CN116694077A - High-strength polyphenylene sulfide-based plastic and preparation method thereof - Google Patents
High-strength polyphenylene sulfide-based plastic and preparation method thereof Download PDFInfo
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- CN116694077A CN116694077A CN202310503941.6A CN202310503941A CN116694077A CN 116694077 A CN116694077 A CN 116694077A CN 202310503941 A CN202310503941 A CN 202310503941A CN 116694077 A CN116694077 A CN 116694077A
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 67
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 67
- 239000004033 plastic Substances 0.000 title claims abstract description 39
- 229920003023 plastic Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000835 fiber Substances 0.000 claims abstract description 58
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000004952 Polyamide Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229920002647 polyamide Polymers 0.000 claims abstract description 14
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- 239000004677 Nylon Substances 0.000 claims abstract description 7
- 229920001778 nylon Polymers 0.000 claims abstract description 7
- 238000005469 granulation Methods 0.000 claims abstract description 6
- 230000003179 granulation Effects 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000003365 glass fiber Substances 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 23
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000012065 filter cake Substances 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000013067 intermediate product Substances 0.000 claims description 12
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- 230000004224 protection Effects 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 22
- 239000003963 antioxidant agent Substances 0.000 abstract description 6
- 230000003078 antioxidant effect Effects 0.000 abstract description 6
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229920002943 EPDM rubber Polymers 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000000412 dendrimer Substances 0.000 description 3
- 229920000736 dendritic polymer Polymers 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000412 polyarylene Polymers 0.000 description 2
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910001125 Pa alloy Inorganic materials 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-strength polyphenylene sulfide-based plastic and a preparation method thereof, belonging to the technical field of polyphenylene sulfide-based plastics, and comprising the following components in parts by weight: 100 parts of polyphenylene sulfide, 35-50 parts of nylon, 25-35 parts of fiber components, 5-10 parts of compatilizer and 1-3 parts of lubricant; the preparation method comprises the following steps: drying polyphenylene sulfide, polyamide and compatilizer in an oven at 110-130 ℃ for 6-8 hours, weighing raw materials according to the proportion in the formula, placing the raw materials in a mixer, mixing for 5-10min, transferring the raw materials into a double screw extruder, and carrying out melt extrusion and granulation, wherein the extrusion temperature is 280-310 ℃; based on the problems of poor ageing resistance and poor mechanical strength of the existing polyphenylene sulfide-based plastic, the self-made fiber component is introduced, so that the ageing resistance of the polyphenylene sulfide-based plastic is endowed under the condition of ensuring the good mechanical strength of the polyphenylene sulfide-based plastic, and the problems of easy migration and precipitation, instability and the like of the existing antioxidant are overcome.
Description
Technical Field
The invention belongs to the technical field of polyphenylene sulfide-based plastics, and particularly relates to a high-strength polyphenylene sulfide-based plastic and a preparation method thereof.
Background
Polyphenylene sulfide belongs to one of polyarylene sulfide, a molecular main chain is formed by alternately connecting sulfur and aryl structures, and is totally called polyarylene sulfide (PPS), also called polyphenylene ether, is a special engineering plastic with potential and application value, commonly called plastic gold, and is widely applied to manufacturing automobile parts such as an air inlet pipe, a gasification pump, a seat base, a radiator part, a water tank water chamber and the like due to the characteristics of good mechanical property, high dimensional accuracy, high temperature resistance, corrosion resistance and the like.
Because the solubility parameters (12.5) of the PPS and the amide polymers such as PA6, PA66 and the like are very similar, the PPS/PA alloy has good compatibility, and is a hot spot for PPS blending modification research, for example, chinese patent CN109749015B provides a polyphenylene sulfide polyamide resin composition and a preparation method thereof, and the polyphenylene sulfide polyamide resin composition comprises the following components in parts by weight: 50-75 parts of polyamide; 10-20 parts of polyphenylene sulfide; 10-20 parts of functionalized polyphenylene sulfide; 3-10 parts of toughening agent, wherein polyamide and polyphenylene sulfide are used as main materials, functionalized polyphenylene sulfide is added to obtain alloy materials with relatively good performance, but sulfur in polyphenylene sulfide molecules is positive bivalent, unstable, amide groups in polyamide have strong polarity, so that polyamide molecular chains are easily oxidized and attacked to become macromolecular free radicals, and therefore, the aging resistance of the polyamide molecular chains is poor, and the antioxidant component is not introduced to improve the aging resistance of the composition, so that the practical application of the composition is severely restricted, and therefore, the aging-resistant and high-strength polyphenylene sulfide-based plastic is necessary.
