CN113861671A - High-fluidity glass fiber reinforced polyphenyl ether polyamide composite material and preparation method thereof - Google Patents
High-fluidity glass fiber reinforced polyphenyl ether polyamide composite material and preparation method thereof Download PDFInfo
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Abstract
The invention discloses a high-fluidity glass fiber reinforced polyphenyl ether polyamide composite material, which comprises the following components: 30-50% of polyamide resin, 14-30% of polyphenyl ether, 2.4-4% of toughening agent, 3-5% of compatilizer, 0.3-0.5% of fluidity improver, 10-50% of glass fiber and 0.3-0.5% of compound antioxidant; the fluidity improver is an N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound, wherein alkyl is methyl or ethyl or saturated alkyl with carbon atoms less than 4; according to the invention, PPO-g-MAH, ethylene, acrylic ester and glycidyl methacrylate (AX8900) are adopted to improve the compatibility and toughness of PPO/PA interface, and meanwhile, a fluidity improver N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound is added through extrusion reaction, and through high-temperature extrusion reaction, hydrogen bonds are formed with PPO and PA molecular chains, so that the fluidity of PPO/PA is improved.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a high-flow glass fiber reinforced polyphenyl ether polyamide composite material and a preparation method thereof.
Background
As a typical representative of engineering plastic alloy, the PPO/PA alloy combines the advantages of two materials of PPO and PA, and the PPO/PA alloy material with the combination property superior to that of any single component is obtained through the complementation of the properties of the components.
PPO is a non-polar amorphous polymer and has poor flowability, PA is a polar crystalline polymer, and simple blending of the two inevitably leads to two-phase separation, thereby influencing the use value of the PPO. A common approach is to add a suitable compatibilizer to the system to improve the compatibility of the blend, and then to add a silicone-based or long chain fatty acid lubricant to improve material flow.
The Chinese invention patent (CN111073277A) discloses a PA/PPO alloy plastic capable of being sprayed on line and a preparation method thereof, PPO-g-MAH or SEBS-g-MAH is used as a toughening agent, so that the problem of PPO/PA interface compatibility is solved, but description on whether the system is suitable for a glass fiber system or not, and description on material performance and appearance after adding glass fibers is not mentioned.
The Chinese invention patent (CN103436000A) discloses a heat conduction reinforced PPO/PA alloy and a preparation method thereof, wherein the heat conduction reinforced PPO/PA alloy is reinforced by carbon fibers and other heat conduction fillers, butadiene acrylonitrile rubber and POE-g-MAH are used as compatilizers, the addition amount is very high, although the comprehensive mechanical property is very high, the addition amount of the compatilizers is too high, and the fluidity of the material is influenced.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the problem of the interface compatibility of PPO/PA and improve the fluidity of PPO/PA, and can be suitable for injection molding of thin-walled products (the wall thickness is less than 1.5mm), the invention provides a high-fluidity glass fiber reinforced polyphenyl ether polyamide composite material and a preparation method thereof.
The invention is realized by the following technical scheme: high-flow glass fiber reinforced polyphenyl ether polyamide composite material: the composite material comprises the following components in percentage by weight:
30 to 50 percent of polyamide resin
14-30% of polyphenyl ether
2.4 to 4 percent of toughening agent
3 to 5 percent of compatilizer
0.3-0.5% of fluidity improver
10 to 50 percent of glass fiber
0.3 to 0.5 percent of compound antioxidant.
The fluidity improver is an N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound, wherein alkyl is methyl or ethyl or saturated alkyl with carbon atom less than 4.
The polyamide resin is PA6 resin, and the viscosity of the polyamide resin is 2.5-3.2 g/dl.
The polyphenyl ether is PP0 polyphenyl ether resin, and the viscosity of the polyphenyl ether resin is 35-53 g/dl.
The toughening agent is a copolymer of ethylene-acrylate-glycidyl methacrylate.
The compatilizer is PPO-g-MAH maleic anhydride grafted polyphenyl ether.
The compound antioxidant is a compound of N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine (1098), high-performance phosphite S9228 and zinc oxide, and the compound ratio is 1:1: 0.8.
Further, the glass fiber is flat glass fiber, and the difference of the glass fiber is 1: (3-4) the diameter is 10-14 μm.
