CN114316586B - 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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- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 101
- 239000004952 Polyamide Substances 0.000 title claims abstract description 57
- 229920002647 polyamide Polymers 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 14
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000012745 toughening agent Substances 0.000 claims abstract description 26
- 239000002667 nucleating agent Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 5
- -1 carboxylate calcium salt Chemical class 0.000 claims description 32
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 26
- 229920001897 terpolymer Polymers 0.000 claims description 20
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 13
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 claims description 10
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 10
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 7
- 239000004760 aramid Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000005389 magnetism Effects 0.000 claims description 7
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 6
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
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- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000004611 light stabiliser Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 2
- 229920006153 PA4T Polymers 0.000 claims description 2
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006375 polyphtalamide Polymers 0.000 claims description 2
- 229940116351 sebacate Drugs 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 9
- 239000003733 fiber-reinforced composite Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- CBKQEKDIYBVVOF-UHFFFAOYSA-L calcium;nonadecanoate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCC([O-])=O CBKQEKDIYBVVOF-UHFFFAOYSA-L 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- IWVKTOUOPHGZRX-UHFFFAOYSA-M methyl 2-methylprop-2-enoate;2-methylprop-2-enoate Chemical compound CC(=C)C([O-])=O.COC(=O)C(C)=C IWVKTOUOPHGZRX-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000561 Twaron Polymers 0.000 description 1
- CCWFPXHGWPJNHP-UHFFFAOYSA-N [2-(carboxyamino)phenyl]carbamic acid Chemical compound OC(=O)NC1=CC=CC=C1NC(O)=O CCWFPXHGWPJNHP-UHFFFAOYSA-N 0.000 description 1
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- 238000005461 lubrication Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- QDYRBWYSFLEGLW-UHFFFAOYSA-N octadecyl 3-[2-(3,5-ditert-butylphenyl)-4-hydroxyphenyl]propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC=C(O)C=C1C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1 QDYRBWYSFLEGLW-UHFFFAOYSA-N 0.000 description 1
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- 229920006389 polyphenyl polymer Polymers 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an aramid fiber reinforced polyamide composite material, which comprises the following components in percentage by mass: 3-5% of toughening agent, 1-3% of compatilizer, 0.5-1% of compound nucleating agent, 0.3-0.5% of lubricant, 10-50% of aramid fiber, 0.3-0.5% of compound UV-resistant agent, 0.2-0.4% of compound antioxidant and the balance of polyamide resin. The aramid fiber reinforced polyamide composite material has higher mechanical strength, high wear resistance, greatly improved dimensional stability and excellent comprehensive performance. The aramid fiber is subjected to pre-coating treatment by adopting caprolactam, and then is processed into short fiber bundles with the length of 3-5mm, so that the problem that the aramid fiber cannot be metered and added in the use process is solved, and meanwhile, the aramid fiber can be uniformly dispersed in a polyamide matrix through melt blending with polyamide, so that the aramid fiber reinforced composite material with excellent comprehensive performance is obtained. The compatilizer is compounded with the compound nucleating agent, so that the mechanical property of the polyamide material can be effectively improved, and the compatibility of the aramid fiber and the polyamide can be improved.
Description
Technical Field
The invention relates to the technical field of polyamide composite materials, in particular to an aramid fiber reinforced polyamide composite material and a preparation method thereof.
Background
Polyamide resin, named polyamide, PA for short. The Nylon (Nylon) is the variety with the largest yield, the largest variety and the largest application in five engineering plastics, has the advantages of toughness, wear resistance, self lubrication and wide application temperature range, and becomes an engineering plastic widely applied in the current industry. The PA is widely used for replacing copper and nonferrous metal manufacturing machinery, chemical industry and electrical parts, such as a gear of a fuel pump of a diesel engine, a water pump, a high-pressure sealing ring, an oil delivery pipe and the like. Because of the strong polarity of PA, it has strong hygroscopicity, but poor dimensional stability, but can be improved by modification.
