CN116874908B - High-temperature-resistant PE composite material and synthesis process thereof - Google Patents
High-temperature-resistant PE composite material and synthesis process thereof Download PDFInfo
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- CN116874908B CN116874908B CN202310880582.6A CN202310880582A CN116874908B CN 116874908 B CN116874908 B CN 116874908B CN 202310880582 A CN202310880582 A CN 202310880582A CN 116874908 B CN116874908 B CN 116874908B
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- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 86
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 86
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000004698 Polyethylene Substances 0.000 claims abstract description 62
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 31
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 31
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 polyethylene Polymers 0.000 claims abstract description 17
- 229920000573 polyethylene Polymers 0.000 claims abstract description 17
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 34
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 30
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 25
- OPOJRMTZHYUKLY-UHFFFAOYSA-N 1h-1,3,5-triazin-2-one Chemical compound O=C1N=CN=CN1 OPOJRMTZHYUKLY-UHFFFAOYSA-N 0.000 claims description 24
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 22
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 11
- 239000001632 sodium acetate Substances 0.000 claims description 11
- 235000017281 sodium acetate Nutrition 0.000 claims description 11
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 230000020477 pH reduction Effects 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229920001903 high density polyethylene Polymers 0.000 abstract description 12
- 239000004700 high-density polyethylene Substances 0.000 abstract description 12
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 238000004804 winding Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000035882 stress Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of polyethylene, and discloses a high-temperature-resistant PE composite material and a synthesis process thereof, wherein maleic anhydride grafted polyethylene, an antioxidant, polyether sulfone grafted carbon nanotube hybrid particles containing terminal phenolic hydroxyl groups and triazine structural units and polyethylene resin are uniformly mixed in a high-speed mixer, and then are melt-mixed in a torque rheometer to prepare the high-temperature-resistant PE composite material, and the invention has the advantages that: the molecular chain winding is formed by the polyether sulfone grafted by the carbon nano tube hybrid particles and the high-density polyethylene, so that the molecular chain movement of the polyethylene is blocked, the molecular chain movement is inhibited, the thermal decomposition temperature of the PE composite material is improved, namely the melting point and the high temperature resistance degree of the PE composite material are improved, and meanwhile, the polyether sulfone grafted carbon nano tube forms organic-inorganic rigid hybrid particles, so that the PE composite material can bear larger stress, namely the durability and the toughness of the PE composite material are improved.
Description
Technical Field
The invention relates to the technical field of polyethylene, in particular to a high-temperature-resistant PE composite material and a synthesis process thereof.
Background
Polyethylene PE is a thermoplastic polymer material, is widely applied to products such as plastic, fiber, film and pipe packaging, has the advantages of low density, low cost, good chemical stability, good electrical insulation and the like, plays an important role in various fields of industrial production and daily life, but has the problems of poor high temperature resistance and the like, so that the polyethylene PE composite material with excellent performance needs to be developed, and is beneficial to expanding the application of the polyethylene PE composite material in high-performance materials and special fields.
The polyarylethersulfone has the advantages of excellent heat stability, good toughness, high strength and the like, can be used as a filler to be applied to materials such as epoxy resin, polyethylene, polystyrene and the like, improves the compatibility between the polyarylethersulfone and the materials such as the polyethylene and the like, and can effectively improve the performance of the polyethylene by adding a compatibilizer such as polyethylene grafted polyethylene glycol and the like.
The carbon nano tube has small size, large specific surface area, nano small size effect and surface interface effect, can show unique mechanical property and electrochemical property, has wide application in polyethylene and other materials, grafts organic functional groups on the surface of the carbon nano tube, can realize functional modification of the carbon nano tube, and improves interface property and compatibility with a material matrix; the invention provides a PE composite material containing polyether sulfone grafted carbon nanotube hybrid particles, which can improve the high temperature resistance and other properties of a polyethylene material.
Disclosure of Invention
The invention solves the technical problems that: provides a PE composite material containing polyether sulfone grafted carbon nanotube hybrid particles, which solves the problem of poor high temperature resistance and other performances of polyethylene materials.