Disclosure of Invention
The invention aims to provide high-strength polyphenylene sulfide-based plastic and a preparation method thereof, which are used for solving the problems in the background technology.
The aim of the invention can be achieved by the following technical scheme:
the high-strength polyphenylene sulfide-based plastic comprises the following components in parts by weight:
100 parts of polyphenylene sulfide, 35-50 parts of nylon, 25-35 parts of fiber components, 5-10 parts of compatilizer and 1-3 parts of lubricant;
the high-strength polyphenylene sulfide-based plastic is prepared by the following steps:
drying polyphenylene sulfide, polyamide and compatilizer in a baking oven at 110-130 ℃ for 6-8 hours, weighing raw materials according to the proportion in the formula, placing the raw materials in a mixer, mixing for 5-10min, transferring the raw materials into a double screw extruder, and carrying out melt extrusion and granulation, wherein the extrusion temperature is 280-310 ℃.
Further, the fiber component is made by the steps of:
step S1, adding formic acid into an ethanol water solution, adjusting the pH value to be 3-4, adding a silane coupling agent KH-550, stirring, heating to 70-80 ℃, adding hybrid fibers, stirring for reacting for 10-12 hours, filtering after the reaction is finished, alternately washing a filter cake with absolute ethanol and deionized water, and drying at 80 ℃ to obtain amino hybrid fibers;
s2, adding amino hybrid fiber, methanol and methyl acrylate into a flask under the protection of nitrogen, stirring at 50 ℃ for reaction for 24 hours, filtering, and washing a filter cake with methanol to obtain an intermediate product; under the protection of nitrogen, adding an intermediate product, methanol and 4,4' -diaminodiphenylamine into a reaction kettle, reacting for 12 hours at 60 ℃, filtering after the reaction is finished, and washing a filter cake with methanol to obtain a first-generation product;
step S3, repeating the operation of the step S2, replacing the amino hybridized fiber with a first generation product, and controlling the dosage ratio of the first generation product, methyl acrylate and 4,4' -diaminodiphenylamine to be 6-8g:4-6mL:0.08-0.1mol, and obtaining a second generation product after the treatment is finished;
and S4, adding the second-generation product and absolute ethyl alcohol into a flask, stirring, then dropwise adding epichlorohydrin, stirring at 55 ℃ for reaction for 5-6 hours, cooling to 30 ℃, adding a potassium hydroxide aqueous solution, carrying out heat preservation for reaction for 2 hours, cooling to room temperature, filtering, washing a filter cake with deionized water until a washing solution is neutral, and drying to obtain the fiber component.
The invention firstly utilizes a silane coupling agent KH-550 to carry out surface treatment on hybrid fibers to introduce a large amount of amino groups, then utilizes the addition reaction between the amino groups and unsaturated double bonds of methyl acrylate to introduce ester groups, further utilizes the amide reaction between the ester groups and 4,4' -diaminodiphenylamine to obtain first-generation products, and after repeating the operation, the hybrid fibers of the surface grafted dendritic polyamidoamine, namely second-generation products, are obtained, and then utilizes the elimination reaction of epoxy chloropropane and the amino groups on the surfaces of the second-generation products to introduce active epoxy groups, so that the fiber component is obtained.
Further, in the step S1, the dosage ratio of the ethanol aqueous solution, the silane coupling agent KH-550 and the hybrid fiber is 50-70mL:3-5mL:2g, ethanol aqueous solution is prepared from absolute ethanol and deionized water according to the volume ratio of 80-90:10-20 parts.
Further, the dosage ratio of the amino hybrid fiber, the methyl acrylate and the 4,4' -diaminodiphenylamine in the step S2 is 6-8g:2-3mL:0.04-0.05mol.
Further, the usage ratio of the second generation product, the absolute ethyl alcohol, the epichlorohydrin and the aqueous solution of potassium hydroxide in the step S4 is 4g:40-60mL:4.5-6.2g:4mL, 50% by mass of potassium hydroxide aqueous solution.