The Aramid fiber is called as "polyphenyl dicarboxyl phenylenediamine", english is Aramid fiber (the commercial name of the Aramid fiber is Kevlar of Twaron DuPont company), and is a novel high-tech synthetic fiber, which has excellent performances of super-high strength, high modulus, high temperature resistance, acid and alkali resistance, light weight and the like, the strength is 5-6 times of that of steel wire, the modulus is 2-3 times of that of steel wire or glass fiber, the toughness is 2 times of that of steel wire, the weight is only about 1/5 of that of steel wire, and the fiber is not decomposed and not melted at the temperature of 560 ℃. It has good insulation and ageing resistance, and has a long life cycle.
At present, the aramid fiber reinforced polyamide composite material has few production in the market, mainly has poor compatibility between untreated aramid fiber and polyamide, so that the composite material has lower performance, and the surface of the aramid fiber needs to be subjected to radiation treatment, so that the compatibility between the aramid fiber and polyamide is improved, and the mechanical property is improved. The other function of the aramid fiber is to improve the wear resistance of the material, the aramid fiber is processed into powder, and the powder and nylon are melted and extruded together to improve the wear resistance of the polyamide.
The aramid fiber is a material with high crystallinity and high orientation degree formed by rigid molecular chains, which is first developed by DuPont in the United states, has a series of excellent properties of small relative density, fatigue resistance, shearing resistance and the like, and is widely used for aramid fiber reinforced composite materials in the fields of rubber industry and the like. The performance of the composite material is related to the combination condition of the matrix phase, the reinforcing phase and the two-phase interface, and the good interface combination can lead the composite material to better exert the mechanical property. The aramid fiber has a rigid molecular structure, high molecular symmetry, weak intermolecular acting force, weak intermolecular hydrogen bond and low transverse strength, so that the aramid fiber is easy to break under the action of compression and shearing force. The high crystallinity makes the fiber surface smooth and non-reactive, so that the interface adhesion between the fiber and most of matrixes is poor, and therefore, the excellent mechanical properties of the aramid fiber are fully exerted to improve the interface combination condition of the aramid fiber and the composite material, and the surface of the aramid fiber is subjected to modification treatment.
Disclosure of Invention
The invention aims to provide an aramid fiber reinforced polyamide composite material and a preparation method thereof, and aims to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions:
an aramid fiber reinforced polyamide composite material comprises the following components in percentage by mass: 3-5% of toughening agent, 1-3% of compatilizer, 0.5-1% of compound nucleating agent, 0.3-0.5% of lubricant, 10-50% of aramid fiber, 0.3-0.5% of compound UV resistant agent, 0.2-0.4% of compound antioxidant and the balance of polyamide resin; the preparation method comprises the steps of pre-coating the aramid fiber by adopting caprolactam, specifically heating the caprolactam to 75-85 ℃ to obtain molten caprolactam, slowly soaking the continuous aramid fiber in the molten caprolactam, passing through a caprolactam melt pool with the length of 50cm at the speed of 8-12m/min, drying, and cutting off to 3-5 mm.
In the aramid fiber treatment method, after the aramid fiber is coated with caprolactam, the fiber is not easy to scatter, and is processed into short fiber with the length of 3-5mm, so that the short fiber can be well metered. The treated aramid fiber can improve the interface combination condition with other components in the system, fully exert the excellent mechanical property of the aramid fiber and improve the wear resistance of the polyamide.
Further, the toughening agent is two or more than two 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 toughening agent is added into the polyamide composite material, so that the mechanical properties such as tensile strength, elongation, notch impact strength and the like of the polyamide composite material are obviously improved compared with those of the polyamide composite material without the toughening agent.
Further, the toughening agent is a mixture of polyolefin elastomer grafted maleic anhydride and polyolefin elastomer grafted glycidyl methacrylate, and the mass ratio of the polyolefin elastomer grafted maleic anhydride to the polyolefin elastomer grafted glycidyl methacrylate is 1:1. In the composite material formula system, the molecular structures of the polyolefin elastomer grafted maleic anhydride and the polyolefin elastomer grafted glycidyl methacrylate are greatly different, one of the polyolefin elastomer grafted maleic anhydride and the polyolefin elastomer grafted glycidyl methacrylate is singly used, the toughness and the strength of the system are not obviously improved, and the two are compounded for use, so that the overall toughness and the impact strength of the material can be effectively improved.
