CN116462900A - Antioxidant carbon nanotube modified polyethylene composite material and preparation method thereof - Google Patents
Antioxidant carbon nanotube modified polyethylene composite material and preparation method thereof Download PDFInfo
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 88
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 64
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 64
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 49
- -1 polyethylene Polymers 0.000 title claims abstract description 49
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical compound OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 238000002347 injection Methods 0.000 claims abstract description 19
- 239000007924 injection Substances 0.000 claims abstract description 19
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZXUKNOGFRSOORK-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl chloride Chemical compound CC(C)(C)C1=CC(CCC(Cl)=O)=CC(C(C)(C)C)=C1O ZXUKNOGFRSOORK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 13
- YGPLZBDXFXBLMZ-UHFFFAOYSA-N 1,1-dichloro-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)C(O)(Cl)Cl YGPLZBDXFXBLMZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 10
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 10
- 238000001746 injection moulding Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 230000002441 reversible effect Effects 0.000 claims description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- FANGQVKSFHFPBY-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FANGQVKSFHFPBY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 238000007112 amidation reaction Methods 0.000 abstract 1
- 230000032050 esterification Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 20
- 230000032683 aging Effects 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 230000006698 induction Effects 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010525 oxidative degradation reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- INKDAKMSOSCDGL-UHFFFAOYSA-N [O].OC1=CC=CC=C1 Chemical compound [O].OC1=CC=CC=C1 INKDAKMSOSCDGL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000007970 thio esters Chemical class 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of polyethylene, and discloses an oxidation-resistant carbon nano tube modified polyethylene composite material and a preparation method thereof. And (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride intermediate reacts with diethanolamine for amidation reaction to obtain N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide, the N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride intermediate reacts with dichloropentaerythritol diphosphite intermediate under the catalysis of triethylamine to obtain poly (hindered phenol-phosphite) antioxidant, the acidified carbon nano tube and the poly (hindered phenol-phosphite) antioxidant react with each other for esterification under the catalysis of dicyclohexylcarbodiimide and 4-dimethylaminopyridine to obtain antioxidant grafted carbon nano tube, and finally the antioxidant grafted carbon nano tube and polyethylene resin are uniformly mixed, extruded, granulated, dried and injection molded by a double-screw extruder to obtain the antioxidant carbon nano tube modified polyethylene composite material.
Description
Technical Field
The invention relates to the technical field of polyethylene, in particular to an oxidation-resistant carbon nano tube modified polyethylene composite material and a preparation method thereof.
Background
Polyethylene is thermoplastic resin prepared by ethylene polymerization, has relatively good chemical stability, low temperature resistance and electrical insulation, is widely applied to the fields of films, packaging materials, wires and cables, daily necessities and the like, but the materials are easily subjected to oxidative degradation under the action of heat, oxygen and mechanical stress in the processing and using processes, so that the oxidation resistance of the materials is relatively poor, and therefore, how to improve the oxidation resistance of the polyethylene, so that the application field range and the use time of the polyethylene are further improved, and the polyethylene is a research and development focus, for example, the patent of patent application No. CN112048030A, namely the polyethylene grafted hindered phenol antioxidant, the preparation method and the application thereof, are disclosed.
