CN116355410A - Polyphenylene sulfide polyamide composite material and preparation and application thereof - Google Patents
Polyphenylene sulfide polyamide composite material and preparation and application thereof Download PDFInfo
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- CN116355410A CN116355410A CN202310574132.4A CN202310574132A CN116355410A CN 116355410 A CN116355410 A CN 116355410A CN 202310574132 A CN202310574132 A CN 202310574132A CN 116355410 A CN116355410 A CN 116355410A
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- polyphenylene sulfide
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- 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
Abstract
The invention belongs to the field of composite materials, and discloses a polyphenylene sulfide polyamide composite material, and preparation and application thereof. The polyphenylene sulfide polyamide composite material comprises the following components in parts by weight: 35-96 parts of polyphenylene sulfide resin; 3-35 parts of copolyamide; 0-50 parts of glass fiber; 0-2.0 parts of coupling agent and 0-1.0 parts of nucleating agent; 0-1.0 parts of lubricant; 0-1.0 part of antioxidant, wherein the copolyamide is copolyamide with a melting point of 50-200 ℃. Compared with conventionally used polyamide resins such as PPA, PA66, PA6 and the like, the polyphenylene sulfide polyamide composite material prepared by the invention has obviously improved tensile strength, notch impact strength, CTI, bonding strength and the like. The method has good application in the fields of electronics, electrical appliances, automobiles, nano injection molding, precise instruments, 5G communication, chemical industry, aerospace, aviation and the like.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a polyphenylene sulfide polyamide composite material, and preparation and application thereof.
Background
PPS is one of the most heat-resistant varieties of engineering plastics, and after glass fiber modification, the heat distortion temperature is more than 260 ℃, and the chemical resistance is inferior to polytetrafluoroethylene. In addition, the PPS plastic has the advantages of small molding shrinkage, low water absorption, good fire resistance, good fatigue resistance, high breakdown voltage and the like, and particularly has excellent electrical insulation under high-temperature and high-humidity environments, but the PPS plastic has the defects of poor toughness, low impact strength, low CTI (comparative tracking index), weak mutual adhesion performance and the like, so that the application field of the PPS plastic is limited. It is therefore necessary to modify it to solve the above drawbacks and to obtain excellent overall properties.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the primary aim of the invention is to provide a polyphenylene sulfide polyamide composite material.
The invention also aims to provide a preparation method of the polyphenylene sulfide polyamide composite material.
The invention also aims to provide application of the polyphenylene sulfide polyamide composite material in the fields of electronics, electrical appliances, automobiles, nano injection molding, precision instruments, 5G communication, chemical industry, aerospace, aviation and the like.
The aim of the invention is achieved by the following scheme:
the polyphenylene sulfide polyamide composite material comprises the following components in parts by weight:
35-96 parts of polyphenylene sulfide resin; 3-35 parts of copolyamide; 0-50 parts of glass fiber; 0-2.0 parts of coupling agent and 0-1.0 parts of nucleating agent; 0-1.0 parts of lubricant; 0-1.0 part of antioxidant.
Preferably, the polyphenylene sulfide polyamide composite material comprises the following components in parts by weight:
40-70 parts of polyphenylene sulfide resin; 3-20 parts of copolyamide; 30-40 parts of glass fiber; 0.1-0.5 part of coupling agent and 0.1-0.5 part of nucleating agent; 0.1-0.5 part of lubricant; 0.1-0.5 part of antioxidant.
The polyphenylene sulfide resin is selected from the resins with the melt index range of 250-700g/10min measured under the condition of 316 ℃/5 kg.
The copolyamide is preferably a copolyamide having a melting point of 50℃to 200℃and more preferably at least one of the copolyamides having a melting point of 95℃to 170 ℃. The further preferable copolyamide is synthesized by taking caprolactam, hexamethylenediamine, decanediamine, sebacic acid and dodecanedioic acid as raw materials in a certain mass molar ratio, wherein the molar ratio of the caprolactam, the hexamethylenediamine, the decanediamine, the decanedioic acid and the dodecanedioic acid is 8 (2-10): (2:10): (3-6): (6-9).