Further, the compatilizer is an ethylene-acrylic ester-glycidyl methacrylate terpolymer, and the melt index of the ethylene-acrylic ester-glycidyl methacrylate terpolymer is 4-8g/10min,190 ℃/2.16kg. The ethylene-acrylic ester-glycidyl methacrylate terpolymer can ensure that the compatibility among the components is better, so that the mechanical properties of the polyamide composite material are obviously improved compared with those of the polyamide composite material without the compatilizer.
Further, the compound nucleating agent is one or more of long-chain carboxylate calcium salt, modified polyethylene wax zinc salt, talcum powder, superfine barium sulfate and calcined kaolin, and the mesh number of the talcum powder is 12000-20000 meshes.
The compound nucleating agent improves the creep resistance of the polyamide composite material and improves the dimensional stability. The carbon chain length of the long-chain carboxylate calcium salt is 18-36 carbon, the long-chain carboxylate calcium salt is specifically octadecyl calcium carboxylate, and the modified polyethylene wax zinc salt is a common nucleating agent.
Further, the compound nucleating agent is a mixture of talcum powder and long-chain carboxylate calcium salt, the mass ratio of the talcum powder to the long-chain carboxylate calcium salt is 4:1, the mesh number of the talcum powder is 15000 meshes, and the long-chain carboxylate calcium salt is octadecyl carboxylate calcium. The compounding of talcum powder and long-chain carboxylate calcium salt further improves the dimensional stability of the polyamide composite material.
Further, the lubricant is one or more of pentaerythritol stearate, ethylene acrylic acid copolymer, polydimethylsiloxane and high molecular weight hyperbranched polymer.
Further, the compound UV resistant agent is 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- [ 2-hydroxy-5-tert-octylphenyl ] benzotriazole, a polymer of succinic acid and 4-hydroxy-2, 6-tetramethyl-1-piperidinol,
Two or more of light stabilizer 622, bis-2, 6-tetramethyl piperidinol sebacate and hindered amine 770 are compounded; the compound antioxidant is one or more of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-stearyl beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionate, tri (2, 4-di-tert-butylphenyl) phosphite and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
Further, the polyamide resin is one or more of PA6, PA66, PA56, PA4T, PA6T, PA T and PPA.
The compound anti-UV agent is 2- [ 2-hydroxy-5-tert-octylphenyl ] benzotriazole and light stabilizer 622 in a mass ratio of 1:1, wherein the compound antioxidant is a mixture of n-stearyl beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionate and tri (2, 4-di-tert-butylphenyl) phosphite according to a mass ratio of 1:1; the polyamide resin is PA66, and the intrinsic viscosity of the PA66 is 2.5-3.0 Pa.s.
The invention also provides a preparation method of the aramid fiber reinforced polyamide composite material, which comprises the following steps: 1) Mixing the polyamide resin dried at 100 ℃ for 3-5 hours with a toughening agent, a compatilizer, a compound nucleating agent, a lubricant, a compound UV resistant agent and a compound antioxidant in a high-speed mixer at room temperature, wherein the mixing and stirring speed is 400-600 r/min, and the stirring time is 5-10min, so that the components are fully stirred and uniformly dispersed; 2) Adding the mixed materials into a double-screw extruder with the length-diameter ratio of 40/1 for melt extrusion, wherein the melt extrusion temperature is 250-300 ℃, the screw rotation speed is 300-500 rpm, and the aramid fibers are metered and added through side feeding;
3) And cooling, air-drying, granulating and performing strong magnetism on the extruded material to obtain the aramid fiber reinforced polyamide composite material.
The aramid fiber in the prior art is difficult to shear, disperse and compatible in a double-screw extruder, caprolactam is adopted to carry out pretreatment on the aramid fiber, and then the aramid fiber is processed into short fiber bundles with the length of 3-5mm, so that the problem that the aramid fiber cannot be metered and added for use in the using process is solved, and the aramid fiber can be uniformly dispersed in a polyamide matrix through melt blending with polyamide, so that the aramid fiber reinforced composite material is obtained.
Compared with the prior art, the aramid fiber reinforced polyamide composite material and the preparation method thereof provided by the invention have the following beneficial effects:
the aramid fiber reinforced polyamide composite material has higher mechanical strength, high wear resistance, greatly improved dimensional stability and excellent comprehensive performance. The aramid fiber is subjected to pre-coating treatment by adopting caprolactam, and then is processed into short fiber bundles with the length of 3-5mm, so that the problem that the aramid fiber cannot be metered and added in the use process is solved, and meanwhile, the aramid fiber can be uniformly dispersed in a polyamide matrix through melt blending with polyamide, so that the aramid fiber reinforced composite material with excellent comprehensive performance is obtained. The compatilizer is compounded with the compound nucleating agent, so that the mechanical property of the polyamide material can be effectively improved, and the compatibility of the aramid fiber and the polyamide can be improved. Compared with glass fibers in the prior art, the aramid fiber subjected to modification treatment can better enhance the comprehensive performance of the polyamide composite material.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
An aramid fiber reinforced polyamide composite material comprises the following components in percentage by mass: toughening agent: 2.5% of polyolefin elastomer grafted maleic anhydride and 2.5% of polyolefin elastomer grafted glycidyl methacrylate, and compatilizer: ethylene-acrylic ester-glycidyl methacrylate terpolymer 1%, and compound nucleating agent: talc powder 0.8%, calcium octadecylcarboxylate 0.2%, lubricant: pentaerythritol stearate 0.1%, ethylene acrylic acid copolymer 0.2%, aramid fiber 10%, and compound anti-UV agent: 0.1% of 2- [ 2-hydroxy-5-tert-octylphenyl ] benzotriazole, 0.2% of 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole, and antioxidant: tetrakis [ beta- (3, 5 di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester 0.2%, polyamide resin: PA 66.2%.
The melt index of the ethylene-acrylic ester-glycidyl methacrylate terpolymer is 8g/10min,190 ℃/2.16kg; the intrinsic viscosity of the PA66 is 2.7pa·s.
The preparation method of the embodiment comprises the following steps: 1) PA66, which is dried at 100 ℃ for 4 hours, is mixed with polyolefin elastomer grafted maleic anhydride, polyolefin elastomer grafted glycidyl methacrylate, ethylene-acrylic ester-glycidyl methacrylate terpolymer, superfine barium sulfate, pentaerythritol stearate, ethylene acrylic acid copolymer, 2- [ 2-hydroxy-5-tert-octylphenyl ] benzotriazole, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester in a high-speed mixer at room temperature, the mixing and stirring speed is 600 revolutions per minute, and the stirring time is 5 minutes, so that all components are fully stirred and dispersed uniformly;
2) Adding the mixed materials into a double-screw extruder with the length-diameter ratio of 40/1 for melt extrusion, wherein the melt extrusion temperature is 250 ℃, the screw rotation speed is 300 revolutions per minute, and the aramid fibers are metered and added through side feeding; 3) Cooling, air-drying, granulating and performing strong magnetism on the extruded material to obtain an aramid fiber reinforced polyamide composite material;
the aramid fiber in the step (2) is subjected to pre-coating treatment by adopting caprolactam, specifically, the caprolactam is heated to 85 ℃ to obtain molten caprolactam, then the continuous aramid fiber is slowly soaked in the molten caprolactam, passes through a caprolactam melt pool with the length of 50cm at the speed of 12m/min, is dried, and is cut off to 3mm, so that the aramid fiber is obtained.
Example 2
An aramid fiber reinforced polyamide composite material comprises the following components in percentage by mass: toughening agent: butadiene-styrene-methyl methacrylate toughening agent 2%, organic silicon rubber-methyl methacrylate toughening agent 2.5%, compatilizer: ethylene-acrylic ester-glycidyl methacrylate terpolymer 1.5 percent, compound nucleating agent: talc 0.64%, calcium octadecylcarboxylate 0.16%, lubricant: ethylene acrylic acid copolymer 0.1%, high molecular weight hyperbranched polymer 0.2%, aramid fiber 20%, and compound anti-UV agent: 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole 0.2%, hindered amine 7700.2%, compounding antioxidant: pentaerythritol tetrakis [ beta- (3, 5 di-tert-butyl-4-hydroxyphenyl) propionate ] 0.1%, n-stearyl beta- (3, 5 di-tert-butylphenyl-4-hydroxy-phenyl) propionate 0.2%, polyamide resin: PA6672.2%.
The melt index of the ethylene-acrylic ester-glycidyl methacrylate terpolymer is 4g/10min,190 ℃/2.16kg; the mesh number of the talcum powder is 12000 meshes; the intrinsic viscosity of the PA66 is 2.7pa·s.
The preparation method of the embodiment comprises the following steps: 1) Mixing PA66 dried at 100 ℃ for 3 hours with butadiene-styrene-methyl methacrylate toughener, organic silicon rubber-methyl methacrylate toughener, ethylene-acrylic ester-glycidyl methacrylate terpolymer, talcum powder, calcined kaolin, ethylene acrylic acid copolymer, high molecular weight hyperbranched polymer, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole, hindered amine 770, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionic acid n-octadecyl ester in a high-speed mixer at room temperature, wherein the mixing and stirring speed is 550 r/min and the stirring time is 6min, so that all components are fully and uniformly stirred and dispersed;
2) Adding the mixed materials into a double-screw extruder with the length-diameter ratio of 40/1 for melt extrusion, wherein the melt extrusion temperature is 250 ℃, the screw rotation speed is 450 rpm, and the aramid fibers are metered and added through side feeding; 3) And cooling, air-drying, granulating and performing strong magnetism on the extruded material to obtain the aramid fiber reinforced polyamide composite material.
The preparation method comprises the steps of pre-coating the aramid fiber by adopting caprolactam, specifically heating the caprolactam to 75 ℃ to obtain molten caprolactam, slowly soaking the continuous aramid fiber in the molten caprolactam, passing through a caprolactam melt pool with the length of 50cm at the speed of 11m/min, drying, and cutting to 4 mm.
Example 3
An aramid fiber reinforced polyamide composite material comprises the following components in percentage by mass: toughening agent: 2% of polyolefin elastomer grafted maleic anhydride, 2% of polyolefin elastomer grafted glycidyl methacrylate, and a compatilizer: 2% of ethylene-acrylic ester-glycidyl methacrylate terpolymer and a compound nucleating agent: talc powder 0.56%, calcium octadecylcarboxylate 0.14%, lubricant: pentaerythritol stearate 0.1%, polydimethylsiloxane 0.3%, aramid fiber 30%, and compound anti-UV agent: 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole 0.2%, 2- [ 2-hydroxy-5-tert-octylphenyl ] benzotriazole 0.2%, compounding antioxidant: pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] 0.3%, polyamide resin: PA 66.2%.
The melt index of the ethylene-acrylic ester-glycidyl methacrylate terpolymer is 7g/10min,190 ℃/2.16kg; the mesh number of the talcum powder is 20000 meshes; the intrinsic viscosity of the PA66 is 2.7pa·s.
The preparation method of the embodiment comprises the following steps: 1) PA66, which is dried at 100 ℃ for 4 hours, is mixed with polyolefin elastomer grafted maleic anhydride, polyolefin elastomer grafted glycidyl methacrylate, ethylene-acrylic ester-glycidyl methacrylate terpolymer, talcum powder, calcium octadecyl carboxylate, pentaerythritol stearate, polydimethylsiloxane, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- [ 2-hydroxy-5-tert-octylphenyl ] benzotriazole and tetra- [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester in a high-speed mixer at room temperature, wherein the mixing and stirring speed is 500 revolutions per minute, and the stirring time is 8 minutes, so that all components are fully and uniformly stirred and dispersed;
2) Adding the mixed materials into a double-screw extruder with the length-diameter ratio of 40/1 for melt extrusion, wherein the melt extrusion temperature is 280 ℃, the screw rotation speed is 400 rpm, and the aramid fibers are metered and added through side feeding; 3) Cooling, air-drying, granulating and performing strong magnetism on the extruded material to obtain an aramid fiber reinforced polyamide composite material;
and (3) pre-coating the aramid fiber in the step (2) by adopting caprolactam, specifically heating the caprolactam to 80 ℃ to obtain molten caprolactam, slowly soaking the continuous aramid fiber in the molten caprolactam, passing through a caprolactam melt pool with the length of 50cm at the speed of 10m/min, drying, and cutting to 4 mm.