The technical scheme of the invention is as follows: a process for synthesizing a high-temperature-resistant PE composite material comprises the following raw materials, by weight, 0.2-3% of maleic anhydride grafted polyethylene, 0.05-0.2% of an antioxidant, 0.5-10% of polyether sulfone grafted carbon nano tube hybrid particles containing terminal phenolic hydroxyl groups and triazine structural units, and the balance of polyethylene;
the synthesis process of the high-temperature-resistant PE composite material comprises the following steps of: mixing maleic anhydride grafted polyethylene, an antioxidant, polyether sulfone grafted carbon nanotube hybrid particles containing terminal phenolic hydroxyl groups and triazine structural units and polyethylene resin uniformly in a high-speed mixer, and then carrying out melt mixing in a torque rheometer to obtain the high-temperature-resistant PE composite material.
Further, the temperature of the melt mixing in the torque rheometer is 155-170 ℃, the time is 10-20min, and the rotating speed is 50-100r/min.
Further, the synthesis process of the polyether sulfone grafted carbon nanotube hybrid particles containing the terminal phenolic hydroxyl group and the triazine structural unit comprises the following steps: adding N-methyl pyrrolidone, toluene and phenolic hydroxyl group s-triazine grafted carbon nano tube into a flask, performing ultrasonic dispersion, and adding three polymerization monomers: the preparation method comprises the steps of heating phenolic hydroxyl s-triazine intermediate, hydroquinone, 4-dichloro diphenyl sulfone and potassium carbonate to 150-160 ℃, azeotropic refluxing and dehydrating for 2-4h, heating to 180-200 ℃, reacting for 3-6h, cooling, centrifugally separating, washing with water and ethanol in sequence, and drying to obtain the polyarylether sulfone grafted carbon nanotube hybrid particles containing terminal phenolic hydroxyl and triazine structural units.
Further, the molar amounts of the phenolic hydroxyl s-triazine, the hydroquinone and the potassium carbonate are respectively (15-30)%, (80-95)% and (110-130)% of 4, 4-dichloro diphenyl sulfone.
Further, the dosage of the phenolic hydroxyl group s-triazine grafted carbon nano tube is 10-40% of the total mass of the polymerized monomer.
Further, the synthesis process of the phenolic hydroxyl group s-triazine grafted carbon nano tube comprises the following steps:
(1) Adding cyanuric chloride and p-aminophenol into butanone solvent in nitrogen atmosphere in ice water bath, stirring for 20-40min, adding aqueous solution of sodium acetate, heating to 75-85 deg.c for refluxing for 2-5 hr, cooling, concentrating to eliminate butanone, adding ethyl acetate and water, extracting, concentrating organic phase, petroleum ether washing, re-crystallizing the product in ethyl acetate to obtain phenolic hydroxyl s-triazine intermediate.
(2) Adding the carbon nano tube into concentrated sulfuric acid and concentrated nitric acid for acidification; adding the acidified carbon nano tube into N, N-dimethylacetamide, performing ultrasonic dispersion, adding hexamethylene diisocyanate, heating to 65-80 ℃ for reaction for 6-18h, performing centrifugal separation, washing with acetone, and drying to obtain the HDI grafted carbon nano tube;
(3) Adding the HDI grafted carbon nano tube into N, N-dimethylacetamide, performing ultrasonic dispersion, adding a phenolic hydroxyl group s-triazine intermediate, heating to 65-80 ℃ for reaction for 6-12h, performing centrifugal separation, washing with water and ethanol in sequence, and drying to obtain the phenolic hydroxyl group s-triazine grafted carbon nano tube.
Further, the molar amounts of the para-aminophenol and the sodium acetate in the step (1) are respectively (320-380)% and (330-400)% of cyanuric chloride.
Further, the phenolic hydroxyl group s-triazine intermediate in the step (3) accounts for 80-200% of the HDI grafted carbon nano tube.
