CN116063844A - High-strength high-toughness plastic material, preparation method thereof and high-strength high-toughness plastic product - Google Patents
High-strength high-toughness plastic material, preparation method thereof and high-strength high-toughness plastic product Download PDFInfo
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- 229920003023 plastic Polymers 0.000 title claims abstract description 82
- 239000004033 plastic Substances 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 239000003365 glass fiber Substances 0.000 claims abstract description 97
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 43
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 40
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000004952 Polyamide Substances 0.000 claims abstract description 35
- 229920002647 polyamide Polymers 0.000 claims abstract description 35
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 29
- 239000004417 polycarbonate Substances 0.000 claims abstract description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
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- 238000002791 soaking Methods 0.000 claims abstract description 10
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- 238000000151 deposition Methods 0.000 claims abstract description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 32
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000007822 coupling agent Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 18
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052621 halloysite Inorganic materials 0.000 claims description 16
- 239000002071 nanotube Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 13
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 13
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 10
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical class C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 10
- 229920001046 Nanocellulose Polymers 0.000 claims description 9
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 8
- 238000004513 sizing Methods 0.000 claims description 7
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- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 230000004888 barrier function Effects 0.000 abstract description 17
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229960003638 dopamine Drugs 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
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- 239000001257 hydrogen Substances 0.000 description 4
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- 229910052582 BN Inorganic materials 0.000 description 3
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- 238000005452 bending Methods 0.000 description 3
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- 239000002270 dispersing agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920001112 grafted polyolefin Polymers 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
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- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical class C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- FCZCIXQGZOUIDN-UHFFFAOYSA-N ethyl 2-diethoxyphosphinothioyloxyacetate Chemical compound CCOC(=O)COP(=S)(OCC)OCC FCZCIXQGZOUIDN-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
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- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the field of high polymer materials, and particularly discloses a high-strength high-toughness plastic material, a preparation method thereof and a high-strength high-toughness plastic product. The high-strength high-toughness plastic material comprises the following components in parts by weight: 20-80 parts of polyamide, 15-70 parts of polycarbonate, 0.1-1.1 parts of antioxidant, 0.1-1.5 parts of lubricant, 10-40 parts of modified glass fiber and 1.5-2.5 parts of compatilizer; the preparation method of the modified glass fiber comprises the following steps: soaking glass fiber in impregnating agent, suction filtering, drying, soaking in dichloromethane solution of polytetrafluoroethylene, suction filtering, drying, depositing polydopamine on the surface of glass fiber, soaking in silica dispersion, suction filtering, and drying. The high-strength high-toughness plastic material can be used for preparing high-strength high-toughness plastic products. The high-strength high-toughness plastic material has the advantages of high strength, high toughness and good barrier property.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a high-strength high-toughness plastic material, a preparation method thereof and a high-strength high-toughness plastic product.
Background
Because of its special molecular structure, polyamide has excellent mechanical properties, self-lubricating properties and thermal stability, and is widely used as engineering plastic in the fields of automobiles, electronic appliances, machinery, sports equipment, daily plastic products and the like. However, polyamide has the disadvantages of high molding shrinkage, high water absorption and the like, so that the dimensional stability of the prepared product is poor, and the use of polyamide is limited.
In order to enhance the performance of the PA, the application range is enlarged, and the PA material is generally modified and enhanced by adopting glass fiber. In the prior art, the Chinese patent document with the application number of CN201310344778X discloses a high-strength and high-toughness glass fiber reinforced PA/ABS composite material, which is prepared from the following raw material components in percentage by weight: 10-65% of polyamide, 10-50% of ABS, 5-15% of compatilizer, 10-40% of glass fiber, 0.1-1% of antioxidant and 0.1-1% of lubricating dispersant, wherein the polyamide is polyamide 6, the intrinsic viscosity of the polyamide is 2.4dL/g, the glass fiber is alkali-free glass fiber, the surface of the glass fiber is treated by a silane coupling agent, and the compatilizer is maleic anhydride and glycidyl methacrylate difunctional co-grafted polyolefin elastomer.