Wherein the melting point and density of the copolyamide resin are shown in Table 1 below:
TABLE 1 melting Point and Density of Polyamide resins of different brands
Preferably, the mole ratio of caprolactam, hexamethylenediamine, decanediamine, sebacic acid and dodecanedioic acid in the copolyamide No. 1 is 8:6:6:6:6; the mole ratio of caprolactam, hexamethylenediamine, decanediamine, sebacic acid and dodecanedioic acid in the copolyamide No. 2 is 8:6:6:3:9; the mole ratio of caprolactam, hexamethylenediamine, decanediamine, sebacic acid and dodecanedioic acid in the copolyamide 3# is 8:2:10:3:9; the mole ratio of caprolactam, hexamethylenediamine, decanediamine, sebacic acid and dodecanedioic acid in the copolyamide No. 4 is 8:10:2:3:9.
The glass fiber is preferably round glass fiber with diameter of 9-13 μm and short cutting length of 3.0-5.0mm or flat glass fiber with flattening ratio of 2-5.
The coupling agent is at least one of amino silane coupling agent, acyloxy silane coupling agent, alkoxy silane coupling agent and epoxy silane coupling agent, preferably at least one of N- (2-aminoethyl) -3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, vinyl tri (methoxyethoxy) silane, vinyl trimethoxy silane and 3 (2, 3-epoxypropoxy) propyl trimethoxy silane, more preferably at least one of commercial N-beta- (aminoethyl) gamma-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane and 3 (2, 3-epoxypropoxy) propyl trimethoxy silane;
the nucleating agent is at least one of talcum powder, calcium carbonate, glass beads, silicon dioxide, calcium oxide, magnesium oxide, carbon black, mica and molybdenum disulfide, and more preferably talcum powder.
The lubricant is at least one of metal stearate, pentaerythritol stearate, ethylene bis-stearamide, erucamide, oleamide, silicone, polyolefin wax and the like, and preferably pentaerythritol stearate.
The antioxidant is at least one of hindered phenol antioxidants, hindered amine antioxidants, o-hydroxy phenyl triazine antioxidants, phosphite antioxidants and thioester antioxidants.
The preparation method of the polyphenylene sulfide polyamide composite material comprises the following steps:
premixing the rest raw materials except glass fibers to obtain a premix, then discharging the premix from a main feeding port of a double-screw extruder, discharging glass fibers from a side feeding port of the double-screw extruder, melting and extruding the premix and the glass fibers at 250-330 ℃ through the double-screw extruder, cooling and granulating to obtain the polyphenylene sulfide polyamide composite material.
Or premixing the rest raw materials except the glass fiber and the coupling agent to obtain a premix, then discharging the premix from a main feeding port of a double-screw extruder, discharging the glass fiber from a side feeding port of the double-screw extruder, metering and adding the coupling agent into a liquid filling port of the extruder according to a set proportion, melting and extruding the premix, the glass fiber and the coupling agent at 250-330 ℃ through the double-screw extruder, cooling and granulating to obtain the polyphenylene sulfide polyamide composite material.
The nucleating agent, the lubricant and the antioxidant are preferably mixed uniformly to prepare a compound package, and then premixed with other raw materials to obtain the premix.
The polyphenylene sulfide polyamide composite material is applied to the fields of electronics, electrical appliances, automobiles, nano injection molding, precise instruments, 5G communication, chemical industry, aerospace, aviation and the like.
Compared with the prior art, the invention has the following advantages:
the invention provides a scheme for preparing a polyphenylene sulfide polyamide composite material, and the tensile strength, notch impact strength, CTI, bonding strength and the like of the obtained polyphenylene sulfide polyamide composite material are obviously improved.
Detailed Description
The present invention will be described in further detail with reference to comparative examples and examples, but embodiments of the present invention are not limited thereto. The comparative examples and examples were conducted under conventional conditions or conditions recommended by the manufacturer, where no specific conditions were noted. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The preparation methods of the copolyamides in the comparative examples and examples are described in the description of the preparation methods, and the remaining raw materials are commercially available, and are specifically as follows: polyphenylene sulfide is new and formed 1150C, PA66 is Basoff Ultramid A3L, PA6 is Yue-formation YH-800, PPA is new and formed NH600, glass fiber is Chongqing International ECS10-03-584, coupling agent is Xinyue KBE-903, antioxidant is Tianjin An Long 1010, nucleating agent is Xufeng BHS-503, and lubricant is LOXIOL P861/3.5 of Kening company.