The carbon nanotube is a one-dimensional nano material, has excellent mechanical, electrical and chemical properties, and is widely applied to the fields of films, coatings, semiconductors, fabrics and the like. Antioxidants are substances which can prevent or retard the oxidation of materials and can capture and neutralize active free radicals so as to generate inactive free radicals, thereby stopping the chain reaction; or can scavenge hydroperoxides generated during oxidation to form stable, inactive products, thereby interrupting the chain reaction. The hindered phenol antioxidant is used as one of antioxidants, is a chain termination type antioxidant and has better compatibility, heat resistance and oxidation resistance. Phosphite antioxidants are auxiliary antioxidants, have excellent heat resistance and discoloration resistance, high efficiency, low toxicity and compatibility, can capture and decompose hydroperoxides, have synergistic effects when being used together with phosphite antioxidants, such as a compound antioxidant for isoprene rubber reported in patent application number CN104387636B, wherein hindered phenol antioxidants, thioester antioxidants and phosphite antioxidants are compounded and applied to isoprene rubber, and have excellent heat-oxidative aging resistance and excellent heat-oxidative aging stability. The micromolecular antioxidant is easy to volatilize at high temperature, has poor compatibility with materials due to low molecular weight, is easy to volatilize and lose, has poor heat resistance and causes poor oxidation resistance, and the polymeric antioxidant has low volatility, high heat resistance and solvent extraction resistance on the basis of the micromolecular antioxidant due to the increased molecular weight, so that the oxidation resistance of the materials is better improved, and the polymeric antioxidant has become a new trend for research due to the excellent performance of the polymeric antioxidant.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides an oxidation-resistant carbon nano tube modified polyethylene composite material and a preparation method thereof, and the prepared polyethylene composite material has excellent mechanical and oxidation resistance.
(II) technical scheme
An oxidation-resistant carbon nano tube modified polyethylene composite material comprises the following components in parts by weight:
90-99.5 parts by weight of polyethylene resin and 0.5-10 parts by weight of antioxidant grafted carbon nano tube;
the oxidation resistance carbon nano tube modified polyethylene composite material is prepared by the following steps:
s1: placing 100 parts by weight of acidified carbon nano tubes into a flask filled with N, N-dimethylformamide solvent, stirring and dispersing for 50-100min, after the reaction is finished, sequentially adding 120-180 parts of poly (hindered phenol-phosphite) antioxidant, 400-700 parts by weight of dicyclohexylcarbodiimide and 60-90 parts by weight of 4-dimethylaminopyridine into the flask, continuing stirring and reacting, filtering, sequentially washing with ethanol and deionized water, and drying to obtain antioxidant grafted carbon nano tubes;
s2: and (3) placing the antioxidant grafted carbon nano tube and the polyethylene resin into a high-speed mixer at 100-150 ℃ for mixing for 5-15min, extruding, granulating, drying and injection molding the high-mixing powder by a double-screw extruder to obtain the antioxidant carbon nano tube modified polyethylene composite material.
Specifically, the reaction temperature in the step S1 is 90-110 ℃, and the stirring reaction time is 5-8h.
Specifically, the extrusion process conditions in step S2 are as follows: the temperature of the first area is 140-145 ℃, the temperature of the second area is 150-155 ℃, the temperature of the third area is 160-165 ℃, the temperature of the fourth area is 170-175 ℃, the temperature of the machine head is 160-165 ℃, and the rotating speed is 150-250r/min.
Specifically, the injection process conditions in step S2: the first stage temperature is 180-185 ℃, the second stage temperature is 170-175 ℃, the third stage temperature is 150-155 ℃ and the head temperature is 175-180 ℃, the injection pressure is 6.0-7.0MPa, the holding pressure is 5.5-6MPa, and the cooling time is 15-20s.
Specifically, the preparation method of the poly (hindered phenol-phosphite) antioxidant comprises the following steps:
(1) 100 parts by weight of (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and 100-130 parts by weight of thionyl chloride are reacted to obtain a (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride intermediate; sequentially adding 100 parts of (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride and 70-100 parts of diethanolamine into a flask filled with acetone, stirring and dissolving for reaction, and evaporating out a solvent and washing with petroleum ether after the reverse reaction is finished to obtain N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide;
(2) Dissolving 100-140 parts by weight of a dichloro pentaerythritol diphosphite intermediate in a flask filled with toluene, stirring and dissolving, adding 1-3 parts of a triethylamine catalyst and a toluene solution containing 100 parts of N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide into the mixture, heating the mixture for reaction, evaporating the solvent after the reaction, and washing the solvent with ethanol to obtain the poly (hindered phenol-phosphite) antioxidant.
Specifically, in the step (1), the stirring and dissolving temperature is 20-35 ℃ and the time is 2-4h.
Specifically, the temperature rise in the step (2) is 80-120 ℃, and the duration of the reaction is 3-8 hours.
