CN118146612B - Modified PEEK polymer composite material, cable prepared from modified PEEK polymer composite material and application of cable - Google Patents
Modified PEEK polymer composite material, cable prepared from modified PEEK polymer composite material and application of cable Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical class OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 title claims abstract 16
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 100
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 100
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 26
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 26
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 229920001400 block copolymer Polymers 0.000 claims abstract description 11
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000012965 benzophenone Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- VINASSTWBVKERF-UHFFFAOYSA-N (3-aminophenyl)-(2,4-dihydroxyphenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C(=CC(O)=CC=2)O)=C1 VINASSTWBVKERF-UHFFFAOYSA-N 0.000 claims 3
- VMJXNOKTPKNUJR-MTJSOVHGSA-N 1-[2-[(z)-(9-hydroxy-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-5-ylidene)methyl]thiophen-3-yl]ethanone Chemical compound C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1C(C)=O VMJXNOKTPKNUJR-MTJSOVHGSA-N 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 18
- 230000032683 aging Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 4
- 229910000905 alloy phase Inorganic materials 0.000 abstract description 3
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 6
- 210000000170 cell membrane Anatomy 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- OFUDNGNUCIBARK-UHFFFAOYSA-N (3-amino-2,4-dihydroxyphenyl)-phenylmethanone Chemical compound NC1=C(O)C=CC(C(=O)C=2C=CC=CC=2)=C1O OFUDNGNUCIBARK-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- HMHFERXOZSZRML-UHFFFAOYSA-M trimethyl-(3-methyloxiran-2-yl)azanium;chloride Chemical compound [Cl-].CC1OC1[N+](C)(C)C HMHFERXOZSZRML-UHFFFAOYSA-M 0.000 description 4
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/02—Condensation polymers of aldehydes or ketones with phenols only of ketones
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/36—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes condensation products of phenols with aldehydes or ketones
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The invention relates to the technical field of polyether-ether-ketone, and discloses a modified PEEK polymer composite material, a cable prepared from the modified PEEK polymer composite material and application thereof, wherein the modified PEEK polymer composite material comprises, by mass, 55-82 parts of anti-ultraviolet modified polyether-ether-ketone, 18-45 parts of polyphenylene sulfide, 0.3-0.8 part of compatibilizer and 0.2-0.4 part of antioxidant. The 2-hydroxy diphenyl ketone ultraviolet resistant structure is chemically bonded into the polyether-ether-ketone molecular chain, so that the composite material has excellent ultraviolet aging resistance and antibacterial property. The maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer or the maleic anhydride grafted styrene-butadiene-styrene block copolymer is used as a compatibilizer, so that the polyether-ether-ketone and the polyphenylene sulfide have better interfacial compatibility, an alloy phase is formed between the polyether-ether-ketone and the polyphenylene sulfide, and the impact strength of the composite material is remarkably improved. Has good application effect in the fields of wire and cable sheath materials and the like.
Description
Technical Field
The invention relates to the technical field of polyether-ether-ketone, in particular to a modified PEEK polymer composite material, a cable prepared from the modified PEEK polymer composite material and application of the cable.
Background
The electric wire and cable mainly comprises a conductor, an insulating layer, a sheath material and the like, wherein the sheath material has great influence on the service performance of the cable. The current cable sheath material is mainly prepared from polyvinyl chloride, polyethylene, rubber, polyether ether ketone (PEEK) and the like. The polyether-ether-ketone has excellent high temperature resistance, insulating property and corrosion resistance, and can be widely applied to the fields of engineering plastics, cable sheath materials and the like. And the polyether-ether-ketone is compounded with high polymer materials such as polyphenylene sulfide and polyimide, so that alloy or composite materials with better performance can be obtained. Improving the comprehensive properties of the polyether-ether-ketone, such as mechanical strength, ultraviolet resistance, antibacterial property and the like, and expanding the practical application of the polyether-ether-ketone in the fields of cable sheath materials and the like is a research hot spot field. Chinese patent CN105482454B discloses a polyphenylene sulfide/polyether ether ketone conductive composite material, and a preparation method and application thereof, wherein the composite material obtained by using polyphenylene sulfide, polyether ether ketone, carbon nanotubes, graphene and the like as raw materials has excellent conductive performance, but the patent uses graphene and carbon nanotubes which are expensive. And the compatibility between the polyphenylene sulfide and the polyether-ether-ketone is poor, and the polyphenylene sulfide and the polyether-ether-ketone are physically blended, so that a composite material with excellent mechanical properties is difficult to obtain.