The copolyamide 1# in examples 1 to 11 and comparative example 6, copolyamide 2# and copolyamide 3# were prepared by using caprolactam, hexamethylenediamine, sebacic acid, decanediamine and dodecanedioic acid as raw materials and adopting a monomer melt polymerization method to prepare polyamide # resin, wherein the specific raw material amounts and the synthesis process are shown in the following table 2:
TABLE 2 copolyamid # 1, copolyamid # 2, copolyamid # 3, raw material types and molar amounts of copolyamid # 4
The preparation method of the composite materials in comparative examples 1 to 5 and examples 1 to 8 comprises the following steps:
(1) Weighing the raw materials according to the proportion of the raw material components, carrying out premixing treatment on the resin and the auxiliary agent compound package in a stirrer for 3min, and then discharging the obtained premix through a main feeding port of a double-screw extruder;
(2) Discharging glass fibers through a side feeding port of a double-screw extruder;
(3) The coupling agent is added in the liquid filling port of the extruder;
(4) And (3) carrying out melt extrusion on the premix, the glass fiber and the coupling agent at the temperature of 250-330 ℃ through a double-screw extruder, cooling and granulating to prepare the polyphenylene sulfide polyamide composite material.
Injection molded test specimens of thermoplastic materials were then prepared according to the ISO294-1-2018 standard, wherein the mold temperature was processed: 135 deg.c; injection molding temperature: 295-330 ℃. The obtained test sample is subjected to corresponding tensile strength, notch impact, flame retardant property and CTI test and bonding strength test. The tensile strength test adopts the ISO 527 standard, the impact strength test adopts the ISO 180 standard, the flame retardant test adopts the IEC60695-11-10 standard, and the CTI index adopts the IEC 60112 standard method. The bonding performance test simulates ISO 527-2 standard test, adopts the middle position after injection molding of 1A dumbbell-shaped sample strips, is cut and then is coated with glue, and the bonding area between two sample strips is 40mm 2 The glue layer thickness is 0.2mm, the glue adopts Wilden 5354 (the heating temperature of the glue is 125 ℃), and after curing for 24 hours in the environment with the temperature of 23 ℃ and the humidity of 55% relative humidity, the tensile strength test is carried out.
Comparative examples 1 to 5 and examples 1 to 8
The formulations of the composites in comparative examples 1-5 and examples 1-8 and the results of the material test items are shown in Table 3 below:
table 3 formulations of the composite materials in comparative examples 1-5 and examples 1-8 and results of material test items
The dosages of the resin, the glass fiber, the coupling agent and the auxiliary agent are all the weight percent, and the unit is percent.
As can be seen from Table 3, when the copolyamide and the polyphenylene sulfide were selected and compounded, the tensile strength, notched impact strength, CTI, adhesive strength and the like of the obtained composite material were remarkably improved, and more excellent properties were obtained, as compared with those of the conventional PPA, PA66, PA6 and the like. In example 8, when the ratio of copolyamide to polyphenylene sulfide resin in the compound was 20:39, the flame retardant property of the material is V1 grade, and the flame retardant property of the compound is V0 when the proportion of the copolyamide and the polyphenylene sulfide in the examples 1-7 is lower than that in the example 8.
Comparative examples 6 to 8 and examples 9 to 11
The formulations of the composites in comparative examples 6-8 and examples 9-11 and the results of the material test items are shown in Table 4 below:
table 4 formulas and material test item results for the composite materials of comparative examples 6-8 and examples 9-11
The preparation methods of the composite materials in comparative examples 6 to 8 and examples 9 to 11 are substantially the same as examples 1 to 8, except that the coupling agent is added in a different manner, specifically as follows:
(1) Weighing the raw materials according to the proportion of the raw material components in the table 4, then compounding and packaging the resin, the coupling agent and the auxiliary agent in a stirrer for premixing for 3min, and then discharging the obtained premix through a main feeding port of a double-screw extruder;
(2) Discharging glass fibers through a side feeding port of a double-screw extruder;
(3) The premix and the side material are melted and extruded at the temperature of 250-330 ℃ by a double screw extruder, cooled and pelletized to prepare the polyphenylene sulfide polyamide composite material;
sample preparation tests were then carried out in the same manner as in examples 1 to 8, and the test results are shown in Table 4.