The preparation method of the high-flow glass fiber reinforced polyphenyl ether polyamide composite material comprises the following steps:
a: weighing polyamide resin, polyphenyl ether resin, a toughening agent and a compatilizer according to the weight percentage, drying for 4 hours at the temperature of 100 ℃, putting into a high-speed mixer, mixing at room temperature, and stirring at the speed: 300 times of 500 turns/minute, the stirring time is 3-5 minutes, so that all the components are fully stirred and uniformly dispersed;
b, adding the mixed materials into a double-screw extruder with the length-diameter ratio of 48/1 for melt extrusion, wherein the melt extrusion temperature is 200-300 ℃, and the screw rotation speed is 300-500 r/m; adding the glass fiber from a fifth area of the extruder;
c, cooling, air-drying, granulating and strong magnetic treatment are carried out on the extruded material to obtain the polyamide composite material;
in the step B, the heating process of the double-screw extruder is as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 280 ℃, the temperature of the third zone is 300 ℃, the temperature of the fourth zone is 300 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃, the temperature of the ninth zone is 250 ℃, the temperature of the tenth zone is 250 ℃, and the temperature of the head is 260 DEG C
Has the advantages that:
1. in the invention, PPO-g-MAH, ethylene, acrylic ester and glycidyl methacrylate (AX8900) are adopted to improve the compatibility and toughness of PPO/PA interface, meanwhile, a fluidity improver N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-phthalic amide compound is added by adopting extrusion reaction, and through high-temperature extrusion reaction, hydrogen bonds are formed with PPO and PA molecular chains to improve the fluidity of PPO/PA, thus the method is suitable for the application range in the fields of injection molding of thin-wall products with the wall thickness of less than 1.5mm and the like.
2. In the invention, the composite material prepared by the method and the formula has excellent mechanical properties and good fluidity; different from the conventional low-temperature 200-cost 250-cost extrusion modification, the high-temperature 200-cost 300-degree extrusion granulation is adopted, so that the fluidity improving effect of the fluidity improver is fully exerted, the fluidity improver can be fully melted in a melt, and the fluidity improver can fully react with PA and PPO molecular chains, thereby improving the fluidity, the surface effect and the mechanical property of the composite material.
Detailed Description
The present invention will be further described below.
Example 1
High-flow glass fiber reinforced polyphenyl ether polyamide composite material: the composite material comprises the following components in percentage by weight:
50% of polyamide resin, 30% of polyphenyl ether, 4% of toughening agent, 5% of compatilizer, 0.5% of fluidity improver, 10% of glass fiber and 0.5% of compound antioxidant;
wherein the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound, the polyamide resin is PA6 resin, and the viscosity of the polyamide resin is 2.8 g/dl; the polyphenyl ether is PP0 polyphenyl ether resin with the viscosity of 41 g/dl; the toughening agent is a copolymer of ethylene-acrylic ester-glycidyl methacrylate, is selected from toughening agents produced by Akoma, and has a commercial brand of AX 8900; the compatilizer is PPO-g-MAH maleic anhydride grafted polyphenyl ether; the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound; the compound antioxidant is a compound of N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine (1098), high-performance phosphite S9228 and zinc oxide, and the compound proportion is 1:1: 0.8; the glass fiber is flat glass fiber, and the specific gravity is 1: (3-4) the diameter is 10-14 μm.
The preparation method of the high-fluidity glass fiber reinforced polyphenyl ether polyamide composite material comprises the following steps:
a: weighing polyamide resin, polyphenyl ether resin, a toughening agent and a compatilizer according to the weight percentage, drying for 4 hours at the temperature of 100 ℃, putting into a high-speed mixer, mixing at room temperature, and stirring at the speed: 300 times of 500 turns/minute, the stirring time is 3-5 minutes, so that all the components are fully stirred and uniformly dispersed;
b, adding the mixed materials into a double-screw extruder with the length-diameter ratio of 48/1 for melt extrusion, wherein the melt extrusion temperature is 200-300 ℃, and the screw rotation speed is 300-500 r/m; adding the glass fiber from a fifth area of the extruder;
c, cooling, air-drying, granulating and strong magnetic treatment are carried out on the extruded material to obtain the polyamide composite material;
in the step B, the heating process of the double-screw extruder is as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 280 ℃, the temperature of the third zone is 300 ℃, the temperature of the fourth zone is 300 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃, the temperature of the ninth zone is 250 ℃, the temperature of the tenth zone is 250 ℃, and the temperature of the head is 260 DEG C
The mechanical properties of the polyamide composite material obtained were measured and the results are shown in Table 3.