Further, the hybrid fiber is produced by the steps of:
placing the glass fiber in a muffle furnace, roasting for 4 hours at 500 ℃, taking out, immersing in the mixed solution a for 1 hour, taking out, repeatedly flushing with deionized water until the washing solution is neutral, and drying to obtain the hydroxylated glass fiber; mixing zinc sulfate, ammonia water and deionized water, transferring to a high-pressure reaction, adding hydroxylated glass fiber, introducing nitrogen to pressurize to 5MPa, reacting for 5 hours at 150 ℃, filtering after the reaction is finished, washing a filter cake with deionized water, and drying to obtain the hybridized glass fiber;
wherein the dosage ratio of the glass fiber to the mixed solution a is 1g:10mL, the mixed solution a is prepared from concentrated sulfuric acid and hydrogen peroxide solution according to the volume ratio of 7:3, the mass fraction of concentrated sulfuric acid is 95%, the mass fraction of hydrogen peroxide solution is 35%, and the dosage ratio of zinc sulfate, ammonia water, deionized water and hydroxylated glass fiber is 0.05-0.1mol:5mL:450-500mL:20-30g of ammonia water with mass fraction of 25-28%, firstly, treating the glass fiber by using the mixed solution a to generate a large amount of oxygen-containing groups on the surface, and generating zinc oxide on the glass fiber in situ by using the characteristic that oxygen atoms rich in electrons in the groups can react with metal oxygen ions to obtain the hybrid fiber.
Further, the glass fiber is short glass fiber, and the length is 3-10mm.
Further, the weight average molecular weight of the polyphenylene sulfide is 40000-60000.
Further, the nylon is one or more of nylon 6, nylon 66 and nylon 1010.
Further, the compatilizer is maleic anhydride grafted styrene-ethylene/butylene-styrene block copolymer (SEBS-g-MAH), maleic anhydride grafted ethylene propylene diene monomer (EPDM-g-MAH) and glycidyl methacrylate grafted ethylene propylene diene monomer (EPDM-g-GMA).
Further, the lubricant is one or two of stearic acid and pentaerythritol stearate.
The invention has the beneficial effects that:
1. based on the problems of poor ageing resistance and poor mechanical strength of the existing polyphenylene sulfide-based plastic, the invention provides the high-strength polyphenylene sulfide-based plastic and the preparation method thereof, and the existing commercial antioxidant is not added into the base material, so that the ageing resistance of the polyphenylene sulfide-based plastic is endowed under the condition of ensuring the good mechanical strength of the polyphenylene sulfide-based plastic by introducing self-made fiber components, and the problems of easy migration, precipitation, instability and the like of the existing antioxidant are overcome.
2. The invention introduces fiber components into polyphenylene sulfide-based plastics, and the surface of the fiber components contains a plurality of active epoxy groups, which can react with-SH groups in polyphenylene sulfide and-NH groups in nylon 2 When the composite material is acted by external force, the matrix transmits the external force to the fiber through the interface, so that the mechanical property of the composite material is improved, dendritic polyamide amine is grafted on the surface of the fiber component, the dendritic polyamide amine has the commonality of dendrimers and the characteristics of the dendrimers, the dendrimers contain a large number of cavities in the molecule, the internal cavity structure can play a role in stabilizing and coating free radicals, the ageing of the composite material is inhibited, the cavity structure can also absorb the impact capability, the impact resistance of the composite material is improved, and the dendritic polyamide amine structure contains diphenylamine, so that the ageing resistance of the composite material is further improved.
3. The fiber component is obtained by surface treatment by taking the hybrid fiber as a base material, wherein the hybrid fiber has the advantages of both glass fiber and zinc oxide, the toughness and ageing resistance of the composite material can be effectively increased, the zinc oxide is generated on the glass fiber in situ, and the dispersibility of the zinc oxide in the composite material is improved while the surface roughness of the glass fiber is increased.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A hybrid fiber made by the steps of:
30g of glass fiber was put in a muffle furnace and baked at 500 ℃ for 4 hours, and taken out and immersed in 300mL of a solution of 95wt% concentrated sulfuric acid and 35wt% hydrogen peroxide according to a volume ratio of 7:3, taking out the mixed solution a formed by the step 3 after 1h, repeatedly flushing the mixed solution a with deionized water until the washing solution is neutral, and drying the mixed solution to obtain the hydroxylated glass fiber; mixing 0.05mol of zinc sulfate, 5mL of ammonia water and 450mL of deionized water, transferring to a high-pressure reaction, adding 20g of hydroxylated glass fiber, pressurizing to 5MPa by introducing nitrogen, reacting for 5 hours at the temperature of 150 ℃, filtering after the reaction is finished, washing a filter cake by deionized water, and drying to obtain the hybrid glass fiber, wherein the mass fraction of the ammonia water is 25%, and the glass fiber is short glass fiber with the length of 3-10mm.