The invention has the technical effects that: the trimeric chloride and the para-aminophenol react in a sodium acetate catalytic system to prepare a phenolic hydroxyl s-triazine intermediate; then acidizing the carbon nano tube by mixed acid to generate hydroxyl on the surface, and then sequentially reacting with hexamethylene diisocyanate and a phenolic hydroxyl s-triazine intermediate to prepare the phenolic hydroxyl s-triazine grafted carbon nano tube; finally, the grafted phenolic hydroxyl forms a polymerization site, so that the phenolic hydroxyl s-triazine intermediate, hydroquinone and 4, 4-dichloro diphenyl sulfone undergo in-situ graft polymerization on the surface of the carbon nanotube, and the polyarylether sulfone grafted carbon nanotube hybrid particle containing terminal phenolic hydroxyl and triazine structural units is prepared; and (3) melting and mixing the PE composite material with a maleic anhydride grafted polyethylene compatilizer and high-density polyethylene to prepare the high-temperature-resistant PE composite material.
In the melt mixing process, the maleic anhydride grafted polyethylene compatilizer can react with the phenolic hydroxyl groups at the ends of the polyether sulfone grafted carbon nanotube hybrid particles, so that the polyether sulfone grafted carbon nanotube hybrid particles and the high-density polyethylene have good interface compatibility, the polyether sulfone grafted by the carbon nanotube hybrid particles has a branched network structure, forms molecular chain winding with the high-density polyethylene to form a space crosslinking structure, so that the movement of the polyethylene molecular chain is blocked, and the movement of the molecular chain is inhibited, thereby the thermal decomposition temperature of the PE composite material is improved, and the polyether sulfone contains a heat-resistant triazine structural unit, and obviously improves the melting point and the high-temperature resistance degree of the PE composite material under the synergistic effect.
The polyether sulfone grafted carbon nano tube forms organic-inorganic rigid hybrid particles which can be uniformly dispersed in high-density polyethylene, so that the defect formed in the PE composite material is reduced, and the phenomenon of stress concentration is caused, thereby avoiding the initiation of crack extension, the rigid hybrid particles form a space crosslinking structure in a polyethylene matrix, and when external stress is applied, the rigid hybrid particles can bear load, absorb and consume stress, so that the PE composite material can bear larger stress, and the mechanical property of the composite material is improved, namely the durability and toughness of the PE composite material are improved.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
(1) Adding 10mmol of cyanuric chloride and 35mmol of para-aminophenol into 120mL of butanone solvent in nitrogen atmosphere under ice water bath, stirring for 30min, then adding aqueous solution containing 38mmol of sodium acetate, heating to 80 ℃ for refluxing for 2h, cooling, concentrating to remove butanone, adding ethyl acetate and water, concentrating an organic phase after extraction, washing with petroleum ether, and recrystallizing a product in ethyl acetate to obtain a phenolic hydroxyl s-triazine intermediate; synthetic reaction route:
(2) Adding 0.3g of carbon nano tube into concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1 for acidification; and then adding the acidified carbon nano tube into 50mL of N, N-dimethylacetamide, performing ultrasonic dispersion, adding 0.6g of hexamethylene diisocyanate, heating to 80 ℃ for reaction for 12 hours, performing centrifugal separation, washing with acetone, and drying to obtain the HDI grafted carbon nano tube.