(III) beneficial technical effects
(3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid is subjected to chlorination reaction with thionyl chloride to obtain a (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride intermediate, and then the (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride intermediate is amidated with diethanolamine to obtain N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide. Phosphorus trichloride reacts with pentaerythritol to obtain a dichloro pentaerythritol diphosphite intermediate, and the intermediate reacts with N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide under the catalysis of triethylamine to obtain a hydroxyl-terminated poly (hindered phenol-phosphite) antioxidant. The acidified carbon nano tube and the poly (hindered phenol-phosphite) antioxidant are subjected to esterification reaction under the catalysis of dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and the poly (hindered phenol-phosphite) antioxidant is grafted into the carbon nano tube, so that the antioxidant grafted carbon nano tube is obtained. The antioxidant grafted carbon nano tube and the polyethylene resin are uniformly mixed, and the antioxidant carbon nano tube modified polyethylene composite material is obtained through the processes of extrusion, injection molding and the like of a double-screw extruder.
The poly (hindered phenol-phosphite) antioxidant prepared by the invention has the functions of both a main antioxidant and an auxiliary antioxidant. Under the action of light and heat, the macromolecular material can generate macromolecular chain free radical R or ROO, wherein the hindered phenol component is used as a main antioxidant and has relatively active hydrogen atoms, the active hydrogen atoms can react with the free radicals in the macromolecular chain to generate hydroperoxide and phenol oxygen free radicals, the reaction is stopped, the oxidative degradation and thermal degradation of the material are inhibited, the purpose of resisting oxidation is achieved, and the hydroperoxide is of an unstable structure and is easily broken into RO, HO and free radicals to cause further aging of the resin. The phosphite component is used as an auxiliary antioxidant, and is subjected to oxidation-reduction reaction with active hydroperoxide, the active hydroperoxide is reduced into alcohol, and phosphite is oxidized into phosphate, so that the aging of the material is stopped or delayed. Compared with a small molecular antioxidant, the poly (hindered phenol-phosphite) antioxidant prepared by the invention has the advantages of strong thermal stability, difficult volatilization, migration resistance, good compatibility and the like, and the carbon nano tube has poor compatibility with organic polyethylene as an inorganic substance, and the poly (hindered phenol-phosphite) antioxidant can react with the carbon nano tube to graft the carbon nano tube on the surface of the carbon nano tube, so that the compatibility between the carbon nano tube and the polyethylene is improved, and the carbon nano tube can better enhance the mechanical property of the polyethylene composite material.
Drawings
FIG. 1 is a route to poly (hindered phenol-phosphite) antioxidants.
Detailed Description
Specific embodiments of the present invention are described in further detail below. It should be understood that the description herein of the embodiments of the invention is not intended to limit the scope of the invention.
The preparation method of the acidified carbon nano tube comprises the following steps: placing 0.5g of multi-wall carbon nano tube into a flask filled with a mixed solution of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3:1, carrying out reflux reaction for 60min at 140 ℃, washing with deionized water, filtering and drying to obtain the acidified carbon nano tube.
The preparation method of the (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride intermediate comprises the following steps: placing 0.02mol of (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid into a flask, adding 50ml of chloroform into the flask, stirring and dissolving, adding 4ml of thionyl chloride into the solution under the nitrogen atmosphere at 50 ℃ for stirring and reacting for 5 hours, and after the reaction is finished, distilling under reduced pressure, filtering and washing to obtain (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride intermediate with the structural formula of
The preparation method of the dichloropentaerythritol diphosphite intermediate comprises the following steps: 185g of toluene and 34.4g of phosphorus trichloride are added into a flask, stirred and dissolved at 40 ℃, 17g of pentaerythritol is slowly added in 1h, the mixture is reacted for 10h under the vacuum condition of 30mmHg, cooled to 25 ℃, filtered, evaporated and crystallized to obtain the intermediate of the dichloro pentaerythritol diphosphite. The structural formula is as follows:
example 1
(1) 100 parts by weight of (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride intermediate and 80 parts of diethanolamine are sequentially added into a flask filled with acetone, stirring and dissolving are carried out for 3 hours at 30 ℃, and after the reverse reaction is finished, the solvent and petroleum ether are distilled off for washing, thus obtaining N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide.
