CN113861687B - Polyphenylene sulfide composition and preparation method thereof - Google Patents

Polyphenylene sulfide composition and preparation method thereof Download PDF

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CN113861687B
CN113861687B CN202111263008.3A CN202111263008A CN113861687B CN 113861687 B CN113861687 B CN 113861687B CN 202111263008 A CN202111263008 A CN 202111263008A CN 113861687 B CN113861687 B CN 113861687B
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polyphenylene sulfide
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chain alkyl
chloride
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CN113861687A (en
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郑俊
杨建军
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Jiangxi Juzhen Technology Development Co ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00Characterised by the use 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; Polysulfones; Derivatives of such polymers
    • C08J2381/02Polythioethers; Polythioether-ethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/08Copolymers of ethene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2481/00Characterised by the use 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; Polysulfones; Derivatives of such polymers
    • C08J2481/02Polythioethers; Polythioether-ethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432Six-membered rings
    • C08K5/3435Piperidines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/521Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass

Abstract

The invention relates to a polyphenylene sulfide composition which is prepared from the following raw materials in parts by weight: 60-90 parts of polyphenylene sulfide resin, 10-40 parts of glass fiber, 5-15 parts of long-chain alkyl acylation modified polyphenylene sulfide and 2-10 parts of compatilizer containing epoxy groups, wherein the sum of the parts by weight of the polyphenylene sulfide and the glass fiber is 100 parts. Aiming at the defect of poor processability of glass fiber reinforced PPS, the processing performance of the PPS composition is improved by adding a small amount of long-chain alkyl acylation modified polyphenylene sulfide, and the PPS composition has excellent mechanical properties. Can be applied to the fields of electronics, electrics, mechanical manufacturing, automobile manufacturing, chemical instrument and instrument, aerospace industry and the like.

Description

Polyphenylene sulfide composition and preparation method thereof
Technical Field
The invention relates to the field of polymer materials, in particular to a polyphenylene sulfide composition and a preparation method thereof.
Background
Polyphenylene Sulfide (PPS) is a novel special engineering plastic with a macromolecular linear rigid structure, good heat resistance, flame retardance, corrosion resistance, fatigue resistance and wear resistance. However, PPS has insufficient toughness and insufficient impact strength in terms of mechanical strength. In order to increase the toughness of the PPS material, inorganic fillers such as glass fibers or polymer elastomers are generally added to enhance the comprehensive properties of the PPS, but the processing temperature of the PPS is further increased, the molding processing is more difficult, and the application of the PPS in the fields of electronics, electrical engineering, mechanical manufacturing, automobile manufacturing, chemical instruments, aerospace industry and the like is affected. In addition, the added filler has the problem of poor compatibility, so that the weather resistance and stability of the material are insufficient.
In the prior art, additives such as hyperbranched polymer type additives are added to improve the processing performance of the PPS composition, but the additives are expensive, and the compatibility of the hyperbranched polymer and the PPS is poor, so that the performance of the modified PPS composition is poor. Some studies have been made in the prior art on high flow polyphenylene sulfide composition systems, such as: chinese patent CN107880551A discloses a high-flow low-warpage PPS, which comprises the following components in parts by weight: 40-60 parts of PPS resin, 0.2-0.5 part of silane coupling agent, 0.4-1 part of EBS dispersing flowing agent, 1-5 parts of SEBS, 1-3 parts of epoxy resin, 1-3 parts of organic silicon defoamer, and 40-60 parts of glass fiber; chinese patent CN109251530A discloses a high-flow high-impact glass fiber reinforced PPS modified material, which comprises the following components in parts by weight: 45-55 parts of middle-low melting PPS raw material A with a melting index range of 100-500, 2-10 parts of middle-high melting PPS raw material B with a melting index range of 500-800, 40-50 parts of glass fiber, 0.2-5 parts of coupling agent, 0.1-1 part of fluoropolymer processing aid PPA, 1-5 parts of ethylene copolymer and 0.5-2 parts of aromatic acid; chinese patent CN104877341A discloses a high-fluidity fiber-reinforced PPS/ABS composite material and a product thereof, wherein the composite material comprises the following components in parts by weight: a thermoplastic resin comprising 35 to 50 parts of a PPS polymer and 0.1 to 10 parts of an ABS resin; a reinforcing filler comprising 40 to 60 parts of flat cross-section glass fibers and 0.5 to 2 parts of a particulate glass filler; 0.5-2 parts of a compatilizer; chinese patent CN109651815A discloses a high-fluidity high-metal-filled PPS composite material and a preparation method thereof, and the PPS composite material is prepared from the following raw materials in parts by weight: 5-30 Parts of Polyphenylene Sulfide (PPS) resin, 5-70 parts of metal powder, 0-5 parts of high-mesh talcum powder, 0-5 parts of siloxane dispersing lubricant and 0-5 parts of fluorine-containing polymer lubricant.
