CN113956653A - Aramid fiber reinforced polyamide composite material and preparation method thereof - Google Patents
Aramid fiber reinforced polyamide composite material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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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
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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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- C08J2477/00—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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- C08J2477/00—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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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
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Abstract
The invention discloses an aramid fiber reinforced polyamide composite material and a preparation method thereof, wherein the composite material comprises the following components in percentage by weight: aramid fiber reinforced polyamide composite material: the composite material comprises the following components in percentage by weight: 82.2% of polyamide resin; 5% of a toughening agent; 1% of a compatilizer; 1% of inorganic nucleating agent; 0.3% of a lubricant; 10% of aramid fiber; 0.3 percent of compound UV resistant agent; 0.2 percent of compound antioxidant; the polyamide resin is selected from one or more of PA6, PA66, PA56, PA4T, PA6T, PA9T and PPA; the invention adopts polyethylene glycol terephthalate (PET) to carry out pre-coating treatment on aramid fiber, and then the aramid fiber is processed into fiber with the length of 3-5mm, thereby solving the problems that the aramid fiber cannot be measured and is added and used in the using process, and simultaneously the aramid fiber can be uniformly dispersed in a polyamide matrix through melt blending with polyamide to obtain the aramid fiber reinforced composite material.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to an aramid fiber reinforced polyamide composite material and a preparation method thereof.
Background
The aramid fiber is called poly phenylene terephthalamide completely, and Aramidfiber (the trade name of the aramid fiber is Twaron DuPont) is Kevlar, is a novel high-tech synthetic fiber, has the excellent performances of ultrahigh strength, high modulus, high temperature resistance, acid and alkali resistance, light weight and the like, has the strength of 5-6 times that of a steel wire, the modulus of 2-3 times that of the steel wire or glass fiber, the toughness of 2 times that of the steel wire, and the weight of only about 1/5 that of the steel wire, and does not decompose or melt at the temperature of 560 ℃. It has good insulating property and ageing resistance, and has long life cycle.
The aramid fiber is an organic fiber material with ultrahigh strength, high modulus, high temperature resistance, acid and alkali resistance and high toughness, and when the aramid fiber is not coated, the aramid fiber is like cotton, and is clustered on a screw, and the aramid fiber is not discharged, so that the aramid fiber is difficult to use in a double-screw extruder, and is difficult to cut in the double-screw extruder due to good toughness of the aramid fiber; the aramid fiber can not be melt blended with other matrix resins to form the aramid fiber reinforced composite material, and the problem that the aramid fiber can not be added and used through metering in the blending and using process is caused.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides an aramid fiber reinforced polyamide composite material and a preparation method thereof, and aims to solve the problems that the aramid fiber is difficult to shear and disperse in a double-screw extruder, so that the aramid fiber cannot be formed into the aramid fiber reinforced composite material with other matrix resins in a melt blending mode, and the problem that the aramid fiber cannot be added and used by metering in the using process.
The invention is realized by the following technical scheme: aramid fiber reinforced polyamide composite material: the composite material comprises the following components in percentage by weight:
30 to 50 percent of polyamide resin
3 to 5 percent of toughening agent
1 to 3 percent of compatilizer
0.5 to 1 percent of inorganic nucleating agent
0.3 to 0.5 percent of lubricant
10 to 50 percent of aramid fiber
0.3 to 0.5 percent of compound anti-UV agent
0.2 to 0.4 percent of compound antioxidant.
Further, the polyamide resin is selected from one or more of PA6, PA66, PA56, PA4T, PA6T, PA9T and PPA.
Further, the toughening agent is a compound of two or more of polyolefin elastomer grafted maleic anhydride, polyolefin elastomer grafted glycidyl methacrylate, styrene-acrylonitrile-glycidyl methacrylate copolymer, ethylene propylene diene monomer grafted maleic anhydride, cross-linked methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent and organic silicon rubber-methyl methacrylate toughening agent.
Preferably, the compatilizer is styrene maleic anhydride copolymer, the content of the maleic anhydride is 10-20%, and the melt index (230 ℃/2.16kg) of the styrene maleic anhydride copolymer is 4-6g/10 min.
Furthermore, the inorganic nucleating agent is one or more of talcum powder, superfine barium sulfate and calcined kaolin, and the mesh number of the inorganic nucleating agent is 12000-20000 meshes.
Further, the lubricant is any one or more of pentaerythritol stearate, ethylene acrylic acid copolymer, polydimethylsiloxane and high molecular weight hyperbranched polymer.