(2) 100 parts by weight of a dichloro pentaerythritol diphosphite intermediate is dissolved in a flask filled with toluene, stirred and dissolved, 1 part of triethylamine catalyst and a toluene solution containing 100 parts of N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide are added into the mixture, the temperature is raised to 80 ℃ for continuous reaction for 3 hours, and after the reaction, the solvent is distilled off and ethanol is washed, so that the poly (hindered phenol-phosphite) antioxidant is obtained.
(3) Placing 100 parts by weight of acidified carbon nano tubes into a flask filled with N, N-dimethylformamide solvent at 90 ℃, stirring and dispersing for 100min, after the reaction is finished, sequentially adding 150 parts of poly (hindered phenol-phosphite) antioxidant, 500 parts of dicyclohexylcarbodiimide and 80 parts of 4-dimethylaminopyridine into the mixture, continuously stirring and reacting for 6h, carrying out suction filtration, sequentially washing with ethanol and deionized water, and drying to obtain the antioxidant grafted carbon nano tubes.
(4) Placing 0.5 part by weight of antioxidant grafted carbon nano tube and 99.5 parts by weight of polyethylene resin into a high-speed mixer at 150 ℃ for mixing for 10min, and extruding the high-mixed powder through a double-screw extruder under the extrusion process conditions: the temperature of the first area is 140 ℃, the temperature of the second area is 150 ℃, the temperature of the third area is 160 ℃, the temperature of the fourth area is 170 ℃, the temperature of the machine head is 160 ℃, and the rotating speed is 150r/min; granulating, drying, injection molding and injection process conditions: the first stage temperature is 185 ℃, the second stage temperature is 175 ℃, the third stage temperature is 155 ℃ and the temperature of the machine head is 180 ℃, the injection pressure is 7.0MPa, the holding pressure is 6MPa, and the cooling time is 20s; obtaining the carbon nano tube modified polyethylene composite material with oxidation resistance.
Example 2
(1) 100 parts by weight of (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride intermediate and 90 parts of diethanolamine are sequentially added into a flask filled with acetone, stirring and dissolving are carried out for 3 hours at 30 ℃, and after the reverse reaction is finished, the solvent and petroleum ether are distilled off for washing, thus obtaining N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide.
(2) Dissolving 120 parts by weight of a dichloro pentaerythritol diphosphite intermediate in a flask filled with toluene, stirring and dissolving, adding 2 parts of a triethylamine catalyst and a toluene solution containing 100 parts of N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide into the mixture, heating to 100 ℃, continuously reacting for 5 hours, evaporating the solvent after the reaction, and washing with ethanol to obtain the poly (hindered phenol-phosphite) antioxidant.
(3) Placing 100 parts by weight of acidified carbon nano tubes into a flask filled with N, N-dimethylformamide solvent at 90 ℃, stirring and dispersing for 50min, after the reaction is finished, sequentially adding 120 parts of poly (hindered phenol-phosphite) antioxidant, 400 parts of dicyclohexylcarbodiimide and 60 parts of 4-dimethylaminopyridine into the flask, continuously stirring and reacting for 5h, carrying out suction filtration, sequentially washing with ethanol and deionized water, and drying to obtain the antioxidant grafted carbon nano tubes.
(4) Placing 2 parts by weight of antioxidant grafted carbon nano tubes and 98 parts by weight of polyethylene resin into a high-speed mixer at 120 ℃ for mixing for 12min, and extruding the high-mixed powder through a double-screw extruder under the extrusion process conditions: the temperature of the first area is 145 ℃, the temperature of the second area is 155 ℃, the temperature of the third area is 165 ℃, the temperature of the fourth area is 175 ℃, the temperature of the machine head is 165 ℃, and the rotating speed is 250r/min; granulating, drying, injection molding and injection process conditions: the first stage temperature is 180 ℃, the second stage temperature is 170 ℃, the third stage temperature is 150 ℃, the temperature of the machine head is 175 ℃, the injection pressure is 6.0MPa, the holding pressure is 5.8MPa, and the cooling time is 18s; obtaining the carbon nano tube modified polyethylene composite material with oxidation resistance.