(3) Adding 0.3g of HDI grafted carbon nano tube into 100mL of N, N-dimethylacetamide, performing ultrasonic dispersion, adding 2.4g of phenolic hydroxyl s-triazine intermediate, heating to 80 ℃ for reaction for 8 hours, performing centrifugal separation, washing with water and ethanol in sequence, and drying to obtain the phenolic hydroxyl s-triazine grafted carbon nano tube; synthetic reaction mechanism:
(4) 50mL of N-methylpyrrolidone, 20mL of toluene and 10% of phenolic hydroxyl group s-triazine grafted carbon nano tube with the total mass of three polymerization monomers are added into a flask, ultrasonic dispersion is carried out, and three polymerization monomers are added: 3mmol of phenolic hydroxyl s-triazine intermediate, 19mmol of hydroquinone and 20mmol of 4, 4-dichlorodiphenyl sulfone, and 22mmol of potassium carbonate; heating to 155 ℃, azeotropic refluxing and dehydrating for 2 hours, heating to 180 ℃, reacting for 6 hours, cooling, centrifugally separating, washing with water and ethanol in sequence, and drying to obtain the polyether sulfone grafted carbon nanotube hybrid particles containing terminal phenolic hydroxyl and triazine structural units; synthetic reaction mechanism:
(5) Mixing maleic anhydride grafted polyethylene accounting for 0.2 percent, antioxidant 1076 accounting for 0.2 percent, polyether sulfone grafted carbon nano tube hybrid particles containing terminal phenolic hydroxyl groups and triazine structural units accounting for 0.5 percent and high-density polyethylene accounting for 99.1 percent uniformly in a high-speed mixer, and then carrying out melt mixing in a torque rheometer at the temperature of 170 ℃ for 15min and the rotating speed of 50r/min to obtain the high-temperature-resistant PE composite material.
Example 2
(1) 10mmol of cyanuric chloride and 32mmol of para-aminophenol are added into 120mL of butanone solvent under ice water bath and nitrogen atmosphere, stirring is carried out for 20min, then an aqueous solution containing 33mmol of sodium acetate is added, the temperature is raised to 85 ℃ and reflux is carried out for 4h, cooling is carried out, butanone is removed by concentration, ethyl acetate and water are added, an organic phase is concentrated after extraction, petroleum ether is washed, and a product is recrystallized from ethyl acetate, thus obtaining the phenolic hydroxyl s-triazine intermediate.
(2) Adding 0.3g of carbon nano tube into concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1 for acidification; adding the acidified carbon nano tube into 50mL of N, N-dimethylacetamide, performing ultrasonic dispersion, adding 0.6g of hexamethylene diisocyanate, heating to 65 ℃ for reaction for 18h, performing centrifugal separation, washing with acetone, and drying to obtain the HDI grafted carbon nano tube;
(3) Adding 0.3g of HDI grafted carbon nano tube into 150mL of N, N-dimethylacetamide, performing ultrasonic dispersion, adding 4g of phenolic hydroxyl group s-triazine intermediate, heating to 70 ℃ for reaction for 12 hours, performing centrifugal separation, washing with water and ethanol in sequence, and drying to obtain the phenolic hydroxyl group s-triazine grafted carbon nano tube.
(4) 100mL of N-methylpyrrolidone, 30mL of toluene and a phenolic hydroxyl group s-triazine grafted carbon nano tube with the amount of 15% of the total mass of three polymerization monomers are added into a flask, ultrasonic dispersion is carried out, and three polymerization monomers are added: 4mmol of phenolic hydroxyl s-triazine intermediate, 18mmol of hydroquinone and 20mmol of 4, 4-dichlorodiphenyl sulfone, and 23mmol of potassium carbonate; heating to 160 ℃, azeotropic reflux and dehydration for 2 hours, heating to 200 ℃, reacting for 3 hours, cooling, centrifugally separating, washing with water and ethanol in sequence, and drying to obtain the polyether sulfone grafted carbon nanotube hybrid particles containing terminal phenolic hydroxyl and triazine structural units.
(5) Mixing maleic anhydride grafted polyethylene accounting for 0.8 percent, antioxidant 1076 accounting for 0.1 percent, polyether sulfone grafted carbon nano tube hybrid particles containing terminal phenolic hydroxyl groups and triazine structural units accounting for 2 percent and high-density polyethylene accounting for 97.1 percent uniformly in a high-speed mixer, and then carrying out melt mixing in a torque rheometer at the temperature of 155 ℃ for 20min at the rotating speed of 100r/min to obtain the high-temperature-resistant PE composite material.