Disclosure of Invention
Based on the above, the present invention aims to provide a polyphenylene sulfide composition having excellent mechanical properties and processability, which can be applied to the fields of electronics and electrics, machine manufacturing, automobile manufacturing, chemical instrumentation, aerospace industry, etc.
In order to achieve the purpose, the invention adopts the following scheme:
the polyphenylene sulfide composition is prepared from the following raw materials in parts by weight: 60-90 parts of polyphenylene sulfide resin, 10-40 parts of glass fiber, 5-15 parts of long-chain alkyl acylation modified polyphenylene sulfide and 2-10 parts of compatilizer containing epoxy groups, wherein the sum of the parts by weight of the polyphenylene sulfide and the glass fiber is 100 parts.
Preferably, the polyphenylene sulfide composition provided by the invention is prepared from the following raw materials in parts by weight: 80-90 parts of polyphenylene sulfide resin, 10-20 parts of glass fiber, 7-10 parts of long-chain alkyl acylation modified polyphenylene sulfide and 3-6 parts of compatilizer containing epoxy groups, wherein the sum of the parts by weight of the polyphenylene sulfide and the glass fiber is 100 parts.
In some embodiments of the present invention, the polyphenylene sulfide resin has a number average molecular weight of 3.5 to 5.0 ten thousand.
In some embodiments of the invention, the glass fibers have a length of 2 to 4mm and a diameter of 9 to 11 μm. The length and diameter of the glass fibers have a large effect on the mechanical properties and appearance of the PPS composition. The longer the glass fiber is, the higher the tensile property of the resin composite material is, and the possibility of the glass fiber being exposed is increased; the smaller the diameter of the glass fiber, the higher the tensile strength, but the higher the cost of its manufacture, and the more coupling agent required per unit area. Therefore, the selection of the proper length and diameter of the glass fibers is important for the preparation of a PPS composition having excellent performance and high cost performance. The preferred length of the glass fiber is 2-4 mm, the diameter is 9-11 μm, and the PPS composition has better mechanical property and higher performance-price ratio.
In some embodiments of the present invention, the long-chain alkyl acylation modified polyphenylene sulfide is obtained by reacting polyphenylene sulfide resin and long-chain alkyl acyl chloride, and the reaction conditions can refer to the method described in patent CN102504256 a. The mass ratio of the polyphenylene sulfide resin to the long-chain alkyl acyl chloride is 1.5-1, and the long-chain alkyl acyl chloride is selected from C6-14 alkyl acyl chloride and comprises at least one of hexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride, heptadecanoyl chloride, dodecyl acyl chloride and tetradecyl acyl chloride.
In a preferred embodiment of the present invention, the preparation method of the long-chain alkyl acylation modified polyphenylene sulfide comprises the following steps: adding polyphenylene sulfide resin powder and an organic solvent into a reaction container for swelling, adding long-chain alkyl acyl chloride and a catalyst under an inert atmosphere, reacting for 3-6h at 30-45 ℃, cooling, pouring the reaction liquid into 30-50wt% of ice hydrochloric acid for continuing to react for 5-8h, and carrying out aftertreatment on the product to obtain the long-chain alkyl acylation modified polyphenylene sulfide.
The catalyst is aluminum trichloride, and the dosage of the catalyst is 50-100% of the mass of the polyphenylene sulfide resin powder. The post-treatment is well known in the art, and in one embodiment of the present invention, the long chain alkyl acylation modified polyphenylene sulfide is obtained by washing with an alkaline solution (5-10% NaOH aqueous solution) for 3-5 times after suction filtration, then washing with distilled water and ethanol for 3-5 times, respectively, extracting the final product with ethanol-distilled water in a Soxhlet fat extractor for 18-30 hours, and drying.