Example 2
High-flow glass fiber reinforced polyphenyl ether polyamide composite material: the composite material comprises the following components in percentage by weight:
45% of polyamide resin, 25.2% of polyphenyl ether, 4% of toughening agent, 5% of compatilizer, 0.4% of fluidity improver, 20% of glass fiber and 0.4% of compound antioxidant;
wherein the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound, the polyamide resin is PA6 resin, and the viscosity of the polyamide resin is 2.8 g/dl; the polyphenyl ether is PP0 polyphenyl ether resin with the viscosity of 41 g/dl; the toughening agent is a copolymer of ethylene-acrylic ester-glycidyl methacrylate, is selected from toughening agents produced by Akoma, and has a commercial brand of AX 8900; the compatilizer is PPO-g-MAH maleic anhydride grafted polyphenyl ether; the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound; the compound antioxidant is a compound of N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine (1098), high-performance phosphite S9228 and zinc oxide, and the compound proportion is 1:1: 0.8; the glass fiber is flat glass fiber, and the specific gravity is 1: (3-4) the diameter is 10-14 μm.
The preparation method is the same as that of example 1, and the obtained polyamide composite material is subjected to mechanical property detection, and the result is shown in table 3.
Example 3
High-flow glass fiber reinforced polyphenyl ether polyamide composite material: the composite material comprises the following components in percentage by weight:
40% of polyamide resin, 21.7% of polyphenyl ether, 3.5% of toughening agent, 4% of compatilizer, 0.4% of fluidity improver, 30% of glass fiber and 0.4% of compound antioxidant;
wherein the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound, the polyamide resin is PA6 resin, and the viscosity of the polyamide resin is 2.8 g/dl; the polyphenyl ether is PP0 polyphenyl ether resin with the viscosity of 41 g/dl; the toughening agent is a copolymer of ethylene-acrylic ester-glycidyl methacrylate, is selected from toughening agents produced by Akoma, and has a commercial brand of AX 8900; the compatilizer is PPO-g-MAH maleic anhydride grafted polyphenyl ether; the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound; the compound antioxidant is a compound of N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine (1098), high-performance phosphite S9228 and zinc oxide, and the compound proportion is 1:1: 0.8; the glass fiber is flat glass fiber, and the specific gravity is 1: (3-4) the diameter is 10-14 μm.
The preparation method is the same as that of example 1, and the obtained polyamide composite material is subjected to mechanical property detection, and the result is shown in table 3.
Example 4
High-flow glass fiber reinforced polyphenyl ether polyamide composite material: the composite material comprises the following components in percentage by weight:
35% of polyamide resin, 17.8% of polyphenyl ether, 3% of toughening agent, 3.5% of compatilizer, 0.4% of fluidity improver, 40% of glass fiber and 0.3% of compound antioxidant;
wherein the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound, the polyamide resin is PA6 resin, and the viscosity of the polyamide resin is 2.8 g/dl; the polyphenyl ether is PP0 polyphenyl ether resin with the viscosity of 41 g/dl; the toughening agent is a copolymer of ethylene-acrylic ester-glycidyl methacrylate, is selected from toughening agents produced by Akoma, and has a commercial brand of AX 8900; the compatilizer is PPO-g-MAH maleic anhydride grafted polyphenyl ether; the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound; the compound antioxidant is a compound of N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine (1098), high-performance phosphite S9228 and zinc oxide, and the compound proportion is 1:1: 0.8; the glass fiber is flat glass fiber, and the specific gravity is 1: (3-4) the diameter is 10-14 μm.
The preparation method is the same as that of example 1, and the obtained polyamide composite material is subjected to mechanical property detection, and the result is shown in table 3.