Disclosure of Invention
The invention solves the problems of poor ultraviolet resistance, no antibacterial property and the like of the polyether-ether-ketone material. Practical application of the polyether-ether-ketone in the electric wire and cable is expanded.
The technical scheme of the invention is as follows:
The modified PEEK polymer composite material comprises, by mass, 55-82 parts of ultraviolet-resistant modified polyether-ether-ketone, 18-45 parts of polyphenylene sulfide, 0.3-0.8 part of compatibilizer and 0.2-0.4 part of antioxidant.
Further, the preparation method of the ultraviolet resistant modified polyether-ether-ketone comprises the following steps:
(1) Adding 2, 4-dihydroxyl-3-aminobenzophenone and 2, 3-epoxypropyl trimethyl ammonium chloride into ethanol, reacting for 18-24 hours at 40-70 ℃ in nitrogen atmosphere, concentrating under reduced pressure, washing with distilled water, and recrystallizing with ethanol to obtain 2, 4-dihydroxyl-3-quaternary ammonium salt benzophenone; the structural formula is as follows: 。
(2) Adding sulfonated polyether-ether-ketone into dimethyl sulfoxide, stirring, adding sodium hydroxide to control the pH of the solution to 8-9, adding 2, 4-dihydroxyl-3-quaternary ammonium salt benzophenone, reacting at 30-50 ℃ for 12-24h, adding ethanol into the reacted solution until a large amount of precipitate is separated out, filtering, washing with ethanol, and drying at 80 ℃ for 3h to obtain the anti-ultraviolet modified polyether-ether-ketone.
Further, the compatibilizer is a maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer or a maleic anhydride grafted styrene-butadiene-styrene block copolymer.
Further, the molar amount of 2, 3-epoxypropyl trimethyl ammonium chloride in (1) is 100-110% of the molar amount of 2, 4-dihydroxy-3-aminobenzophenone.
Further, the mass of the 2, 4-dihydroxyl-3-quaternary ammonium salt benzophenone in the step (2) is 4-20% of the mass of the sulfonated polyether-ether-ketone.
Further, the preparation method of the modified PEEK polymer composite material comprises the following steps: adding 55-82 parts of uvioresistant modified polyether-ether-ketone, 18-45 parts of polyphenylene sulfide, 0.3-0.8 part of compatibilizer and 0.2-0.4 part of antioxidant into a high-speed mixer, uniformly mixing, adding into a torque rheometer, melting and blending at 270-300 ℃ for 15-30min, and discharging to obtain the modified PEEK polymer composite material.
Further, the sheath material and the cable are prepared from the modified PEEK polymer composite material.
Further, the modified PEEK polymer composite material is applied to sheath materials and cables.
The invention has the technical effects that: the sulfonated polyether-ether-ketone is alkalized by sodium hydroxide to generate sodium sulfonate groups, and the sodium sulfonate groups can be subjected to electrostatic interaction with quaternary ammonium salt cations of 2, 4-dihydroxyl-3-quaternary ammonium salt benzophenone, so that the 2-hydroxybenzophenone ultraviolet-resistant structure is chemically bonded into a polyether-ether-ketone molecular chain, the compatibility between an ultraviolet-resistant absorbent and the polyether-ether-ketone is improved, and therefore the impact strength and other mechanical properties of the polyether-ether-ketone composite material are not influenced. The 2-hydroxy diphenyl ketone ultraviolet resistant structure can absorb the energy of ultraviolet radiation, the enol-quinone type interconversion structure is used for converting the ultraviolet energy into heat energy, the ultraviolet light is prevented from photodegradation on the polyether-ether-ketone composite material, and the impact strength of the composite material is hardly reduced through an ultraviolet ageing experiment, so that the excellent ultraviolet ageing resistance is shown.
The modified PEEK polymer composite material is added with the maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer or the maleic anhydride grafted styrene-butadiene-styrene block copolymer as the compatibilizer, the compatibilizer has good interfacial compatibility with polyphenylene sulfide, the compatibilizer contains anhydride groups and can react with hydroxyl groups of 2, 4-dihydroxyl-3-quaternary ammonium salt benzophenone bonded in a polyether-ether-ketone molecular chain, so that the compatibilizer has good interfacial force with the polyether-ether-ketone, and under the action of the compatibilizer, the polyether-ether-ketone and the polyphenylene sulfide have better interfacial compatibility, an alloy phase is formed between the two, and the impact strength of the composite material is remarkably improved.
The 2, 4-dihydroxyl-3-quaternary ammonium salt benzophenone of the invention contains a unique quaternary ammonium salt antibacterial structure, and is bonded into a molecular chain of polyether-ether-ketone to form an antibacterial macromolecular polymer, compared with a small molecular antibacterial agent, the macromolecular polymer has better high temperature resistance, the phenomenon of thermal decomposition of the antibacterial agent is difficult to occur in the high-temperature melting and blending process, N + cation contained in the quaternary ammonium salt antibacterial structure can act with a bacterial cell membrane to change the permeability of the cell membrane, so that substances in the bacterial cell membrane flow out, thereby influencing the reproduction metabolism of bacteria and playing an excellent bactericidal effect.
The modified PEEK polymer composite material has excellent mechanical strength, ultraviolet aging resistance and antibacterial property, and has good practical application in the fields of wire and cable sheath materials and the like.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are 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.
According to the method of "study of ultraviolet resistant reactive dye" of university of great company's university paper, 2, 4-dihydroxy-3-aminobenzophenone is prepared with the structural formula of。
And (3) drying 10g of polyether-ether-ketone, adding the dried polyether-ether-ketone into 98% of concentrated sulfuric acid, reacting for 6 hours at room temperature, pouring the solution into ice water, uniformly mixing, filtering, washing with distilled water, and drying to obtain the sulfonated polyether-ether-ketone.
The polyether-ether-ketone model KT-820 SL10 is a plastic raw material for the Shandong Fengyu in Dongguan city.
Polyphenylene sulfide, raw material specification PPS 0335; shenzhen Maite plastic product.
Maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer with the brand FG1901, MAH-SEBS and Dongguan Xin Lili plastic new material.
Example 1:
(1) 60mmol of 2, 4-dihydroxy-3-aminobenzophenone and 66mmol of 2, 3-epoxypropyl trimethyl ammonium chloride are added into 200mL of ethanol, the reaction is carried out for 18h at 70 ℃ in nitrogen atmosphere, the concentration is reduced pressure, the distilled water is used for washing, and the ethanol is used for recrystallization, thus obtaining the 2, 4-dihydroxy-3-quaternary ammonium salt benzophenone. The preparation reaction formula is as follows:
(2) 50g of sulfonated polyether-ether-ketone is added into 500mL of dimethyl sulfoxide, the pH of the solution is controlled to be 8 after stirring, then 2g of 2, 4-dihydroxyl-3-quaternary ammonium salt benzophenone is added, the reaction is carried out for 12 hours at the temperature of 40 ℃, ethanol is added into the solution until a large amount of precipitate is separated out, the solution is washed by ethanol after suction filtration, and the solution is dried for 3 hours at the temperature of 80 ℃ to prepare the ultraviolet-resistant modified polyether-ether-ketone.
(3) 820G of ultraviolet resistant modified polyether-ether-ketone, 180g of polyphenylene sulfide, 8g of compatibilizer maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer and 4g of antioxidant 9228 are put into a high-speed mixer to be uniformly mixed, then are added into a torque rheometer, are subjected to melt blending for 30min at 300 ℃, and are discharged to prepare the modified PEEK polymer composite material.
Example 2:
(1) 60mmol of2, 4-dihydroxy-3-aminobenzophenone and 66mmol of2, 3-epoxypropyl trimethyl ammonium chloride are added into 150mL of ethanol, the reaction is carried out for 18h at 65 ℃ in nitrogen atmosphere, the concentration is reduced, the distilled water is used for washing, and the ethanol is used for recrystallization, thus obtaining the 2, 4-dihydroxy-3-quaternary ammonium salt benzophenone.
(2) 50G of sulfonated polyether-ether-ketone is added into 600mL of dimethyl sulfoxide, the pH of the solution is controlled to be 9 after stirring, then 6g of 2, 4-dihydroxyl-3-quaternary ammonium salt benzophenone is added, the reaction is carried out for 12 hours at the temperature of 50 ℃, ethanol is added into the solution until a large amount of precipitate is separated out, the solution is washed by ethanol after suction filtration, and the solution is dried for 3 hours at the temperature of 80 ℃ to prepare the ultraviolet-resistant modified polyether-ether-ketone.
(3) 620G of anti-ultraviolet modified polyether-ether-ketone, 380g of polyphenylene sulfide, 5g of compatibilizer maleic anhydride grafted styrene-butadiene-styrene block copolymer and 4g of antioxidant 9228 are put into a high-speed mixer to be mixed uniformly, then are added into a torque rheometer, melt-mixed for 15min at 300 ℃, and are discharged to prepare the modified PEEK polymer composite material.
Example 3:
(1) 60mmol of2, 4-dihydroxy-3-aminobenzophenone and 60mmol of2, 3-epoxypropyl trimethyl ammonium chloride are added into 150mL of ethanol, the reaction is carried out for 24 hours at the temperature of 40 ℃ in nitrogen atmosphere, the mixture is concentrated under reduced pressure, washed by distilled water and recrystallized by ethanol, and the 2, 4-dihydroxy-3-quaternary ammonium salt benzophenone is prepared.
(2) 50G of sulfonated polyether-ether-ketone is added into 800mL of dimethyl sulfoxide, the pH of the solution is controlled to be 8 after stirring, then 10g of 2, 4-dihydroxyl-3-quaternary ammonium salt benzophenone is added, the reaction is carried out for 24 hours at the temperature of 30 ℃, ethanol is added into the solution until a large amount of precipitate is separated out, the solution is washed by ethanol after suction filtration, and the solution is dried for 3 hours at the temperature of 80 ℃ to prepare the ultraviolet-resistant modified polyether-ether-ketone.
(3) 550G of anti-ultraviolet modified polyether-ether-ketone, 450g of polyphenylene sulfide, 3g of compatibilizer maleic anhydride grafted styrene-butadiene-styrene block copolymer and 2g of antioxidant 9228 are put into a high-speed mixer to be mixed uniformly, then are added into a torque rheometer, are subjected to melt blending for 30min at 270 ℃, and are discharged to prepare the modified PEEK polymer composite material.
Comparative example 1:
(1) 820g of sulfonated polyether-ether-ketone, 180g of polyphenylene sulfide, 8g of compatibilizer maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer and 4g of antioxidant 9228 are put into a high-speed mixer to be mixed uniformly, then are added into a torque rheometer, are subjected to melt blending for 30min at 300 ℃, and are discharged to prepare the modified PEEK polymer composite material.
Comparative example 2:
(1) 60mmol of2, 4-dihydroxy-3-aminobenzophenone and 66mmol of2, 3-epoxypropyl trimethyl ammonium chloride are added into 200mL of ethanol, the reaction is carried out for 18h at 70 ℃ in nitrogen atmosphere, the concentration is reduced pressure, the distilled water is used for washing, and the ethanol is used for recrystallization, thus obtaining the 2, 4-dihydroxy-3-quaternary ammonium salt benzophenone.
(2) 50G of polyether-ether-ketone and 2g of 2, 4-dihydroxy-3-quaternary ammonium salt benzophenone are added into 500mL of dimethyl sulfoxide, and the mixture is blended for 12 hours at the temperature of 40 ℃ and dried for 3 hours at the temperature of 80 ℃ to prepare the ultraviolet-resistant modified polyether-ether-ketone.
(3) 820G of ultraviolet resistant modified polyether-ether-ketone, 180g of polyphenylene sulfide, 8g of compatibilizer maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer and 4g of antioxidant 9228 are put into a high-speed mixer to be uniformly mixed, then are added into a torque rheometer, are subjected to melt blending for 30min at 300 ℃, and are discharged to prepare the modified PEEK polymer composite material.
Comparative example 3:
(1) 60mmol of2, 4-dihydroxy-3-aminobenzophenone and 66mmol of2, 3-epoxypropyl trimethyl ammonium chloride are added into 200mL of ethanol, the reaction is carried out for 18h at 70 ℃ in nitrogen atmosphere, the concentration is reduced pressure, the distilled water is used for washing, and the ethanol is used for recrystallization, thus obtaining the 2, 4-dihydroxy-3-quaternary ammonium salt benzophenone.
(2) 50G of sulfonated polyether-ether-ketone is added into 500mL of dimethyl sulfoxide, the pH of the solution is controlled to be 8 after stirring, then 2g of 2, 4-dihydroxyl-3-quaternary ammonium salt benzophenone is added, the reaction is carried out for 12 hours at the temperature of 40 ℃, ethanol is added into the solution until a large amount of precipitate is separated out, the solution is washed by ethanol after suction filtration, and the solution is dried for 3 hours at the temperature of 80 ℃ to prepare the ultraviolet-resistant modified polyether-ether-ketone.
(3) 820G of ultraviolet resistant modified polyether-ether-ketone, 180g of polyphenylene sulfide and 4g of antioxidant 9228 are put into a high-speed mixer to be mixed uniformly, then are added into a torque rheometer, are melt-blended for 30min at 300 ℃, and are discharged to prepare the modified PEEK polymer composite material.
Impact strength of the composite material according to GB/T1843-2008. Each sample was tested 5 times and averaged.
And (3) carrying out an artificial accelerated aging test on the composite material by adopting an ultraviolet aging test box. The ultraviolet lamp source is a 800W high-pressure mercury lamp, the test temperature is 80 ℃, and the aging time is 90 days. The impact strength was then measured again. Each sample was tested 5 times and averaged. The test results are shown in Table 1.
Table 1 impact strength test of modified PEEK polymer composites:
The modified PEEK polymer composites of examples 1 to 3 were tested to have an impact strength of 44.5-59.3 kJ/m 2. The sulfonated polyether-ether-ketone is alkalized by sodium hydroxide to generate sodium sulfonate groups, and the sodium sulfonate groups can be subjected to electrostatic interaction with quaternary ammonium salt cations of 2, 4-dihydroxyl-3-quaternary ammonium salt benzophenone, so that the ultraviolet-resistant structure of the 2-hydroxybenzophenone is chemically bonded into a polyether-ether-ketone molecular chain, the compatibility between an ultraviolet-resistant absorbent and the polyether-ether-ketone is improved, and the impact strength and other mechanical properties of the polyether-ether-ketone composite material are not influenced. The 2-hydroxy diphenyl ketone ultraviolet resistant structure can absorb the energy of ultraviolet radiation, the enol-quinone type interconversion structure is used for converting the ultraviolet energy into heat energy, the ultraviolet light is prevented from photodegradation on the polyether-ether-ketone composite material, the impact strength of the composite material is hardly reduced through an ultraviolet ageing experiment, the retention rate reaches 98.65-99.83%, and the excellent ultraviolet ageing resistance is shown.