Aiming at the related technology, the inventor finds that the compatilizer can solve the compatibility of the PA and the ABS, and has certain influence on the adhesion degree and the compatibility of the glass fiber and the PA along with the increase of the proportion of the glass fiber added in the PA, so that part of the glass fiber in the prepared plastic particle product is debonded with the PA resin, thereby greatly reducing the mechanical property of the plastic product produced subsequently.
Disclosure of Invention
In order to improve mechanical properties such as strength and toughness of plastic products, the application provides a high-strength and high-toughness plastic material, a preparation method thereof and the high-strength and high-toughness plastic products.
In a first aspect, the present application provides a high-strength and high-toughness plastic material, which adopts the following technical scheme:
the high-strength high-toughness plastic material comprises the following components in parts by weight: 20-80 parts of polyamide, 15-70 parts of polycarbonate, 0.1-1.1 parts of antioxidant, 0.1-1.5 parts of lubricant, 10-40 parts of modified glass fiber and 1.5-2.5 parts of compatilizer;
the preparation method of the modified glass fiber comprises the following steps: soaking glass fiber in impregnating agent, suction filtering, drying, soaking in dichloromethane solution of polytetrafluoroethylene, suction filtering, drying, depositing polydopamine on the surface of glass fiber, soaking in silica dispersion, suction filtering, and drying.
By adopting the technical scheme, the polycarbonate and the polyamide are used as main base materials of the high-strength high-toughness plastic material, the polycarbonate has outstanding impact toughness, good transparency and dimensional stability, the interfacial adhesion between the polycarbonate and the polyamide is improved by using the compatilizer, the mechanical strength of a blending system is improved, the impact strength of the polyamide is improved by the polycarbonate, the low-temperature brittleness of the polyamide is improved, the water absorption rate is reduced, and the creep resistance and the dimensional stability are improved; glass fiber is used for enhancing the strength and toughness of the blend of polycarbonate and polyamide, after the glass fiber is modified, the interfacial adhesion between the glass fiber and the polycarbonate and the polyamide is increased, and the compatibility is improved; the modified glass fiber is wetted by the impregnating compound, the surface of the glass fiber can be effectively protected by the impregnating compound, the interface bonding fastness of the glass fiber and polytetrafluoroethylene resin can be improved to a certain extent, polytetrafluoroethylene is dried to form a polytetrafluoroethylene film on the glass fiber, the glass fiber is dispersed in polyamide to play a role in bearing and transmitting stress, the mechanical strength of the glass fiber can be improved by coating the polytetrafluoroethylene on the surface, but the compatibility of the glass fiber and the polyamide is still to be improved due to coating of the polytetrafluoroethylene on the surface, so that dopamine is deposited on the polytetrafluoroethylene surface, the dopamine is subjected to an oxidation G crosslinking reaction on the polytetrafluoroethylene to generate a polydopamine composite layer capable of being adsorbed on the polytetrafluoroethylene film, the hydrophilicity of the polytetrafluoroethylene is improved, the adhesiveness of the polydopamine is recycled, the silicon dioxide is adhered on the polytetrafluoroethylene surface, the roughness of the polytetrafluoroethylene surface is increased, the bending strength and the tensile strength of the glass fiber are enhanced, the compatibility of the polytetrafluoroethylene and the polyamide are improved, the interface strength of the polytetrafluoroethylene and the silicon dioxide are improved, more silicon dioxide particles are adhered on the polytetrafluoroethylene surface, the dispersion of the silicon dioxide is facilitated, and the mechanical strength is improved.
Optionally, the impregnating compound comprises the following components in parts by weight:
1.9-2 parts of coupling agent KH550, 2.4-3 parts of coupling agent Z6214, 0.8-1.2 parts of nano boron nitride, 1-2 parts of modified corn starch and 10-12 parts of ethanol.