Example 5
High-flow glass fiber reinforced polyphenyl ether polyamide composite material: the composite material comprises the following components in percentage by weight:
30% of polyamide resin, 14% of polyphenyl ether, 2.4% of toughening agent, 3% of compatilizer, 0.3% of fluidity improver, 50% of glass fiber and 0.3% of compound antioxidant;
wherein the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound, the polyamide resin is PA6 resin, and the viscosity of the polyamide resin is 2.8 g/dl; the polyphenyl ether is PP0 polyphenyl ether resin with the viscosity of 41 g/dl; the toughening agent is a copolymer of ethylene-acrylic ester-glycidyl methacrylate, is selected from toughening agents produced by Akoma, and has a commercial brand of AX 8900; the compatilizer is PPO-g-MAH maleic anhydride grafted polyphenyl ether; the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound; the compound antioxidant is a compound of N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine (1098), high-performance phosphite S9228 and zinc oxide, and the compound proportion is 1:1: 0.8; the glass fiber is flat glass fiber, and the specific gravity is 1: (3-4) the diameter is 10-14 μm.
The preparation method is the same as that of example 1, and the obtained polyamide composite material is subjected to mechanical property detection, and the result is shown in table 3.
Comparative example 1
High-flow glass fiber reinforced polyphenyl ether polyamide composite material: the composite material comprises the following components in percentage by weight:
45% of polyamide resin, 24.2% of polyphenyl ether, 0.4% of fluidity improver, 30% of glass fiber and 0.4% of compound antioxidant;
wherein the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound, the polyamide resin is PA6 resin, and the viscosity of the polyamide resin is 2.8 g/dl; the polyphenyl ether is PP0 polyphenyl ether resin with the viscosity of 41 g/dl; the compound antioxidant is a compound of N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine (1098), high-performance phosphite S9228 and zinc oxide, and the compound proportion is 1:1: 0.8; the glass fiber is flat glass fiber, and the specific gravity is 1: (3-4) the diameter is 10-14 μm.
The preparation method is the same as that of example 1, and the obtained polyamide composite material is subjected to mechanical property detection, and the result is shown in table 3.
Comparative example 2
High-flow glass fiber reinforced polyphenyl ether polyamide composite material: the composite material comprises the following components in percentage by weight:
40% of polyamide resin, 21.7% of polyphenyl ether, 7.5% of toughening agent, 0.4% of fluidity improving agent, 30% of glass fiber and 0.4% of compound antioxidant;
wherein the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound, the polyamide resin is PA6 resin, and the viscosity of the polyamide resin is 2.8 g/dl; the polyphenyl ether is PP0 polyphenyl ether resin with the viscosity of 41 g/dl; the toughening agent is a copolymer of ethylene-acrylic ester-glycidyl methacrylate, is selected from toughening agents produced by Akoma, and has a commercial brand of AX 8900; the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound; the compound antioxidant is a compound of N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine (1098), high-performance phosphite S9228 and zinc oxide, and the compound proportion is 1:1: 0.8; the glass fiber is flat glass fiber, and the specific gravity is 1: (3-4) the diameter is 10-14 μm.
The preparation method is the same as that of example 1, and the obtained polyamide composite material is subjected to mechanical property detection, and the result is shown in table 3.
Comparative example 3
High-flow glass fiber reinforced polyphenyl ether polyamide composite material: the composite material comprises the following components in percentage by weight:
40% of polyamide resin, 21.7% of polyphenyl ether, 7.5% of compatilizer, 0.4% of fluidity improver, 30% of glass fiber and 0.4% of compound antioxidant;
wherein the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound, the polyamide resin is PA6 resin, and the viscosity of the polyamide resin is 2.8 g/dl; the polyphenyl ether is PP0 polyphenyl ether resin with the viscosity of 41 g/dl; the compatilizer is PPO-g-MAH maleic anhydride grafted polyphenyl ether; the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound; the compound antioxidant is a compound of N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine (1098), high-performance phosphite S9228 and zinc oxide, and the compound proportion is 1:1: 0.8; the glass fiber is flat glass fiber, and the specific gravity is 1: (3-4) the diameter is 10-14 μm.
The preparation method is the same as that of example 1, and the obtained polyamide composite material is subjected to mechanical property detection, and the result is shown in table 3.