Preferably, the diameter of the aramid fiber is 10-14 μm, the length of the aramid fiber is 3-5mm, and the aramid fiber is aramid 1414 short fiber.
Further, the compound anti-UV agent is a compound of two or more of benzotriazole light stabilizer, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (UV326), 2- [ 2-hydroxy-5-tert-octylphenyl) benzotriazole (UV-5411), polymer of hindered amine light stabilizer succinic acid and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol, light stabilizer 622, sebacic acid bis-2, 2,6, 6-tetramethylpiperidinol ester and hindered amine 770.
Further, the compound antioxidant is any one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionic acid n-octadecyl ester (1076), tris (2, 4-di-tert-butylphenyl) phosphite (168) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (627A).
The preparation method of the aramid fiber reinforced polyamide composite material comprises the following steps:
s1: weighing polyamide resin according to the weight percentage, drying for 4 hours at 100 ℃, then putting the polyamide resin, a toughening agent, a compatilizer, an inorganic nucleating agent, a lubricant, a compound anti-UV agent and a compound antioxidant into a high-speed mixer together for mixing under the condition of room temperature, wherein the stirring speed is as follows: 300 times of 500 turns/minute, the stirring time is 3-5 minutes, so that all the components are fully stirred and uniformly dispersed;
s2: dissolving PET in hexafluoroisopropanol to form a mixed solution, controlling the concentration to be 50-60% wt, heating to 40-50 ℃, slowly soaking continuous aramid fibers in the mixed solution, mixing the continuous aramid fibers in a mixed solution pool with the length of 1 meter at the speed of 10m/min, drying at 80 ℃, and cutting into 3-5cm small sections to form the aramid fibers.
S3, adding the mixed material in the S1 into a 40/1 double-screw extruder for melt extrusion, wherein the melt extrusion temperature is 250-300 ℃, and the screw rotation speed is 300-500 r/m; adding the aramid fiber in the S2 from the fifth area of the extruder by side feeding and metering;
and S4, cooling, air drying, granulating and strong magnetic treatment are carried out on the materials extruded by the double-screw extruder to obtain the aramid fiber reinforced polyamide composite material.
Has the advantages that:
according to the invention, polyethylene terephthalate (PET) is adopted to carry out pre-coating treatment on aramid fibers, so that the PET is coated on the surface of the aramid fibers to form a layer of film, and then the film is processed into a fiber with the length of 3-5mm, so that the PET can be added as much as possible through the fiber with the common length, and the fiber is a bundle of fibers without bridging, so that the feeding is well carried out in a double-screw extruder, the problems that the aramid fibers cannot be metered and are difficult to add and use in the using process are solved, and the aramid fibers and polyamide can be uniformly dispersed in a polyamide matrix through melting and blending to obtain the aramid fiber reinforced composite material.
Detailed Description
The present invention will be further described with reference to examples and comparative examples.
Example 1
Aramid fiber reinforced polyamide composite material: the composite material comprises the following components in percentage by weight: 82.2% of polyamide resin; 5% of a toughening agent; 1% of a compatilizer; 1% of inorganic nucleating agent; 0.3% of a lubricant; 10% of aramid fiber; 0.3 percent of compound UV resistant agent; 0.2 percent of compound antioxidant;
wherein the polyamide resin is selected from one or more of PA6, PA66, PA56, PA4T, PA6T, PA9T and PPA.
The toughening agent is compounded by two or more of polyolefin elastomer grafted maleic anhydride, polyolefin elastomer grafted glycidyl methacrylate, styrene-acrylonitrile-glycidyl methacrylate copolymer, ethylene propylene diene monomer grafted maleic anhydride, cross-linked methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent and organic silicon rubber-methyl methacrylate toughening agent.
The compatilizer is styrene maleic anhydride copolymer, the content of the maleic anhydride is 10-20%, and the melt index (230 ℃/2.16kg) of the styrene maleic anhydride copolymer is 4-6g/10 min.
The inorganic nucleating agent is one or more of talcum powder, superfine barium sulfate and calcined kaolin, and the mesh number of the inorganic nucleating agent is 12000-20000 meshes.
The lubricant is any one or more of pentaerythritol stearate, ethylene acrylic acid copolymer, polydimethylsiloxane and high molecular weight hyperbranched polymer.
The diameter of the aramid fiber is 10-14 mu m, the length of the aramid fiber is 3-5mm, and the aramid fiber is aramid 1414 short fiber.
The compound anti-UV agent is a compound of two or more than two of benzotriazole light stabilizer, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (UV326), 2- [ 2-hydroxy-5-tert-octylphenyl) benzotriazole (UV-5411), hindered amine light stabilizer succinic acid and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol polymer, light stabilizer 622, sebacic acid bis-2, 2,6, 6-tetramethylpiperidinol ester and hindered amine 770.