By adopting the technical scheme, corn starch in the wetting agent is used as a film forming agent, a protective film can be formed on the surface of the glass fiber so as to improve the interface bonding fastness between the glass fiber and polytetrafluoroethylene, hydrogen atoms with small electronegativity on the amino surface in the coupling agent KH550 are easy to form hydrogen bonds with fluorine atoms with strong electronegativity in the polytetrafluoroethylene, so that dichloromethane of the glass fiber and polytetrafluoroethylene is easy to disperse uniformly, the interface compatibility of the glass fiber and the polytetrafluoroethylene is improved, the interface bonding strength of a composite material is improved, the coupling agent Z6214 can promote the film forming compactness of the impregnating agent, and the coupling agent Z6214 contains a benzene ring structure, so that the coupling agent Z can be convenient to intertwine with long and twisted long molecular chains of the polytetrafluoroethylene, the long molecular chains of the polytetrafluoroethylene can penetrate through the benzene ring so that the connection of the polytetrafluoroethylene and the glass fiber is more compact, the connection stability of the polytetrafluoroethylene and the glass fiber is improved, a uniform layer of dot-shaped particles is formed on the glass fiber, the surface roughness is increased, the roughness of the surface of the glass fiber is improved, the surface energy of the glass fiber is improved, and the interface adhesion of the glass fiber and polytetrafluoroethylene is better, and the mechanical property is excellent.
Optionally, the impregnating compound is prepared by the following method:
uniformly mixing a coupling agent KH550, a coupling agent Z6214, nano boron nitride and modified corn starch, adding ethanol, and performing ultrasonic dispersion to obtain the sizing agent.
By adopting the technical scheme, the preparation method of the impregnating compound is simple, and the impregnating compound is prepared by mixing all substances and then carrying out ultrasonic treatment, so that all components are convenient to disperse uniformly in ethanol, and the impregnating compound with mild and uniform properties is prepared.
Optionally, the silica dispersion is prepared by mixing nano silica, PET and ethanol in a mass ratio of 1-1.5:0.1-0.3:10.
By adopting the technical scheme, the silica dispersion liquid not only contains silica, but also contains PET, under the adhesion effect of polydopamine, the PET and the silica are adhered on a polytetrafluoroethylene film on the surface of glass fiber, the roughness of the surface of polytetrafluoroethylene is increased, the compatibility of polytetrafluoroethylene and polyamide is improved, and when a plastic material is prepared, the PET is not fused by hot melting because the temperature of the PET is higher than that of polyamide, so that the PET on the glass fiber is not fused by hot melting when the glass fiber and the polyamide are extruded and granulated, and still exists in the form of solid particles, thereby improving the compatibility of the glass fiber and the polyamide, improving the interfacial adhesion and improving the strength and toughness of the plastic material.
Optionally, the plastic material also comprises 10-15 parts by weight of modified ethylene-vinyl acetate copolymer, wherein the modified ethylene-vinyl acetate copolymer is prepared by mixing, extruding and granulating 0.3-0.6 part by weight of halloysite nanotubes, 1-2 parts by weight of EVA, 0.5-1 part by weight of polyvinyl alcohol and 0.4-0.8 part by weight of nanocellulose fibrils.
According to the technical scheme, the modified EVA prepared by mixing and extruding EVA, halloysite nanotubes, polyvinyl alcohol and nanocellulose fibrils is added, the halloysite nanotubes are formed by curling sheets of kaolin under natural conditions, the chemical composition of the halloysite nanotubes is the same as that of the kaolin, but the halloysite nanotubes have unique nano properties and larger length-diameter ratio and specific surface area, but due to the action of hydrogen bonds, the compatibility with polymers is poor, the aggregation phenomenon is easy to occur, when the modified EVA is mixed and extruded with EVA, polyvinyl alcohol is added, and due to the fact that the polyvinyl alcohol is similar to the EVA in structure, the polyvinyl alcohol has certain compatibility, the hydrogen bonding action among halloysite nanotubes is broken, the acting force among molecules is weakened, the interface binding force between the halloysite nanotubes and the EVA is improved, the halloysite nanotubes are uniformly dispersed in the EVA, the action of transferring stress is achieved, and the EVA is enhanced; the nano cellulose fiber has higher crystallinity and cohesive energy density, is an efficient oxygen barrier substance, can form a dense and complex network structure, can reduce the permeability of oxygen, and the hydroxyl on the nano cellulose fiber can form stronger hydrogen bond with the hydroxyl on the polyvinyl alcohol, so that the number of exposed hydroxyl is reduced, and the water vapor barrier property of the composite material is further improved; and the halloysite nanotube and the nanocellulose fibril play a heterogeneous nucleation role in the EVA, so that the crystallinity of the modified EVA is improved, and the barrier property and the tensile strength are improved.
