CN114316585B - High-strength nylon 66 composite material and processing technology thereof - Google Patents
High-strength nylon 66 composite material and processing technology thereof Download PDFInfo
- Publication number
- CN114316585B CN114316585B CN202210016977.7A CN202210016977A CN114316585B CN 114316585 B CN114316585 B CN 114316585B CN 202210016977 A CN202210016977 A CN 202210016977A CN 114316585 B CN114316585 B CN 114316585B
- Authority
- CN
- China
- Prior art keywords
- glass fiber
- nylon
- heating
- composite material
- mixing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 229920002302 Nylon 6,6 Polymers 0.000 title claims abstract description 57
- 238000012545 processing Methods 0.000 title claims abstract description 27
- 238000005516 engineering process Methods 0.000 title claims abstract description 13
- 239000003365 glass fiber Substances 0.000 claims abstract description 146
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000010438 heat treatment Methods 0.000 claims abstract description 64
- 238000002156 mixing Methods 0.000 claims abstract description 63
- -1 amine salt Chemical class 0.000 claims abstract description 41
- 239000004677 Nylon Substances 0.000 claims abstract description 38
- 229920001778 nylon Polymers 0.000 claims abstract description 38
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001746 injection moulding Methods 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- 239000004472 Lysine Substances 0.000 claims abstract description 14
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229920000768 polyamine Polymers 0.000 claims abstract description 14
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims abstract description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 66
- 239000008367 deionised water Substances 0.000 claims description 62
- 229910021641 deionized water Inorganic materials 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 238000001035 drying Methods 0.000 claims description 51
- 238000001816 cooling Methods 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 41
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 35
- 239000001361 adipic acid Substances 0.000 claims description 33
- 235000011037 adipic acid Nutrition 0.000 claims description 33
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 25
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 19
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 18
- 235000019253 formic acid Nutrition 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000003822 epoxy resin Substances 0.000 claims description 16
- 229920000647 polyepoxide Polymers 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 14
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 10
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 8
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000001993 wax Substances 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 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 claims description 5
- 239000012024 dehydrating agents Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 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 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002050 silicone resin Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 29
- 239000000243 solution Substances 0.000 description 15
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZKXBDPZAQUNPOY-UHFFFAOYSA-N 1-azaniumylhexylazanium;hexanedioate Chemical compound CCCCCC(N)N.OC(=O)CCCCC(O)=O ZKXBDPZAQUNPOY-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012693 lactam polymerization Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
The invention discloses a high-strength nylon 66 composite material and a processing technology thereof, comprising the following processing technologies: (1) Taking hexamethylenediamine and 1,3, 5-triglycidyl-S-triazinetrione to react to obtain a polyamine-based compound; taking 1,3, 5-tri (4-phenyl formate) benzene and a polyamine-based compound to react to obtain amine salt; taking caprolactam, amine salt and lysine, and heating to react to obtain branched nylon; (2) Mixing nylon 66, glass fiber, branched nylon, antioxidant and lubricant, extruding, and injection molding to obtain the composite material. According to the invention, the glass fiber is subjected to surface treatment, a large number of active functional groups are introduced, chemical bond combination occurs in the processing process of preparing the composite material by blending the glass fiber and nylon 66, the interface bonding strength of the glass fiber and nylon 66 piece is enhanced, and the mechanical property of the prepared composite material is improved.
Description
Technical Field
The invention relates to the technical field of nylon 66 composite materials, in particular to a high-strength nylon 66 composite material and a processing technology thereof.
Background
Nylon is a thermoplastic polyamide resin having a recurring amide group in the molecular main chain, and is generally obtained by polycondensation of a diamine and a diacid or by polycondensation of a lactam and ring-opening polymerization. The wear-resistant and corrosion-resistant plastic has the characteristics of excellent wear resistance, excellent corrosion resistance, high strength and the like, has wide application, and is an important engineering plastic using plastics to replace metals such as steel, iron, copper and the like. Nylon 66 is one of nylon materials, is obtained by polycondensation of adipic acid and hexamethylenediamine, and has the advantages of high mechanical strength and hardness, stable chemical property and excellent tensile, bending and compression strength. However, nylon has amide bonds with high polarity, poor weather resistance and low-temperature impact strength, so that nylon 66 is reinforced, and glass fibers are often added in the nylon processing process. However, the existence of the interface between the glass fiber and the nylon 66 can have adverse effects on the impact properties of the nylon 66 composite material. Therefore, we propose a high strength nylon 66 composite material and its processing technique.
Disclosure of Invention
The invention aims to provide a high-strength nylon 66 composite material and a processing technology thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the high-strength nylon 66 composite material comprises the following components in parts by weight: 100 parts of nylon 66, 20-40 parts of glass fiber, 10-20 parts of branched nylon, 2.0-2.5 parts of antioxidant and 0.9-1.2 parts of lubricant.
Further, the antioxidant comprises 1.2-1.5 parts of antioxidant 1010 and 0.8-1.0 parts of antioxidant 168.
Further, the glass fiber is cylindrical, has a cross-sectional diameter of 8-10 μm and a length of 2.7-3.0 mm.
Further, the lubricant is one or more of paraffin wax, polypropylene wax, polyethylene wax, amide wax, pentaerythritol stearate, polyacrylamide and silicone resin.
A processing technology of a high-strength nylon 66 composite material comprises the following processing technology:
(1) Preparation of branched nylon: preparing branched nylon by taking amine salt and caprolactam as raw materials;
(2) Preparation of the composite material: mixing nylon 66, glass fiber, branched nylon, antioxidant and lubricant, extruding, and injection molding to obtain the composite material.
Further, the (1) comprises the following processes:
tetrahydrofuran is taken, hexamethylenediamine is added, the temperature is raised to 40-70 ℃,1, 3, 5-triglycidyl-S-triazinetrione is slowly added, and the reaction is carried out for 20-60 min; cooling, washing and drying to obtain a polyamine-based compound;
adding 1,3, 5-tri (4-phenyl formate) benzene into deionized water, heating to 40-50 ℃ in nitrogen atmosphere, and stirring and mixing; adding a fused polyamine-based compound until the pH value of the system is 7.2-7.5, and preserving heat for 30-40 min; cooling, taking precipitate, washing, and drying to obtain amine salt;
mixing caprolactam, amine salt, lysine and deionized water, heating to 240-250 ℃ in nitrogen atmosphere, and maintaining the pressure for 150-200 min; heating to 260-270 ℃ to react for 80-100 min, cooling to 255-265 ℃ to react for 80-100 min, cooling to 250-260 ℃ to react for 60-75 min, cooling to 245-255 ℃ to react for 60-90 min; vacuum-pumping and standing for 3-5 min, extracting at 97-100 ℃ for 36h, and drying to obtain the branched nylon.