Example 2
A hybrid fiber made by the steps of:
mixing 0.1mol of zinc sulfate, 5mL of ammonia water and 500mL of deionized water, transferring to a high-pressure reaction, adding 30g of hydroxylated glass fiber, pressurizing to 5MPa by introducing nitrogen, reacting for 5 hours at 150 ℃, filtering after the reaction is finished, washing a filter cake with deionized water, and drying to obtain the hybrid glass fiber, wherein the mass fraction of the ammonia water is 28%, and the preparation process of the hydroxylated glass fiber is the same as that of the example 1.
Comparative example 1
This comparative example is the hydroxylated glass fiber obtained in example 1.
Example 3
The fiber component is prepared by the following steps:
step S1, adding formic acid into 50mL of ethanol aqueous solution, adjusting the pH to 3, adding 3mL of silane coupling agent KH-550, stirring, heating to 70 ℃, adding 2g of the hybrid fiber of the embodiment 1, stirring and reacting for 10 hours, filtering, alternately washing a filter cake with absolute ethanol and deionized water, and drying at 80 ℃ to obtain the amino hybrid fiber, wherein the ethanol aqueous solution is prepared from absolute ethanol and deionized water according to a volume ratio of 80:20 parts;
s2, under the protection of nitrogen, adding 6g of amino hybrid fiber, 80mL of methanol and 2mL of methyl acrylate into a flask, stirring at 50 ℃ for reaction for 24 hours, filtering, and washing a filter cake with methanol to obtain an intermediate product; under the protection of nitrogen, adding the intermediate product, 80mL of methanol and 0.04mol of 4,4' -diaminodiphenylamine into a reaction kettle, reacting for 12 hours at 60 ℃, filtering after the reaction is finished, and washing a filter cake with methanol to obtain a first-generation product;
step S3, adding 6g of first-generation product, 80mL of methanol and 4mL of methyl acrylate into a flask under the protection of nitrogen, stirring at 50 ℃ for reaction for 24 hours, filtering, and washing a filter cake with methanol to obtain an intermediate product; under the protection of nitrogen, adding the intermediate product, 150mL of methanol and 0.08mol of 4,4' -diaminodiphenylamine into a reaction kettle, reacting for 12 hours at 60 ℃, filtering after the reaction is finished, and washing a filter cake with methanol to obtain a second-generation product;
and S4, adding 4g of the second-generation product and 40mL of absolute ethyl alcohol into a flask, dropwise adding 4.5g of epoxy chloropropane after stirring, stirring at 55 ℃ for reaction for 5 hours, cooling to 30 ℃, adding 4mL of 50wt% potassium hydroxide aqueous solution, carrying out heat preservation for reaction for 2 hours, cooling to room temperature, filtering, washing a filter cake with deionized water until a washing solution is neutral, and drying to obtain a fiber component.