Optionally, the compatilizer comprises a styrene-maleic anhydride copolymer and a glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer with a mass ratio of 2-3:5.
By adopting the technical scheme, the styrene-maleic anhydride copolymer and the glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer are used as the compatilizer, so that amino exchange reaction between polyamide and polycarbonate can be prevented during blending, the performance reduction of a mixed material caused by the reduction of the molecular weight of a matrix is avoided, an anhydride group in the styrene-maleic anhydride copolymer can be subjected to chemical reaction with a hydroxyl group at the tail end in the polycarbonate to generate a graft of maleic anhydride and polycarbonate, the styrene chain segment in the glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer and the polycarbonate have better compatibility, and an epoxy group in the glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer can be subjected to chemical reaction with the polycarbonate, so that under the combined action of the two compatilizers, the compatilizer and the matrix are subjected to chemical reaction during the blending process, the interfacial tension between the polyamide and the polycarbonate is obviously reduced, the polycarbonate is gradually refined and dispersed in the melting process, and the blend with sufficiently refined dispersed particles and small particle size distribution and good dispersibility is finally obtained.
Optionally, the antioxidant is selected from one or more of antioxidant 168, antioxidant 1076 and antioxidant 1010; the lubricant is ethylene bis stearamide and silicone with the mass ratio of 1:0.4-0.7.
Optionally, the PA is PA66, and the relative viscosity of PA66 is 1.5-3.5;
the polycarbonate is selected from bisphenol A type polycarbonate with a weight average molecular weight of 15000-45000 g/mol.
By adopting the technical scheme, if the viscosity of the polyamide is too low, the fluidity of the blending system is possibly too good, and the polyamide is not easy to be stretched and granulated; if the viscosity is too high, the fluidity is too poor, which is unfavorable for even mixing with the polycarbonate; bisphenol A polycarbonate has good impact resistance and creep resistance, high transparency and good dimensional stability.
In a second aspect, the present application provides a method for preparing a high-strength and high-toughness plastic material, which adopts the following technical scheme: a preparation method of a high-strength high-toughness plastic material comprises the following steps:
mixing polyamide, polycarbonate, compatilizer, antioxidant and lubricant to obtain premix;
extruding and granulating the premix, adding the modified glass fiber into a lateral feeding port in the extrusion process, and extruding and granulating to obtain the high-strength high-toughness plastic material.
By adopting the technical scheme, the modified glass fiber is added from the lateral feeding port, so that the dispersion uniformity of the modified glass fiber is improved.
In a third aspect, the present application provides a high-strength and high-toughness plastic product, which adopts the following technical scheme:
a high-strength high-toughness plastic product comprises a high-strength high-toughness plastic material.
In summary, the present application has the following beneficial effects:
1. according to the method, polycarbonate is adopted as the strength modified material of the polyamide, the compatilizer is added, the compatibility of the polycarbonate and the polyamide is improved, the mechanical strength of the mixed material is improved, the impregnating compound is used for soaking, then polytetrafluoroethylene is coated, the modified glass fiber is prepared by a method that the polydopamine is adhered to the polytetrafluoroethylene, the dispersibility and the compatibility of the glass fiber and the polytetrafluoroethylene are improved by the impregnating compound, the strength of the glass fiber is improved by the coating of the polytetrafluoroethylene, the hydrophilicity of the polytetrafluoroethylene is improved by the polydopamine, the adhesion of the polytetrafluoroethylene and the silicon dioxide is improved, the roughness of the polytetrafluoroethylene is improved, and the interfacial adhesion of the glass fiber and the polyamide is improved, so that the mechanical property of the prepared plastic material is more excellent.
2. In the application, preferably, a coupling agent KH550, a coupling agent Z6214, boron nitride and the like are used as impregnating agents, the compatibility of polytetrafluoroethylene and glass fibers can be improved by adding the two coupling agents, and the roughness of the surface of the glass fibers can be increased by the boron nitride, so that the adhesive force of the glass fibers and the polytetrafluoroethylene is increased.