The compound antioxidant is any one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionic acid n-octadecyl ester (1076), tris (2, 4-di-tert-butylphenyl) phosphite (168) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (627A).
The preparation method of the aramid fiber reinforced polyamide composite material comprises the following steps:
s1: weighing polyamide resin according to the weight percentage, drying for 4 hours at 100 ℃, then putting the polyamide resin, a toughening agent, a compatilizer, an inorganic nucleating agent, a lubricant, a compound anti-UV agent and a compound antioxidant into a high-speed mixer together for mixing under the condition of room temperature, wherein the stirring speed is as follows: 300 times of 500 turns/minute, the stirring time is 3-5 minutes, so that all the components are fully stirred and uniformly dispersed;
s2: dissolving PET in hexafluoroisopropanol to form a mixed solution, controlling the concentration to be 50-60% wt, heating to 40-50 ℃, slowly soaking continuous aramid fibers in the mixed solution, mixing the continuous aramid fibers in a mixed solution pool with the length of 1 meter at the speed of 10m/min, drying at 80 ℃, and cutting into 3-5cm small sections to form the aramid fibers.
S3, adding the mixed material in the S1 into a 40/1 double-screw extruder for melt extrusion, wherein the melt extrusion temperature is 250-300 ℃, and the screw rotation speed is 300-500 r/m; adding the aramid fiber in the S2 from the fifth area of the extruder by side feeding and metering;
s4, cooling, air drying, granulating and strong magnetic treatment are carried out on the materials extruded by the double-screw extruder to obtain the aramid fiber reinforced polyamide composite material
The obtained aramid fiber reinforced polyamide composite material was subjected to performance test, and the results are shown in table 3.
Example 2
Aramid fiber reinforced polyamide composite material: the composite material comprises the following components in percentage by weight: 72.2% of polyamide resin; 4.5 percent of toughening agent; 1.5% of a compatilizer; 0.8 percent of inorganic nucleating agent; 0.3% of a lubricant; 20% of aramid fiber; 0.4 percent of compound UV resistant agent; 0.3 percent of compound antioxidant;
wherein the polyamide resin is selected from one or more of PA6, PA66, PA56, PA4T, PA6T, PA9T and PPA.
The toughening agent is compounded by two or more of polyolefin elastomer grafted maleic anhydride, polyolefin elastomer grafted glycidyl methacrylate, styrene-acrylonitrile-glycidyl methacrylate copolymer, ethylene propylene diene monomer grafted maleic anhydride, cross-linked methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent and organic silicon rubber-methyl methacrylate toughening agent.
The compatilizer is styrene maleic anhydride copolymer, the content of the maleic anhydride is 10-20%, and the melt index (230 ℃/2.16kg) of the styrene maleic anhydride copolymer is 4-6g/10 min.
The inorganic nucleating agent is one or more of talcum powder, superfine barium sulfate and calcined kaolin, and the mesh number of the inorganic nucleating agent is 12000-20000 meshes.
The lubricant is any one or more of pentaerythritol stearate, ethylene acrylic acid copolymer, polydimethylsiloxane and high molecular weight hyperbranched polymer.
The diameter of the aramid fiber is 10-14 mu m, the length of the aramid fiber is 3-5mm, and the aramid fiber is aramid 1414 short fiber.
The compound anti-UV agent is a compound of two or more than two of benzotriazole light stabilizer, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (UV326), 2- [ 2-hydroxy-5-tert-octylphenyl) benzotriazole (UV-5411), hindered amine light stabilizer succinic acid and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol polymer, light stabilizer 622, sebacic acid bis-2, 2,6, 6-tetramethylpiperidinol ester and hindered amine 770.
The compound antioxidant is any one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionic acid n-octadecyl ester (1076), tris (2, 4-di-tert-butylphenyl) phosphite (168) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (627A).
The preparation method is the same as that of example 1, and the performance of the obtained aramid fiber reinforced polyamide composite material is detected, and the result is shown in table 3.
Example 3
Aramid fiber reinforced polyamide composite material: the composite material comprises the following components in percentage by weight: 62.2% of polyamide resin; 4% of a toughening agent; 2% of a compatilizer; 0.7 percent of inorganic nucleating agent; 0.4% of a lubricant; 30% of aramid fiber; 0.4 percent of compound UV resistant agent; 0.3 percent of compound antioxidant;
wherein the polyamide resin is selected from one or more of PA6, PA66, PA56, PA4T, PA6T, PA9T and PPA.
