorine-containing groups, and one vertex angle is not closed and is respectively three hydroxyl groups; further, the remaining one corner of the resulting POSS contains the reactive functional group acryloyloxy by reaction with acryloyloxy methyltrimethoxysilane. The acryloyloxy active functional group can carry out cross-linking polymerization reaction with the reactive surfactant and the acrylic ester monomer, a compact functional coating layer is formed on the surface of the composite fiber, and the functional coating layer is grafted with fluorine-containing groups and nano POSS groups, so that the modified polyether-ether-ketone composite material has the effects of corrosion resistance, weather resistance, self lubrication and nano particle small size of the POSS groups of the fluorine-containing groups, the comprehensive performance of the polyether-ether-ketone composite material is obviously improved, and the performances of 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 azo-type initiator or peroxide-type initiator.
In another aspect, the invention provides a modified polyetheretherketone-based composite material, which is prepared by the preparation method of the modified polyetheretherketone-based composite material.
The invention has the beneficial effects that:
the modified polyether-ether-ketone-based composite material prepared by the invention has good comprehensive mechanical properties and environmental properties, has excellent high-temperature resistance, corrosion resistance, stripping resistance and wear resistance, has excellent self-lubricating, flame-retarding and shock resistance, and can meet the high-performance requirements of continuous and stable use for a long time under severe working conditions.
The composite material based on the modified polyether-ether-ketone 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 enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
Example 1
The preparation method of the modified polyether-ether-ketone based composite material comprises the following steps:
s1: the mass ratio is 1:1, putting a composite fiber consisting of ceramic fibers and glass fibers into an autoclave, introducing carbon dioxide into the autoclave, heating and boosting to keep the autoclave in a supercritical state for 5min, and swelling; after pressure release, adding a solution compounded by potassium permanganate and 1-butyl-3-methylimidazole chloride ionic liquid, introducing carbon dioxide again, heating and boosting the pressure to keep the supercritical state for 1min; after pressure relief, washing for many times by using absolute ethyl alcohol to be neutral, and drying to constant weight for standby; the mass ratio of the potassium permanganate, the ionic liquid and 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 butyl acrylate monomers, a fluorosilicone additive and an initiator azo diisobutylamidine 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, preparing a base material; the molar ratio of the reactive surfactant to the butyl acrylate monomer to the fluorosilicone additive is 2:1:1, a step of; the initiator is added with a catalytic amount;
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, a step of;
s4: and (3) carrying out melt extrusion on the materials mixed in the step (S3), cooling and granulating, wherein the melt extrusion 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 1-bromo-2-methylhexane was added to effect the reaction, with the molar ratio of 4-vinylpyridine to 1-bromo-2-methylhexane being 1:1, then adding excessive sodium fluoborate aqueous solution to precipitate the solution, filtering the precipitate and recrystallizing the filter cake.
The preparation method of the fluorosilicone additive comprises the following steps: 20g of 3, 3-trifluoro propyl trimethoxy silane is dissolved in 250mL of dichloromethane solvent, 3mL of diluted hydrochloric acid (10 wt% concentration, the same applies below) is added for hydrolysis reaction to obtain a cage type polysilsesquioxane intermediate, and then a triethylamine solution of 20% mass concentration of acryloyloxy methyl trimethoxy silane is added for ring closure reaction to obtain the fluorosilicone additive. Wherein, the molar ratio of the acryloxymethyl trimethoxysilane to the cage polysilsesquioxane intermediate is 1: 1.
Example 2
The preparation method of the modified polyether-ether-ketone based composite material comprises the following steps:
S1: the mass ratio is 3:1, putting a composite fiber consisting of ceramic fibers and glass fibers into an autoclave, introducing carbon dioxide into the autoclave, heating and boosting to keep the autoclave in a supercritical state for 7min, and swelling; after pressure release, adding a solution compounded by potassium permanganate and 1-butyl-3-methylimidazole chloride ionic liquid, introducing carbon dioxide again, heating and boosting the pressure to keep the supercritical state for 3min; after pressure relief, washing for many times by using absolute ethyl alcohol to be neutral, and drying to constant weight for standby; 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 ethyl acrylate monomer, a fluorosilicone additive and an initiator azo diisobutylamidine hydrochloride, heating to a temperature of 150 ℃, and reacting to obtain a modified composite fiber; the mass ratio of the composite fiber to the reactive surfactant is 20:13; the mol ratio of the reactive surfactant to the ethyl acrylate monomer to the fluorosilicone additive is 3:2:1, a step of; the initiator is added with a catalytic amount;
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, a step of;
s4: and (3) carrying out melt extrusion on the materials mixed in the step (S3), cooling and granulating, wherein the melt extrusion 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 1-bromo-6-methylheptane was added to react, with the molar ratio of 4- (1-penten-3-yl) pyridine to 1-bromo-6-methylheptane being 1:1, then adding excessive sodium fluoborate aqueous solution to precipitate the solution, filtering the precipitate and recrystallizing the filter cake.
The preparation method of the fluorosilicone additive is the same as in example 1.
Example 3
The preparation method of the modified polyether-ether-ketone based composite material comprises the following steps:
S1: the mass ratio is 5:1, putting a composite fiber consisting of ceramic fibers and glass fibers into an autoclave, introducing carbon dioxide into the autoclave, heating and boosting to keep the autoclave in a supercritical state for 10min, and swelling; after pressure release, adding a solution compounded by potassium permanganate and 1-butyl-3-methylimidazole chloride ionic liquid, introducing carbon dioxide again, heating and boosting the pressure to keep the supercritical state for 5min; after pressure relief, washing for many times by using absolute ethyl alcohol to be neutral, and drying to constant weight for standby; the mass ratio of the potassium permanganate, the ionic liquid and 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 methyl methacrylate monomer, a fluorosilicone additive and an initiator azo diisobutylamidine 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 mole ratio of the reactive surfactant to the methyl methacrylate monomer and the fluorosilicone additive is 5:2:1, a step of; the initiator is added with a catalytic amount;
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, a step of;
s4: and (3) carrying out melt extrusion on the materials mixed in the step (S3), cooling and granulating, wherein the melt extrusion 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 2, 6-dimethyl-4-vinylpyridine is dissolved in tetrahydrofuran, 1-bromo-2-methyl-octane is added for reaction, and the molar ratio of the 2, 6-dimethyl-4-vinylpyridine to the 1-bromo-2-methyl-octane is 1:1, then adding excessive sodium fluoborate aqueous solution to precipitate the solution, filtering the precipitate and recrystallizing the filter cake.
The preparation method of the fluorosilicone additive is the same as in example 1.
Comparative example 1
The preparation method of the modified polyetheretherketone-based composite material of the present comparative example is basically the same as that of example 1, except that in the preparation method of the composite material of the present comparative example, the composite fiber is not treated in step S1.
Comparative example 2
The preparation method of the modified polyetheretherketone-based composite material of the present comparative example is basically the same as that of example 1, except that 4-vinylpyridine, which is the raw material in the preparation method of the reactive surfactant in step S2, is replaced with 4-methylpyridine.
Comparative example 3
The preparation method of the modified polyetheretherketone-based composite material of the present comparative example is basically the same as that of example 1, except that the fluorosilicone additive is not added in step S2.
The modified polyetheretherketone-based composite materials prepared in examples 1 to 3 and comparative examples 1 to 3 were prepared into polyetheretherketone composite filaments under the same process conditions and woven into plain fabrics (the warp density and the weft density were 32/cm), and then subjected to corresponding performance tests, the performance results of which are shown in table 1:
wherein, the impact strength of the cantilever beam 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 national standard GB/T2406. Abrasion resistance test: the test was carried out with reference to standard GB/T13775 (test conditions: weight mass 395g, sample size 100mm diameter circular fabric, friction test was carried out by covering the surface of the abrasion-resistant instrument, and the amount of abrasion of the fabric after 5 ten thousand times of friction was tested). Coefficient of thermal expansion test: the test is performed with reference to ISO 11359.
Corrosion resistance test: the samples prepared in examples 1 to 3 and comparative examples 1 to 3 were immersed in hydrochloric acid, sodium hydroxide and sodium chloride solutions having a concentration of 10wt% for 72 hours, respectively, 3 parts each, and the surface change was observed.
TABLE 1
The foregoing has shown and described the basic 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, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims.
Claims (5)
1. The preparation method of the modified polyether-ether-ketone based composite material is characterized by comprising the following steps of:
S1: putting the composite fiber into an autoclave, introducing carbon dioxide into the autoclave, 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 pressure to keep the supercritical state for 1-5 min; after pressure relief, washing for many times by using absolute ethyl alcohol to be neutral, and drying to constant weight for standby;
S2: uniformly dispersing the composite fiber treated in the step S1 in a reactive surfactant, adding a mixed solution compounded by acrylate monomers, a fluorosilicone 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: carrying out melt extrusion on the materials mixed in the step S3, and cooling and granulating to obtain a modified polyether-ether-ketone-based composite material;
The mass ratio of the composite fiber is 1-5: 1 ceramic fibers and glass fibers; the ionic liquid is at least one of pyridine ionic liquid, carboxylic acid ionic liquid or imidazole ionic liquid; the reactive surfactant comprises the following components in percentage by mole: 1, then adding an aqueous solution of sodium fluoborate to precipitate the solution, filtering the precipitate, and recrystallizing a filter cake; the pyridine compound is at least one of 4-vinyl pyridine, 4- (1-pentene-3-yl) pyridine and 2, 6-dimethyl-4-vinyl pyridine; the preparation method of the fluorosilicone additive comprises the following steps: dissolving 20-30 g of 3, 3-trifluoro propyl trimethoxy silane in 250mL of dichloromethane solvent, adding 3-7 mL of dilute hydrochloric acid for hydrolysis reaction to obtain a cage polysilsesquioxane intermediate, and then adding a triethylamine solution of 20-40% of acryloyloxy methyl trimethoxy silane for ring closure reaction to obtain the fluorosilicone additive.
2. The method for preparing a modified polyetheretherketone-based composite material according to claim 1, 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.
3. The method for preparing a modified polyetheretherketone-based composite material according to claim 1, wherein the acrylate monomer is at least one of butyl acrylate, ethyl acrylate, methyl methacrylate and butyl methacrylate.
4. The method for preparing a modified polyetheretherketone-based composite material according to claim 1, wherein the initiator is at least one of azo-type initiator or peroxide-type initiator.
5. A modified polyetheretherketone-based composite material, wherein the composite material is prepared by the method for preparing a modified polyetheretherketone-based composite material according to any one of claims 1 to 4.
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| 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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