Example 4
The fiber component is prepared by the following steps:
step S1, adding formic acid into 70mL of ethanol aqueous solution, adjusting the pH to be 4, adding 5mL of silane coupling agent KH-550, stirring, heating to 80 ℃, adding 2g of the hybrid fiber of the example 2, stirring for reaction for 12h, filtering, alternately washing a filter cake with absolute ethanol and deionized water, and drying at 80 ℃ to obtain amino hybrid fiber, wherein the ethanol aqueous solution is prepared from absolute ethanol and deionized water according to a volume ratio of 90:10, the composition is as follows;
s2, under the protection of nitrogen, adding 8g of amino hybrid fiber, 80mL of methanol and 3mL of methyl acrylate into a flask, stirring at 50 ℃ for reaction for 24 hours, filtering, and washing a filter cake with methanol to obtain an intermediate product; under the protection of nitrogen, adding the intermediate product, 80mL of methanol and 0.05mol of 4,4' -diaminodiphenylamine into a reaction kettle, reacting for 12 hours at 60 ℃, filtering after the reaction is finished, and washing a filter cake with methanol to obtain a first-generation product;
step S3, under the protection of nitrogen, adding 8g of first-generation product, 80mL of methanol and 6mL of methyl acrylate into a flask, stirring at 50 ℃ for reaction for 24 hours, filtering, and washing a filter cake with methanol to obtain an intermediate product; under the protection of nitrogen, adding the intermediate product, 200mL of methanol and 0.1mol of 4,4' -diaminodiphenylamine into a reaction kettle, reacting for 12 hours at 60 ℃, filtering after the reaction is finished, and washing a filter cake with methanol to obtain a second-generation product;
and S4, adding 4g of the second-generation product and 60mL of absolute ethyl alcohol into a flask, dropwise adding 6.2g of epoxy chloropropane after stirring, stirring at 55 ℃ for reaction for 6 hours, cooling to 30 ℃, adding 4mL of 50wt% potassium hydroxide aqueous solution, carrying out heat preservation for reaction for 2 hours, cooling to room temperature, filtering, washing a filter cake with deionized water until a washing solution is neutral, and drying to obtain a fiber component.
Comparative example 2
This comparative example provides a fiber component that replaces the hybrid fiber of example 3 with the material of comparative example 1, the remaining materials and the process of preparation of example 3, as compared to example 3.
Example 5
The high-strength polyphenylene sulfide-based plastic comprises the following components in parts by weight:
100 parts of polyphenylene sulfide, 35 parts of nylon 6, 25 parts of the fiber component of example 3, 5 parts of compatilizer and 1 part of lubricant;
the high-strength polyphenylene sulfide-based plastic is prepared by the following steps:
drying polyphenylene sulfide, polyamide and a compatilizer in a baking oven at 110 ℃ for 6 hours, weighing raw materials according to the proportion in the formula, placing the raw materials in a mixer, mixing for 5 minutes, transferring the raw materials into a double-screw extruder, and carrying out melt extrusion and granulation, wherein the extrusion temperature is as follows: one 280 ℃, two 295 ℃, three 310 ℃, four 310 ℃, five 305 ℃ and the temperature of the machine head of 300 ℃.
Wherein the weight average molecular weight of the polyphenylene sulfide is 40000-60000, the compatilizer is maleic anhydride grafted styrene-ethylene/butylene-styrene block copolymer, and the lubricant is stearic acid.
Example 6
The high-strength polyphenylene sulfide-based plastic comprises the following components in parts by weight:
100 parts of polyphenylene sulfide, 45 parts of nylon 66, 30 parts of the fiber component of example 4, 8 parts of compatilizer and 2 parts of lubricant;
the high-strength polyphenylene sulfide-based plastic is prepared by the following steps:
drying polyphenylene sulfide, polyamide and compatilizer in an oven at 120 ℃ for 7 hours, weighing raw materials according to the proportion in the formula, placing the raw materials in a mixer, mixing for 8 minutes, transferring the raw materials into a double-screw extruder, and carrying out melt extrusion and granulation, wherein the extrusion temperature is as follows: one 280 ℃, two 295 ℃, three 310 ℃, four 310 ℃, five 305 ℃ and the temperature of the machine head of 300 ℃.
Wherein the weight average molecular weight of the polyphenylene sulfide is 40000-60000, the compatilizer is maleic anhydride grafted ethylene propylene diene monomer rubber, and the lubricant is pentaerythritol stearate.
Example 7
The high-strength polyphenylene sulfide-based plastic comprises the following components in parts by weight:
100 parts of polyphenylene sulfide, 1010 50 parts of nylon, 35 parts of the fiber component of example 4, 10 parts of compatilizer and 3 parts of lubricant;
the high-strength polyphenylene sulfide-based plastic is prepared by the following steps:
drying polyphenylene sulfide, polyamide and a compatilizer in a baking oven at 130 ℃ for 8 hours, weighing raw materials according to the proportion in the formula, placing the raw materials in a mixer, mixing for 10 minutes, transferring the raw materials into a double-screw extruder, and carrying out melt extrusion and granulation, wherein the extrusion temperature is as follows: one 280 ℃, two 295 ℃, three 310 ℃, four 310 ℃, five 305 ℃ and the temperature of the machine head of 300 ℃.