Example 3
(1) 10mmol of cyanuric chloride and 38mmol of para-aminophenol are added to 150mL of butanone solvent under ice water bath and nitrogen atmosphere, stirred for 30min, then aqueous solution containing 40mmol of sodium acetate is added, the temperature is raised to 75 ℃ and reflux is carried out for 5h, cooling is carried out, butanone is removed by concentration, ethyl acetate and water are added, organic phase is concentrated after extraction, petroleum ether is washed, and the product is recrystallized from ethyl acetate, thus obtaining the phenolic hydroxyl s-triazine intermediate. A step of
(2) Adding 0.3g of carbon nano tube into concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1 for acidification; adding the acidified carbon nano tube into 50mL of N, N-dimethylacetamide, performing ultrasonic dispersion, adding 0.6g of hexamethylene diisocyanate, heating to 70 ℃ for reaction for 12 hours, performing centrifugal separation, washing with acetone, and drying to obtain the HDI grafted carbon nano tube;
(3) Adding 0.3g of HDI grafted carbon nano tube into 80mL of N, N-dimethylacetamide, performing ultrasonic dispersion, adding 5g of phenolic hydroxyl group s-triazine intermediate, heating to 65 ℃ for reaction for 12h, performing centrifugal separation, washing with water and ethanol in sequence, and drying to obtain the phenolic hydroxyl group s-triazine grafted carbon nano tube.
(4) 100mL of N-methylpyrrolidone, 40mL of toluene and 25% of phenolic hydroxyl group s-triazine grafted carbon nano tube with the total mass of three polymerization monomers are added into a flask, ultrasonic dispersion is carried out, and three polymerization monomers are added: 5mmol of phenolic hydroxyl s-triazine intermediate, 17mmol of hydroquinone and 20mmol of 4, 4-dichlorodiphenyl sulfone, and 24mmol of potassium carbonate; heating to 160 ℃, azeotropic reflux and dehydration for 2 hours, heating to 180 ℃, reacting for 6 hours, cooling, centrifugally separating, washing with water and ethanol in sequence, and drying to obtain the polyether sulfone grafted carbon nanotube hybrid particles containing terminal phenolic hydroxyl and triazine structural units.
(5) Mixing 1.4% of maleic anhydride grafted polyethylene, 0.05% of antioxidant 1076, 5% of polyether sulfone grafted carbon nanotube hybrid particles containing terminal phenolic hydroxyl groups and triazine structural units and 93.55% of high-density polyethylene uniformly in a high-speed mixer, and then carrying out melt mixing in a torque rheometer at 160 ℃ for 10min at 80r/min to obtain the high-temperature-resistant PE composite material.
Example 4
(1) 10mmol of cyanuric chloride and 38mmol of para-aminophenol are added to 150mL of butanone solvent under ice water bath and nitrogen atmosphere, stirred for 40min, then aqueous solution containing 40mmol of sodium acetate is added, the temperature is raised to 80 ℃ and reflux is carried out for 5h, cooling is carried out, butanone is removed by concentration, ethyl acetate and water are added, organic phase is concentrated after extraction, petroleum ether is washed, and the product is recrystallized from ethyl acetate, thus obtaining the phenolic hydroxyl s-triazine intermediate.
(2) Adding 0.3g of carbon nano tube into concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1 for acidification; adding the acidified carbon nano tube into 50mL of N, N-dimethylacetamide, performing ultrasonic dispersion, adding 0.6g of hexamethylene diisocyanate, heating to 70 ℃ for reaction for 18h, performing centrifugal separation, washing with acetone, and drying to obtain the HDI grafted carbon nano tube;
(3) Adding 0.3g of HDI grafted carbon nano tube into 80mL of N, N-dimethylacetamide, performing ultrasonic dispersion, adding 6g of phenolic hydroxyl group s-triazine intermediate, heating to 80 ℃ for reaction for 6 hours, performing centrifugal separation, washing with water and ethanol in sequence, and drying to obtain the phenolic hydroxyl group s-triazine grafted carbon nano tube.
