CN116462963A - Halogen-free flame-retardant reinforced nylon composition and preparation method and application thereof - Google Patents
Halogen-free flame-retardant reinforced nylon composition and preparation method and application thereof Download PDFInfo
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- CN116462963A CN116462963A CN202310336168.9A CN202310336168A CN116462963A CN 116462963 A CN116462963 A CN 116462963A CN 202310336168 A CN202310336168 A CN 202310336168A CN 116462963 A CN116462963 A CN 116462963A
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- glass fiber
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- flat glass
- halogen
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- 239000004677 Nylon Substances 0.000 title claims abstract description 30
- 229920001778 nylon Polymers 0.000 title claims abstract description 30
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 239000003063 flame retardant Substances 0.000 title claims abstract description 21
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000835 fiber Substances 0.000 claims abstract description 40
- 239000005357 flat glass Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 238000005507 spraying Methods 0.000 claims abstract description 21
- 229920003231 aliphatic polyamide Polymers 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 239000002667 nucleating agent Substances 0.000 claims abstract description 10
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 6
- 229920002635 polyurethane Polymers 0.000 claims description 23
- 239000004814 polyurethane Substances 0.000 claims description 23
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 13
- 238000007334 copolymerization reaction Methods 0.000 claims description 11
- -1 polyhexamethylene sebacamide Polymers 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 claims description 7
- 229920002943 EPDM rubber Polymers 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920006152 PA1010 Polymers 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920006122 polyamide resin Polymers 0.000 claims description 2
- WXBUUJNOVQVTFV-UHFFFAOYSA-N 10-(azacycloundec-1-yl)-10-oxodecanamide Chemical compound NC(=O)CCCCCCCCC(=O)N1CCCCCCCCCC1 WXBUUJNOVQVTFV-UHFFFAOYSA-N 0.000 claims 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- UTOPWMOLSKOLTQ-UHFFFAOYSA-M octacosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O UTOPWMOLSKOLTQ-UHFFFAOYSA-M 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 30
- 239000002131 composite material Substances 0.000 abstract description 10
- 239000004952 Polyamide Substances 0.000 description 24
- 229920002647 polyamide Polymers 0.000 description 24
- 230000000694 effects Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000003365 glass fiber Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000013615 primer Substances 0.000 description 5
- 239000002987 primer (paints) Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 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 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229920003233 aromatic nylon Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- FIASKJZPIYCESA-UHFFFAOYSA-L calcium;octacosanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O FIASKJZPIYCESA-UHFFFAOYSA-L 0.000 description 1
- VDBXLXRWMYNMHL-UHFFFAOYSA-N decanediamide Chemical compound NC(=O)CCCCCCCCC(N)=O VDBXLXRWMYNMHL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexamethylene diamine Natural products NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical class CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 229920006114 semi-crystalline semi-aromatic polyamide Polymers 0.000 description 1
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a halogen-free flame-retardant reinforced nylon composition, a preparation method and application thereof, and the composition comprises the following components: aliphatic PA resin, copolymerized PA resin, compatilizer, halogen-free flame retardant, modified flat glass fiber, antioxidant, lubricant and nucleating agent. The composite material prepared by the invention has excellent mechanical property, and the appearance of a sample after paint spraying has no sink mark and no orange peel phenomenon.
Description
Technical Field
The invention belongs to the field of processing plastics, and particularly relates to a halogen-free flame-retardant reinforced nylon composition, and a preparation method and application thereof.
Background
Nylon, polyamide (PA), is a generic term for thermoplastic resins containing recurring amide groups (-NHCO-) in the molecular backbone, and includes aliphatic nylon, aromatic nylon, semi-aromatic nylon, and specialty nylon new varieties. Because of the properties of the material itself, such as mechanical properties, paint spraying properties and uneven surface after the material is shaped, orange peel phenomenon occurs, and the application requirements cannot be met, such as the semi-crystalline polyamide shows shrinkage during crystallization in a mold, it is necessary to modify it to meet the properties of on-line paint spraying, excellent appearance, high mechanical strength and flame retardance.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a halogen-free flame-retardant reinforced nylon composition with excellent appearance on the surface capable of being sprayed with paint, and a preparation method and application thereof.