The toughening agent is compounded by two or more of polyolefin elastomer grafted maleic anhydride, polyolefin elastomer grafted glycidyl methacrylate, styrene-acrylonitrile-glycidyl methacrylate copolymer, ethylene propylene diene monomer grafted maleic anhydride, cross-linked methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent and organic silicon rubber-methyl methacrylate toughening agent.
The compatilizer is styrene maleic anhydride copolymer, the content of the maleic anhydride is 10-20%, and the melt index (230 ℃/2.16kg) of the styrene maleic anhydride copolymer is 4-6g/10 min.
The inorganic nucleating agent is one or more of talcum powder, superfine barium sulfate and calcined kaolin, and the mesh number of the inorganic nucleating agent is 12000-20000 meshes.
The lubricant is any one or more of pentaerythritol stearate, ethylene acrylic acid copolymer, polydimethylsiloxane and high molecular weight hyperbranched polymer.
The diameter of the aramid fiber is 10-14 mu m, the length of the aramid fiber is 3-5mm, and the aramid fiber is aramid 1414 short fiber.
The compound anti-UV agent is a compound of two or more than two of benzotriazole light stabilizer, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (UV326), 2- [ 2-hydroxy-5-tert-octylphenyl) benzotriazole (UV-5411), hindered amine light stabilizer succinic acid and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol polymer, light stabilizer 622, sebacic acid bis-2, 2,6, 6-tetramethylpiperidinol ester and hindered amine 770.
The compound antioxidant is any one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionic acid n-octadecyl ester (1076), tris (2, 4-di-tert-butylphenyl) phosphite (168) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (627A).
The preparation method is the same as that of example 1, and the performance of the obtained aramid fiber reinforced polyamide composite material is detected, and the result is shown in table 3.
Example 4
Aramid fiber reinforced polyamide composite material: the composite material comprises the following components in percentage by weight: 52.1% of polyamide resin; 3.5 percent of toughening agent; 2.5% of a compatilizer; 0.6 percent of inorganic nucleating agent; 0.4% of a lubricant; 40% of aramid fiber; 0.5 percent of compound UV resistant agent; 0.4 percent of compound antioxidant;
wherein the polyamide resin is selected from one or more of PA6, PA66, PA56, PA4T, PA6T, PA9T and PPA.
The toughening agent is compounded by two or more of polyolefin elastomer grafted maleic anhydride, polyolefin elastomer grafted glycidyl methacrylate, styrene-acrylonitrile-glycidyl methacrylate copolymer, ethylene propylene diene monomer grafted maleic anhydride, cross-linked methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent and organic silicon rubber-methyl methacrylate toughening agent.
The compatilizer is styrene maleic anhydride copolymer, the content of the maleic anhydride is 10-20%, and the melt index (230 ℃/2.16kg) of the styrene maleic anhydride copolymer is 4-6g/10 min.
The inorganic nucleating agent is one or more of talcum powder, superfine barium sulfate and calcined kaolin, and the mesh number of the inorganic nucleating agent is 12000-20000 meshes.
The lubricant is any one or more of pentaerythritol stearate, ethylene acrylic acid copolymer, polydimethylsiloxane and high molecular weight hyperbranched polymer.
The diameter of the aramid fiber is 10-14 mu m, the length of the aramid fiber is 3-5mm, and the aramid fiber is aramid 1414 short fiber.
The compound anti-UV agent is a compound of two or more than two of benzotriazole light stabilizer, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (UV326), 2- [ 2-hydroxy-5-tert-octylphenyl) benzotriazole (UV-5411), hindered amine light stabilizer succinic acid and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol polymer, light stabilizer 622, sebacic acid bis-2, 2,6, 6-tetramethylpiperidinol ester and hindered amine 770.
The compound antioxidant is any one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionic acid n-octadecyl ester (1076), tris (2, 4-di-tert-butylphenyl) phosphite (168) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (627A).
The preparation method is the same as that of example 1, and the performance of the obtained aramid fiber reinforced polyamide composite material is detected, and the result is shown in table 3.
Example 5
Aramid fiber reinforced polyamide composite material: the composite material comprises the following components in percentage by weight: 42.1% of polyamide resin; 3% of a toughening agent; 3% of a compatilizer; 0.5 percent of inorganic nucleating agent; 0.5% of a lubricant; 50% of aramid fiber; 0.5 percent of compound UV resistant agent; 0.4 percent of compound antioxidant;
wherein the polyamide resin is selected from one or more of PA6, PA66, PA56, PA4T, PA6T, PA9T and PPA.