The compatilizer containing the epoxy group is selected from the compound of at least one of styrene-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, styrene-acrylonitrile-glycidyl methacrylate, glycidyl methacrylate and glycidyl acrylate and hyperbranched epoxy resin. The hyperbranched epoxy resin is polyether type or polyester type, and the epoxy value is 0.12-0.2mol/100g.
The epoxy group can react with the sulfhydryl group of the polyphenylene sulfide resin and the terminal hydroxyl group of the coupling agent coating the glass fiber, thereby improving the compatibility and the interface cohesiveness between the glass fiber and the PPS resin. Preferably, the mass ratio of at least one of styrene-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, styrene-acrylonitrile-glycidyl methacrylate, glycidyl methacrylate and glycidyl acrylate to the hyperbranched epoxy resin is 1-2:1. the inventors have unexpectedly discovered that the use of the above-described compounded epoxy compound as a compatibilizer improves the compatibility of the PPS and glass fibers while also improving the toughness of the composite.
Preferably, the high-fluidity polyphenylene sulfide composition also comprises auxiliary materials, wherein the auxiliary materials comprise 0.1-3 parts of metal passivator, 0.1-0.5 part of stabilizer and 0.1-0.5 part of antioxidant. Further preferably, the metal deactivator is selected from N, N '-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, the stabilizer is N, N' -bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,3-benzenedicarboxamide, and the antioxidant is bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate.
The metal deactivator has several functional groups, including nitrogen, oxygen, sulfur, etc. in the molecule, and may form thermally stable complex with metal to deactivate metal ion, wherein the hydroxyl group in the molecule is first combined with copper salt to form soluble complex, and the nitrogen atom in the amide group is then coordinated with copper ion to form insoluble polymer-like complex. The metal deactivator has the main functions of inhibiting the catalytic oxidation of metal ions on the PPS resin, when the PPS resin is contacted with metal, particularly copper metal, even if the PPS resin contains a large amount of hindered phenol antioxidants, the catalytic action of the metal ions cannot be controlled, and the catalytic oxidation of the metal on the PPS resin can be effectively prevented only by adding the metal deactivator, so that the application range of the PPS composition is expanded, particularly in the electronic and electrical field; the melting point of N, N' -bis (2,2,6,6-tetramethyl-4-piperidyl) -1,3-benzenedicarboxamide adopted by the invention is 272 ℃, the boiling point is more than 360 ℃, the thermal stability in the blending process of the PPS composition is better, and the hindered piperidyl can provide an antioxidant effect and improve the dyeing property of the composition; the bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphates adopted by the invention have the melting point of 239 ℃ and the thermal decomposition temperature of over 350 ℃, have good heat resistance and hydrolysis resistance, can provide excellent color stability and melt stability for the PPS composition in the blending process, simultaneously prevent the thermal degradation of the PPS composition in the high-temperature process, inhibit the thermal oxidative discoloration of the PPS composition caused by long-time extrusion processing, and also provide Nitrogen Oxides (NO) x ) Color stability in gas environment, and prevention of discoloration of fumigant.
The invention also aims to provide a preparation method of the high-flow polyphenylene sulfide composition, which comprises the following steps:
(1) The polyphenylene sulfide resin is dried and then mixed with N, N' -bis (2,2,6,6-tetramethyl-4-piperidyl) -1,3-benzenedicarboxamide and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate;
(2) Mixing long-chain alkyl acylation modified polyphenylene sulfide, a compatilizer containing an epoxy group and a metal passivator;
(3) And (2) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder in the lateral direction (for example, the fourth zone) of the parallel double-screw extruder (total eight zones), and adding the glass fiber into the parallel double-screw extruder in the other lateral direction (for example, the third zone) of the parallel double-screw extruder for melt extrusion and granulation.
In some of the embodiments, the drying temperature in the step (1) is 80-110 ℃, and the drying time is 4-8 hours.