Further, the molar ratio of the 1,3, 5-triglycidyl-S-triazinetrione to the hexamethylenediamine is 1 (1.05-1.10);
the mass ratio of caprolactam, amine salt, lysine and deionized water is 100 (20-50) (0.5-1.0) (6.0-8.5).
In the technical scheme, 1,3, 5-triglycidyl-S-triazinetrione is taken as a core, and amine salts are obtained by utilizing the reaction between epoxy groups and amino groups in hexamethylenediamine; ring-opening polymerization of caprolactam and the prepared amine salt to obtain branched amide; the product has high strength, chemical resistance, ageing resistance and processing fluidity; the processing performance of the prepared composite material can be improved, the uniform dispersion of glass fibers in nylon 66 is promoted, and the bonding performance between the glass fibers and the nylon 66 is improved; in the blending process, the initial crystallization temperature of the nylon 66 is reduced, the crystallization temperature range of the composite material is enlarged, the crystallization difficulty is reduced, and the branched nylon and the nylon 66 can synchronously enter the crystallization process to impregnate and cover glass fibers; meanwhile, the introduction of branched nylon increases reactive functional groups in an organic phase, the acting force of a molecular chain is improved, the curing reaction of epoxy groups on the surface of the modified glass fiber is promoted, and the mechanical property of the prepared composite material can be effectively improved; the branched nylon is utilized to toughen the nylon 66, so that the friction between the modified glass fiber and the nylon 66 can be effectively reduced, and the fracture toughness of the composite material is improved, thereby realizing better wear resistance and processability;
further, the (2) comprises the following processes:
2.1. extrusion:
taking nylon 66, glass fiber, branched nylon, an antioxidant and a lubricant, and mixing at a high speed for 3-5 min; the double screw extrusion process comprises the following steps: the temperature is 260-280 ℃, and the rotating speed of the screw is 300-400 r/min; traction, cooling, granulating, drying at 100 ℃ for 4-5 hours to obtain granules;
2.2. injection molding:
taking granules for injection molding, wherein the injection molding process comprises the following steps: the temperature is 260-280 ℃, the injection molding speed is 60mm/s, the injection molding pressure is 80MPa, the pressure is maintained, the cooling is carried out for 15s, and the standing cooling is carried out for 24h, so that the composite material is obtained.
Further, the glass fiber is modified, and the modification process comprises the following steps:
(1) Mixing deionized water, methanol and formic acid, adding gamma-glycidol ether oxypropyl trimethoxy silane, stirring for dissolving, adding glass fiber, heating to 65-75 ℃, and stirring for reacting for 3-5 h; filtering, washing and drying to obtain glass fiber A;
mixing dimethylacetamide, aminopropyl heptaisobutyl POSS and glass fiber A, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst benzyl triethyl ammonium chloride, heating to 140-150 ℃ in a nitrogen atmosphere, and stirring for reaction for 24 hours; suction filtering, washing and drying to obtain glass fiber B;
(2) Mixing glass fiber B, adipic acid and deionized water, adding triphenylphosphine serving as a catalyst, heating to 100-130 ℃ and reacting for 5-24 hours to obtain glass fiber C;
(3) Mixing caprolactam, adipic acid and glass fiber C, adding deionized water, heating to 105-115 ℃, and stirring in a nitrogen atmosphere; heating to 120-130 ℃ and reacting for 30-60 min; suction filtering, washing and drying to obtain glass fiber D;
(4) Mixing epoxy resin, n-butanol and triphenylphosphine serving as a catalyst, stirring, heating to 130-140 ℃, adding glass fiber D, and reacting for 5-6 h; filtering, washing and drying to obtain the modified glass fiber.
Further, the method comprises the steps of: the mass ratio of deionized water, methanol and formic acid in the step (1) is 100 (7.0-7.5) (0.1-0.5); the mass ratio of the glass fiber to the gamma-glycidol ether oxypropyl trimethoxy silane is 100 (0.5-3); the mass ratio of the gamma-glycidoxypropyl trimethoxy silane to the deionized water is 1 (3.0-3.5); the mass ratio of the glass fiber A to the aminopropyl heptaisobutyl POSS is 100 (1-2).
Further, the mass ratio of the glass fiber B to the adipic acid in the step (2) is 100 (1.2-2.3).
Further, the mass ratio of caprolactam, adipic acid and glass fiber C in the step (3) is (1.6-2.0): 0.64-1.29): 100.
Further, the mass ratio of the glass fiber D to the epoxy resin in the step (4) is 100 (2-4).
When the modified glass fiber is directly added into a nylon 66 blending system, the strength of the prepared composite material can be improved to a certain extent, but the toughness of the composite material is deteriorated, and the impact resistance of the material is reduced.