(4) 150mL of N-methylpyrrolidone, 50mL of toluene and the phenolic hydroxyl group s-triazine grafted carbon nano tube accounting for 30% of the total mass of the three polymerization monomers are added into a flask, ultrasonic dispersion is carried out, and three polymerization monomers are added: 5mmol of phenolic hydroxyl s-triazine intermediate, 17mmol of hydroquinone and 20mmol of 4, 4-dichlorodiphenyl sulfone, and 26mmol of potassium carbonate; heating to 150 ℃, azeotropic reflux and dehydration for 4 hours, heating to 190 ℃, reacting for 5 hours, cooling, centrifugally separating, washing with water and ethanol in sequence, and drying to obtain the polyether sulfone grafted carbon nanotube hybrid particles containing terminal phenolic hydroxyl and triazine structural units.
(5) Mixing maleic anhydride grafted polyethylene accounting for 2.2 percent, antioxidant 1076 accounting for 0.1 percent, polyether sulfone grafted carbon nanotube hybrid particles containing terminal phenolic hydroxyl groups and triazine structural units accounting for 7 percent and high-density polyethylene accounting for 90.7 percent uniformly in a high-speed mixer, and then carrying out melt mixing in a torque rheometer at the temperature of 170 ℃ for 10min at the rotating speed of 100r/min to obtain the high-temperature-resistant PE composite material.
Example 5
(1) 10mmol of cyanuric chloride and 38mmol of para-aminophenol are added to 150mL of butanone solvent under ice water bath and nitrogen atmosphere, stirred for 20min, then aqueous solution containing 36mmol of sodium acetate is added, the temperature is raised to 75 ℃ and reflux is carried out for 4h, cooling is carried out, butanone is removed by concentration, ethyl acetate and water are added, organic phase is concentrated after extraction, petroleum ether is washed, and the product is recrystallized from ethyl acetate, thus obtaining the phenolic hydroxyl s-triazine intermediate.
(2) Adding 0.3g of carbon nano tube into concentrated sulfuric acid and concentrated nitric acid with the volume ratio of 3:1 for acidification; adding the acidified carbon nano tube into 50mL of N, N-dimethylacetamide, performing ultrasonic dispersion, adding 0.6g of hexamethylene diisocyanate, heating to 70 ℃ for reaction for 12 hours, performing centrifugal separation, washing with acetone, and drying to obtain the HDI grafted carbon nano tube;
(3) Adding 0.3g of HDI grafted carbon nano tube into 120mL of N, N-dimethylacetamide, performing ultrasonic dispersion, adding 6g of phenolic hydroxyl group s-triazine intermediate, heating to 70 ℃ for reaction for 6 hours, performing centrifugal separation, washing with water and ethanol in sequence, and drying to obtain the phenolic hydroxyl group s-triazine grafted carbon nano tube.
(4) 150mL of N-methylpyrrolidone, 50mL of toluene and 40% of phenolic hydroxyl group s-triazine grafted carbon nano tube with the total mass of three polymerization monomers are added into a flask, ultrasonic dispersion is carried out, and three polymerization monomers are added: 6mmol of phenolic hydroxyl s-triazine intermediate, 16mmol of hydroquinone and 20mmol of 4, 4-dichlorodiphenyl sulfone, and 26mmol of potassium carbonate; heating to 150 ℃, azeotropic refluxing and dewatering for 3 hours, heating to 200 ℃, reacting for 3 hours, cooling, centrifugally separating, washing with water and ethanol in sequence, and drying to obtain the polyether sulfone grafted carbon nanotube hybrid particles containing terminal phenolic hydroxyl and triazine structural units.
(5) Mixing 3% of maleic anhydride grafted polyethylene, 0.1% of antioxidant 1076, 10% of polyether sulfone grafted carbon nanotube hybrid particles containing terminal phenolic hydroxyl groups and triazine structural units and 86.9% of high-density polyethylene uniformly in a high-speed mixer, and then carrying out melt mixing in a torque rheometer at 160 ℃ for 10min at a rotating speed of 100r/min to obtain the high-temperature-resistant PE composite material.
Comparative example 1
(1) Uniformly mixing maleic anhydride grafted polyethylene with the weight ratio of 0.2%, antioxidant 1076 with the weight ratio of 0.2%, carbon nano tube with the weight ratio of 0.5% and high-density polyethylene with the weight ratio of 99.1% in a high-speed mixer, and then carrying out melt mixing in a torque rheometer at the temperature of 160 ℃ for 15min and the rotating speed of 100r/min to obtain the PE composite material.
Comparative example 2
(1) 10mmol of cyanuric chloride 32mmol and p-aminophenol are added into 100mL of butanone solvent under an ice water bath and a nitrogen atmosphere, stirring is carried out for 40min, then an aqueous solution containing 35mmol of sodium acetate is added, the temperature is raised to 85 ℃ and reflux is carried out for 2h, cooling is carried out, butanone is removed by concentration, ethyl acetate and water are added, an organic phase is concentrated after extraction, petroleum ether is washed, and a product is recrystallized from ethyl acetate, thus obtaining the phenolic hydroxyl s-triazine intermediate.
(2) To the flask were added 100mL of N-methylpyrrolidone, 40mL of toluene, three polymerized monomers: 3mmol of phenolic hydroxyl s-triazine intermediate, 19mmol of hydroquinone and 20mmol of 4, 4-dichlorodiphenyl sulfone, and 22mmol of potassium carbonate; heating to 150 ℃, azeotropic reflux and dehydration for 4 hours, heating to 200 ℃, reacting for 4 hours, cooling, centrifugally separating, washing with water and ethanol in sequence, and drying to obtain the polyarylethersulfone containing the terminal phenolic hydroxyl and triazine structural units.
(3) Uniformly mixing maleic anhydride grafted polyethylene accounting for 0.2 percent, antioxidant 1076 accounting for 0.2 percent, polyarylethersulfone containing terminal phenolic hydroxyl groups and triazine structural units accounting for 0.5 percent and high-density polyethylene accounting for 99.1 percent in a high-speed mixer, and then carrying out melt mixing in a torque rheometer at the temperature of 160 ℃ for 20min and the rotating speed of 80r/min to obtain the PE composite material.
The thermal performance of the PE composite material is tested by a thermogravimetric analyzer, the nitrogen atmosphere, the heating rate of 20 ℃/min and the maximum temperature of 800 ℃.
The tensile properties were tested by means of a tensile tester at a tensile rate of 10mm/min with a sample of 80mm by 5mm.
The polyethylene resin of the embodiment 1-5 is added with a maleic anhydride grafted polyethylene compatilizer and polyether sulfone grafted carbon nano tube hybrid particles containing terminal phenolic hydroxyl groups and triazine structural units, so that the heat resistance of the polyethylene resin is obviously improved; in example 4, when the weight ratio of the polyether sulfone grafted carbon nanotube hybrid particles in the PE composite material is 7%, the mass loss temperature is 462.1 ℃ at maximum and the mass loss temperature is 509.2 ℃ at maximum; in example 5, the mass residual rate at 800℃was 29.7% at the maximum when the weight ratio of the polyether sulfone grafted carbon nanotube hybrid particles was 10%. Comparative example 1 was added with only 0.5% carbon nanotubes and comparative example 2 was added with only 0.5% polyarylethersulfones containing terminal phenolic hydroxyl and triazine structural units. The mass loss temperatures of both 10% and 50% are much lower than those of the PE composite prepared in example 1.