The process parameters of the parallel twin-screw extruder are well known in the art, and in one embodiment of the invention, the process parameters are as follows: the temperature of the first zone is 285-305 ℃, the temperature of the second zone is 290-310 ℃, the temperature of the third zone is 290-310 ℃, the temperature of the fourth zone is 295-315 ℃, the temperature of the fifth zone is 295-315 ℃, the temperature of the sixth zone is 290-310 ℃, the temperature of the seventh zone is 290-310 ℃, the temperature of the eighth zone is 290-310 ℃, the temperature of the die head is 290-310 ℃ and the rotating speed of the screw is 200-600 rpm.
In some of these embodiments, the screw shape of the parallel twin-screw extruder is a single-thread, and the ratio L/D of the length L of the screw to the diameter D of the screw of the twin-screw extruder is 35 to 50. In the step (1) and/or the step (2), a stirrer is adopted for carrying out the mixing step, and the rotating speed of the stirrer is 500-1500 rpm.
Compared with the prior art, the invention has the following beneficial effects:
1. aiming at the defect of poor processability of glass fiber reinforced PPS, the invention improves the processability of the PPS composition by adding a small amount of long-chain alkyl acylation modified polyphenylene sulfide.
2. Adding a conventional alkenyl copolymer compatilizer with epoxy groups and a compound of hyperbranched epoxy resin as compatilizers to improve the compatibility and interface cohesiveness between the glass fiber and the PPS resin; the inventors have also unexpectedly discovered that the addition of a small amount of hyperbranched epoxy resin can also simultaneously improve the toughness and notch sensitivity of the PPS composition.
3. According to the invention, a metal passivator is added to inhibit the catalytic oxidation of metal ions on PPS resin, so that the application range of the PPS composition is expanded, N' -bis (2,2,6,6-tetramethyl-4-piperidyl) -1,3-benzenedicarboxamide and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate are compounded to improve the yellowing phenomenon and the thermal stability of the PPS composition in the blending processing process, and the PPS composition obtained by mutually matching the raw material components has excellent mechanical properties and processing properties, and can be applied to the fields of electronics and electrics, mechanical manufacturing, automobile manufacturing, chemical instruments and instruments, aerospace industry and the like.
4. The preparation method of the PPS composition provided by the invention has the advantages of simple process, easiness in control and low requirements on equipment, and the used equipment is general polymer processing equipment, so that the investment is low, and the industrial production is facilitated.
Drawings
FIG. 1 is a flow chart of a process for preparing a PPS composition in accordance with one embodiment of the present invention.
Detailed Description
In order to further understand the features and technical means of the present invention and achieve the specific objects and functions, the advantages and spirit of the present invention are further illustrated by the following embodiments.
Polyphenylene sulfide resin with a number average molecular weight of 4.2 ten thousand selected from Chongqing PolyShi New materials science and technology Co., ltd;
glass fibers selected from the group consisting of Megaku, china, 3mm in length and 10 μm in diameter;
ethylene-methyl acrylate-glycidyl methacrylate copolymer purchased from arkema, france;
the hyperbranched epoxy resin HyPer E10 is purchased from Wuhan hyperbranched resin science and technology Co., ltd, and has an epoxy value of 0.16mol/100g.
Preparation example 1
Placing 1kg of polyphenylene sulfide resin powder in a stirring type reaction kettle, adding 10kg of anhydrous treated dichloromethane, stirring for 10 hours for swelling, vacuumizing and filling nitrogen in the stirring type reaction kettle, repeating for 6 times, adding 0.75kg of octanoyl chloride and 0.75kg of catalyst aluminum trichloride at the same time at the reaction temperature of 37 ℃, reacting for 4.5 hours under the system, taking out a reaction product, placing the reaction product in 5% of glacial hydrochloric acid, washing for 4 times by using 5% of sodium hydroxide solution after reacting for 6 hours, then washing for 4 times by using distilled water and ethanol respectively, extracting the product in a soxhlet fat extractor for 24 hours by using ethanol-distilled water, and drying to obtain the octanoyl group graft modified polyphenylene sulfide.
Preparation example 2
The other conditions and operations are the same as those in preparation example 1, except that octanoyl chloride is replaced by equal mass of hexanoyl chloride, and finally hexanoyl graft-modified polyphenylene sulfide is obtained.