In the technical scheme, the surface treatment is carried out on the glass fiber, firstly, siloxane (gamma-glycidol ether oxypropyl trimethoxy silane) containing epoxy groups is introduced on the surface of the glass fiber, and cage-shaped polysilsesquioxane is introduced on the surface of the glass fiber by utilizing the reaction of the epoxy groups and aminopropyl heptaisobutyl POSS; forming a layer of silica compound on the surface of the glass fiber, carrying out surface enhancement on the glass fiber, and improving the monofilament strength of the modified glass fiber; meanwhile, the surface roughness of the prepared glass fiber B is improved, the mechanical meshing effect between the surface of the glass fiber and an organic phase can be enhanced, the wettability of the modified glass fiber in nylon 66 is improved, and the dispersion of the prepared modified glass fiber in nylon 66 is promoted; the glass fiber and the organic phase are combined through strong chemical bonds and Van der Waals force, so that the interface area between the glass fiber and nylon 66 is reduced, the improvement of the interface bonding strength between the glass fiber and the organic phase is effectively promoted, and the mechanical properties such as impact strength and the like of the prepared composite material are improved; and is favorable for improving the heat resistance and the processing performance thereof;
introducing carboxyl by adipic acid, and mixing with caprolactam and adipic acid for reaction to obtain an amino-terminated amide molecular chain; the organic phase low polyamide is introduced into the surface of the glass fiber B, so that uniform dispersion and stable performance of the prepared glass fiber in the nylon 66 mixing processing process are facilitated, the surface brittleness of the prepared glass fiber is reduced, the friction and abrasion among the prepared modified glass fibers are reduced, and the reinforcing effect of the modified glass fiber on the nylon 66 is effectively improved;
finally, the modified glass fiber reacts with epoxy groups in the epoxy resin, a large number of active groups are introduced to the surface of the modified glass fiber, so that the modified glass fiber can react with nylon 66 molecular chains in the blending processing process, the wetting effect of the glass fiber in nylon 66 is improved, the interface bonding strength of the fiber and a matrix is enhanced, the mechanical property of the composite material is improved, and the impact strength of the material is improved; in the blending process, the epoxy groups in the epoxy resin react with the terminal amino groups of the nylon 66 to restrict the movement of nylon 66 molecular chains and prevent the growth of nylon 66 molecular crystals, so that heterogeneous nucleation can be promoted, the crystallization rate is improved, and the crystallization performance of the nylon 66 is improved, thereby improving the thermal stability and mechanical properties of the prepared composite material.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the high-strength nylon 66 composite material and the processing technology thereof, the glass fiber is subjected to surface treatment, a large number of active functional groups are introduced, chemical bond bonding occurs in the processing process of preparing the composite material by blending the glass fiber and the nylon 66, the interface bonding strength of the glass fiber and a nylon 66 piece is enhanced, and the mechanical property of the prepared composite material is improved.
2. According to the high-strength nylon 66 composite material and the processing technology thereof, POSS, amide molecular chains and epoxy resin are sequentially introduced to the surface of glass fibers through modification, so that the surface roughness is improved, the mechanical engagement between the glass fibers and organic phases such as nylon 66 and branched nylon is enhanced, the glass fibers are enhanced and toughened, the stability of the glass fibers in the processing process is promoted, the strength of the modified glass fibers is improved, the reinforcing effect of the nylon 66 is improved, and the impact resistance of the composite material can be effectively improved.
3. According to the high-strength nylon 66 composite material and the processing technology thereof, the friction between the modified glass fiber and the nylon 66 is reduced through the introduction of the branched nylon, the epoxy curing reaction is promoted, and the processing performance of the prepared composite material is improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Preparation of branched nylon:
1.1. taking tetrahydrofuran, adding hexamethylenediamine, heating to 40 ℃, slowly adding 1,3, 5-triglycidyl-S-triazinetrione, and reacting for 60min; cooling, washing and drying to obtain a polyamine-based compound; the molar ratio of the 1,3, 5-triglycidyl-S-triazinetrione to the hexamethylenediamine is 1:1.05;
adding 1,3, 5-tri (4-phenyl formate) benzene into deionized water, heating to 40 ℃ in nitrogen atmosphere, and stirring and mixing; adding a fused polyamine-based compound until the pH value of the system is 7.2, and preserving heat for 30min; cooling, taking precipitate, washing, and drying to obtain amine salt; deionized water and 1,3, 5-tri (4-phenyl formate) benzene in a mass ratio of 2:1;
1.2. mixing caprolactam, amine salt, lysine and deionized water, heating to 240 ℃ in nitrogen atmosphere, and maintaining the pressure for 150min; heating to 260 ℃ to react for 80min, cooling to 255 ℃ to react for 80min, cooling to 250 ℃ to react for 60min, cooling to 245 ℃ to react for 60min; vacuum-pumping and standing for 3min, extracting at 97 ℃ for 36h, and drying to obtain branched nylon; caprolactam, amine salt, lysine and deionized water in the mass ratio of 100:20:0.5:6.0;
(3) Preparation of the composite material:
3.1. extrusion:
taking 100 parts of nylon 66, 20 parts of glass fiber, 10 parts of branched nylon, 2.0 parts of antioxidant and 0.9 part of lubricant, and mixing at a high speed for 3min; the double screw extrusion process comprises the following steps: the temperature is 260 ℃ and the screw rotating speed is 300r/min; traction, cooling, granulating, drying at 100 ℃ for 4 hours to obtain granules; wherein the antioxidant comprises 1.2 parts of antioxidant 1010 and 0.8 part of antioxidant 168; the lubricant is amide wax;
3.2. injection molding:
taking granules for injection molding, wherein the injection molding process comprises the following steps: the temperature is 260 ℃, the injection molding speed is 60mm/s, the injection molding pressure is 80MPa, the pressure is maintained, the cooling is carried out for 15s, and the standing cooling is carried out for 24h, so that the composite material is obtained.