Comparative example 4
High-flow glass fiber reinforced polyphenyl ether polyamide composite material: the composite material comprises the following components in percentage by weight:
40% of polyamide resin, 22.1% of polyphenyl ether, 3.5% of toughening agent, 4% of compatilizer, 30% of glass fiber and 0.4% of compound antioxidant;
wherein the polyamide resin is PA6 resin, and the viscosity of the polyamide resin is 2.8 g/dl; the polyphenyl ether is PP0 polyphenyl ether resin with the viscosity of 41 g/dl; the toughening agent is a copolymer of ethylene-acrylic ester-glycidyl methacrylate, is selected from toughening agents produced by Akoma, and has a commercial brand of AX 8900; the compatilizer is PPO-g-MAH maleic anhydride grafted polyphenyl ether; the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound; the compound antioxidant is a compound of N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine (1098), high-performance phosphite S9228 and zinc oxide, and the compound proportion is 1:1: 0.8; the glass fiber is flat glass fiber, and the specific gravity is 1: (3-4) the diameter is 10-14 μm.
The preparation method is the same as that of example 1, and the obtained polyamide composite material is subjected to mechanical property detection, and the result is shown in table 3.
Comparative example 5
High-flow glass fiber reinforced polyphenyl ether polyamide composite material: the composite material comprises the following components in percentage by weight:
40% of polyamide resin, 21.7% of polyphenyl ether, 3.5% of toughening agent, 4% of compatilizer, 30% of glass fiber and 0.4% of compound antioxidant; 0.4% of a lubricant;
wherein the polyamide resin is PA6 resin, and the viscosity of the polyamide resin is 2.8 g/dl; the polyphenyl ether is PP0 polyphenyl ether resin with the viscosity of 41 g/dl; the toughening agent is a copolymer of ethylene-acrylic ester-glycidyl methacrylate, is selected from toughening agents produced by Akoma, and has a commercial brand of AX 8900; the compatilizer is PPO-g-MAH maleic anhydride grafted polyphenyl ether; the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound; the compound antioxidant is a compound of N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine (1098), high-performance phosphite S9228 and zinc oxide, and the compound proportion is 1:1: 0.8; the lubricant is silicone; the glass fiber is flat glass fiber, and the specific gravity is 1: (3-4) the diameter is 10-14 μm.
The preparation method is the same as that of example 1, the obtained polyamide composite material is subjected to mechanical property detection, and the result is shown in Table 3
Comparative example 6
High-flow glass fiber reinforced polyphenyl ether polyamide composite material: the composite material comprises the following components in percentage by weight:
40% of polyamide resin, 21.7% of polyphenyl ether, 3.5% of toughening agent, 4% of compatilizer, 0.4% of fluidity improver, 30% of glass fiber and 0.4% of compound antioxidant;
wherein the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound, the polyamide resin is PA6 resin, and the viscosity of the polyamide resin is 2.8 g/dl; the polyphenyl ether is PP0 polyphenyl ether resin with the viscosity of 41 g/dl; the toughening agent is a copolymer of ethylene-acrylic ester-glycidyl methacrylate, is selected from toughening agents produced by Akoma, and has a commercial brand of AX 8900; the compatilizer is PPO-g-MAH maleic anhydride grafted polyphenyl ether; the fluidity improver is N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound; the compound antioxidant is a compound of N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine (1098), high-performance phosphite S9228 and zinc oxide, and the compound proportion is 1:1: 0.8; the glass fiber is flat glass fiber, and the specific gravity is 1: (3-4) the diameter is 10-14 μm.
The preparation method of the high-fluidity glass fiber reinforced polyphenyl ether polyamide composite material comprises the following steps:
a: weighing polyamide resin, polyphenyl ether resin, a toughening agent and a compatilizer according to the weight percentage, drying for 4 hours at the temperature of 100 ℃, putting into a high-speed mixer, mixing at room temperature, and stirring at the speed: 300 times of 500 turns/minute, the stirring time is 3-5 minutes, so that all the components are fully stirred and uniformly dispersed;
b, adding the mixed materials into a double-screw extruder with the length-diameter ratio of 48/1 for melt extrusion, wherein the melt extrusion temperature is 200-300 ℃, and the screw rotation speed is 300-500 r/m; adding the glass fiber from a fifth area of the extruder;
c, cooling, air-drying, granulating and strong magnetic treatment are carried out on the extruded material to obtain the polyamide composite material;
in the step B, the heating process of the double-screw extruder is as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 240 ℃, the temperature of the fourth zone is 230 ℃, the temperature of the fifth zone is 230 ℃, the temperature of the sixth zone is 220 ℃, the temperature of the seventh zone is 220 ℃, the temperature of the eighth zone is 220 ℃, the temperature of the ninth zone is 220 ℃, the temperature of the tenth zone is 240 ℃ and the temperature of the machine head is 250 ℃.