The modified PEEK polymer composite materials of examples 1 to 3 are added with maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer or maleic anhydride grafted styrene-butadiene-styrene block copolymer as a compatibilizer, the compatibilizer has good interfacial compatibility with polyphenylene sulfide, and the compatibilizer contains anhydride groups and can react with hydroxyl groups of 2, 4-dihydroxy-3-quaternary ammonium salt benzophenone bonded in a polyether-ether-ketone molecular chain, so that the compatibilizer has good interfacial force with polyether-ether-ketone, and under the action of the compatibilizer, the polyether-ether-ketone and the polyphenylene sulfide have better interfacial compatibility, an alloy phase is formed between the two, and the impact strength of the composite material is remarkably improved.
The compatibilizer maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer is added in the comparative example 1, the interface compatibility between the polyether-ether-ketone and the polyphenylene sulfide is good, the impact strength of the composite material is high, but the composite material does not contain the 2-hydroxybenzophenone anti-ultraviolet structure, and through ultraviolet aging experiments, the impact strength of the composite material is greatly reduced, and the anti-ultraviolet aging performance is poor.
The polyether-ether-ketone of comparative example 2 does not contain sodium sulfonate groups, cannot interact electrostatically with 2, 4-dihydroxy-3-quaternary ammonium salt benzophenone, and is in a physical blending state, so that the ultraviolet-resistant absorbent cannot have chemical bonding effect with the polyether-ether-ketone, and the poor compatibility of the ultraviolet-resistant absorbent and the polyether-ether-ketone can influence the impact strength of the composite material, namely, the impact strength is only 53.1 kJ/m 2. The impact strength of the composite material is obviously reduced through ultraviolet ageing experiments, namely 2, 4-dihydroxyl-3-quaternary ammonium salt benzophenone is not chemically bonded into polyether-ether-ketone, a macromolecular polymer with high thermal stability is not formed by the two, and the compound still exists in the composite material in the form of a micromolecular compound, so that the phenomenon of thermal decomposition of the 2, 4-dihydroxyl-3-quaternary ammonium salt benzophenone possibly exists in the subsequent high-temperature melt blending process, and the ultraviolet ageing performance of the composite material is poor.
Comparative example 3, in which the compatibilizer maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer was not added, had poor interfacial compatibility between polyetheretherketone and polyphenylene sulfide, and the impact strength of the composite material was very low, only 38.6 kJ/m 2.
Antibacterial property test of modified PEEK polymer composite: taking escherichia coli or staphylococcus aureus as a test strain; the antibacterial performance of the composite material is tested according to the method of QB/T2591-2003, and the composite material is treated by adopting a film sticking method; the modified PEEK polymer composite of comparative example 1 was used as a blank control. The modified PEEK polymer composites of examples 1-3 and comparative examples 2-3 were used as antibacterial test samples, respectively.
And (3) determining the total number of colonies after the composite material is contacted with the test strain for 24 hours according to a GB/T4789.2-2003 method, and calculating the bacteriostasis rate R.
R= (B-C)/bx 100%. B is the average number of recovered colonies for the control blank. C is the average number of recovered colonies of the antibacterial coupon samples. The test results are shown in Table 2.
Table 2 antibacterial performance test of modified PEEK polymer composites:
The modified PEEK polymer composites of examples 1-3, and comparative example 3, were tested to show good antimicrobial properties against both E.coli and Staphylococcus aureus. The 2, 4-dihydroxy-3-quaternary ammonium salt diphenyl ketone contains a unique quaternary ammonium salt antibacterial structure, and is bonded into a molecular chain of polyether-ether-ketone to form an antibacterial macromolecular polymer, compared with a micromolecular antibacterial agent, the macromolecular polymer has better high-temperature resistance, and in the high-temperature melt blending process, the phenomenon of thermal decomposition of the antibacterial agent is difficult to occur, N + cations contained in the quaternary ammonium salt antibacterial structure can act with the cell membrane of bacteria, so that the permeability of the cell membrane is changed, substances in the cell membrane of the bacteria are caused to flow out, the reproduction metabolism of the bacteria is affected, and an excellent sterilization effect is achieved.