Example 4
An aramid fiber reinforced polyamide composite material comprises the following components in percentage by mass: toughening agent: 1.5% of cross-linked methacrylate-methyl methacrylate toughening agent, 2% of butadiene-styrene-methyl methacrylate toughening agent, and compatilizer: ethylene-acrylic ester-glycidyl methacrylate terpolymer 2.5 percent, compound nucleating agent: talc powder 0.48%, calcium octadecylcarboxylate 0.12%, lubricant: ethylene acrylic acid copolymer 0.2%, polydimethylsiloxane 0.2%, aramid fiber 40%, and compounded anti-UV agent: 0.2% of polymer of succinic acid and 4-hydroxy-2, 6-tetramethyl-1-piperidinol and 0.3% of hindered amine 770, and an antioxidant is compounded: 0.4% of n-stearyl beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionate, polyamide resin: PA 66.1%.
The melt index of the ethylene-acrylic ester-glycidyl methacrylate terpolymer is 5g/10min,190 ℃/2.16kg; the intrinsic viscosity of the PA66 is 2.7pa·s.
The preparation method of the embodiment comprises the following steps: 1) PA66 after being dried at 100 ℃ for 3 hours is mixed with a cross-linked methyl methacrylate toughening agent, a butadiene-styrene-methyl methacrylate toughening agent, an ethylene-acrylate-glycidyl methacrylate terpolymer, a modified polyethylene wax zinc salt, an ethylene acrylic acid copolymer, polydimethylsiloxane, a polymer of succinic acid and 4-hydroxy-2, 6-tetramethyl-1-piperidinol, hindered amine 770 and beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionic acid n-octadecyl alcohol ester in a high-speed mixer at room temperature, the mixing stirring speed is 400 rpm, and the stirring time is 10min, so that all components are fully stirred and dispersed uniformly;
2) Adding the mixed materials into a double-screw extruder with the length-diameter ratio of 40/1 for melt extrusion, wherein the melt extrusion temperature is 250 ℃, the screw rotation speed is 500 revolutions per minute, and the aramid fibers are metered and added through side feeding; 3) Cooling, air-drying, granulating and performing strong magnetism on the extruded material to obtain an aramid fiber reinforced polyamide composite material;
and (3) pre-coating the aramid fiber in the step (2) by adopting caprolactam, specifically heating the caprolactam to 85 ℃ to obtain molten caprolactam, slowly soaking the continuous aramid fiber in the molten caprolactam, passing through a caprolactam melt pool with the length of 50cm at the speed of 12m/min, drying, and cutting to 5 mm.
Example 5
An aramid fiber reinforced polyamide composite material comprises the following components in percentage by mass: toughening agent: 2% of polyolefin elastomer grafted maleic anhydride, 2% of polyolefin elastomer grafted glycidyl methacrylate, and a compatilizer: ethylene-acrylic ester-glycidyl methacrylate terpolymer 3%, and compound nucleating agent: talc powder 0.4%, calcium octadecylcarboxylate 0.1%, lubricant: ethylene acrylic acid copolymer 0.5%, aramid fiber 50%, and compound anti-UV agent: light stabilizer 622.25%, 2- [ 2-hydroxy-5-tert-octylphenyl) benzotriazole 0.25%, compounding antioxidant: beta- (3, 5-di-tert-butylphenyl-4-)
N-stearyl hydroxy-phenyl) propionate 0.2%, tris (2, 4 di-t-butylphenyl) phosphite 0.2%, polyamide resin: PA 66.1%.
The melt index of the ethylene-acrylic ester-glycidyl methacrylate terpolymer is 6/10min,190 ℃/2.16kg; the mesh number of the talcum powder is 15000 meshes; the intrinsic viscosity of the PA66 is 2.7pa·s.