The invention relates to a nylon composition, which comprises the following components in parts by weight:
wherein the weight content of PA6T in the copolymerized PA resin is not higher than 41%;
the modified flat glass fiber is waterborne polyurethane coated flat glass fiber.
Preferably, the relative viscosity of the aliphatic PA resin is 2.4-2.7, the polyamide viscosity is determined according to ISO 307-2007, the PA resin is dissolved with 96% concentrated sulfuric acid to prepare a 1%g/ml nylon solution, and the viscosity of the material is measured with an unoccupied viscometer.
Further, the aliphatic PA resin is polyamide resin formed by polymerizing dibasic acid and diamine, and is selected from one or more of polycaprolactam PA6, polyhexamethylene sebacamide PA66, sebacamide PA1010, polyhexamethylene sebacamide PA612 and polyhexamethylene sebacamide PA 610.
Preferably, the copolymerized PA resin is a polyterephthaloyl hexamethylenediamine/polymetaphthaloyl hexamethylenediamine copolymer PA6T/6I. Preferably, the weight content of the PA6T in the copolymerized PA resin is 30-40%.
Preferably, the compatibilizer is a maleic anhydride graft modified polymer; the maleic anhydride grafted modified polymer is one or more of maleic anhydride grafted polypropylene PP-g-MAH, maleic anhydride grafted POE and ethylene propylene diene monomer rubber maleic anhydride grafted EPDM; the halogen-free flame retardant is one of organic aluminum hypophosphite.
Preferably, the mass ratio of the aqueous polyurethane to the flat fiber in the modified flat glass fiber is (0.1-1): 10.
further preferably, the mass ratio of the aqueous polyurethane to the flat fiber in the modified flat glass fiber is (0.3-0.5): 10. the preparation method of the modified flat glass fiber comprises the following steps: uniformly spraying the aqueous polyurethane solution prepared according to the weight ratio on the surface of the flat fiber, and then placing the flat glass fiber in a baking oven at 60-80 ℃ for 12-16h.
Preferably, the antioxidant is at least one of hindered phenol antioxidants (such as antioxidants 1010, 1076, 1098, etc.), phosphite antioxidants (such as antioxidant 168, etc.); the lubricant is at least one of esters (such as calcium stearate and zinc stearate), montanic acid salts (such as sodium montanate and calcium montanate), ethylene bisstearamide and polyethylene wax.
Preferably, the nucleating agent is nano-silica.
Preferably, the components comprise, by weight:
the preparation method of the nylon composition provided by the invention comprises the following steps:
uniformly spraying the aqueous polyurethane solution on the surface of flat fibers, and then placing the flat glass fibers in an oven at 60-80 ℃ for drying for 12-16 hours;
premixing the dried aliphatic PA resin, the copolymerization PA resin, the compatilizer and the nucleating agent according to the proportion, plasticizing by a double screw, respectively adding the modified flat glass fiber and the halogen-free flame retardant according to the proportion by different side feeding ports, and obtaining the halogen-free flame retardant reinforced nylon composition after traction, cooling, granulating and drying.
The nylon composition is applied to paint spraying parts.
Further, the nylon composition is used in parts of automobiles or tools requiring paint spraying, such as radiator blades, tool shells and other paint spraying parts.