Example 2
(1) Preparation of branched nylon:
1.1. taking tetrahydrofuran, adding hexamethylenediamine, heating to 55 ℃, slowly adding 1,3, 5-triglycidyl-S-triazinetrione, and reacting for 40min; cooling, washing and drying to obtain a polyamine-based compound; the molar ratio of the 1,3, 5-triglycidyl-S-triazinetrione to the hexamethylenediamine is 1:1.08;
adding 1,3, 5-tri (4-phenyl formate) benzene into deionized water, heating to 45 ℃ in nitrogen atmosphere, and stirring and mixing; adding a fused polyamine-based compound until the pH value of the system is 7.4, and preserving heat for 35min; cooling, taking precipitate, washing, and drying to obtain amine salt; deionized water and 1,3, 5-tri (4-phenyl formate) benzene in a mass ratio of 2:1;
1.2. mixing caprolactam, amine salt, lysine and deionized water, heating to 245 ℃ in a nitrogen atmosphere, and maintaining the pressure for 175min; heating to 265 ℃ for reaction for 90min, cooling to 260 ℃ for reaction for 90min, cooling to 255 ℃ for reaction for 68min, and cooling to 250 ℃ for reaction for 75min; vacuumizing, standing for 4min, extracting at 98 ℃ for 36h, and drying to obtain branched nylon; caprolactam, amine salt, lysine and deionized water in the mass ratio of 100:35:0.8:7.2;
(2) Modification of glass fibers:
2.1. mixing deionized water, methanol and formic acid, adding gamma-glycidol ether oxypropyl trimethoxy silane, stirring for dissolving, adding glass fiber, heating to 70 ℃, and stirring for reacting for 4 hours; filtering, washing and drying to obtain glass fiber A; deionized water, methanol and formic acid in the mass ratio of 100:7.2:0.3; the mass ratio of the glass fiber to the gamma-glycidoxypropyl trimethoxysilane is 100:1.8; the mass ratio of the gamma-glycidoxypropyl trimethoxysilane to the deionized water is 1:3.2; the glass fiber is cylindrical, the diameter of the section is 9 mu m, and the length is 2.8mm;
mixing dimethylacetamide, aminopropyl heptaisobutyl POSS and glass fiber A, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst benzyl triethyl ammonium chloride, heating to 145 ℃ in a nitrogen atmosphere, and stirring for reaction for 24 hours; suction filtering, washing and drying to obtain glass fiber B; the mass ratio of the glass fiber A to the aminopropyl heptaisobutyl POSS is 100:1.5;
2.2. mixing glass fiber B, adipic acid and deionized water, adding triphenylphosphine serving as a catalyst, heating to 115 ℃ and reacting for 15 hours to obtain glass fiber C; the mass ratio of the glass fiber B to the adipic acid is 100:1.7;
2.3. mixing caprolactam, adipic acid and glass fiber C, adding deionized water, heating to 110 ℃, and stirring in a nitrogen atmosphere; heating to 125 ℃, and reacting for 45min; suction filtering, washing and drying to obtain glass fiber D; the mass ratio of caprolactam to adipic acid to glass fiber C is 1.8:0.96:100;
2.4. mixing epoxy resin, n-butanol and triphenylphosphine serving as a catalyst, stirring, heating to 135 ℃, adding glass fiber D, and reacting for 5.5 hours; filtering, washing and drying to obtain modified glass fiber; the mass ratio of the glass fiber D to the epoxy resin is 100:3;
(3) Preparation of the composite material:
3.1. extrusion:
taking 100 parts of nylon 66, 30 parts of glass fiber, 15 parts of branched nylon, 2.2 parts of antioxidant and 1.0 part of lubricant, and mixing at a high speed for 4min; the double screw extrusion process comprises the following steps: the temperature is 270 ℃ and the screw rotating speed is 350r/min; traction, cooling, granulating, drying at 100 ℃ for 4.5 hours to obtain granules; wherein the antioxidant comprises 1.3 parts of antioxidant 1010 and 0.9 part of antioxidant 168; the lubricant is silicone resin;
3.2. injection molding:
taking granules for injection molding, wherein the injection molding process comprises the following steps: the temperature is 270 ℃, the injection molding speed is 60mm/s, the injection molding pressure is 80MPa, the pressure is maintained, the cooling is carried out for 15s, and the standing cooling is carried out for 24h, so that the composite material is obtained.
Example 3
(1) Preparation of branched nylon:
1.1. taking tetrahydrofuran, adding hexamethylenediamine, heating to 70 ℃, slowly adding 1,3, 5-triglycidyl-S-triazinetrione, and reacting for 20min; cooling, washing and drying to obtain a polyamine-based compound; the molar ratio of the 1,3, 5-triglycidyl-S-triazinetrione to the hexamethylenediamine is 1:1.10;
adding 1,3, 5-tri (4-phenyl formate) benzene into deionized water, heating to 50 ℃ in nitrogen atmosphere, and stirring and mixing; adding a fused polyamine-based compound until the pH value of the system is 7.5, and preserving heat for 40min; cooling, taking precipitate, washing, and drying to obtain amine salt; deionized water and 1,3, 5-tri (4-phenyl formate) benzene in a mass ratio of 2:1;
1.2. mixing caprolactam, amine salt, lysine and deionized water, heating to 250 ℃ in nitrogen atmosphere, and maintaining the pressure for 200min; heating to 270 ℃ to react for 100min, cooling to 265 ℃ to react for 100min, cooling to 260 ℃ to react for 75min, cooling to 255 ℃ to react for 90min; vacuumizing, standing for 5min, extracting at 100 ℃ for 36h, and drying to obtain branched nylon; caprolactam, amine salt, lysine and deionized water in the mass ratio of 100:50:1.0:8.5;
(2) Modification of glass fibers:
2.1. mixing deionized water, methanol and formic acid, adding gamma-glycidol ether oxypropyl trimethoxy silane, stirring for dissolving, adding glass fiber, heating to 75 ℃, and stirring for reacting for 5 hours; filtering, washing and drying to obtain glass fiber A; deionized water, methanol and formic acid in the mass ratio of 100:7.5:0.5; the mass ratio of the glass fiber to the gamma-glycidoxypropyl trimethoxysilane is 100:3; the mass ratio of the gamma-glycidoxypropyl trimethoxysilane to the deionized water is 1:3.5; the glass fiber is cylindrical, the diameter of the section is 10 mu m, and the length is 3.0mm;
mixing dimethylacetamide, aminopropyl heptaisobutyl POSS and glass fiber A, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst benzyl triethyl ammonium chloride, heating to 150 ℃ in a nitrogen atmosphere, and stirring for reaction for 24 hours; suction filtering, washing and drying to obtain glass fiber B; the mass ratio of the glass fiber A to the aminopropyl heptaisobutyl POSS is 100:2;
2.2. mixing glass fiber B, adipic acid and deionized water, adding triphenylphosphine serving as a catalyst, heating to 130 ℃ and reacting for 24 hours to obtain glass fiber C; the mass ratio of the glass fiber B to the adipic acid is 100:2.3;
2.3. mixing caprolactam, adipic acid and glass fiber C, adding deionized water, heating to 115 ℃, and stirring in a nitrogen atmosphere; heating to 130 ℃, and reacting for 60min; suction filtering, washing and drying to obtain glass fiber D; the mass ratio of caprolactam to adipic acid to glass fiber C is 2:1.29:100;
2.4. mixing epoxy resin, n-butanol and triphenylphosphine serving as a catalyst, stirring, heating to 140 ℃, adding glass fiber D, and reacting for 6 hours; filtering, washing and drying to obtain modified glass fiber; the mass ratio of the glass fiber D to the epoxy resin is 100:4;
(3) Preparation of the composite material:
3.1. extrusion:
taking 100 parts of nylon 66, 40 parts of glass fiber, 20 parts of branched nylon, 2.5 parts of antioxidant and 1.2 parts of lubricant, and mixing at a high speed for 5min; the double screw extrusion process comprises the following steps: the temperature is 280 ℃, and the rotating speed of the screw is 400r/min; traction, cooling, granulating, drying at 100 ℃ for 5 hours to obtain granules; wherein the antioxidant comprises 1.5 parts of antioxidant 1010 and 1.0 part of antioxidant 168; the lubricant is pentaerythritol stearate;
3.2. injection molding:
taking granules for injection molding, wherein the injection molding process comprises the following steps: the temperature is 280 ℃, the injection molding speed is 60mm/s, the injection molding pressure is 80MPa, the pressure is maintained, the cooling is carried out for 15s, and the standing cooling is carried out for 24h, so that the composite material is obtained.