Example 3
(1) 100 parts by weight of (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride intermediate and 70 parts of diethanolamine are sequentially added into a flask filled with acetone, stirring and dissolving are carried out for 2 hours at 20 ℃, and after the reverse reaction is finished, the solvent and petroleum ether are distilled off for washing, thus obtaining N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide.
(2) Dissolving 140 parts by weight of a dichloro pentaerythritol diphosphite intermediate in a flask filled with toluene, stirring and dissolving, adding 3 parts of a triethylamine catalyst and a toluene solution containing 100 parts of N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide into the mixture, heating to 120 ℃, continuously reacting for 8 hours, evaporating the solvent after the reaction, and washing with ethanol to obtain the poly (hindered phenol-phosphite) antioxidant.
(3) Placing 100 parts by weight of acidified carbon nano tubes into a flask filled with N, N-dimethylformamide solvent at 100 ℃, stirring and dispersing for 80min, after the reaction is finished, sequentially adding 150 parts of poly (hindered phenol-phosphite) antioxidant, 600 parts of dicyclohexylcarbodiimide and 80 parts of 4-dimethylaminopyridine into the mixture, continuously stirring and reacting for 6h, carrying out suction filtration, sequentially washing with ethanol and deionized water, and drying to obtain the antioxidant grafted carbon nano tubes.
(4) Placing 6 parts by weight of antioxidant grafted carbon nano tubes and 94 parts by weight of polyethylene resin into a high-speed mixer at 100 ℃ for mixing for 5min, and extruding the high-mixed powder through a double-screw extruder under the extrusion process conditions: the temperature of the first area is 140 ℃, the temperature of the second area is 150 ℃, the temperature of the third area is 160 ℃, the temperature of the fourth area is 170 ℃, the temperature of the machine head is 160 ℃, and the rotating speed is 150r/min; granulating, drying, injection molding and injection process conditions: the first stage temperature is 180 ℃, the second stage temperature is 170 ℃, the third stage temperature is 150 ℃, the temperature of the machine head is 175 ℃, the injection pressure is 6.0MPa, the holding pressure is 5.5MPa, and the cooling time is 15s; obtaining the carbon nano tube modified polyethylene composite material with oxidation resistance.
Example 4
(1) 100 parts by weight of (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride intermediate and 80 parts of diethanolamine are sequentially added into a flask filled with acetone, stirring and dissolving are carried out for 3 hours at 25 ℃, and after the reverse reaction is finished, the solvent and petroleum ether are distilled off for washing, thus obtaining N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide.
(2) Dissolving 120 parts by weight of a dichloro pentaerythritol diphosphite intermediate in a flask filled with toluene, stirring and dissolving, adding 2 parts of a triethylamine catalyst and a toluene solution containing 100 parts of N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide into the mixture, heating to 110 ℃, continuously reacting for 5 hours, evaporating the solvent after the reaction, and washing with ethanol to obtain the poly (hindered phenol-phosphite) antioxidant.
(3) Placing 100 parts by weight of acidified carbon nano tubes into a flask filled with N, N-dimethylformamide solvent at 100 ℃, stirring and dispersing for 100min, after the reaction is finished, sequentially adding 160 parts of poly (hindered phenol-phosphite) antioxidant, 600 parts of dicyclohexylcarbodiimide and 80 parts of 4-dimethylaminopyridine into the mixture, continuously stirring and reacting for 7h, carrying out suction filtration, sequentially washing with ethanol and deionized water, and drying to obtain the antioxidant grafted carbon nano tubes.