The invention mainly utilizes flat glass fiber, nucleating agent, copolymerized PA resin and compatilizer which are subjected to surface treatment of aqueous polyurethane to improve the mechanical property and flame retardant property of the halogen-free flame retardant reinforced nylon material, improve the appearance of the material, reduce the sink mark and orange peel phenomena and achieve good paint spraying effect. The flat glass fiber subjected to the surface treatment of the waterborne polyurethane can effectively improve the compatibility of the composite material and the primer, improve the adhesion of the primer and improve the warping performance of the product; the addition of the compatilizer improves the polarity of the nylon and improves the binding force of glass fiber, nylon and paint surfaces; the specific copolymerization PA resin is added, has good compatibility with nylon, effectively improves the appearance, strength, flame retardant property and paint spraying effect of the composite material, has higher rigidity of PA6T/6I material at the moment when the content of PA6T is higher (the weight content of PA6T in the copolymerization PA resin is higher than 41%), has weaker molecular chain movement capability, has poor mixing effect with the PA resin, is unfavorable for processing the material, has enhanced molecular chain movement capability when the weight content of PA6T in the copolymerization PA resin is not higher than 41%, can have good mixing effect with the PA material, and has both mechanical property and appearance of the material.
The nucleating agent is preferably nano silicon dioxide (SiO 2 ) Or the nano silicon dioxide compound can be uniformly dispersed into the composite material, has heterogeneous nucleation effect, refines grains of the PA resin, accelerates the crystallization speed, ensures that the crystallization of the material is more uniform, and effectively reduces the problem of sink marks on the surface.
The beneficial effects are that:
the composite material prepared by the invention has excellent mechanical property, and the appearance of a sample after paint spraying has no sink mark and no orange peel phenomenon.
Drawings
FIG. 1 is a schematic representation of the "orange peel" degree test of the paint surface of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
1. Raw material source
Aliphatic PA resin-1: PA66 resin, a group of supernatural horses, typically branded EPR24, ISO 307-2007 test, relative viscosity 2.4;
aliphatic PA resin-2: PA66 resin, a group of supernatural horses, typically identified as EPR27, ISO 307-2007 test, with a relative viscosity of 2.7;
aliphatic PA resin-3: PA66 resin, a group of supernatural horses, typically identified as EPR32, ISO 307-2007 test, with a relative viscosity of 3.2;
aliphatic PA resin-4: PA612 a150 shandong guangdong boundary ISO 307-2007 test with a relative viscosity of 2.4;
copolymerization of PA resin-1: PA6T/6I, wherein the weight content of the PA6T is 30%, the glass transition temperature Tg is approximately equal to 130 ℃, and the Shandong is Ruisen;
copolymerization of PA resin-2: PA6T/6I, 40% by weight of PA6T, tg of about 135 ℃ Shandong Ruisen;
copolymerization of PA resin-3: PA6T/6I, PA6T weight content 20%, glass transition temperature Tg approximately equal to 125 ℃, shandong Ruisen;
copolymerization of PA resin-4: PA6T/6I, 50% by weight of PA6T, melting point Tm is approximately equal to 305 ℃, shandong Chengruisen;
and (3) a compatilizer: from DuPont, typically of the brand nameN493 maleic anhydride grafted POE
Halogen-free flame retardant: from Craien, with a typical designation OP1230, an organic aluminum hypophosphite;
aqueous polyurethane: isocyanates, bayhydro HU 340/1, bayer
Flat glass fiber: the typical brand is TFG-3.0-T436, taishan glass fiber;
common glass fiber: the typical trade mark is ECS10-3.0-T435N, taishan glass fiber;
an antioxidant: antioxidant 1010, commercially available;
and (3) a lubricant: polyethylene wax, commercially available;
nucleating agent-1: nano silicon dioxide; from winning, typical brand R972;
nucleating agent-2: talc, commercially available;
modified flat glass fiber-1: the mass ratio of the aqueous polyurethane to the flat glass fiber is 0.5:10;
modified flat glass fiber-2: the mass ratio of the aqueous polyurethane to the flat glass fiber is 0.3:10;
modified flat glass fiber-3: the mass ratio of the aqueous polyurethane to the flat glass fiber is 0.1:10;
modified flat glass fiber-4: the mass ratio of the aqueous polyurethane to the flat glass fiber is 1:10;
modified flat glass fiber-5: the mass ratio of the aqueous polyurethane to the flat glass fiber is 0.05:10;
modified flat glass fiber-6: the mass ratio of the aqueous polyurethane to the flat glass fiber is 2:10;
modified glass fiber-7: the mass ratio of the aqueous polyurethane to the common glass fiber is 0.5:10;
modified glass fiber-8: the mass ratio of the coupling agent to the flat glass fiber is 0.5:10;
wherein the coupling agent is silane coupling agent KH-550, and is derived from Nanjing dawn;
the preparation of the modified flat glass fiber comprises the following steps: uniformly spraying the aqueous polyurethane solution prepared according to the weight ratio on the surface of the flat fiber, and then placing the flat glass fiber in a 60 ℃ oven for drying for 12 hours.
The preparation of the modified glass fiber-7 comprises the following steps: uniformly spraying the aqueous polyurethane solution prepared according to the weight ratio on the surface of the common glass fiber, and then placing the common glass fiber in a 60 ℃ oven for drying for 12 hours.
The preparation of the modified glass fiber-8 comprises the following steps: uniformly spraying the coupling agent solution prepared according to the weight ratio on the surface of the flat glass fiber, and then placing the flat glass fiber in a 60 ℃ oven for drying for 12 hours.
The antioxidants and lubricants used in the parallel comparative examples and examples are all the same commercial products.
2. Preparation methods of examples and comparative examples:
premixing the dried aliphatic PA resin, the copolymerization PA resin, the compatilizer, the antioxidant, the lubricant and the nucleating agent according to the proportion, plasticizing by a double screw, respectively adding the modified flat glass fiber and the halogen-free flame retardant according to the proportion by different side feeding ports, and obtaining the halogen-free flame retardant reinforced nylon composition after traction, cooling, granulating and drying. Wherein the set temperature of the double-screw extruder is 220-250 ℃, and the screw rotating speed is 300-400 rpm.
3. Test criteria and methods
1. Tensile strength: the sample was injection molded into 150mm 10mm 4mm dumbbell bars, tested according to ISO 527 method, with a tensile rate of 5mm/min;
2. flame retardant performance test: sample injection molding is carried out to form 127mm 12.7mm 1.6mm sample bars, the sample is tested according to the method of UL94-2016, the burning time is recorded, and the flame retardant grade is judged according to the burning time;
3. evaluation of paint spray Effect
The prepared nylon composite material is injection molded into a sample plate with the thickness of 150mm multiplied by 200mm multiplied by 3mm, and the paint spraying property of the material is evaluated from two dimensions of paint adhesion and the degree of orange peel of a paint surface, wherein the specific test standard is as follows:
paint adhesion: and (3) carrying out evaluation by adopting a high-pressure flushing test method, carrying out paint spraying on the whole surface of the sample plate, sequentially spraying a primer with the thickness of 10 mu m, a colored paint with the thickness of 15 mu m and a varnish with the thickness of 35 mu m, wherein the used primer, colored paint and varnish are all Ackesu paint, carrying out a condensate water test by using DIN EN ISO6270-2, carrying out a high-pressure flushing test according to a PV 1503A method, and judging the higher the grade of the high-pressure flushing result, wherein the lower the paint adhesion is.
Table 1: high pressure flushing result judging grade rule
| Grade | Area of paint falling, mm 2 |
| 1 | ≤1 |
| 2 | More than 1 and less than or equal to 9 |
| 3 | More than 9 and less than or equal to 100 |
| 4 | ＞100 |
Degree of "orange peel" of paint surface: the panels were painted using the primer, paint and varnish all of the axsu paint, a reflective light source (typically a straight double tube fluorescent lamp) was found on the painted panel, and then the clarity of the reflective light source was observed by the human eye to evaluate the appearance orange peel condition of the paint film. As shown in fig. 1, the boundary between the reflected light (white portion) and the painted surface (black portion) changes from blurred to clear, while the more blurred the boundary between the reflected light and the painted surface, the poorer the quality of the "orange peel" is represented. For better standard evaluation, a set of standard plates are compared during evaluation, the orange peel is rough to smooth, each plate is marked with a corresponding rated value (from 1 to 10 in sequence), the visual effect of the orange peel is poor to excellent, and the larger the number is, the higher the quality of the sample plate is.