The mechanical properties of the polyamide composite material obtained were measured and the results are shown in Table 3.
Table 1 is a summary of the material ratios of examples 1-5
| Name of Material | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Polyamide resin: PA6 | 50 | 45 | 40 | 35 | 30 |
| Polyphenylene ether: PPO (polyphenylene oxide) | 30 | 25.2 | 21.7 | 17.8 | 14 |
| A toughening agent: AX8900 | 4 | 4 | 3.5 | 3 | 2.4 |
| A compatilizer: PPO-g-MAH | 5 | 5 | 4 | 3.5 | 3 |
| Fluidity improver | 0.5 | 0.4 | 0.4 | 0.4 | 0.3 |
| Glass fiber | 10 | 20 | 30 | 40 | 50 |
| Compound antioxidant | 0.5 | 0.4 | 0.4 | 0.3 | 0.3 |
Table 2 is a summary of the material ratios of comparative examples 1 to 6
| Name of Material | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Polyamide resin: PA6 | 45 | 40 | 40 | 40 | 40 | 40 |
| Polyphenylene ether: PPO (polyphenylene oxide) | 24.2 | 21.7 | 21.7 | 22.1 | 21.7 | 21.7 |
| A toughening agent: AX8900 | 0 | 7.5 | 0 | 3.5 | 3.5 | 3.5 |
| A compatilizer: PPO-g-MAH | 0 | 0 | 7.5 | 4 | 4 | 4 |
| Fluidity improver | 0.4 | 0.4 | 0.4 | 0 | 0 | 0.4 |
| Glass fiber | 30 | 30 | 30 | 30 | 30 | 30 |
| Compound antioxidant | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Lubricant silicones | 0 | 0 | 0 | 0 | 0.4 | 0 |
And (3) product performance testing: the high-flow glass fiber reinforced polyphenylene ether polyamide composite materials obtained in the above examples 1 to 5 and comparative examples 1 to 6 were tested according to the relevant standards of ASTM D792/(GB/T1033), ASTM D638/(GB/T1040), ASTM D790/(GB/T9341), ASTM D256/(GB/T1843), ASTM D648(GB/T1643.1) and ASTM D1238/(GB/T3682) for tensile strength, elongation at break, flexural strength, flexural modulus, notched impact strength, heat distortion temperature and melt index, respectively, and the performance test data are as shown in Table 3:
as can be seen from tables 1-2 in conjunction with the performance test results in Table 3:
1. as can be seen from examples 1-5 and comparative examples 1-5, the addition amount of the glass fibers has a very obvious effect on the mechanical properties of the material, and the more the glass fibers are added, the better the comprehensive mechanical properties are.
2. As can be seen from example 3 and comparative examples 4 to 5, in example 3 with the addition of the fluidity improver, the melt index test value of example 3 is 13.2 which is much higher than the melt index test values of comparative examples 4 to 5, i.e., 6.4 and 7.2, compared with comparative examples 4 to 5 without the addition of the fluidity improver, the fluidity improver can effectively improve the fluidity of the material without affecting other properties, and the fluidity is much better than that of the silicone product of the same lubricant in comparative example 5.
3. Through the embodiment 3 and the comparative examples 1-3, it can be seen that the effect of adopting the compounded toughening agent AX8900 and the compatilizer PPO-g-MAH is better for improving the two compatability of PPO/PA than that of using one of the toughening agent AX8900 and the compatilizer PPO-g-MAH, and simultaneously, the comprehensive mechanical property is higher than that of using one of the compatilizer and the compatilizer.
4. As can be seen from example 3 and comparative example 6, except that the extrusion temperature is different, under the condition that the material ratio and the preparation method are the same, the fluidity and the comprehensive mechanical property are better when the high-temperature extrusion at 200 ℃ and 300 ℃ is adopted than when the conventional low-temperature extrusion at 200 ℃ and 250 ℃ is adopted.