(4) Placing 8 parts by weight of antioxidant grafted carbon nano tubes and 92 parts by weight of polyethylene resin into a high-speed mixer at 150 ℃ for mixing for 15min, and extruding the high-mixed powder through a double-screw extruder under the extrusion process conditions: the temperature of the first area is 145 ℃, the temperature of the second area is 155 ℃, the temperature of the third area is 165 ℃, the temperature of the fourth area is 175 ℃, the temperature of the machine head is 165 ℃, and the rotating speed is 250r/min; granulating, drying, injection molding and injection process conditions: the first stage temperature is 185 ℃, the second stage temperature is 175 ℃, the third stage temperature is 155 ℃ and the temperature of the machine head is 180 ℃, the injection pressure is 7.0MPa, the holding pressure is 6MPa, and the cooling time is 20s; obtaining the carbon nano tube modified polyethylene composite material with oxidation resistance.
Example 5
(1) 100 parts by weight of (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride intermediate and 100 parts of diethanolamine are sequentially added into a flask filled with acetone, stirring and dissolving are carried out for 4 hours at 35 ℃, and after the reverse reaction is finished, the solvent and petroleum ether are distilled off for washing, thus obtaining N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide.
(2) Dissolving 120 parts by weight of a dichloro pentaerythritol diphosphite intermediate in a flask filled with toluene, stirring and dissolving, adding 2 parts of a triethylamine catalyst and a toluene solution containing 100 parts of N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide into the mixture, heating to 110 ℃, continuously reacting for 5 hours, evaporating the solvent after the reaction, and washing with ethanol to obtain the poly (hindered phenol-phosphite) antioxidant.
(3) Placing 100 parts by weight of acidified carbon nano tubes into a flask filled with N, N-dimethylformamide solvent at 110 ℃, stirring and dispersing for 100min, after the reaction is finished, sequentially adding 180 parts of poly (hindered phenol-phosphite) antioxidant, 700 parts of dicyclohexylcarbodiimide and 90 parts of 4-dimethylaminopyridine into the mixture, continuously stirring and reacting for 8h, carrying out suction filtration, sequentially washing with ethanol and deionized water, and drying to obtain the antioxidant grafted carbon nano tubes.
(4) Placing 10 parts by weight of antioxidant grafted carbon nano tubes and 90 parts by weight of polyethylene resin into a high-speed mixer at 120 ℃ for mixing for 12min, and extruding the high-mixed powder through a double-screw extruder under the extrusion process conditions: the temperature of the first area is 140 ℃, the temperature of the second area is 150 ℃, the temperature of the third area is 160 ℃, the temperature of the fourth area is 170 ℃, the temperature of the machine head is 160 ℃, and the rotating speed is 150r/min; granulating, drying, injection molding and injection process conditions: the first stage temperature is 185 ℃, the second stage temperature is 175 ℃, the third stage temperature is 155 ℃ and the temperature of the machine head is 180 ℃, the injection pressure is 7.0MPa, the holding pressure is 6MPa, and the cooling time is 18s; obtaining the carbon nano tube modified polyethylene composite material with oxidation resistance.
Comparative example 1
(1) Placing 0.5 part by weight of carbon nano tube and 99.5 parts by weight of polyethylene resin into a high-speed mixer at 130 ℃ for mixing for 10min, and extruding the high-mixed powder through a double-screw extruder under the extrusion process conditions: the temperature of the first area is 145 ℃, the temperature of the second area is 155 ℃, the temperature of the third area is 165 ℃, the temperature of the fourth area is 175 ℃, the temperature of the machine head is 165 ℃, and the rotating speed is 250r/min; granulating, drying, injection molding and injection process conditions: the first stage temperature is 185 ℃, the second stage temperature is 175 ℃, the third stage temperature is 155 ℃ and the temperature of the machine head is 180 ℃, the injection pressure is 7.0MPa, the holding pressure is 6MPa, and the cooling time is 18s; obtaining the carbon nano tube modified polyethylene composite material.
Comparative example 2
(1) 100 parts by weight of (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride intermediate and 90 parts of diethanolamine are sequentially added into a flask filled with acetone, stirring and dissolving are carried out for 2 hours at 20 ℃, and after the reverse reaction is finished, the solvent and petroleum ether are distilled off for washing, thus obtaining N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide.