Wherein the weight average molecular weight of the polyphenylene sulfide is 40000-60000, the compatilizer is maleic anhydride grafted ethylene propylene diene monomer rubber, and the lubricant is pentaerythritol stearate.
Comparative example 3
In comparison with example 5, the fiber composition of example 5 was replaced with the material of comparative example 2, and the remaining raw materials and the production process were the same as in example 5.
Comparative example 4
Compared with example 5, the fiber component in example 5 was used in place of the hybrid fiber obtained in example 2, and the remainder of the raw materials and the production process were the same as in example 5.
The polyphenylene sulfide-based plastics obtained in examples 5 to 7 and comparative examples 3 to 4 were dried in an oven at 110℃for 8 hours, and then subjected to preparation of standard bars by an injection molding machine, wherein the first stage temperature was 280℃in the preparation of standard bars by the injection molding machine, the second stage temperature was 310℃in the preparation of standard bars, the third stage temperature was 305℃in the preparation of standard bars, and the machine head temperature was 295℃in the preparation of standard bars, and performance was measured, tensile properties were measured according to the standard GB/T1040-1992 test, impact strength was measured according to the specification of the standard GB/T1843-1996, and each group of standard bars was placed in an MTS-25 ultraviolet aging oven, and the ultraviolet aging was conducted for 200 hours, and the impact strength was again measured according to the above standard, with a larger change in impact strength, and a poorer aging resistance, and the results shown in Table 1:
TABLE 1
| Project | Example 5 | Example 6 | Example 7 | Comparative example 3 | Comparative example 4 |
| Tensile Strength/MPa | 83.7 | 85.4 | 88.2 | 80.2 | 78.6 |
| Impact Strength before aging/KJ.m -2 | 14.1 | 14.6 | 15.4 | 12.4 | 11.6 |
| Impact Strength after aging/KJ.m -2 | 13.1 | 13.8 | 14.9 | 9.8 | 8.2 |
As can be seen from Table 1, the polyphenylene sulfide-based plastics obtained in examples 5 to 6 have tensile strengths of 83.7 to 88.2MPa and impact strengths of 14.1 to 15.4 KJ.m before aging -2 The impact strength after aging is 13.1-14.9 KJ.m -2 Compared with comparative examples 3-4, the fiber component base material adopted in comparative example 3 is a hydroxylated glass fiber, is not a hybrid fiber, has no introduction of nano zinc oxide, lacks the ultraviolet resistance effect of zinc oxide, cannot increase the roughness of the surface of the glass fiber, cannot form particles on the surface of the glass fiber, and absorbs impact capacity, so that the mechanical strength and the ageing resistance are reduced, and the hybrid fiber directly adopted in comparative example 4 is not subjected to surface treatment, has poor interfacial bonding property with a resin base material and lacks an ageing resistance group, and therefore has reduced mechanical strength and ageing resistance; in summary, based on the problems of poor ageing resistance and poor mechanical strength of the existing polyphenylene sulfide-based plastic, the invention provides the high-strength polyphenylene sulfide-based plastic and the preparation method thereof, and the existing commercial antioxidant is not added into the base material, so that the ageing resistance of the polyphenylene sulfide-based plastic is endowed under the condition of ensuring good mechanical strength of the polyphenylene sulfide-based plastic by introducing self-made fiber components, and the problems of easy migration, precipitation, instability and the like of the existing antioxidant are overcome.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The high-strength polyphenylene sulfide-based plastic is characterized by comprising the following components in parts by weight:
100 parts of polyphenylene sulfide, 35-50 parts of nylon, 25-35 parts of fiber components, 5-10 parts of compatilizer and 1-3 parts of lubricant;
the fiber component is prepared by the following steps:
step S1, adjusting the pH of an ethanol water solution to 3-4, adding a silane coupling agent KH-550, stirring, heating to 70-80 ℃, adding the hybridized fiber, and stirring for reaction for 10-12 hours to obtain amino hybridized fiber;
s2, mixing amino hybrid fiber, methanol and methyl acrylate under the protection of nitrogen, stirring at 50 ℃ for reaction for 24 hours, filtering, washing a filter cake to obtain an intermediate product, mixing the intermediate product, methanol and 4,4' -diaminodiphenylamine, and reacting at 60 ℃ for 12 hours to obtain a first-generation product;
s3, replacing the amino hybridized fiber with a first-generation product, and repeating the operation of the step S2 to obtain a second-generation product;
and S4, mixing the second-generation product with absolute ethyl alcohol, dropwise adding epoxy chloropropane after stirring, stirring at 55 ℃ for reaction for 5-6 hours, cooling to 30 ℃, adding a potassium hydroxide aqueous solution, and reacting for 2 hours under heat preservation to obtain the fiber component.