The preparation method of the embodiment comprises the following steps:
1) Mixing PA66 after being dried at 100 ℃ with polyolefin elastomer grafted maleic anhydride, polyolefin elastomer grafted glycidyl methacrylate, ethylene-acrylic ester-glycidyl methacrylate terpolymer, talcum powder, calcium stearyl carboxylate, ethylene acrylic acid copolymer, light stabilizer 622, 2- [ 2-hydroxy-5-tert-octylphenyl) benzotriazole, beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) n-stearyl propionate and tri (2, 4-di-tert-butylphenyl) phosphite in a high-speed mixer at room temperature, wherein the mixing and stirring speed is 450 rpm, and the stirring time is 7min, so that all components are fully and uniformly stirred and dispersed;
2) Adding the mixed materials into a double-screw extruder with the length-diameter ratio of 40/1 for melt extrusion, wherein the melt extrusion temperature is 280 ℃, the screw rotation speed is 350 revolutions per minute, and the aramid fibers are metered and added through side feeding; 3) Cooling, air-drying, granulating and performing strong magnetism on the extruded material to obtain an aramid fiber reinforced polyamide composite material;
and (2) pre-coating the aramid fiber by adopting caprolactam, specifically heating the caprolactam to 80 ℃ to obtain molten caprolactam, slowly soaking the continuous aramid fiber in the molten caprolactam, passing through a caprolactam melt pool with the length of 50cm at the speed of 9m/min, drying, and cutting to 4 mm.
Comparative example 1
The difference from example 3 is that no compatibilizing agent and no compounding nucleating agent were added in comparative example 1.
Comparative example 2
The difference from example 3 is that no built-up nucleating agent was added in comparative example 2.
Comparative example 3
The difference from example 3 is that the amount of the compatibilizing agent added in comparative example 3 was 4%.
Comparative example 4
The difference from example 3 is that glass fiber was used instead of aramid fiber in comparative example 4.
The composites prepared in examples 1-5 and comparative examples 1-4 were subjected to performance testing, and the results are shown in Table 1 below:
TABLE 1
Note that:
specific gravity was measured according to ASTM D792/(GB/T1033);
notched impact strength was measured according to ASTM D256/(GB/T1843); units Kj/m 2 Tensile property testing is performed according to ASTM D638/(GB/T1040); (tensile Strength/MPa)
Elongation at break was tested according to ASTM D638/(GB/T1040) and elongation at break/% flexural strength was tested according to ASTM D790/(GB/T9341); (flexural Strength/MPa)
Flexural modulus test (flexural modulus/MPa) melt index test according to ASTM D790/(GB/T9341) standard and test according to ASTM D1238/(GB/T3682) standard; 220 ℃/10kg; g/10min
Heat distortion temperature test was measured according to ASTM D648 (GB/T1643.1), 0.45MPa, unannealed.
It can be seen from examples 1 to 5 that the addition amount of the aramid fiber has a remarkable effect on the mechanical properties of the polyamide material, and the more the aramid fiber is added, the better the comprehensive mechanical properties are. As can be seen from example 3 and comparative examples 1-3, under the condition that 30% of the aramid fiber is added, the compatibility agent is compounded with the compound nucleating agent, so that the mechanical property of the material and the compatibility of the aramid fiber and polyamide can be effectively improved, and other properties are not influenced, and as can be seen from comparative example 2 and comparative example 3, the improvement of the addition amount of the compatibility agent has obvious improvement on the toughness of the material, but the flowability of the material is influenced, and the melt index is reduced. It can be seen from examples 3 and 4 that the specific gravity of the aramid fiber reinforced polyamide is smaller and the reinforcing effect is better than that of the glass fiber reinforced polyamide compounded.
The above-described embodiments and features of the embodiments may be combined with each other without conflict. Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (6)
1. The aramid fiber reinforced polyamide composite material is characterized by comprising the following components in percentage by mass: 3-5% of toughening agent, 1-3% of compatilizer, 0.5-1% of compound nucleating agent, 0.3-0.5% of lubricant, 10-50% of aramid fiber, 0.3-0.5% of compound UV resistant agent, 0.2-0.4% of compound antioxidant and the balance of polyamide resin; the preparation method comprises the steps of pre-coating the aramid fiber by adopting caprolactam, specifically heating the caprolactam to 75-85 ℃ to obtain molten caprolactam, slowly soaking the continuous aramid fiber in the molten caprolactam, passing through a caprolactam melt pool with the length of 50cm at the speed of 8-12m/min, drying, and cutting off to 3-5 mm;
the compatilizer is an ethylene-acrylic ester-glycidyl methacrylate terpolymer, and the melt index of the ethylene-acrylic ester-glycidyl methacrylate terpolymer is 4-8g/10min,190 ℃/2.16kg; the compound nucleating agent is a mixture of talcum powder and long-chain carboxylate calcium salt, the mass ratio of the talcum powder to the long-chain carboxylate calcium salt is 4:1, the mesh number of the talcum powder is 15000 meshes, and the long-chain carboxylate calcium salt is octadecyl calcium carboxylate; the toughening agent is a mixture of polyolefin elastomer grafted maleic anhydride and polyolefin elastomer grafted glycidyl methacrylate, and the mass ratio of the polyolefin elastomer grafted maleic anhydride to the polyolefin elastomer grafted glycidyl methacrylate is 1:1.