The toughening agent is compounded by two or more of polyolefin elastomer grafted maleic anhydride, polyolefin elastomer grafted glycidyl methacrylate, styrene-acrylonitrile-glycidyl methacrylate copolymer, ethylene propylene diene monomer grafted maleic anhydride, cross-linked methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent and organic silicon rubber-methyl methacrylate toughening agent.
The compatilizer is styrene maleic anhydride copolymer, the content of the maleic anhydride is 10-20%, and the melt index (230 ℃/2.16kg) of the styrene maleic anhydride copolymer is 4-6g/10 min.
The inorganic nucleating agent is one or more of talcum powder, superfine barium sulfate and calcined kaolin, and the mesh number of the inorganic nucleating agent is 12000-20000 meshes.
The lubricant is any one or more of pentaerythritol stearate, ethylene acrylic acid copolymer, polydimethylsiloxane and high molecular weight hyperbranched polymer.
The diameter of the aramid fiber is 10-14 mu m, the length of the aramid fiber is 3-5mm, and the aramid fiber is aramid 1414 short fiber.
The compound anti-UV agent is a compound of two or more than two of benzotriazole light stabilizer, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (UV326), 2- [ 2-hydroxy-5-tert-octylphenyl) benzotriazole (UV-5411), hindered amine light stabilizer succinic acid and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol polymer, light stabilizer 622, sebacic acid bis-2, 2,6, 6-tetramethylpiperidinol ester and hindered amine 770.
The compound antioxidant is any one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionic acid n-octadecyl ester (1076), tris (2, 4-di-tert-butylphenyl) phosphite (168) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (627A).
The preparation method is the same as that of example 1, and the performance of the obtained aramid fiber reinforced polyamide composite material is detected, and the result is shown in table 3.
Comparative example 1
Aramid fiber reinforced polyamide composite material: the composite material comprises the following components in percentage by weight: 64.9% of polyamide resin; 4% of a toughening agent; 0% of a compatilizer; 0% of inorganic nucleating agent; 0.4% of a lubricant; 30% of aramid fiber; 0.4 percent of compound UV resistant agent; 0.3 percent of compound antioxidant;
wherein the polyamide resin is selected from one or more of PA6, PA66, PA56, PA4T, PA6T, PA9T and PPA.
The toughening agent is compounded by two or more of polyolefin elastomer grafted maleic anhydride, polyolefin elastomer grafted glycidyl methacrylate, styrene-acrylonitrile-glycidyl methacrylate copolymer, ethylene propylene diene monomer grafted maleic anhydride, cross-linked methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent and organic silicon rubber-methyl methacrylate toughening agent.
The compatilizer is styrene maleic anhydride copolymer, the content of the maleic anhydride is 10-20%, and the melt index (230 ℃/2.16kg) of the styrene maleic anhydride copolymer is 4-6g/10 min.
The inorganic nucleating agent is one or more of talcum powder, superfine barium sulfate and calcined kaolin, and the mesh number of the inorganic nucleating agent is 12000-20000 meshes.
The lubricant is any one or more of pentaerythritol stearate, ethylene acrylic acid copolymer, polydimethylsiloxane and high molecular weight hyperbranched polymer.
The diameter of the aramid fiber is 10-14 mu m, the length of the aramid fiber is 3-5mm, and the aramid fiber is aramid 1414 short fiber.
The compound anti-UV agent is a compound of two or more than two of benzotriazole light stabilizer, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (UV326), 2- [ 2-hydroxy-5-tert-octylphenyl) benzotriazole (UV-5411), hindered amine light stabilizer succinic acid and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol polymer, light stabilizer 622, sebacic acid bis-2, 2,6, 6-tetramethylpiperidinol ester and hindered amine 770.
The compound antioxidant is any one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionic acid n-octadecyl ester (1076), tris (2, 4-di-tert-butylphenyl) phosphite (168) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (627A).
The preparation method is the same as that of example 1, and the performance of the obtained aramid fiber reinforced polyamide composite material is detected, and the result is shown in table 3.
Comparative example 2
Aramid fiber reinforced polyamide composite material: the composite material comprises the following components in percentage by weight: 62.9% of polyamide resin; 4% of a toughening agent; 2% of a compatilizer; 0% of inorganic nucleating agent; 0.4% of a lubricant; 30% of aramid fiber; 0.4 percent of compound UV resistant agent; 0.3 percent of compound antioxidant;
wherein the polyamide resin is selected from one or more of PA6, PA66, PA56, PA4T, PA6T, PA9T and PPA.