As can be seen from Table 4, the performance of the scheme of metering the coupling agent at the liquid filler of the extruder is significantly better than that of the conventional process of feeding the coupling agent through a premix at the main feed. Because the traditional process needs a mechanical mixer to operate for 3-10min to uniformly mix when the main feed is mixed, the silane coupling agent is hung on an arm and volatilized and lost in the mixing process, and the coupling agent is extremely easy to react with air moisture or material surface moisture, the substrate can also generate caking after the reaction, so that the processing is difficult and uneven, and the effect is reduced compared with the actual adding amount. The timeliness and the accuracy are higher than those of the traditional main feed mixing performance by directly injecting the liquid into the liquid injection port of the extruder.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The polyphenylene sulfide polyamide composite material is characterized by comprising the following components in parts by weight:
35-96 parts of polyphenylene sulfide resin; 3-35 parts of copolyamide; 0-50 parts of glass fiber; 0-2.0 parts of coupling agent and 0-1.0 parts of nucleating agent; 0-1.0 parts of lubricant; 0-1.0 part of antioxidant;
the copolyamide is a copolyamide with a melting point of 50-200 ℃.
2. The polyphenylene sulfide polyamide composite material according to claim 1, which is characterized by comprising the following components in parts by mass:
40-70 parts of polyphenylene sulfide resin; 3-20 parts of copolyamide; 30-40 parts of glass fiber; 0.1-0.5 part of coupling agent and 0.1-0.5 part of nucleating agent; 0.1-0.5 part of lubricant; 0.1-0.5 part of antioxidant.
3. The polyphenylene sulfide polyamide composite material according to claim 1, characterized in that:
the polyphenylene sulfide resin is selected from the resins with the melt index range of 250-700g/10min measured under the condition of 316 ℃/5 kg.
4. The polyphenylene sulfide polyamide composite material according to claim 1, characterized in that:
the copolyamide is a copolyamide with a melting point of 95-170 ℃; further preferred are copolyamides having a melting point of 115 to 160 ℃.
5. The polyphenylene sulfide polyamide composite material according to claim 1, characterized in that:
the copolyamide is synthesized by taking caprolactam, hexamethylenediamine, decanediamine, sebacic acid and dodecanedioic acid as raw materials.
6. The polyphenylene sulfide polyamide composite material according to claim 1, characterized in that:
the glass fiber is round glass fiber with diameter of 9-13 μm and short cutting length of 3.0-5.0mm or flat glass fiber with flat rate of 2-5.
7. The polyphenylene sulfide polyamide composite material according to claim 1, characterized in that:
the coupling agent is at least one of amino silane coupling agent, acyloxy silane coupling agent, alkoxy silane coupling agent and epoxy silane coupling agent, preferably at least one of N- (2-aminoethyl) -3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, vinyl tri (methoxyethoxy) silane, vinyl trimethoxy silane and 3 (2, 3-epoxypropoxy) propyl trimethoxy silane.
8. The polyphenylene sulfide polyamide composite material according to claim 1, characterized in that:
the nucleating agent is at least one of talcum powder, calcium carbonate, glass beads, silicon dioxide, calcium oxide, magnesium oxide, carbon black, mica and molybdenum disulfide;
the lubricant is at least one of metal stearate, pentaerythritol stearate, ethylene bis-stearamide, erucamide, oleamide, silicone and polyolefin wax;
the antioxidant is at least one of hindered phenol antioxidants, hindered amine antioxidants, o-hydroxy phenyl triazine antioxidants, phosphite antioxidants and thioester antioxidants.
9. A method for preparing the polyphenylene sulfide polyamide composite material according to any one of claims 1 to 8, characterized by comprising the steps of:
premixing the rest raw materials except glass fibers to obtain a premix, then discharging the premix from a main position feed opening of a double-screw extruder, discharging glass fibers from a side position feed opening of the double-screw extruder, melting and extruding the premix and the glass fibers at 250-330 ℃ through the double-screw extruder, cooling and granulating to obtain the polyphenylene sulfide polyamide composite material;
or premixing the rest raw materials except the glass fiber and the coupling agent to obtain a premix, then discharging the premix from a main feeding port of the double-screw extruder, discharging the glass fiber from a side feeding port of the double-screw extruder, adding the coupling agent into a liquid filling port of the extruder, melting and extruding the premix, the glass fiber and the coupling agent at 250-330 ℃ through the double-screw extruder, cooling and granulating to obtain the polyphenylene sulfide polyamide composite material.
10. Use of the polyphenylene sulfide polyamide composite material according to any one of claims 1-8 in electronics, electrical appliances, automobiles, laser welding, precision instruments, 5G applications, chemical and aerospace applications.
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| CN202310574132.4A CN116355410A (en) | 2023-05-22 | 2023-05-22 | Polyphenylene sulfide polyamide composite material and preparation and application thereof |
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