Comparative example 1
(1) Preparation of branched nylon:
mixing caprolactam, adipic acid hexanediamine salt, lysine and deionized water, heating to 240 ℃ in a nitrogen atmosphere, and maintaining the pressure for 150min; heating to 260 ℃ to react for 80min, cooling to 255 ℃ to react for 80min, cooling to 250 ℃ to react for 60min, cooling to 245 ℃ to react for 60min; vacuum-pumping and standing for 3min, extracting at 97 ℃ for 36h, and drying to obtain branched nylon; caprolactam, adipic acid hexamethylenediamine salt, lysine and deionized water in a mass ratio of 100:20:0.5:6.0;
steps (2) and (3) were the same as in example 1, to obtain a composite material.
Comparative example 2
(2) Modification of glass fibers:
2.1. mixing deionized water, methanol and formic acid, adding gamma-glycidol ether oxypropyl trimethoxy silane, stirring for dissolving, heating to 65 ℃, and stirring for reacting for 3 hours; filtering, washing and drying to obtain a product A; deionized water, methanol and formic acid in the mass ratio of 100:7.0:0.1; the mass ratio of the gamma-glycidoxypropyl trimethoxysilane to the deionized water is 1:3.0;
mixing dimethylacetamide, aminopropyl heptaisobutyl POSS and a product A, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst benzyltriethylammonium chloride, heating to 140 ℃ in a nitrogen atmosphere, and stirring for reaction for 24 hours; suction filtering, washing and drying to obtain a product B; the mass ratio of the product A to the aminopropyl heptaisobutyl POSS is 1:1;
2.2. mixing a product B, adipic acid and deionized water, adding a catalyst triphenylphosphine, heating to 100 ℃ and reacting for 5 hours to obtain a product C; the mass ratio of the product B to the adipic acid is 1:1.2;
2.3. mixing caprolactam, adipic acid and a product C, adding deionized water, heating to 105 ℃, and stirring in a nitrogen atmosphere; heating to 120 ℃, and reacting for 30min; suction filtering, washing and drying to obtain a product D; caprolactam, adipic acid and product C in a mass ratio of 1.6:0.64:1.0;
2.4. mixing epoxy resin, n-butanol and triphenylphosphine serving as a catalyst, stirring, heating to 130 ℃, adding a product D, and reacting for 5 hours; a solution with the mass fraction of 2 percent is prepared; the molar ratio of the product D to the epoxy resin is 1:10;
drying the glass fiber in the dipping solution for 10s at 160 ℃ to obtain modified glass fiber; the glass fiber is cylindrical, the diameter of the section is 8 mu m, and the length is 2.7mm;
steps (1) and (3) were the same as in comparative example 1, to obtain a composite material.
Comparative example 3
(2) Modification of glass fibers:
2.1. mixing deionized water, methanol and formic acid, adding gamma-aminopropyl triethoxysilane, stirring for dissolving, heating to 65 ℃, and stirring for reacting for 3 hours; filtering, washing and drying to obtain a product A; deionized water, methanol and formic acid in the mass ratio of 100:7.0:0.1; the mass ratio of the gamma-aminopropyl triethoxysilane to the deionized water is 1:3.0;
2.2. mixing a product A, adipic acid and deionized water, adding a catalyst triphenylphosphine, heating to 100 ℃ and reacting for 5 hours to obtain a product B; the mass ratio of the product A to the adipic acid is 1:1.2;
2.3. mixing caprolactam, adipic acid and a product B, adding deionized water, heating to 105 ℃, and stirring in a nitrogen atmosphere; heating to 120 ℃, and reacting for 30min; suction filtering, washing and drying to obtain a product C; caprolactam, adipic acid and product B in a mass ratio of 1.6:0.64:1.0;
2.4. mixing epoxy resin, n-butanol and triphenylphosphine serving as a catalyst, stirring, heating to 130 ℃, adding a product C, and reacting for 5 hours; a solution with the mass fraction of 2 percent is prepared; the molar ratio of the product C to the epoxy resin is 1:10;
drying the glass fiber in the dipping solution for 10s at 160 ℃ to obtain modified glass fiber; the glass fiber is cylindrical, the diameter of the section is 8 mu m, and the length is 2.7mm;
steps (1) and (3) were the same as in comparative example 1, to obtain a composite material.
Comparative example 4
(2) Modification of glass fibers:
2.1. mixing deionized water, methanol and formic acid, adding gamma-aminopropyl triethoxysilane, stirring for dissolving, heating to 65 ℃, and stirring for reacting for 3 hours; filtering, washing and drying to obtain a product A; deionized water, methanol and formic acid in the mass ratio of 100:7.0:0.1; the mass ratio of the gamma-aminopropyl triethoxysilane to the deionized water is 1:3.0;
2.2. mixing a product A, adipic acid and deionized water, adding a catalyst triphenylphosphine, heating to 100 ℃ and reacting for 5 hours to obtain a product B; the mass ratio of the product A to the adipic acid is 1:1.2;
2.3. mixing caprolactam, adipic acid and a product B, adding deionized water, heating to 105 ℃, and stirring in a nitrogen atmosphere; heating to 120 ℃, and reacting for 30min; suction filtering, washing and drying to obtain a product C; caprolactam, adipic acid and product B in a mass ratio of 1.6:0.64:1.0; a solution with the mass fraction of 2 percent is prepared;
drying the glass fiber in the dipping solution for 10s at 160 ℃ to obtain modified glass fiber; the glass fiber is cylindrical, the diameter of the section is 8 mu m, and the length is 2.7mm;
steps (1) and (3) were the same as in comparative example 1, to obtain a composite material.