According to the invention, on the basis of PA6 resin and PPO resin, glass fiber and a compound antioxidant are added, a plasticizer PPO-g-MAH and toughening agents ethylene, acrylic ester and glycidyl methacrylate are added to improve the compatibility and toughness, a fluidity improver N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound is added, a hydrogen bond is formed with PPO and PA molecular chains through a high-temperature extrusion reaction, the fluidity of PPO/PA is improved, the interface compatibility of PPO/PA is improved, meanwhile, the fluidity of PPO/PA is improved, and the application range of the fields of injection molding of thin-wall products with the wall thickness of less than 1.5mm and the like is realized.
The above is only a preferred embodiment of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (9)
1. The high-fluidity glass fiber reinforced polyphenyl ether polyamide composite material is characterized in that: the composite material comprises the following components in percentage by weight:
30 to 50 percent of polyamide resin
14-30% of polyphenyl ether
2.4 to 4 percent of toughening agent
3 to 5 percent of compatilizer
0.3-0.5% of fluidity improver
10 to 50 percent of glass fiber
0.3 to 0.5 percent of compound antioxidant.
2. The high flow glass fiber reinforced polyphenylene ether polyamide composite material as claimed in claim 1, wherein: the fluidity improver is an N, N' -bis (2,2,6, 6-tetraalkyl-4-piperidyl) -1, 3-benzenedicarboxamide compound, wherein alkyl is methyl or ethyl or saturated alkyl with carbon atom less than 4.
3. The high flow glass fiber reinforced polyphenylene ether polyamide composite material as claimed in claim 1, wherein: the polyamide resin is PA6 resin, and the viscosity of the polyamide resin is 2.5-3.2g/d l.
4. The high flow glass fiber reinforced polyphenylene ether polyamide composite material as claimed in claim 1, wherein: the polyphenyl ether is PP0 polyphenyl ether resin, and the viscosity of the polyphenyl ether resin is 35-53 g/dl.
5. The high flow glass fiber reinforced polyphenylene ether polyamide composite material as claimed in claim 2, wherein: the toughening agent is a copolymer of ethylene-acrylate-glycidyl methacrylate.
6. The high flow glass fiber reinforced polyphenylene ether polyamide composite material as claimed in claim 5, wherein: the compatilizer is PPO-g-MAH maleic anhydride grafted polyphenyl ether.
7. The high flow glass fiber reinforced polyphenylene ether polyamide composite material as claimed in claim 1, wherein: the compound antioxidant is a compound of N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine (1098), high-performance phosphite S9228 and zinc oxide, and the compound ratio is 1:1: 0.8.
8. The high flow glass fiber reinforced polyphenylene ether polyamide composite material as claimed in claim 1, wherein: the glass fiber is flat glass fiber, and the specific gravity is 1: (3-4) the diameter is 10-14 μm.
9. The preparation method of the high-flow glass fiber reinforced polyphenylene ether polyamide composite material as claimed in claim 1, which comprises the following steps:
a: weighing polyamide resin, polyphenyl ether resin, a toughening agent and a compatilizer according to the weight percentage, drying for 4 hours at the temperature of 100 ℃, putting into a high-speed mixer, mixing at room temperature, and stirring at the speed: 300 times of 500 turns/minute, the stirring time is 3-5 minutes, so that all the components are fully stirred and uniformly dispersed;
b, adding the mixed materials into a double-screw extruder with the length-diameter ratio of 48/1 for melt extrusion, wherein the melt extrusion temperature is 200-300 ℃, and the screw rotation speed is 300-500 r/m; adding the glass fiber from a fifth area of the extruder;
c, cooling, air-drying, granulating and strong magnetic treatment are carried out on the extruded material to obtain the polyamide composite material;
in the step B, the heating process of the double-screw extruder is as follows: the temperature of the first zone is 200 ℃ and 220 ℃, the temperature of the second zone is 280 ℃, the temperature of the third zone is 300 ℃, the temperature of the fourth zone is 300 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the eighth zone is 250 ℃, the temperature of the ninth zone is 250 ℃, the temperature of the tenth zone is 250 ℃ and the temperature of the head is 260 ℃.
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| CN117777702A (en) * | 2023-12-29 | 2024-03-29 | 天合光能股份有限公司 | Modified polyphenyl ether material, and preparation method and application thereof |
| CN118063957A (en) * | 2024-04-17 | 2024-05-24 | 山东祥龙新材料股份有限公司 | Flexible hydrolysis-resistant extrusion polyamide material, preparation method thereof and nylon tube |
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