Preparation example 3
The other conditions and operations were the same as those in preparation example 1 except that octanoyl chloride was replaced with decanoyl chloride of equal mass to finally obtain decanoyl graft-modified polyphenylene sulfide.
Preparation example 4
The other conditions and operations are the same as those in preparation example 1, except that octanoyl chloride is replaced by dodecyl chloride of equal mass, and finally, the lauroyl graft-modified polyphenylene sulfide is obtained.
Example 1
The embodiment provides a high-flow polyphenylene sulfide composition, which is prepared from the following raw materials in parts by weight:
Figure BDA0003326097560000061
Figure BDA0003326097560000071
the preparation method of the high-flow polyphenylene sulfide composition comprises the following steps:
(1) Drying the polyphenylene sulfide resin at 110 ℃ for 4 hours, cooling, and adding the cooled polyphenylene sulfide resin, the N, N' -bis (2,2,6,6-tetramethyl-4-piperidyl) -1,3-benzenedicarboxamide and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate into a stirrer for mixing;
(2) Adding the polyphenylene sulfide grafted octanoyl chloride, the copolymer of ethylene and methyl acrylate grafted glycidyl methacrylate and N, N' -bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine into another stirrer for mixing;
(3) Adding the mixture mixed in the step (1) into a parallel double-screw extruder through a feeder, adding the mixture mixed in the step (2) into a lateral direction (a fourth zone) of the parallel double-screw extruder (total eight zones), adding glass fiber into the other lateral direction (a third zone) of the parallel double-screw extruder for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone was 305 ℃, the temperature of the second zone was 310 ℃, the temperature of the third zone was 310 ℃, the temperature of the fourth zone was 315 ℃, the temperature of the fifth zone was 315 ℃, the temperature of the sixth zone was 310 ℃, the temperature of the seventh zone was 310 ℃, the temperature of the eighth zone was 310 ℃, the temperature of the die head was 310 ℃ and the screw speed was 600rpm.
The screw shape of the parallel double-screw extruder is single thread, the ratio L/D of the length L and the diameter D of the screw is 50, the screw is provided with 2 meshing block areas and 1 back thread area, the stirrer in the step (1) and the step (2) is a high-speed stirrer, and the rotating speed is 1000 revolutions per minute.
Example 2
The other operations and conditions were the same as in example 1 except that the octanoyl graft-modified polyphenylene sulfide prepared in preparation example 1 was replaced with an equal mass of the hexanoyl graft-modified polyphenylene sulfide prepared in preparation example 2.
Example 3
The other operations and conditions were the same as in example 1 except that the octanoyl graft-modified polyphenylene sulfide prepared in preparation example 1 was replaced with an equal mass of the decanoyl graft-modified polyphenylene sulfide prepared in preparation example 3.
Example 4
The other operations and conditions were the same as in example 1 except that the octanoyl group-graft-modified polyphenylene sulfide prepared in preparation example 1 was replaced with an equal mass of dodecanoyl group-graft-modified polyphenylene sulfide prepared in preparation example 4.
Example 5
The other operations and conditions were the same as in example 1 except that the hyperbranched epoxy resin HyPer E102 was not added and the amount of the ethylene-methyl acrylate-glycidyl methacrylate copolymer was changed to 6 parts.
Example 6
The other operations and conditions were the same as in example 1, except that the polyphenylene sulfide composition was prepared from the following raw materials in parts by weight:
Figure BDA0003326097560000081
comparative example 1
The other operations and conditions were the same as in example 1 except that the octanoyl group graft-modified polyphenylene sulfide obtained in preparation example 1 was not added.
The PPS compositions prepared in the above examples and comparative examples were subjected to the following property tests:
tensile property: testing according to GB/T1040-2006 standard, wherein the stretching speed is 50mm/min;
impact property: the thickness of the sample strip is 4mm according to the test of GB/T1843-2008 standard;
melt index: testing according to GB/T3682-2000 standard, wherein the testing temperature is 300 ℃, and the load is 2.16kg;
the results of the performance tests are shown in table 1.
TABLE 1 Properties of PPS compositions of examples and comparative examples
Figure BDA0003326097560000091
As can be seen from the data in Table 1, the flowability of the PPS composition can be significantly improved by adding the long-chain alkyl acylation modified polyphenylene sulfide to improve the processability of the PPS composition. Meanwhile, the compatilizer compounded by the ethylene-methyl acrylate-glycidyl methacrylate copolymer and the hyperbranched epoxy resin is found to improve the compatibility of the PPS and the glass fiber and enhance the toughness of the composition.