Comparative example 5
(2) Modification of glass fibers:
2.1. mixing deionized water, methanol and formic acid, adding gamma-aminopropyl triethoxysilane, stirring for dissolving, heating to 65 ℃, and stirring for reacting for 3 hours; filtering, washing and drying to obtain a product A; deionized water, methanol and formic acid in the mass ratio of 100:7.0:0.1; the mass ratio of the gamma-aminopropyl triethoxysilane to the deionized water is 1:3.0;
2.2. mixing a product A, adipic acid and deionized water, adding a catalyst triphenylphosphine, heating to 100 ℃ and reacting for 5 hours to obtain a product B; the mass ratio of the product A to the adipic acid is 1:1.2; a solution with the mass fraction of 2 percent is prepared;
drying the glass fiber in the dipping solution for 10s at 160 ℃ to obtain modified glass fiber; the glass fiber is cylindrical, the diameter of the section is 8 mu m, and the length is 2.7mm;
steps (1) and (3) were the same as in comparative example 1, to obtain a composite material.
Comparative example 6
(2) Modification of glass fibers:
mixing deionized water, methanol and formic acid, adding gamma-aminopropyl triethoxysilane, stirring for dissolving, heating to 65 ℃, and stirring for reacting for 3 hours; filtering, washing and drying to obtain a product A; deionized water, methanol and formic acid in the mass ratio of 100:7.0:0.1; the mass ratio of the gamma-aminopropyl triethoxysilane to the deionized water is 1:3.0; a solution with the mass fraction of 2 percent is prepared;
drying the glass fiber in the dipping solution for 10s at 160 ℃ to obtain modified glass fiber; the glass fiber is cylindrical, the diameter of the section is 8 mu m, and the length is 2.7mm;
steps (1) and (3) were the same as in comparative example 1, to obtain a composite material.
The parts are weight parts.
Experiment
Taking the composite materials obtained in examples 1-3 and comparative examples 1-6, preparing samples, respectively detecting the properties thereof and recording the detection results:
tensile strength: taking GB/T1040.1-2018 as a standard, adopting an electronic universal tester, and testing at a stretching rate of 10 mm/min;
flexural strength: using GB/T9341-2008 as standard, adopting an electronic universal tester, and testing at a bending rate of 2 mm/min;
notched impact strength: and using GB/T1843.1-2008 as a standard, and adopting a cantilever impact tester for testing.
From the data in the above table, the following conclusions can be clearly drawn:
the composites obtained in examples 1-3 were compared with the composites obtained in comparative examples 1-6, and it was found that the test results,
1. the tensile strength, flexural strength, notched impact strength of the composites obtained in examples 1-3 are significantly higher compared to comparative example 6, which fully demonstrates that the present application achieves an improvement in composite strength;
2. in comparison to example 1, the branched nylon of comparative example 1 replaced the amine salt with hexamethylenediamine adipate; the tensile strength, the bending strength and the notch impact strength are all reduced, and the notch impact strength is slowly reduced; the reason is that: the amine salt in the application contains various rigid functional groups, the prepared branched nylon has better strength, toughness and heat resistance, the processing performance is stable during blending, the composite material can be reinforced and toughened after processing, the branched nylon prepared from the adipic acid hexanediamine salt is low in branching degree and lacks the rigid functional groups, so that the comprehensive strength of the composite material in comparative example 1 is reduced; the branched nylon prepared from adipic acid hexanediamine salt has lower viscosity and better processing fluidity, so that the elongation at break of the composite material is improved, and the reduction of notch impact strength is slowed down;
in comparative example 2, the glass fiber was dip-modified as compared to comparative example 1; in contrast to comparative example 2, the silicone was replaced in the impregnating solution of comparative example 3 and modified without the addition of POSS; in contrast to comparative example 3, the impregnating solution of comparative example 4 was modified without the addition of epoxy resin; in contrast to comparative example 4, the impregnating solution of comparative example 5 was modified without the addition of caprolactam; in contrast to comparative example 5, the impregnating solution of comparative example 6 was modified with gamma-aminopropyl triethoxysilane; the tensile strength, the bending strength and the notch impact strength are all reduced; the glass fiber modification process and the modification materials are arranged, so that the improvement of the comprehensive strength of the prepared composite material can be promoted;
in comparison with comparative example 1, the glass fibers in comparative examples 2 to 6 were all dip-modified; the notch impact strength of the modified polypropylene is obviously reduced; the reason is that: the glass fiber is immersed and modified, the material is coated on the surface of the glass fiber to form a coating layer, and mechanical and chemical bonding is realized; however, since the bonding property between the coating layer and the glass fiber is inferior to that of comparative example 1, when the composite material is impacted, the damage first occurs in the coating layer, the interfacial property between the glass fiber and the organic phase is reduced, the strength is reduced, and the notch impact strength is obviously reduced.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A processing technology of a high-strength nylon 66 composite material is characterized in that: the method comprises the following processing steps:
step one, preparing branched nylon:
taking hexamethylenediamine and 1,3, 5-triglycidyl-S-triazinetrione to react to obtain a polyamine-based compound;
taking 1,3, 5-tri (4-phenyl formate) benzene and a polyamine-based compound to react to obtain amine salt;
taking caprolactam, amine salt and lysine, and heating to react to obtain branched nylon;
step two, preparing a composite material: mixing nylon 66, glass fiber, branched nylon, an antioxidant and a lubricant, extruding, and injection molding to obtain a composite material;
the first step comprises the following processes:
tetrahydrofuran is taken, hexamethylenediamine is added, the temperature is raised to 40-70 ℃,1, 3, 5-triglycidyl-S-triazinetrione is slowly added, and the reaction is carried out for 20-60 min; cooling, washing and drying to obtain a polyamine-based compound;
adding 1,3, 5-tri (4-phenyl formate) benzene into deionized water, heating to 40-50 ℃ in nitrogen atmosphere, and stirring and mixing; adding a fused polyamine-based compound until the pH value of the system is 7.2-7.5, and preserving heat for 30-40 min; cooling, taking precipitate, washing, and drying to obtain amine salt;
mixing caprolactam, amine salt, lysine and deionized water, heating to 240-250 ℃ in nitrogen atmosphere, and maintaining the pressure for 150-200 min; heating to 260-270 ℃ to react for 80-100 min, cooling to 255-265 ℃ to react for 80-100 min, cooling to 250-260 ℃ to react for 60-75 min, cooling to 245-255 ℃ to react for 60-90 min; vacuumizing and standing for 3-5 min, extracting for 36h at 97-100 ℃, and drying to obtain branched nylon;
the molar ratio of the 1,3, 5-triglycidyl-S-triazinetrione to the hexamethylenediamine is 1 (1.05-1.10); the mass ratio of caprolactam, amine salt, lysine and deionized water is 100 (20-50) (0.5-1.0) (6.0-8.5);
the glass fiber is modified, and the modification process comprises the following steps:
(1) Mixing deionized water, methanol and formic acid, adding gamma-glycidol ether oxypropyl trimethoxy silane, stirring for dissolving, adding glass fiber, heating to 65-75 ℃, and stirring for reacting for 3-5 h; filtering, washing and drying to obtain glass fiber A;
mixing dimethylacetamide, aminopropyl heptaisobutyl POSS and glass fiber A, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst benzyl triethyl ammonium chloride, heating to 140-150 ℃ in a nitrogen atmosphere, and stirring for reaction for 24 hours; suction filtering, washing and drying to obtain glass fiber B;
(2) Mixing glass fiber B, adipic acid and deionized water, adding triphenylphosphine serving as a catalyst, heating to 100-130 ℃ and reacting for 5-24 hours to obtain glass fiber C;
(3) Mixing caprolactam, adipic acid and glass fiber C, adding deionized water, heating to 105-115 ℃, and stirring in a nitrogen atmosphere; heating to 120-130 ℃ and reacting for 30-60 min; suction filtering, washing and drying to obtain glass fiber D;
(4) Mixing epoxy resin, n-butanol and triphenylphosphine serving as a catalyst, stirring, heating to 130-140 ℃, adding glass fiber D, and reacting for 5-6 h; filtering, washing and drying to obtain modified glass fiber;
the mass ratio of deionized water, methanol and formic acid in the step (1) is 100 (7.0-7.5) (0.1-0.5); the mass ratio of the glass fiber to the gamma-glycidol ether oxypropyl trimethoxy silane is 100 (0.5-3); the mass ratio of the gamma-glycidoxypropyl trimethoxy silane to the deionized water is 1 (3.0-3.5); the mass ratio of the glass fiber A to the aminopropyl heptaisobutyl POSS is 100 (1-2);
the mass ratio of the glass fiber B to the adipic acid in the step (2) is 100 (1.2-2.3);
the mass ratio of caprolactam, adipic acid and glass fiber C in the step (3) is (1.6-2.0): 0.64-1.29): 100;
the mass ratio of the glass fiber D to the epoxy resin in the step (4) is 100 (2-4).
2. The process for manufacturing a high strength nylon 66 composite according to claim 1, wherein: the second step comprises the following processes:
2.1. extrusion:
taking nylon 66, glass fiber, branched nylon, an antioxidant and a lubricant, and mixing at a high speed for 3-5 min; the double screw extrusion process comprises the following steps: the temperature is 260-280 ℃, and the rotating speed of the screw is 300-400 r/min; traction, cooling, granulating, drying at 100 ℃ for 4-5 hours to obtain granules;
2.2. injection molding:
taking granules for injection molding, wherein the injection molding process comprises the following steps: the temperature is 260-280 ℃, the injection molding speed is 60mm/s, the injection molding pressure is 80MPa, the pressure is maintained, the cooling is carried out for 15s, and the standing cooling is carried out for 24h, so that the composite material is obtained.
3. The high strength nylon 66 composite material produced by the process according to any one of claims 1-2, wherein: comprises the following components in parts by weight: 100 parts of nylon 66, 20-40 parts of glass fiber, 10-20 parts of branched nylon, 2.0-2.5 parts of antioxidant and 0.9-1.2 parts of lubricant.
4. A high strength nylon 66 composite in accordance with claim 3 wherein: the glass fiber is cylindrical, the diameter of the section is 8-10 mu m, and the length is 2.7-3.0 mm.
5. A high strength nylon 66 composite in accordance with claim 3 wherein: the antioxidant comprises 1.2-1.5 parts of antioxidant 1010 and 0.8-1.0 parts of antioxidant 168.