(2) 130 parts by weight of a dichloropentaerythritol diphosphite intermediate is dissolved in a flask filled with toluene, stirred and dissolved, 1 part of triethylamine catalyst and a toluene solution containing 100 parts of N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide are added into the mixture, the temperature is raised to 120 ℃ for continuous reaction for 8 hours, and after the reaction, the solvent is distilled off, and ethanol is used for washing, so that the poly (hindered phenol-phosphite) antioxidant is obtained.
(3) 0.5 parts by weight of poly (hindered phenol-phosphite) antioxidant and 99.5 parts by weight of polyethylene resin are placed in a high-speed mixer at 100 ℃ for mixing for 5min, and the high-mixing powder is extruded by a double-screw extruder under the extrusion process conditions: the temperature of the first area is 140 ℃, the temperature of the second area is 150 ℃, the temperature of the third area is 160 ℃, the temperature of the fourth area is 170 ℃, the temperature of the machine head is 160 ℃, and the rotating speed is 150r/min; granulating, drying, injection molding and injection process conditions: the first stage temperature is 180 ℃, the second stage temperature is 170 ℃, the third stage temperature is 150 ℃, the temperature of the machine head is 175 ℃, the injection pressure is 6.0MPa, the holding pressure is 5.5MPa, and the cooling time is 15s; obtaining the polyethylene material with oxidation resistance.
With reference to GB/T3682-2000, melt flow rates are measured using a melt flow rate meter.
The melt flow rate change rate of the polyethylene materials of examples 1 to 5 and comparative example 2 was minimized because a poly (hindered phenol-phosphite) antioxidant was added to the materials, and thus the addition of the antioxidant carbon nanotube-modified polyethylene composite material was effective in inhibiting thermal oxidative degradation of the materials and effectively preventing thermal oxidation of the materials. Comparative example 1 has a larger rate of change in melt flow rate than examples 1 to 5 and comparative example 2 because only carbon nanotubes were added in comparative example 1, and no poly (hindered phenol-phosphite) antioxidant was added, and thus the oxidation resistance was poor.
With reference to GB/T1040-2008, tensile testing machines were used to test the tensile properties of the materials.
Thermal oxidative aging experiments: according to GJB150.3A-2009, placing the material in a high-low temperature aging test box for 120 hours and performing 110 ℃ high temperature thermo-oxidative aging test; the tensile properties of the materials were again tested.
The tensile strength and the elastic modulus of the polyethylene materials of examples 1-5 and comparative example 1 are both greater than those of the polyethylene material of comparative example 2, because the carbon nanotubes are added to the polyethylene materials of examples 1-5 and comparative example 1, and the carbon nanotubes can enhance the mechanical properties of the polyethylene materials, and the tensile strength and the elastic modulus of the polyethylene materials of examples 1-5 and comparative example 2 after the thermal oxidation test are both less varied than those of the polyethylene materials of comparative example 1, because the antioxidants are added to the polyethylene materials of examples 1-5 and comparative example 2, and the antioxidants can delay the oxidation resistance of the materials, so that the oxidation resistance of the polyethylene materials to which the antioxidants are added is good.
Referring to GB/T2951.1-1994, the oxidation induction period of a material was tested using a differential scanning calorimeter. Under the test condition of nitrogen, the temperature is raised to 200 ℃ at the speed of 20 ℃/min, the temperature is kept for 10min, the nitrogen is replaced by oxygen, the temperature is lowered at the speed of 20 ℃/min, and the temperature is lowered to the room temperature.