In comparative example 2, 4-dihydroxy-3-quaternary ammonium benzophenone and polyetheretherketone were physically blended, and the two were not chemically bonded to each other, and a macromolecular antibacterial polymer was not formed. In the subsequent high-temperature melting process, the 2, 4-dihydroxyl-3-quaternary ammonium salt benzophenone can be thermally decomposed, so that the antibacterial rate of the composite material is obviously reduced.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The modified PEEK polymer composite material is characterized by comprising, by mass, 55-82 parts of anti-ultraviolet modified polyether-ether-ketone, 18-45 parts of polyphenylene sulfide, 0.3-0.8 part of compatibilizer and 0.2-0.4 part of antioxidant;
the preparation method of the anti-ultraviolet modified polyether-ether-ketone comprises the following steps:
(1) Adding 2, 4-dihydroxyl-3 '-aminobenzophenone and 2, 3-epoxypropyl trimethyl ammonium chloride into ethanol, reacting in nitrogen atmosphere, concentrating under reduced pressure, washing, and recrystallizing to obtain 2, 4-dihydroxyl-3' -quaternary ammonium salt benzophenone;
The structural formula of the 2, 4-dihydroxy-3' -aminobenzophenone is as follows: ；
The structural formula of the 2, 4-dihydroxy-3' -quaternary ammonium salt diphenyl ketone is as follows: ；
(2) Adding sulfonated polyether-ether-ketone into dimethyl sulfoxide, stirring, adding sodium hydroxide, adding 2, 4-dihydroxyl-3' -quaternary ammonium salt diphenyl ketone for reaction, adding ethanol into the reaction solution after the reaction, filtering, washing, and drying to obtain the anti-ultraviolet modified polyether-ether-ketone.
2. The modified PEEK polymer composite of claim 1, wherein the compatibilizer is a maleic anhydride grafted styrene-ethylene-butadiene-styrene block copolymer or a maleic anhydride grafted styrene-butadiene-styrene block copolymer.
3. The modified PEEK polymer composite of claim 1, wherein the molar amount of 2, 3-epoxypropyl trimethyl ammonium chloride in (1) is 100-110% of the molar amount of 2, 4-dihydroxy-3' -aminobenzophenone.
4. A modified PEEK polymer composite according to claim 3, wherein the reaction in (1) is carried out at a temperature of 40-70 ℃ for 18-24 hours.
5. The modified PEEK polymer composite of claim 1, wherein the pH of the added sodium hydroxide control solution of (2) is 8-9.
6. The modified PEEK polymer composite of claim 1, wherein the mass of 2, 4-dihydroxy-3' -quaternary ammonium salt benzophenone in (2) is 4-20% of the mass of sulfonated polyetheretherketone.
7. The modified PEEK polymer composite of claim 1, wherein the reaction of (2) is performed at a temperature of 30-50 ℃ for 12-24 hours.
8. The method for preparing the modified PEEK polymer composite material according to any one of claims 1 to 7, wherein 55 to 82 parts of anti-ultraviolet modified polyether ether ketone, 18 to 45 parts of polyphenylene sulfide, 0.3 to 0.8 part of compatibilizer and 0.2 to 0.4 part of antioxidant are put into a high-speed mixer to be uniformly mixed, then the mixture is added into a torque rheometer, and the mixture is subjected to melt blending at 270 to 300 ℃ for 15 to 30 minutes, and then discharged to prepare the modified PEEK polymer composite material.
9. A cable made from the modified PEEK polymer composite of any one of claims 1-7.
10. Use of the modified PEEK polymer composite made by the method of claim 8 in cables.
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