Table 2 example composition (parts by weight)
Table 3 example composition (parts by weight)
Table 4 proportion (parts by weight) of comparative examples
Table 5 shows performance effect data for the examples
Table 6 shows performance effect data for the examples
Table 7 shows the performance effect data of the comparative example
As can be seen from comparative examples 1 to 3, the co-polymerized PA resin in comparative example 1 has too high PA6T content, the aqueous polyurethane modified common glass fiber in comparative example 2 and the flat glass fiber which is not treated by polyurethane solution in comparative example 3 have poor paint spraying effect; as is clear from comparative examples 4-7, too high or too low weight parts of the copolymerized PA resin and the modified flat glass fiber have influence on the flame retardant property, the appearance and the paint spraying effect of the composite material; from examples 1-3, it is clear that the viscosity of the PA resin has an effect on the performance of the composite material, and the overall effect of the aliphatic PA resin-1 is optimal; from examples 4 to 5, when the mass ratio of PA6T in the copolymerized PA resin is not more than 40, the mechanical property of the material is good, and the paint spraying effect is good; from examples 6 to 8, it is found that the composite material has the optimum comprehensive performance when the mass ratio of the aqueous polyurethane to the flat glass fiber is (0.3-0.5): 10; from examples 1 and 9, it can be seen that the composite material obtained using nano-silica as a nucleating agent has better properties than other nucleating agents.
Claims (10)
1. The nylon composition is characterized by comprising the following components in parts by weight:
wherein the weight content of PA6T in the copolymerized PA resin is not higher than 41%;
the modified flat glass fiber is waterborne polyurethane coated flat glass fiber.
2. Nylon composition according to claim 1, characterized in that the relative viscosity of the aliphatic PA resin is 2.4-2.7; the aliphatic PA resin is polyamide resin polymerized by dibasic acid and diamine.
3. The nylon composition of claim 2, wherein the aliphatic PA resin is one or more of polycaprolactam PA6, polyhexamethylene sebacamide PA66, decamethylene sebacamide PA1010, polyhexamethylene dodecamide PA612, and polyhexamethylene sebacamide PA 610.
4. Nylon composition according to claim 1, characterized in that the copolymerized PA resin is a poly-p-xylylenediamine/poly-m-xylylenediamine copolymer PA6T/6I; the weight content of PA6T in the copolymerization PA resin is 30-40%.
5. The nylon composition of claim 1 wherein the compatibilizing agent is a maleic anhydride graft modified polymer; the maleic anhydride grafted modified polymer is one or more of maleic anhydride grafted polypropylene PP-g-MAH, maleic anhydride grafted POE and ethylene propylene diene monomer rubber maleic anhydride grafted EPDM; the halogen-free flame retardant is an organic hypophosphite flame retardant; the nucleating agent is nano silicon dioxide.
6. The nylon composition according to claim 1, wherein the mass ratio of the aqueous polyurethane to the flat fiber in the modified flat glass fiber is (0.1 to 1): 10.
7. the nylon composition of claim 1, wherein the components further comprise 0.1-2 parts of an antioxidant, 0.2-1 part of a lubricant; the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants; the lubricant is at least one of esters, montanate, ethylene bis-stearamide and polyethylene wax.
8. The nylon composition of claim 1, wherein the composition comprises, in parts by weight:
9. a method of making the nylon composition of claim 1, comprising:
uniformly spraying the aqueous polyurethane solution on the surface of flat fiber, and then placing the flat glass fiber in a baking oven at 60-80 ℃ for 12-16 hours to obtain modified flat glass fiber;
premixing the dried aliphatic PA resin, the copolymerization PA resin, the compatilizer and the nucleating agent according to the proportion, plasticizing by a double screw, respectively adding the modified flat glass fiber and the halogen-free flame retardant according to the proportion by different side feeding ports, and obtaining the nylon composition after traction, cooling, granulating and drying.
10. Use of the nylon composition of claim 1 in painting parts.
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