| Oxidation induction period/min | |
| Example 1 | 94 |
| Example 2 | 88 |
| Example 3 | 86 |
| Example 4 | 91 |
| Example 5 | 85 |
| Comparative example 1 | 50 |
| Comparative example 2 | 82 |
The polyethylene material of example 1 had the longest oxidation induction period of 94min, and the polyethylene material of comparative example 1 had the shortest oxidation induction period of 50min, because the antioxidant-grafted carbon nanotubes were added in example 1, whereas the carbon nanotubes alone were added in comparative example 1, indicating that the longer the oxidation induction period, the better the antioxidant effect of the material, so that examples 1 to 5 and comparative example 2, to which the antioxidant was added, were longer than that of comparative example 1, indicating that the oxidation resistance of examples 1 to 5 and comparative example 2 was better than that of comparative example 1.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (7)
1. An oxidation-resistant carbon nanotube modified polyethylene composite material is characterized in that: the composite material comprises the following components in parts by weight:
90-99.5 parts by weight of polyethylene resin and 0.5-10 parts by weight of antioxidant grafted carbon nano tube;
the oxidation resistance carbon nano tube modified polyethylene composite material is prepared by the following steps:
s1: placing 100 parts by weight of acidified carbon nano tubes into a flask filled with N, N-dimethylformamide solvent, stirring and dispersing for 50-100min, after the reaction is finished, sequentially adding 120-180 parts of poly (hindered phenol-phosphite) antioxidant, 400-700 parts by weight of dicyclohexylcarbodiimide and 60-90 parts by weight of 4-dimethylaminopyridine into the flask, continuing stirring and reacting, filtering, sequentially washing with ethanol and deionized water, and drying to obtain antioxidant grafted carbon nano tubes;
s2: and (3) placing the antioxidant grafted carbon nano tube and the polyethylene resin into a high-speed mixer at 100-150 ℃ for mixing for 5-15min, extruding, granulating, drying and injection molding the high-mixing powder by a double-screw extruder to obtain the antioxidant carbon nano tube modified polyethylene composite material.
2. The method for preparing the antioxidant carbon nanotube-modified polyethylene composite material according to claim 1, wherein the method comprises the following steps: the reaction temperature in the step S1 is 90-110 ℃, and the stirring reaction time is 5-8h.
3. The method for preparing the antioxidant carbon nanotube-modified polyethylene composite material according to claim 1, wherein the method comprises the following steps: the extrusion process conditions in the step S2 are as follows: the temperature of the first area is 140-145 ℃, the temperature of the second area is 150-155 ℃, the temperature of the third area is 160-165 ℃, the temperature of the fourth area is 170-175 ℃, the temperature of the machine head is 160-165 ℃, and the rotating speed is 150-250r/min.
4. The method for preparing the antioxidant carbon nanotube-modified polyethylene composite material according to claim 1, wherein the method comprises the following steps: the injection process conditions in the step S2 are as follows: the first stage temperature is 180-185 ℃, the second stage temperature is 170-175 ℃, the third stage temperature is 150-155 ℃ and the head temperature is 175-180 ℃, the injection pressure is 6.0-7.0MPa, the holding pressure is 5.5-6MPa, and the cooling time is 15-20s.
5. The method for preparing the antioxidant carbon nanotube-modified polyethylene composite material according to claim 1, wherein the method comprises the following steps: the preparation method of the poly (hindered phenol-phosphite) antioxidant comprises the following steps:
(1) 100 parts by weight of (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and 100-130 parts by weight of thionyl chloride are reacted to obtain a (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride intermediate; sequentially adding 100 parts of (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride and 70-100 parts of diethanolamine into a flask filled with acetone, stirring and dissolving for reaction, and evaporating out a solvent and washing with petroleum ether after the reverse reaction is finished to obtain N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide;
(2) Dissolving 100-140 parts by weight of a dichloro pentaerythritol diphosphite intermediate in a flask filled with toluene, stirring and dissolving, adding 1-3 parts of a triethylamine catalyst and a toluene solution containing 100 parts of N, N-dihydroxyethyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide into the mixture, heating the mixture for reaction, evaporating the solvent after the reaction, and washing the solvent with ethanol to obtain the poly (hindered phenol-phosphite) antioxidant.
6. The method for preparing the antioxidant carbon nanotube-modified polyethylene composite material according to claim 5, wherein the method comprises the following steps: in the step (1), stirring and dissolving are carried out for 2-4 hours at the temperature of 20-35 ℃.
7. The method for preparing the antioxidant carbon nanotube-modified polyethylene composite material according to claim 5, wherein the method comprises the following steps: the temperature rise in the step (2) is 80-120 ℃, and the duration reaction time is 3-8h.
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