Claims (10)

1. The polyphenylene sulfide composition is prepared from the following raw materials in parts by weight: 60-90 parts of polyphenylene sulfide resin, 10-40 parts of glass fiber, 5-15 parts of long-chain alkyl acylation modified polyphenylene sulfide and 2-10 parts of compatilizer containing epoxy groups, wherein the sum of the parts by weight of the polyphenylene sulfide and the glass fiber is 100 parts;
the compatilizer containing the epoxy group is selected from at least one of styrene-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate terpolymer, styrene-acrylonitrile-glycidyl methacrylate, glycidyl methacrylate and glycidyl acrylate and hyperbranched epoxy resin, and the mass ratio of the compatilizer containing the epoxy group is 1-2:1; the hyperbranched epoxy resin is polyether type or polyester type, and the epoxy value is 0.12-0.2mol/100g.
2. The polyphenylene sulfide composition of claim 1, wherein the polyphenylene sulfide composition is prepared from the following raw materials in parts by weight: 80-90 parts of polyphenylene sulfide resin, 10-20 parts of glass fiber, 7-10 parts of long-chain alkyl acylation modified polyphenylene sulfide and 3-6 parts of compatilizer containing epoxy groups, wherein the sum of the parts by weight of the polyphenylene sulfide and the glass fiber is 100 parts.
3. The polyphenylene sulfide composition according to claim 1, wherein the number average molecular weight of the polyphenylene sulfide resin is 3.5 to 5.0 ten thousand.
4. The polyphenylene sulfide composition of claim 1, wherein the glass fiber has a length of 2 to 4mm and a diameter of 9 to 11 μm.
5. The polyphenylene sulfide composition of claim 1, wherein the long chain alkyl acylation modified polyphenylene sulfide is obtained by reacting a polyphenylene sulfide resin and a long chain alkyl acyl chloride, the mass ratio of the polyphenylene sulfide resin to the long chain alkyl acyl chloride is 1 to 0.5-1, and the long chain alkyl acyl chloride is selected from C6-14 alkyl acyl chloride.
6. The polyphenylene sulfide composition of claim 5, wherein the long chain alkyl acyl chloride comprises at least one of hexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride, heptanoyl chloride, dodecanoyl chloride, and tetradecanoyl chloride.
7. The polyphenylene sulfide composition of claim 1, wherein the preparation method of the long chain alkyl acylation modified polyphenylene sulfide comprises the following steps: adding polyphenylene sulfide resin powder and an organic solvent into a reaction container for swelling, adding long-chain alkyl acyl chloride and a catalyst under an inert atmosphere, reacting for 3-6h at 30-45 ℃, cooling, pouring the reaction liquid into 30-50wt% of ice hydrochloric acid for continuing to react for 5-8h, and carrying out aftertreatment on the product to obtain the long-chain alkyl acylation modified polyphenylene sulfide.
8. The polyphenylene sulfide composition of claim 1, further comprising an auxiliary material, wherein the auxiliary material comprises 0.1-3 parts of a metal deactivator, 0.1-0.5 part of a stabilizer, and 0.1-0.5 part of an antioxidant.
9. The polyphenylene sulfide composition of claim 8, wherein the metal deactivator is selected from the group consisting of N, N '-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, the stabilizer is N, N' -bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,3-benzenedicarboxamide, and the antioxidant is bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate.
10. The method of preparing the polyphenylene sulfide composition of claim 9, comprising the steps of:
(1) The polyphenylene sulfide resin is dried and then mixed with N, N' -bis (2,2,6,6-tetramethyl-4-piperidyl) -1,3-benzenedicarboxamide and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate;
(2) Mixing long-chain alkyl acylation modified polyphenylene sulfide, a compatilizer containing an epoxy group and a metal deactivator;
(3) And (3) adding the mixed material obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed material obtained in the step (2) into the parallel double-screw extruder in the lateral direction, adding the glass fiber into the parallel double-screw extruder in the other lateral direction, performing melt extrusion, and granulating.
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