The toughening agent is compounded by two or more of polyolefin elastomer grafted maleic anhydride, polyolefin elastomer grafted glycidyl methacrylate, styrene-acrylonitrile-glycidyl methacrylate copolymer, ethylene propylene diene monomer grafted maleic anhydride, cross-linked methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent and organic silicon rubber-methyl methacrylate toughening agent.
The compatilizer is styrene maleic anhydride copolymer, the content of the maleic anhydride is 10-20%, and the melt index (230 ℃/2.16kg) of the styrene maleic anhydride copolymer is 4-6g/10 min.
The inorganic nucleating agent is one or more of talcum powder, superfine barium sulfate and calcined kaolin, and the mesh number of the inorganic nucleating agent is 12000-20000 meshes.
The lubricant is any one or more of pentaerythritol stearate, ethylene acrylic acid copolymer, polydimethylsiloxane and high molecular weight hyperbranched polymer.
The diameter of the aramid fiber is 10-14 mu m, the length of the aramid fiber is 3-5mm, and the aramid fiber is aramid 1414 short fiber.
The compound anti-UV agent is a compound of two or more than two of benzotriazole light stabilizer, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (UV326), 2- [ 2-hydroxy-5-tert-octylphenyl) benzotriazole (UV-5411), hindered amine light stabilizer succinic acid and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol polymer, light stabilizer 622, sebacic acid bis-2, 2,6, 6-tetramethylpiperidinol ester and hindered amine 770.
The compound antioxidant is any one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionic acid n-octadecyl ester (1076), tris (2, 4-di-tert-butylphenyl) phosphite (168) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (627A).
The preparation method is the same as that of example 1, and the performance of the obtained aramid fiber reinforced polyamide composite material is detected, and the result is shown in table 3.
Comparative example 3
Aramid fiber reinforced polyamide composite material: the composite material comprises the following components in percentage by weight: 60.9% of polyamide resin; 4% of a toughening agent; 4% of a compatilizer; 0% of inorganic nucleating agent; 0.4% of a lubricant; 30% of aramid fiber; 0.4 percent of compound UV resistant agent; 0.3 percent of compound antioxidant;
wherein the polyamide resin is selected from one or more of PA6, PA66, PA56, PA4T, PA6T, PA9T and PPA.
The toughening agent is compounded by two or more of polyolefin elastomer grafted maleic anhydride, polyolefin elastomer grafted glycidyl methacrylate, styrene-acrylonitrile-glycidyl methacrylate copolymer, ethylene propylene diene monomer grafted maleic anhydride, cross-linked methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent and organic silicon rubber-methyl methacrylate toughening agent.
The compatilizer is styrene maleic anhydride copolymer, the content of the maleic anhydride is 10-20%, and the melt index (230 ℃/2.16kg) of the styrene maleic anhydride copolymer is 4-6g/10 min.
The inorganic nucleating agent is one or more of talcum powder, superfine barium sulfate and calcined kaolin, and the mesh number of the inorganic nucleating agent is 12000-20000 meshes.
The lubricant is any one or more of pentaerythritol stearate, ethylene acrylic acid copolymer, polydimethylsiloxane and high molecular weight hyperbranched polymer.
The diameter of the aramid fiber is 10-14 mu m, the length of the aramid fiber is 3-5mm, and the aramid fiber is aramid 1414 short fiber.
The compound anti-UV agent is a compound of two or more than two of benzotriazole light stabilizer, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (UV326), 2- [ 2-hydroxy-5-tert-octylphenyl) benzotriazole (UV-5411), hindered amine light stabilizer succinic acid and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol polymer, light stabilizer 622, sebacic acid bis-2, 2,6, 6-tetramethylpiperidinol ester and hindered amine 770.
The compound antioxidant is any one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionic acid n-octadecyl ester (1076), tris (2, 4-di-tert-butylphenyl) phosphite (168) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (627A).
The preparation method is the same as that of example 1, and the performance of the obtained aramid fiber reinforced polyamide composite material is detected, and the result is shown in table 3.
Comparative example 4
Aramid fiber reinforced polyamide composite material: the composite material comprises the following components in percentage by weight: 62.2% of polyamide resin; 4% of a toughening agent; 2% of a compatilizer; 0.7 percent of inorganic nucleating agent; 0.4% of a lubricant; aramid fiber 0%; 30% of glass fiber; 0.4 percent of compound UV resistant agent; 0.3 percent of compound antioxidant;
wherein the polyamide resin is selected from one or more of PA6, PA66, PA56, PA4T, PA6T, PA9T and PPA.