2. The aramid fiber reinforced polyamide composite material according to claim 1, wherein the lubricant is one or more of pentaerythritol stearate, ethylene acrylic acid copolymer, polydimethylsiloxane and high molecular weight hyperbranched polymer.
3. The aramid fiber reinforced polyamide composite material according to claim 1, wherein the compounded anti-UV agent is two or more of 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- [ 2-hydroxy-5-tert-octylphenyl ] benzotriazole, a polymer of succinic acid and 4-hydroxy-2, 6-tetramethyl-1-piperidinol, a light stabilizer 622, bis-2, 6-tetramethyl piperidinol sebacate, hindered amine 770; the compound antioxidant is one or more of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-stearyl beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionate, tri (2, 4-di-tert-butylphenyl) phosphite and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
4. The aramid fiber reinforced polyamide composite material of claim 3, wherein the polyamide resin is one or more of PA6, PA66, PA56, PA4T, PA6T, PA T and PPA.
5. The aramid fiber reinforced polyamide composite material according to claim 4, wherein the compounded anti-UV agent is 2- [ 2-hydroxy-5-tert-octylphenyl ] benzotriazole and light stabilizer 622 in a mass ratio of 1:1, wherein the compound antioxidant is a mixture of n-stearyl beta- (3, 5-di-tert-butylphenyl-4-hydroxy-phenyl) propionate and tri (2, 4-di-tert-butylphenyl) phosphite according to a mass ratio of 1:1; the polyamide resin is PA66, and the intrinsic viscosity of the PA66 is 2.5-3.0 Pa.s.
6. A method of preparing an aramid fiber reinforced polyamide composite material according to any one of claims 1 to 5, comprising the steps of:
1) Mixing the polyamide resin dried at 100 ℃ for 3-5 hours with a toughening agent, a compatilizer, a compound nucleating agent, a lubricant, a compound UV resistant agent and a compound antioxidant in a high-speed mixer at room temperature, wherein the mixing and stirring speed is 400-600 r/min, and the stirring time is 5-10min, so that the components are fully stirred and uniformly dispersed;
2) Adding the mixed materials into a double-screw extruder with the length-diameter ratio of 40/1 for melt extrusion, wherein the melt extrusion temperature is 250-300 ℃, the screw rotation speed is 300-500 rpm, and the aramid fibers are metered and added through side feeding;
3) And cooling, air-drying, granulating and performing strong magnetism on the extruded material to obtain the aramid fiber reinforced polyamide composite material.
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| US5094794A (en) * | 1990-04-12 | 1992-03-10 | E. I. Du Pont De Nemours And Company | High performance aramid matrix composites |
| CN105885399A (en) * | 2016-01-25 | 2016-08-24 | 南京德尔隆工程塑料有限公司 | High-strength and wear-resistant polyamide composite material and preparing method thereof |
| CN110684337A (en) * | 2018-07-04 | 2020-01-14 | 中蓝晨光化工研究设计院有限公司 | High-performance scratch-resistant polyamide/polyphenyl ether composite material and preparation method thereof |
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| US5094794A (en) * | 1990-04-12 | 1992-03-10 | E. I. Du Pont De Nemours And Company | High performance aramid matrix composites |
| CN105885399A (en) * | 2016-01-25 | 2016-08-24 | 南京德尔隆工程塑料有限公司 | High-strength and wear-resistant polyamide composite material and preparing method thereof |
| CN110684337A (en) * | 2018-07-04 | 2020-01-14 | 中蓝晨光化工研究设计院有限公司 | High-performance scratch-resistant polyamide/polyphenyl ether composite material and preparation method thereof |
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