3. In the application, modified EVA prepared by mixing and granulating halloysite nanotubes, polyvinyl alcohol, cellulose nanofibrils and EVA is preferably added into the plastic material, the halloysite nanotubes and the cellulose nanofibrils are used as nucleating agents, the barrier property and mechanical strength of the plastic material can be improved, the polyvinyl alcohol is matched with the cellulose nanofibrils, the transmittance of water vapor can be further reduced, and the water vapor barrier property is improved.
Detailed Description
Preparation examples 1 to 4 of impregnating compound
Preparation example 1: 2kg of coupling agent KH550, 3kg of coupling agent Z6214, 1.2kg of nano boron nitride and 2kg of modified corn starch are uniformly mixed, and then 12kg of ethanol is added for ultrasonic dispersion, so as to prepare the impregnating compound.
Preparation example 2: mixing 1.9kg of coupling agent KH550, 2.4kg of coupling agent Z6214, 0.8kg of nano boron nitride and 1kg of modified corn starch uniformly, adding 10kg of ethanol, and performing ultrasonic dispersion to obtain the sizing agent.
Preparation example 3: the difference from preparation example 1 is that no nano boron nitride was added.
Preparation example 4: the difference from preparation 1 is that no coupling agent Z6214 was added.
Preparation examples 5 to 12 of modified glass fibers
Preparation example 5: (1) Placing the glass fiber in a muffle furnace for roasting, heating to 600 ℃ within 1h, preserving heat for 1h, removing organic matters on the surface of the glass fiber, cleaning for 2 times by using deionized water, and drying;
(2) Immersing the glass fiber obtained in the step (1) in an impregnating compound, immersing for 3 hours at 40 ℃, carrying out suction filtration, and drying for 120 minutes at 80 ℃, wherein the impregnating compound is prepared from the preparation example 1;
(3) Immersing the glass fiber obtained in the step (2) in a dichloromethane solution with the concentration of 20wt%, immersing for 3 hours at room temperature, filtering, and drying for 5 hours at 90 ℃;
(4) Mixing the glass fiber obtained in the step (3) with a dopamine aqueous solution, stirring at room temperature for 10 hours, filtering, washing with deionized water, and drying at 60 ℃ under reduced pressure to obtain the glass fiber with the polydopamine deposited on the surface, wherein the concentration of the dopamine aqueous solution is 2g/L, and the pH value of the dopamine aqueous solution is adjusted to 8.5 by Tris-HCl;
(5) Immersing the glass fiber obtained in the step (4) into a silicon dioxide dispersion liquid, immersing for 5 hours at 38 ℃, carrying out suction filtration and drying, wherein the silicon dioxide dispersion liquid is prepared from 1kg of silicon dioxide and 10kg of ethanol.
Preparation example 6: the difference from preparation example 5 is that the impregnating compound was prepared from preparation example 2.
Preparation example 7: the difference from preparation 5 is that the impregnating compound was prepared from preparation 3.
Preparation example 8: the difference from preparation 5 is that the impregnating compound was prepared from preparation 4.
Preparation example 9: the difference from preparation 5 is that the silica dispersion is made of 1kg of nanosilica, 0.1kg of PET having a particle size of 10 μm and 10kg of ethanol.
Preparation example 10: the difference from preparation 5 is that the silica dispersion is made of 1.5kg of nanosilica, 0.3kg of PET having a particle size of 10 μm and 10kg of ethanol.
Preparation example 11: the difference from preparation example 9 is that PET was not added to the silica dispersion.
Preparation example 12: the difference from preparation example 9 is that no nanosilica was added to the silica dispersion.
Examples
Example 1: the high-strength high-toughness plastic material is prepared from polyamide PA66, relative viscosity of 2.5, weight average molecular weight of polycarbonate 30000g/mol, relative viscosity of 2.5, antioxidant 1010, lubricant comprising ethylene bis-stearamide and silicone in a mass ratio of 1:0.7, and compatibilizer comprising styrene-maleic anhydride copolymer and glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer in a mass ratio of 3:5, wherein the modified glass fiber is prepared from preparation example 5.
The preparation method of the high-strength high-toughness plastic raw material comprises the following steps:
(1) Mixing polyamide, polycarbonate, compatilizer, antioxidant and lubricant to obtain premix;
(2) Extruding and granulating the premix, adding the modified glass fiber into a lateral feeding port in the extrusion process, extruding and granulating to obtain the high-strength high-toughness plastic material, wherein the temperature of a first region of a double-screw extruder is 120 ℃, the temperature of a second region of the double-screw extruder is 180 ℃, the temperature of a third region of the double-screw extruder is 190 ℃, the temperature of a fourth region of the double-screw extruder is 210 ℃, the temperature of a fifth region of the double-screw extruder is 220 ℃, the temperature of a sixth region of the double-screw extruder is 210 ℃, the temperature of a machine head is 200 ℃, and the rotating speed of a screw is 100r/min.
TABLE 1 raw material amounts of high-strength and high-toughness Plastic materials in examples 1-4
Example 2: a high-strength and high-toughness plastic product is different from example 1 in that the raw material amounts are shown in Table 1, and the modified glass fiber is prepared from preparation example 6.
Examples 3-4: a high-strength high-toughness plastic product is different from example 1 in that the raw material amounts are shown in Table 1.
Example 5: a high strength, high toughness plastic article differs from example 1 in that modified glass fibers are made from preparation 7.
Example 6: a high strength, high toughness plastic article differs from example 1 in that modified glass fibers are made from preparation 8.
Example 7: a high strength, high toughness plastic article differs from example 1 in that modified glass fibers were made from preparation 9.
Example 8: a high strength, high toughness plastic article differs from example 1 in that modified glass fibers are made from preparation 10.
Example 9: a high strength, high toughness plastic article differs from example 1 in that modified glass fibers are made from preparation 11.
Example 10: a high strength, high toughness plastic article differs from example 1 in that modified glass fibers are made from preparation 12.
Example 11: a high-strength high-toughness glass fiber is different from the embodiment 7 in that in the step S1, 15kg of modified ethylene-vinyl acetate copolymer is also contained in the premix, the modified ethylene-vinyl acetate copolymer is prepared by mixing 0.6kg of halloysite nanotubes, 3kg of EVA, 1kg of polyvinyl alcohol and 0.8kg of nano cellulose filaments, extruding and granulating, wherein the temperature of a compression section of an extruder is 145 ℃, the temperature of a homogenization section is 150 ℃, the temperature of a die is 145 ℃, and the rotating speed of a screw is 20r/min.
Example 12: a high-strength high-toughness glass fiber is different from the embodiment 7 in that in the step S1, 10kg of modified ethylene-vinyl acetate copolymer is also contained in the premix, the modified ethylene-vinyl acetate copolymer is prepared by mixing 0.3kg of halloysite nanotubes, 1kg of EVA, 0.5kg of polyvinyl alcohol and 0.4kg of nano cellulose fibrils, extruding and granulating, wherein the temperature of a compression section of an extruder is 145 ℃, the temperature of a homogenization section is 150 ℃, the temperature of a mouth mold is 145 ℃, and the rotating speed of a screw is 20r/min.
Example 13: a high strength, high toughness plastic material differs from example 11 in that no halloysite nanotubes are added to the modified ethylene-vinyl acetate copolymer.
Example 14: a high strength, high toughness plastic material differs from example 11 in that no nanocellulose fibrils are added to the modified ethylene-vinyl acetate copolymer.
Example 15: a high strength, high toughness plastic material differs from example 11 in that an equivalent amount of EVA is used instead of the modified ethylene vinyl acetate copolymer.
The high-strength high-toughness plastic material can be used for preparing high-strength high-toughness plastic products, such as kitchen and toilet tools, utensils, cups, educational toys, animal toys, fruit trays and the like.
Comparative example
Comparative example 1: a high strength, high toughness plastic material differs from example 1 in that the modified glass fibers are not impregnated with a sizing agent during the preparation of the modified glass fibers.
Comparative example 2: a high strength, high toughness plastic material differs from example 1 in that the modified glass fiber is prepared without impregnating the polytetrafluoroethylene in methylene chloride solution.
Comparative example 3: a high strength and toughness plastic material is different from example 1 in that polydopamine is not deposited on the surface of the glass fiber when the modified glass fiber is prepared.
Comparative example 4: a high-strength, high-toughness plastic material differs from example 1 in that no polycarbonate is added.
Comparative example 5: a high-strength and high-toughness glass fiber reinforced PA/ABS composite material comprises the following components in percentage by weight: 44% of polyamide, 30% of ABS, 5% of compatilizer, 20% of glass fiber, 0.5% of antioxidant and 0.5% of wetting dispersant, wherein the polyamide is PA6, the glass fiber is alkali-free glass fiber with the surface treated by a silane coupling agent, the antioxidant is hindered phenol antioxidant, the lubricating dispersant is silicone, and the compatilizer is maleic anhydride and glycidyl methacrylate difunctional co-grafted polyolefin elastomer; the preparation method of the high-strength and high-toughness glass fiber reinforced PA/ABS composite material comprises the following steps: other raw materials except the glass fiber are put into a high-efficiency mixer to be mixed for 5 minutes, and then discharged; extruding and granulating the obtained premix by a double-screw extruder, wherein glass fibers are added at a lateral feeding port in the extrusion process, the processing temperature is divided into nine sections, the first section is 210 ℃, the second section is 215 ℃, the third section is 220 ℃, the fourth section is 225 ℃, the fifth section is 235 ℃, the sixth section is 225 ℃, the seventh section is 220 ℃, the eighth section is 215 ℃, the ninth section is 210 ℃, and the screw revolution is 35Hz.
Performance test
Plastic materials were prepared according to the methods in examples and comparative examples, and each property was measured according to the following method, and the measurement results are recorded in table 2.
1. Tensile strength: the test is carried out according to GB/T1040-1992 method for testing tensile properties of plastics, and the tensile rate is 10mm/min;
2. flexural strength: the bending speed is 10mm/min according to the detection of GB/T9341-200 method for testing bending Performance of plastics;
3. notched impact strength: notch impact strength according to GB/T1843-1996 plastics cantilever impact test method, test temperature is 23 ℃;
4. water vapor transmission rate: the test was carried out according to GB/T1037-1988 cup method for Water vapor permeability test method for Plastic film and sheet. The test temperature was 38℃and the relative humidity was 60%;
5. oxygen transmission rate: the test is carried out according to GB/T1038-2000 "differential pressure method for gas permeability test method of plastic film and sheet", the test temperature is 23 ℃, and the relative humidity is 60%.
Table 2 performance testing of high strength and toughness plastic materials
The amounts of plastic raw materials used in examples 1-4 were different, and the modified glass fibers prepared in preparation examples 5 and 6 were used in examples 1 and 2, respectively, which had higher strength and toughness.
In example 5, the modified glass fiber prepared in preparation example 7 was used, and boron nitride was not added to the sizing agent in the preparation of the modified glass fiber, so that the plastic material prepared in example 5 was reduced in tensile strength, reduced in flexural strength, reduced in impact resistance, and less in barrier property change than in example 1.
The modified glass fiber prepared in example 6 using preparation example 8, wherein no coupling agent Z6214 was added to the sizing agent, had a reduced tensile strength and flexural strength and increased mechanical properties compared to example 1.
In examples 7 and 8, silica dispersions were prepared using silica, PET and ethanol, and the tensile strength and flexural strength of the plastic material were increased and barrier properties were enhanced as compared with example 1.
In example 9, the modified glass fiber produced in preparation example 11 was used, in which PET was not added to the silica dispersion, and the tensile strength and flexural strength of the plastic material were reduced and the barrier property was reduced as compared with example 7.
The modified glass fiber prepared in example 10 using preparation 12, in which no silica was added, showed in Table 1 that the plastic material prepared in example 10 had slightly lower mechanical properties and lower barrier properties than in example 7.
Examples 11 and 12 also incorporate modified EVA compared to example 7, and table 1 shows that the tensile strength and flexural strength of the plastic materials prepared in examples 11 and 12 are increased and the barrier improvement is significant.
In example 13 and example 14, halloysite nanotubes and cellulose nanofibers were not added to the modified EVA, respectively, but the mechanical strength of the plastic materials in example 13 and example 14 was reduced, and the barrier property was lowered, as compared with example 11.
In example 15, the same amount of unmodified EVA was used instead of the modified EVA, and compared with example 11, the plastic material had an increased water vapor and oxygen transmission rate, a significantly reduced barrier property, and a reduced mechanical strength.
In comparative example 1, the glass fiber was not immersed in the sizing agent, and the tensile strength and flexural strength of the plastic material thus produced were reduced and the barrier properties were not greatly changed, as compared with example 1; comparative example 2 compared with example 1, the mechanical strength of the plastic is reduced and the barrier property is also reduced without immersing the glass fiber in the dichloromethane solution of polytetrafluoroethylene; in comparative example 3, polydopamine was not deposited on the surface of the glass fiber, and the tensile strength and flexural strength of the plastic material prepared in comparative example 3 were reduced as compared with example 1.
Comparative example 4 has a less significant change in barrier properties against water vapor and oxygen, but has a reduced mechanical strength, compared with example 1, without the addition of polycarbonate.
Comparative example 5 is a composite material prepared by the prior art and having PA and ABS as substrates, which has lower tensile strength and flexural strength than example 1, and also has reduced barrier properties.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. The high-strength high-toughness plastic material is characterized by comprising the following components in parts by weight: 20-80 parts of polyamide, 15-70 parts of polycarbonate, 0.1-1.1 parts of antioxidant, 0.1-1.5 parts of lubricant, 10-40 parts of modified glass fiber and 1.5-2.5 parts of compatilizer;
the preparation method of the modified glass fiber comprises the following steps: soaking glass fiber in impregnating agent, suction filtering, drying, soaking in dichloromethane solution of polytetrafluoroethylene, suction filtering, drying, depositing polydopamine on the surface of glass fiber, soaking in silica dispersion, suction filtering, and drying.
2. The high-strength high-toughness plastic material according to claim 1, wherein the impregnating compound comprises the following components in parts by weight:
9-2 parts of coupling agent KH550, 2.4-3 parts of coupling agent Z6214, 0.8-1.2 parts of nano boron nitride, 1-2 parts of modified corn starch and 10-12 parts of ethanol.
3. The high strength, high toughness plastic material of claim 2, wherein: the impregnating compound is prepared by the following steps:
uniformly mixing a coupling agent KH550, a coupling agent Z6214, nano boron nitride and modified corn starch, adding ethanol, and performing ultrasonic dispersion to obtain the sizing agent.
4. The high-strength and high-toughness plastic material according to claim 1, wherein the silica dispersion is prepared by mixing nano silica, PET and ethanol in a mass ratio of 1-1.5:0.1-0.3:10.
5. The high-strength and high-toughness plastic material according to claim 1, further comprising 10-15 parts by weight of a modified ethylene-vinyl acetate copolymer, wherein the modified ethylene-vinyl acetate copolymer is prepared by mixing 0.3-0.6 part by weight of halloysite nanotubes, 1-2 parts by weight of EVA, 0.5-1 part by weight of polyvinyl alcohol and 0.4-0.8 part by weight of nanocellulose fibrils, extruding and granulating.
6. The high strength, high toughness plastic material according to claim 1, wherein the compatibilizer comprises a styrene-maleic anhydride copolymer and a glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer in a mass ratio of 2-3:5.
7. The high-strength and high-toughness plastic material according to claim 1, wherein the antioxidant is one or more selected from the group consisting of antioxidant 168, antioxidant 1076 and antioxidant 1010;
the lubricant is ethylene bis stearamide and silicone with the mass ratio of 1:0.4-0.7.
8. The high-strength high-toughness plastic material according to claim 1, wherein PA is PA66, and the relative viscosity of PA66 is 1.5-3.5;
the polycarbonate is selected from bisphenol A type polycarbonate with a weight average molecular weight of 15000-45000 g/mol.
9. The method for preparing the high-strength and high-toughness plastic material according to any one of claims 1 to 8, which is characterized by comprising the following steps:
mixing polyamide, polycarbonate, compatilizer, antioxidant and lubricant to obtain premix;
extruding and granulating the premix, adding the modified glass fiber into a lateral feeding port in the extrusion process, and extruding and granulating to obtain the high-strength high-toughness plastic material.
10. A high strength, high toughness plastic article comprising the high strength, high toughness plastic material of any one of claims 1-8.
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