The toughening agent is compounded by two or more of polyolefin elastomer grafted maleic anhydride, polyolefin elastomer grafted glycidyl methacrylate, styrene-acrylonitrile-glycidyl methacrylate copolymer, ethylene propylene diene monomer grafted maleic anhydride, cross-linked methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent and organic silicon rubber-methyl methacrylate toughening agent.
The compatilizer is styrene maleic anhydride copolymer, the content of the maleic anhydride is 10-20%, and the melt index (230 ℃/2.16kg) of the styrene maleic anhydride copolymer is 4-6g/10 min.
The inorganic nucleating agent is one or more of talcum powder, superfine barium sulfate and calcined kaolin, and the mesh number of the inorganic nucleating agent is 12000-20000 meshes.
The lubricant is any one or more of pentaerythritol stearate, ethylene acrylic acid copolymer, polydimethylsiloxane and high molecular weight hyperbranched polymer.
The diameter of the aramid fiber is 10-14 mu m, the length of the aramid fiber is 3-5mm, and the aramid fiber is aramid 1414 short fiber.
The compound anti-UV agent is a compound of two or more than two of benzotriazole light stabilizer, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (UV326), 2- [ 2-hydroxy-5-tert-octylphenyl) benzotriazole (UV-5411), hindered amine light stabilizer succinic acid and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol polymer, light stabilizer 622, sebacic acid bis-2, 2,6, 6-tetramethylpiperidinol ester and hindered amine 770.
The compound antioxidant is any one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionic acid n-octadecyl ester (1076), tris (2, 4-di-tert-butylphenyl) phosphite (168) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (627A).
The preparation method is the same as that of the example 1, the performance of the obtained aramid fiber reinforced polyamide composite material is detected, and the result is 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 | 82.2 | 72.2 | 62.2 | 52.1 | 42.1 |
| A toughening agent: PPO-g-MAH | 5 | 4.5 | 4 | 3.5 | 3 |
| A compatilizer: SMA | 1 | 1.5 | 2 | 2.5 | 3 |
| Inorganic nucleating agent | 1 | 0.8 | 0.7 | 0.6 | 0.5 |
| Lubricant agent | 0.3 | 0.3 | 0.4 | 0.4 | 0.5 |
| Aramid fiber | 10 | 20 | 30 | 40 | 50 |
| Compound anti-UV agent | 0.3 | 0.4 | 0.4 | 0.5 | 0.5 |
| Compound antioxidant | 0.2 | 0.3 | 0.3 | 0.4 | 0.4 |
Table 2 is a summary of the material ratios of comparative examples 1 to 3
| Name of Material | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Polyamide resin: PA6 | 64.9 | 62.9 | 60.9 | 62.2 |
| A toughening agent: PPO-g-MAH | 4 | 4 | 4 | 4 |
| A compatilizer: SMA | 0 | 2 | 4 | 2 |
| Inorganic nucleating agent: | 0 | 0 | 0 | 0.7 |
| lubricant agent | 0.4 | 0.4 | 0.4 | 0.4 |
| Aramid fiber | 30 | 30 | 30 | 0 |
| Glass fiber | 0 | 0 | 0 | 30 |
| Compound anti-UV agent | 0.4 | 0.4 | 0.4 | 0.4 |
| Compound antioxidant | 0.3 | 0.3 | 0.3 | 0.3 |
And (3) product performance testing: the aramid fiber reinforced polyamide composite materials obtained in the above examples 1 to 5 and comparative examples 1 to 4 were tested for tensile strength, elongation at break, flexural strength, flexural modulus, notched impact strength, heat distortion temperature, and melt index 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), astm d1238/(GB/T3682), 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 to 5 and comparative examples 1 to 4, the mechanical properties of the material are obviously affected by the addition amount of the aramid fibers, and the more the aramid fibers are added, the better the comprehensive mechanical properties are.
2. It can be seen from example 3 and comparative examples 1,2 and 3 that the compatibilizer SMA and the inorganic nucleating agent can effectively improve the mechanical properties of the material and the compatibility of the aramid fiber and the polyamide without affecting other properties, and the addition amount of the compatibilizer SMA is increased, so that the rigidity of the material is improved more obviously, but the fluidity of the material is affected, and the melt index is reduced.
3. Through the embodiment 3 and the comparative example 4, compared with the compound glass fiber reinforced polyamide, the aramid fiber reinforced polyamide has smaller specific gravity and better reinforcing effect.