2. The high-strength polyphenylene sulfide-based plastic according to claim 1, wherein the ethanol aqueous solution, the silane coupling agent KH-550 and the hybrid fiber in the step S1 are used in an amount ratio of 50 to 70mL:3-5mL:2g, ethanol aqueous solution is prepared from absolute ethanol and deionized water according to the volume ratio of 80-90:10-20 parts.
3. The high-strength polyphenylene sulfide-based plastic according to claim 1, wherein the amino-hybrid fiber, methyl acrylate and 4,4' -diaminodiphenylamine are used in the amount ratio of 6 to 8g in step S2: 2-3mL:0.04-0.05mol.
4. The high-strength polyphenylene sulfide-based plastic according to claim 1, wherein the ratio of the first generation product, methyl acrylate and 4,4' -diaminodiphenylamine in step S3 is 6 to 8g:4-6mL:0.08-0.1mol.
5. The high-strength polyphenylene sulfide-based plastic according to claim 1, wherein the ratio of the amount of the second-generation product, absolute ethyl alcohol, epichlorohydrin and aqueous potassium hydroxide solution in step S4 is 4g:40-60mL:4.5-6.2g:4mL, 50% by mass of potassium hydroxide aqueous solution.
6. The high-strength polyphenylene sulfide-based plastic according to claim 1, wherein the hybrid fiber is produced by:
and (3) mixing zinc sulfate, ammonia water and deionized water, transferring to a high-pressure reaction, adding hydroxylated glass fibers, pressurizing to 5MPa by introducing nitrogen, reacting for 5 hours at 150 ℃, filtering after the reaction is finished, washing a filter cake with deionized water, and drying to obtain the hybrid glass fibers.
7. The high-strength polyphenylene sulfide-based plastic according to claim 6, wherein the ratio of zinc sulfate, ammonia water, deionized water and hydroxylated glass fiber is 0.05 to 0.1mol:5mL:450-500mL:20-30g, and ammonia water with mass fraction of 25-28%.
8. The method for preparing high-strength polyphenylene sulfide-based plastic according to claim 1, comprising the steps of:
drying polyphenylene sulfide, polyamide and compatilizer in a baking oven at 110-130 ℃ for 6-8 hours, weighing raw materials according to the proportion in the formula, placing the raw materials in a mixer, mixing for 5-10min, transferring the raw materials into a double screw extruder, and carrying out melt extrusion and granulation, wherein the extrusion temperature is 280-310 ℃.
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| JP2006111859A (en) * | 2004-09-16 | 2006-04-27 | Toray Ind Inc | Polyamide resin composition and method for producing the same |
| CN104072991A (en) * | 2013-03-25 | 2014-10-01 | 上海杰事杰新材料(集团)股份有限公司 | Polyphenylene sulfide/nylon alloy material and preparation method thereof |
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| CN114941186A (en) * | 2022-07-01 | 2022-08-26 | 广东安拓普聚合物科技有限公司 | PET-based antibacterial wear-resistant fiber and preparation method thereof |
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| JP2006111859A (en) * | 2004-09-16 | 2006-04-27 | Toray Ind Inc | Polyamide resin composition and method for producing the same |
| CN104072991A (en) * | 2013-03-25 | 2014-10-01 | 上海杰事杰新材料(集团)股份有限公司 | Polyphenylene sulfide/nylon alloy material and preparation method thereof |
| CN107419519A (en) * | 2017-07-16 | 2017-12-01 | 长沙善道新材料科技有限公司 | A kind of preparation method of the affine uvioresistant anti bacteria natural silk fiber of zinc oxide |
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