In example 2, when the weight ratio of the polyether sulfone grafted carbon nanotube hybrid particles in the PE composite is 2%, the tensile strength of the PE composite is 46.0MPa at most, which is far higher than that of the PE composites prepared in comparative examples 1 and 2.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (6)
1. A synthesis process of a high-temperature-resistant PE composite material is characterized by comprising the following steps of: the high-temperature-resistant PE composite material comprises the following raw materials, by weight, 0.2-3% of maleic anhydride grafted polyethylene, 0.05-0.2% of antioxidant, 0.5-10% of polyether sulfone grafted carbon nano tube hybrid particles containing terminal phenolic hydroxyl groups and triazine structural units, and the balance of polyethylene; the synthesis process of the high-temperature-resistant PE composite material comprises the following steps of: uniformly mixing maleic anhydride grafted polyethylene, an antioxidant, polyether sulfone grafted carbon nanotube hybrid particles containing terminal phenolic hydroxyl groups and triazine structural units and polyethylene resin in a high-speed mixer, and then melt-mixing in a torque rheometer to obtain a high-temperature-resistant PE composite material;
the synthesis process of the polyether sulfone grafted carbon nanotube hybrid particles containing the terminal phenolic hydroxyl groups and the triazine structural units comprises the following steps: adding N-methyl pyrrolidone, toluene and phenolic hydroxyl group s-triazine grafted carbon nano tube into a flask, performing ultrasonic dispersion, and adding three polymerization monomers: the preparation method comprises the steps of heating phenolic hydroxyl s-triazine intermediate, hydroquinone, 4-dichloro diphenyl sulfone and potassium carbonate to 150-160 ℃, azeotropic refluxing and dehydrating for 2-4 hours, heating to 180-200 ℃, reacting for 3-6 hours, cooling, centrifugally separating, washing and drying to obtain polyether sulfone grafted carbon nanotube hybrid particles containing terminal phenolic hydroxyl and triazine structural units;
the synthesis process of the phenolic hydroxyl group sym-triazine grafted carbon nano tube comprises the following steps:
(1) Adding cyanuric chloride and para-aminophenol into butanone solvent in nitrogen atmosphere in ice water bath, stirring for 20-40min, then adding aqueous solution of sodium acetate, heating to 75-85 ℃ for refluxing for 2-5h, cooling, concentrating, extracting and recrystallizing to obtain phenolic hydroxyl s-triazine intermediate;
(2) Adding the carbon nano tube into concentrated sulfuric acid and concentrated nitric acid for acidification; adding the acidified carbon nano tube into N, N-dimethylacetamide, performing ultrasonic dispersion, adding hexamethylene diisocyanate, heating to 65-80 ℃ for reaction for 6-18h, performing centrifugal separation, washing and drying to obtain the HDI grafted carbon nano tube;
(3) Adding the HDI grafted carbon nano tube into N, N-dimethylacetamide, performing ultrasonic dispersion, adding a phenolic hydroxyl group s-triazine intermediate, heating to 65-80 ℃ for reaction for 6-12h, performing centrifugal separation, washing sequentially, and drying to obtain the phenolic hydroxyl group s-triazine grafted carbon nano tube.
2. The process for synthesizing the high temperature resistant PE composite according to claim 1, wherein the process comprises the following steps: the temperature of the melt mixing in the torque rheometer is 155-170 ℃, the time is 10-20min, and the rotating speed is 50-100r/min.
3. The process for synthesizing the high temperature resistant PE composite according to claim 1, wherein the process comprises the following steps: the molar dosages of the phenolic hydroxyl s-triazine, the hydroquinone and the potassium carbonate are respectively (15-30)%, (80-95)% and (110-130)% of 4, 4-dichloro diphenyl sulfone.
4. The process for synthesizing the high temperature resistant PE composite according to claim 1, wherein the process comprises the following steps: the dosage of the phenolic hydroxyl group sym-triazine grafted carbon nano tube is 10-40% of the total mass of the polymerized monomer.
5. The process for synthesizing the high temperature resistant PE composite according to claim 1, wherein the process comprises the following steps: the molar dosages of the para-aminophenol and the sodium acetate in the (1) are respectively (320-380)% and (330-400)% of cyanuric chloride.
6. The process for synthesizing the high temperature resistant PE composite according to claim 1, wherein the process comprises the following steps: the dosage of the phenolic hydroxyl group s-triazine intermediate in the step (3) is 80-200% of that of the HDI grafted carbon nano tube.
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