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 (10)
1. Aramid fiber reinforced polyamide composite material, its characterized in that: the composite material comprises the following components in percentage by weight:
30 to 50 percent of polyamide resin
3 to 5 percent of toughening agent
1 to 3 percent of compatilizer
0.5 to 1 percent of inorganic nucleating agent
0.3 to 0.5 percent of lubricant
10 to 50 percent of aramid fiber
0.3 to 0.5 percent of compound anti-UV agent
0.2 to 0.4 percent of compound antioxidant.
2. The aramid fiber reinforced polyamide composite material as claimed in claim 1, characterized in that: the polyamide resin is selected from one or more of PA6, PA66, PA56, PA4T, PA6T, PA9T and PPA.
3. The aramid fiber reinforced polyamide composite material as claimed in claim 1, characterized in that: the toughening agent is compounded by two or more of polyolefin elastomer grafted maleic anhydride, polyolefin elastomer grafted glycidyl methacrylate, styrene-acrylonitrile-glycidyl methacrylate copolymer, ethylene propylene diene monomer grafted maleic anhydride, cross-linked methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent and organic silicon rubber-methyl methacrylate toughening agent.
4. The aramid fiber reinforced polyamide composite material as claimed in claim 1, characterized in that: the compatilizer is styrene maleic anhydride copolymer, the content of maleic anhydride is 10-20%, and the melt index (230 ℃/2.16kg) of the styrene maleic anhydride copolymer is 4-6g/10 min.
5. The aramid fiber reinforced polyamide composite material as claimed in claim 1, characterized in that: the inorganic nucleating agent is one or more of talcum powder, superfine barium sulfate and calcined kaolin, and the mesh number of the inorganic nucleating agent is 12000-20000 meshes.
6. The aramid fiber reinforced polyamide composite material as claimed in claim 1, characterized in that: the lubricant is any one or more of pentaerythritol stearate, ethylene acrylic acid copolymer, polydimethylsiloxane and high molecular weight hyperbranched polymer.
7. The aramid fiber reinforced polyamide composite material as claimed in claim 1, characterized in that: the diameter of the aramid fiber is 10-14 mu m, the length of the aramid fiber is 3-5mm, and the aramid fiber is aramid 1414 short fiber.
8. The aramid fiber reinforced polyamide composite material as claimed in claim 1, characterized in that: the compound anti-UV agent is a compound of two or more than two of benzotriazole light stabilizer, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole (UV326), 2- [ 2-hydroxy-5-tert-octylphenyl) benzotriazole (UV-5411), hindered amine light stabilizer succinic acid and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidinol polymer, light stabilizer 622, sebacic acid bis-2, 2,6, 6-tetramethylpiperidinol ester and hindered amine 770.
9. The aramid fiber reinforced polyamide composite material as claimed in claim 1, characterized in that: the compound antioxidant is any one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010), beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionic acid n-octadecyl ester (1076), tris (2, 4-di-tert-butylphenyl) phosphite (168) and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite (627A).
10. A method of preparing the aramid fiber reinforced polyamide composite material as claimed in any one of claims 1 to 9, characterized by comprising the steps of:
s1: weighing polyamide resin according to the weight percentage, drying for 4 hours at 100 ℃, then putting the polyamide resin, a toughening agent, a compatilizer, an inorganic nucleating agent, a lubricant, a compound anti-UV agent and a compound antioxidant into a high-speed mixer together for mixing under the condition of room temperature, wherein the stirring speed is as follows: 300 times of 500 turns/minute, the stirring time is 3-5 minutes, so that all the components are fully stirred and uniformly dispersed;
s2: dissolving PET in hexafluoroisopropanol to form a mixed solution, controlling the concentration to be 50-60% wt, heating to 40-50 ℃, slowly soaking continuous aramid fibers in the mixed solution, mixing the continuous aramid fibers in a mixed solution pool with the length of 1 meter at the speed of 10m/min, drying at 80 ℃, and cutting into 3-5cm small sections to form aramid fibers;
s3, adding the mixed material in the S1 into a 40/1 double-screw extruder for melt extrusion, wherein the melt extrusion temperature is 250-300 ℃, and the screw rotation speed is 300-500 r/m; adding the aramid fiber in the S2 from the fifth area of the extruder by side feeding and metering;
and S4, cooling, air drying, granulating and strong magnetic treatment are carried out on the materials extruded by the double-screw extruder to obtain the aramid fiber reinforced polyamide composite material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117645791A (en) * | 2024-01-30 | 2024-03-05 | 江阴标榜汽车部件股份有限公司 | Nylon connecting pipe and steam forming process thereof |
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