6. A high strength nylon 66 composite in accordance with claim 3 wherein: the lubricant is one or more of paraffin wax, polypropylene wax, polyethylene wax, amide wax, pentaerythritol stearate, polyacrylamide and silicone resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210016977.7A CN114316585B (en) | 2022-01-08 | 2022-01-08 | High-strength nylon 66 composite material and processing technology thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210016977.7A CN114316585B (en) | 2022-01-08 | 2022-01-08 | High-strength nylon 66 composite material and processing technology thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114316585A CN114316585A (en) | 2022-04-12 |
| CN114316585B true CN114316585B (en) | 2024-01-02 |
Family
ID=81025411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210016977.7A Active CN114316585B (en) | 2022-01-08 | 2022-01-08 | High-strength nylon 66 composite material and processing technology thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114316585B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521078B (en) * | 2022-11-08 | 2023-12-12 | 株洲时代新材料科技股份有限公司 | Glass fiber grafting modification method and application |
| CN116041949B (en) * | 2022-12-02 | 2023-10-24 | 苏州优利金新材料有限公司 | Preparation process of high-strength carbon nanotube modified nylon 6 composite material |
| CN116606544B (en) * | 2023-04-03 | 2024-05-03 | 昆明鼎骏塑业有限公司 | Heat-resistant impact-resistant polyamide plastic and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4086295A (en) * | 1976-12-16 | 1978-04-25 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyamide composition |
| JPH083440A (en) * | 1994-06-21 | 1996-01-09 | Japan Synthetic Rubber Co Ltd | Highly flowable nylon resin composition and electronic part |
| CN103044901A (en) * | 2012-12-17 | 2013-04-17 | 株洲时代新材料科技股份有限公司 | High-fluidity halogen-free flame retardant reinforced nylon composite material and preparation method thereof |
| CN104004351A (en) * | 2014-01-15 | 2014-08-27 | 温州聚兴塑化有限公司 | High-glass-fiber reinforced nylon material and preparing method of high-glass-fiber reinforced nylon material |
| CN104059357A (en) * | 2014-06-10 | 2014-09-24 | 金发科技股份有限公司 | Guide rail material of glass lifter for vehicle as well as preparation method and application thereof |
| WO2015058392A1 (en) * | 2013-10-23 | 2015-04-30 | 华南理工大学 | Impregnated nylon 66 compound material and method for producing long glass fibre-reinforced nylon 66 granules using same |
| CN106916324A (en) * | 2017-03-14 | 2017-07-04 | 华南理工大学 | Preparation method with low-k and high-fracture toughness polyimide film |
| CN110156984A (en) * | 2019-06-18 | 2019-08-23 | 北京旭阳科技有限公司 | A kind of semiaromatic branched polyamide block copolymer and preparation method thereof |
| CN110358294A (en) * | 2019-08-21 | 2019-10-22 | 长沙五犇新材料科技有限公司 | A kind of high intensity Heat conduction nylon composite material and its preparation method and application |
-
2022
- 2022-01-08 CN CN202210016977.7A patent/CN114316585B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4086295A (en) * | 1976-12-16 | 1978-04-25 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyamide composition |
| JPH083440A (en) * | 1994-06-21 | 1996-01-09 | Japan Synthetic Rubber Co Ltd | Highly flowable nylon resin composition and electronic part |
| CN103044901A (en) * | 2012-12-17 | 2013-04-17 | 株洲时代新材料科技股份有限公司 | High-fluidity halogen-free flame retardant reinforced nylon composite material and preparation method thereof |
| WO2015058392A1 (en) * | 2013-10-23 | 2015-04-30 | 华南理工大学 | Impregnated nylon 66 compound material and method for producing long glass fibre-reinforced nylon 66 granules using same |
| CN104004351A (en) * | 2014-01-15 | 2014-08-27 | 温州聚兴塑化有限公司 | High-glass-fiber reinforced nylon material and preparing method of high-glass-fiber reinforced nylon material |
| CN104059357A (en) * | 2014-06-10 | 2014-09-24 | 金发科技股份有限公司 | Guide rail material of glass lifter for vehicle as well as preparation method and application thereof |
| CN106916324A (en) * | 2017-03-14 | 2017-07-04 | 华南理工大学 | Preparation method with low-k and high-fracture toughness polyimide film |
| CN110156984A (en) * | 2019-06-18 | 2019-08-23 | 北京旭阳科技有限公司 | A kind of semiaromatic branched polyamide block copolymer and preparation method thereof |
| CN110358294A (en) * | 2019-08-21 | 2019-10-22 | 长沙五犇新材料科技有限公司 | A kind of high intensity Heat conduction nylon composite material and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114316585A (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114316585B (en) | High-strength nylon 66 composite material and processing technology thereof | |
| CN110437611B (en) | Reinforced and toughened ultralow temperature resistant nylon composite material and preparation method and application thereof | |
| CN113929937A (en) | Glass fiber surface modification method and application thereof in PA66/GF composite material | |
| US20230250252A1 (en) | Polyamide recycling process and polyamide obtained by recycling process | |
| RU2692368C2 (en) | Mixture of polyamides with improved flowability | |
| KR102240966B1 (en) | Polyamide resin composition and article comprising the same | |
| CN114410059A (en) | High-strength polyformaldehyde and preparation method thereof | |
| CN112662169A (en) | High-impact-strength PA6 composite material and preparation method thereof | |
| US11440996B2 (en) | Preparation method of polyphenylene sulfide resin, and polyphenylene sulfide resin prepared thereby | |
| CN109468846B (en) | Aramid fiber surface grafting treatment method | |
| JP3466331B2 (en) | Polyamide, polyamide composition and use thereof | |
| CN112029375B (en) | Inorganic-organic hybrid polymer anticorrosive paint and preparation method thereof | |
| CN114231026A (en) | Polyamide composite material and preparation method thereof | |
| CN112759760B (en) | High-low temperature aging resistant toughened polyamide 5X resin and preparation method thereof | |
| KR101811919B1 (en) | Polyamide resin, composition the same, method for preparing the same, and article comprising the same | |
| CN114276678A (en) | Long-term thermal aging resistant toughened PA66 material and preparation method thereof | |
| CN115785659B (en) | Long fiber reinforced wear-resistant self-lubricating bio-based polyamide composite material and preparation method thereof | |
| CN115746542B (en) | High-performance long glass fiber reinforced thermoplastic composite material and preparation method thereof | |
| CN116082834A (en) | Nano injection molding polyamide composite material and preparation method thereof | |
| TWI738137B (en) | Moisture absorption polyamide fiber having lower melting temperature and manufacture process thereof | |
| CN115725070A (en) | High-temperature-resistant semi-aromatic polyamide, preparation method thereof, composition and molded product | |
| CN114276655A (en) | Degradable thermoplastic elastomer and preparation method thereof | |
| CN112480665A (en) | High-fluidity high-impact-toughness nylon composite material and preparation method thereof | |
| CN117986848A (en) | Pultruded polyurethane door and window composite material and preparation method thereof | |
| CN117186633A (en) | Modified polyamide and preparation method and application thereof, and modified polyamide product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 325000, Workshop 101, Building 2, No. 268 Binhai Fifth Road, Xinghai Street, Wenzhou Bay New Area, Wenzhou City, Zhejiang Province Applicant after: Zhejiang Kanier polymer new material Co.,Ltd. Address before: 325000 Building 1, No. 466, Binhai 14th Road, Wenzhou Economic and Technological Development Zone, Wenzhou City, Zhejiang Province Applicant before: Zhejiang Kanier polymer new material Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |