CN114316585A - High-strength nylon 66 composite material and processing technology thereof - Google Patents
High-strength nylon 66 composite material and processing technology thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 229920002302 Nylon 6,6 Polymers 0.000 title claims abstract description 61
- 238000012545 processing Methods 0.000 title claims abstract description 37
- 238000005516 engineering process Methods 0.000 title claims abstract description 25
- 239000003365 glass fiber Substances 0.000 claims abstract description 167
- 238000010438 heat treatment Methods 0.000 claims abstract description 66
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000002156 mixing Methods 0.000 claims abstract description 63
- -1 poly amino compound Chemical class 0.000 claims abstract description 44
- 229920001778 nylon Polymers 0.000 claims abstract description 38
- 239000004677 Nylon Substances 0.000 claims abstract description 37
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 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
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 24
- 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
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 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
- 235000011037 adipic acid Nutrition 0.000 claims description 33
- 239000001361 adipic acid Substances 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
- 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
- 239000003822 epoxy resin Substances 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 16
- 229920000647 polyepoxide Polymers 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000967 suction filtration Methods 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
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 10
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 9
- 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
- 238000002360 preparation method Methods 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
- 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
- 229920002050 silicone resin Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene 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
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 5
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- 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
- 239000000463 material Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
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- 125000003700 epoxy group Chemical group 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 5
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical class [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- ZKXBDPZAQUNPOY-UHFFFAOYSA-N 1-azaniumylhexylazanium;hexanedioate Chemical compound CCCCCC(N)N.OC(=O)CCCCC(O)=O ZKXBDPZAQUNPOY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 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
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a high-strength nylon 66 composite material and a processing technology thereof, wherein the processing technology comprises the following steps: (1) taking hexamethylenediamine and 1,3, 5-triglycidyl-S-triazine trione to react to obtain a poly amino compound; taking 1,3, 5-tri (4-phenyl formate) benzene and a poly amino compound to react to obtain amine salt; taking caprolactam, amine salt and lysine, and heating for reaction to obtain branched nylon; (2) and mixing nylon 66, glass fiber, branched nylon, an antioxidant and a lubricant, extruding and injection molding to obtain the composite material. According to the invention, the surface treatment is carried out on the glass fiber, a large number of active functional groups are introduced, and in the processing process of blending the glass fiber and the nylon 66 to prepare the composite material, chemical bond bonding occurs, so that the interface bonding strength of the glass fiber and the nylon 66 is enhanced, and the improvement of the mechanical property of the prepared composite material is utilized.
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
Nylons are thermoplastic polyamides containing recurring amide groups in the main molecular chain and are generally obtained by polycondensation of diamines and diacids or polycondensation of lactams and ring-opening polymerization. The material has the characteristics of excellent wear resistance and corrosion resistance, high strength and the like, has wide application, and is an important engineering plastic for replacing metals such as steel, iron, copper and the like with plastic. Nylon 66 is one of nylon materials, is obtained by polycondensation of adipic acid and hexamethylene diamine, has high mechanical strength and hardness, stable chemical properties and excellent tensile, bending and compressive strengths. However, nylon has amide bonds with high polarity, poor weather resistance and low-temperature impact strength, so that the nylon 66 is enhanced, and glass fibers are often added in the nylon processing process. However, the impact performance of the nylon 66 composite material is adversely affected due to the presence of the interface between the glass fibers and the nylon 66. Therefore, we propose a high strength nylon 66 composite material and its processing technology.
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: a 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 part of antioxidant 168.
Furthermore, the glass fiber is cylindrical, the diameter of the cross section of the glass fiber is 8-10 mu m, and the length of the glass fiber is 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 technologies:
(1) preparation of branched nylon: preparing branched nylon by using amine salt and caprolactam as raw materials;
(2) preparing a composite material: and mixing nylon 66, glass fiber, branched nylon, an antioxidant and a lubricant, extruding and injection molding to obtain the composite material.
Further, the (1) comprises the following processes:
adding hexamethylene diamine into tetrahydrofuran, heating to 40-70 ℃, slowly adding 1,3, 5-triglycidyl-S-triazinetrione, and reacting for 20-60 min; cooling, washing and drying to obtain a polyamino compound;
adding 1,3, 5-tri (4-phenyl formate) benzene into deionized water, heating to 40-50 ℃ in a nitrogen atmosphere, and stirring and mixing; adding a molten polyamino compound until the pH value of the system is 7.2-7.5, and keeping the temperature for 30-40 min; cooling, washing the precipitate, and drying to obtain amine salt;
mixing caprolactam, amine salt, lysine and deionized water, heating to 240-250 ℃ in a nitrogen atmosphere, and maintaining the pressure for 150-200 min; heating to 260-270 ℃, reacting for 80-100 min, cooling to 255-265 ℃, reacting for 80-100 min, cooling to 250-260 ℃, reacting for 60-75 min, cooling to 245-255 ℃, and reacting for 60-90 min; vacuumizing and standing for 3-5 min, extracting for 36h at 97-100 ℃, and drying to obtain the branched nylon.
Further, the molar ratio of the 1,3, 5-triglycidyl-S-triazine trione to the hexamethylene diamine is 1 (1.05-1.10);
the mass ratio of caprolactam, amine salt, lysine and deionized water is (20-50): (0.5-1.0): 6.0-8.5).
In the technical scheme, 1,3, 5-triglycidyl-S-triazine trione is taken as a core, and amine salt is obtained by utilizing the reaction between an epoxy group and amino in hexamethylene diamine; 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 the glass fiber in the nylon 66 is promoted, and the bonding performance between the glass fiber and the nylon 66 is improved; in the blending processing 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 coat the glass fiber; meanwhile, the introduction of the branched nylon increases reactive functional groups in an organic phase, the acting force of a molecular chain is improved, the curing reaction of an epoxy group 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, so that better wear resistance and processability are realized;
further, the (2) comprises the following processes:
2.1. extruding:
mixing nylon 66, glass fiber, branched nylon, an antioxidant and a lubricant at a high speed for 3-5 min; double-screw extrusion, wherein the extrusion process comprises the following steps: the temperature is 260-280 ℃, and the rotating speed of the screw is 300-400 r/min; drawing, cooling, granulating, and drying at 100 ℃ for 4-5 hours to obtain granules;
2.2. injection molding:
taking the granules for injection molding, wherein the injection molding process comprises the following steps: and (3) keeping the temperature at 260-280 ℃, setting the injection molding speed at 60mm/s and the injection molding pressure at 80MPa, keeping the pressure and cooling for 15s, and standing and cooling for 24h to obtain the composite material.
Further, the glass fiber is modified, and the modification process comprises the following steps:
(1) mixing deionized water, methanol and formic acid, adding gamma-glycidyl ether oxypropyl trimethoxy silane, stirring for dissolving, adding glass fiber, heating to 65-75 ℃, and stirring for reacting for 3-5 hours; 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 benzyltriethylammonium chloride, and heating to 140-150 ℃ in a nitrogen atmosphere to stir and react for 24 hours; carrying out suction filtration, washing and drying to obtain glass fiber B;
(2) mixing the glass fiber B, adipic acid and deionized water, adding a catalyst triphenylphosphine, heating to 100-130 ℃, and reacting for 5-24 hours to obtain a 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; carrying out suction filtration, washing and drying to obtain glass fiber D;
(4) taking epoxy resin, n-butanol and triphenylphosphine serving as a catalyst, stirring and mixing, heating to 130-140 ℃, adding glass fiber D, and reacting for 5-6 hours; filtering, washing and drying to obtain the modified glass fiber.
Further, the method comprises the following steps: the mass ratio of the deionized water, the methanol and the formic acid in the step (1) is 100 (7.0-7.5) to (0.1-0.5); the mass ratio of the glass fiber to the gamma-glycidyl ether oxypropyl trimethoxysilane is 100 (0.5-3); the mass ratio of the gamma-glycidoxypropyltrimethoxysilane 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).
Furthermore, the mass ratio of the glass fiber B to the adipic acid in the step (2) is 100 (1.2-2.3).
Furthermore, the mass ratio of the caprolactam, the adipic acid and the glass fiber C in the step (3) is (1.6-2.0): 0.64-1.29): 100.
Furthermore, the mass ratio of the glass fiber D and the epoxy resin in the step (4) is 100 (2-4).
If 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 is reduced, and the impact resistance of the material is reduced.
In the technical scheme, the glass fiber is subjected to surface treatment, siloxane (gamma-glycidoxypropyltrimethoxysilane) containing epoxy groups is introduced to the surface of the glass fiber, and cage-shaped polysilsesquioxane is introduced to the surface of the glass fiber by utilizing the reaction of the epoxy groups and aminopropyl heptaisobutyl POSS; a layer of silica compound is formed on the surface of the glass fiber, so that the surface of the glass fiber is reinforced, and the monofilament strength of the modified glass fiber is improved; meanwhile, the surface roughness of the prepared glass fiber B is improved, the mechanical meshing effect between the surface of the glass fiber and organic phases can be enhanced, the wettability of the modified glass fiber in the nylon 66 is improved, and the dispersion of the prepared modified glass fiber in the nylon 66 is promoted; the glass fiber is combined with the organic phase through strong chemical bonds and Van der Waals force, so that the interface area between the glass fiber and the 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 beneficial to improving the heat resistance and the processing performance;
introducing carboxyl by using adipic acid, and mixing and reacting with caprolactam and adipic acid to obtain an amino-terminated amide molecular chain; the organic phase oligoamide is introduced into the surface of the glass fiber B, so that the 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 is reacted with an epoxy group in the epoxy resin, and 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 a nylon 66 molecular chain in a blending processing process, the infiltration effect of the glass fiber in the nylon 66 is improved, and simultaneously, 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 group in the epoxy resin and the terminal amino group of the nylon 66 are subjected to chemical reaction, so that the movement of a nylon 66 molecular chain is restrained, the growth of nylon 66 molecular crystals is hindered, the heterogeneous nucleation effect can be promoted, the crystallization rate is increased, and the crystallization performance of the nylon 66 is improved, so that the thermal stability and the mechanical property of the prepared composite material are improved.
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 surface treatment is carried out on the glass fiber, a large number of active functional groups are introduced, and in the processing process of blending the glass fiber and the nylon 66 to prepare the composite material, chemical bond bonding occurs, so that the interface bonding strength between the glass fiber and the 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, through modification of the glass fiber, POSS, amide molecular chains and epoxy resin are sequentially introduced on the surface of the glass fiber, so that the surface roughness is improved, the mechanical meshing between the reinforced glass fiber and organic phases such as nylon 66 and branched nylon is realized, the glass fiber is reinforced and toughened, the stable performance of the glass fiber in the processing process is promoted, the strength of the prepared modified glass fiber and the enhancement effect of the nylon 66 are improved, and the impact resistance of the prepared 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 by introducing the branched nylon, the progress of the epoxy curing reaction is promoted, and the processing performance of the prepared composite material is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparation of branched nylon:
1.1. taking tetrahydrofuran, adding hexamethylene diamine, heating to 40 ℃, slowly adding 1,3, 5-triglycidyl-S-triazine trione, and reacting for 60 min; cooling, washing and drying to obtain a polyamino compound; the mol ratio of the 1,3, 5-triglycidyl-S-triazine trione to the hexamethylene diamine is 1: 1.05;
adding 1,3, 5-tri (4-phenyl formate) benzene into deionized water, heating to 40 ℃ in a nitrogen atmosphere, and stirring and mixing; adding molten polyamino compound until the pH value of the system is 7.2, and keeping the temperature for 30 min; cooling, washing the precipitate, and drying to obtain amine salt; the mass ratio of the deionized water to the 1,3, 5-tri (4-phenyl formate) benzene is 2: 1;
1.2. mixing caprolactam, amine salt, lysine and deionized water, heating to 240 ℃ in a nitrogen atmosphere, and maintaining the pressure for 150 min; heating to 260 deg.C for 80min, cooling to 255 deg.C for 80min, cooling to 250 deg.C for 60min, and cooling to 245 deg.C for 60 min; vacuumizing and standing for 3min, extracting for 36h at 97 ℃, and drying to obtain branched nylon; the mass ratio of caprolactam, amine salt, lysine and deionized water is 100:20:0.5: 6.0;
(3) preparing a composite material:
3.1. extruding:
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 high speed for 3 min; double-screw extrusion, wherein the extrusion process comprises the following steps: the temperature is 260 ℃, and the screw rotating speed is 300 r/min; drawing, cooling, granulating, and drying at 100 ℃ for 4h 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 the 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 and the cooling is carried out for 15s, and the composite material is obtained after standing and cooling for 24 h.
Example 2
(1) Preparation of branched nylon:
1.1. taking tetrahydrofuran, adding hexamethylene diamine, heating to 55 ℃, slowly adding 1,3, 5-triglycidyl-S-triazine trione, and reacting for 40 min; cooling, washing and drying to obtain a polyamino compound; the molar ratio of the 1,3, 5-triglycidyl-S-triazine trione to the hexamethylene diamine is 1: 1.08;
adding 1,3, 5-tri (4-phenyl formate) benzene into deionized water, heating to 45 ℃ in a nitrogen atmosphere, and stirring and mixing; adding molten polyamino compound until the pH value of the system is 7.4, and keeping the temperature for 35 min; cooling, washing the precipitate, and drying to obtain amine salt; the mass ratio of the deionized water to the 1,3, 5-tri (4-phenyl formate) benzene is 2: 1;
1.2. mixing caprolactam, amine salt, lysine and deionized water, heating to 245 ℃ in a nitrogen atmosphere, and maintaining the pressure for 175 min; heating to 265 deg.C for reaction for 90min, cooling to 260 deg.C for reaction for 90min, cooling to 255 deg.C for reaction for 68min, and cooling to 250 deg.C for reaction for 75 min; vacuumizing and standing for 4min, extracting for 36h at 98 ℃, and drying to obtain branched nylon; the mass ratio of caprolactam to amine salt to lysine to deionized water is 100:35:0.8: 7.2;
(2) modification of glass fiber:
2.1. mixing deionized water, methanol and formic acid, adding gamma-glycidyl 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; the mass ratio of the deionized water to the methanol to the formic acid is 100:7.2: 0.3; the mass ratio of the glass fiber to the gamma-glycidyl ether oxypropyl trimethoxysilane is 100: 1.8; the mass ratio of the gamma-glycidoxypropyltrimethoxysilane to the deionized water is 1: 3.2; the glass fiber is cylindrical, the diameter of the cross section of the glass fiber is 9 mu m, and the length of the glass fiber is 2.8 mm;
mixing dimethylacetamide, aminopropyl heptaisobutyl POSS and glass fiber A, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst benzyltriethylammonium chloride, and heating to 145 ℃ in a nitrogen atmosphere to stir and react for 24 hours; carrying out suction filtration, 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 the glass fiber B, adipic acid and deionized water, adding a catalyst triphenylphosphine, 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 45 min; carrying out suction filtration, 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. taking epoxy resin, n-butanol and triphenylphosphine as a catalyst, stirring and mixing, heating to 135 ℃, adding the 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) preparing a composite material:
3.1. extruding:
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 high speed for 4 min; double-screw extrusion, wherein the extrusion process comprises the following steps: the temperature is 270 ℃, and the screw rotating speed is 350 r/min; drawing, cooling, granulating, and drying at 100 ℃ for 4.5h 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 the granules for injection molding, wherein the injection molding process comprises the following steps: and the temperature is 270 ℃, the injection molding speed is 60mm/s, the injection molding pressure is 80MPa, the pressure is maintained and the cooling is carried out for 15s, and the composite material is obtained after standing and cooling for 24 h.
Example 3
(1) Preparation of branched nylon:
1.1. taking tetrahydrofuran, adding hexamethylene diamine, heating to 70 ℃, slowly adding 1,3, 5-triglycidyl-S-triazine trione, and reacting for 20 min; cooling, washing and drying to obtain a polyamino compound; the mol ratio of the 1,3, 5-triglycidyl-S-triazine trione to the hexamethylene diamine is 1: 1.10;
adding 1,3, 5-tri (4-phenyl formate) benzene into deionized water, heating to 50 ℃ in a nitrogen atmosphere, and stirring and mixing; adding molten polyamino compound until the pH value of the system is 7.5, and keeping the temperature for 40 min; cooling, washing the precipitate, and drying to obtain amine salt; the mass ratio of the deionized water to the 1,3, 5-tri (4-phenyl formate) benzene is 2: 1;
1.2. mixing caprolactam, amine salt, lysine and deionized water, heating to 250 ℃ in a nitrogen atmosphere, and maintaining the pressure for 200 min; heating to 270 deg.C for 100min, cooling to 265 deg.C for 100min, cooling to 260 deg.C for 75min, and cooling to 255 deg.C for 90 min; vacuumizing and standing for 5min, extracting for 36h at 100 ℃, and drying to obtain branched nylon; the mass ratio of caprolactam to amine salt to lysine to deionized water is 100:50:1.0: 8.5;
(2) modification of glass fiber:
2.1. mixing deionized water, methanol and formic acid, adding gamma-glycidyl ether oxypropyl trimethoxy silane, stirring to dissolve, adding glass fiber, heating to 75 ℃, and stirring to react for 5 hours; filtering, washing and drying to obtain glass fiber A; the mass ratio of the deionized water to the methanol to the formic acid is 100:7.5: 0.5; the mass ratio of the glass fiber to the gamma-glycidyl ether oxypropyl trimethoxysilane is 100: 3; the mass ratio of the gamma-glycidoxypropyltrimethoxysilane to the deionized water is 1: 3.5; the glass fiber is cylindrical, the diameter of the cross section of the glass fiber is 10 mu m, and the length of the glass fiber is 3.0 mm;
mixing dimethylacetamide, aminopropyl heptaisobutyl POSS and glass fiber A, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst benzyltriethylammonium chloride, and heating to 150 ℃ in a nitrogen atmosphere to stir and react for 24 hours; carrying out suction filtration, 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 the glass fiber B, adipic acid and deionized water, adding a catalyst triphenylphosphine, 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 60 min; carrying out suction filtration, 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. taking epoxy resin, n-butanol and triphenylphosphine serving as a catalyst, stirring and mixing, heating to 140 ℃, adding the 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) preparing a composite material:
3.1. extruding:
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 high speed for 5 min; double-screw extrusion, wherein the extrusion process comprises the following steps: the temperature is 280 ℃, and the screw rotating speed is 400 r/min; drawing, cooling, granulating, and 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 the 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 and the cooling is carried out for 15s, and the composite material is obtained after standing and cooling for 24 h.
Comparative example 1
(1) Preparation of branched nylon:
mixing caprolactam, adipic acid hexamethylene diamine salt, lysine and deionized water, heating to 240 ℃ in a nitrogen atmosphere, and maintaining the pressure for 150 min; heating to 260 deg.C for 80min, cooling to 255 deg.C for 80min, cooling to 250 deg.C for 60min, and cooling to 245 deg.C for 60 min; vacuumizing and standing for 3min, extracting for 36h at 97 ℃, and drying to obtain branched nylon; the mass ratio of caprolactam to adipic acid hexamethylene diamine salt to lysine to deionized water is 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 fiber:
2.1. mixing deionized water, methanol and formic acid, adding gamma-glycidoxypropyltrimethoxysilane, stirring for dissolving, heating to 65 deg.C, and stirring for reaction for 3 hr; filtering, washing and drying to obtain a product A; the mass ratio of the deionized water to the methanol to the formic acid is 100:7.0: 0.1; the mass ratio of the gamma-glycidoxypropyltrimethoxysilane to the deionized water is 1: 3.0;
mixing dimethylacetamide, aminopropyl heptaisobutyl POSS and the product A, adding a dehydrating agent dicyclohexylcarbodiimide and a catalyst benzyltriethylammonium chloride, and heating to 140 ℃ in a nitrogen atmosphere to stir and react for 24 hours; carrying out suction filtration, washing and drying to obtain a product B; the mass ratio of the product A to aminopropyl heptaisobutyl POSS is 1: 1;
2.2. mixing the 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 30 min; carrying out suction filtration, washing and drying to obtain a product D; the mass ratio of caprolactam to adipic acid to product C is 1.6:0.64: 1.0;
2.4. taking epoxy resin, n-butanol and triphenylphosphine as a catalyst, stirring and mixing, heating to 130 ℃, adding the product D, and reacting for 5 hours; preparing a solution with the mass fraction of 2%; the molar ratio of the product D to the epoxy resin is 1: 10;
soaking the glass fiber in the solution for 10s, and drying at 160 ℃ to obtain modified glass fiber; the glass fiber is cylindrical, the diameter of the cross section of the glass fiber is 8 mu m, and the length of the glass fiber is 2.7 mm;
steps (1) and (3) were the same as in comparative example 1 to obtain a composite material.
Comparative example 3
(2) Modification of glass fiber:
2.1. mixing deionized water, methanol and formic acid, adding gamma-aminopropyltriethoxysilane, stirring for dissolving, heating to 65 ℃, and stirring for reacting for 3 hours; filtering, washing and drying to obtain a product A; the mass ratio of the deionized water to the methanol to the formic acid is 100:7.0: 0.1; the mass ratio of the gamma-aminopropyl triethoxysilane to the deionized water is 1: 3.0;
2.2. mixing the product A, adipic acid and deionized water, adding a catalyst triphenylphosphine, and heating to 100 ℃ to react 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 30 min; carrying out suction filtration, washing and drying to obtain a product C; the mass ratio of caprolactam to adipic acid to the product B is 1.6:0.64: 1.0;
2.4. taking epoxy resin, n-butanol and triphenylphosphine as a catalyst, stirring and mixing, heating to 130 ℃, adding the product C, and reacting for 5 hours; preparing a solution with the mass fraction of 2%; the molar ratio of the product C to the epoxy resin is 1: 10;
soaking the glass fiber in the solution for 10s, and drying at 160 ℃ to obtain modified glass fiber; the glass fiber is cylindrical, the diameter of the cross section of the glass fiber is 8 mu m, and the length of the glass fiber is 2.7 mm;
steps (1) and (3) were the same as in comparative example 1 to obtain a composite material.
Comparative example 4
(2) Modification of glass fiber:
2.1. mixing deionized water, methanol and formic acid, adding gamma-aminopropyltriethoxysilane, stirring for dissolving, heating to 65 ℃, and stirring for reacting for 3 hours; filtering, washing and drying to obtain a product A; the mass ratio of the deionized water to the methanol to the formic acid is 100:7.0: 0.1; the mass ratio of the gamma-aminopropyl triethoxysilane to the deionized water is 1: 3.0;
2.2. mixing the product A, adipic acid and deionized water, adding a catalyst triphenylphosphine, and heating to 100 ℃ to react 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 30 min; carrying out suction filtration, washing and drying to obtain a product C; the mass ratio of caprolactam to adipic acid to the product B is 1.6:0.64: 1.0; preparing a solution with the mass fraction of 2%;
soaking the glass fiber in the solution for 10s, and drying at 160 ℃ to obtain modified glass fiber; the glass fiber is cylindrical, the diameter of the cross section of the glass fiber is 8 mu m, and the length of the glass fiber is 2.7 mm;
steps (1) and (3) were the same as in comparative example 1 to obtain a composite material.
Comparative example 5
(2) Modification of glass fiber:
2.1. mixing deionized water, methanol and formic acid, adding gamma-aminopropyltriethoxysilane, stirring for dissolving, heating to 65 ℃, and stirring for reacting for 3 hours; filtering, washing and drying to obtain a product A; the mass ratio of the deionized water to the methanol to the formic acid is 100:7.0: 0.1; the mass ratio of the gamma-aminopropyl triethoxysilane to the deionized water is 1: 3.0;
2.2. mixing the product A, adipic acid and deionized water, adding a catalyst triphenylphosphine, and heating to 100 ℃ to react for 5 hours to obtain a product B; the mass ratio of the product A to the adipic acid is 1: 1.2; preparing a solution with the mass fraction of 2%;
soaking the glass fiber in the solution for 10s, and drying at 160 ℃ to obtain modified glass fiber; the glass fiber is cylindrical, the diameter of the cross section of the glass fiber is 8 mu m, and the length of the glass fiber is 2.7 mm;
steps (1) and (3) were the same as in comparative example 1 to obtain a composite material.
Comparative example 6
(2) Modification of glass fiber:
mixing deionized water, methanol and formic acid, adding gamma-aminopropyltriethoxysilane, stirring for dissolving, heating to 65 ℃, and stirring for reacting for 3 hours; filtering, washing and drying to obtain a product A; the mass ratio of the deionized water to the methanol to the formic acid is 100:7.0: 0.1; the mass ratio of the gamma-aminopropyl triethoxysilane to the deionized water is 1: 3.0; preparing a solution with the mass fraction of 2%;
soaking the glass fiber in the solution for 10s, and drying at 160 ℃ to obtain modified glass fiber; the glass fiber is cylindrical, the diameter of the cross section of the glass fiber is 8 mu m, and the length of the glass fiber is 2.7 mm;
steps (1) and (3) were the same as in comparative example 1 to obtain a composite material.
The parts are all parts by weight.
Experiment of
Taking the composite materials obtained in examples 1-3 and comparative examples 1-6, preparing samples, respectively detecting the performances of the samples and recording the detection results:
tensile strength: taking GB/T1040.1-2018 as a standard, and adopting an electronic universal testing machine to test at a stretching speed of 10 mm/min;
bending strength: testing at a bending rate of 2mm/min by using an electronic universal testing machine according to GB/T9341-2008 as a standard;
notched impact strength: and testing by using a cantilever impact tester by taking GB/T1843.1-2008 as a standard.
From the data in the table above, it is clear that the following conclusions can be drawn:
the composite materials obtained in examples 1 to 3 were compared with the composite materials obtained in comparative examples 1 to 6, and the results of the tests were confirmed,
1. compared with the comparative example 6, the composite materials obtained in the examples 1 to 3 have obviously higher tensile strength, bending strength and notch impact strength, which fully shows that the application realizes the improvement of the strength of the composite material;
2. compared to example 1, the branched nylon in comparative example 1 replaced the amine salt with adipic acid hexamethylenediamine salt; the tensile strength, the bending strength and the notch impact strength are all reduced, and the notch impact strength is reduced slowly; 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 processability is stable during blending, the composite material can be reinforced and toughened after processing, and the branched nylon prepared from the hexanediamine adipate has low branching degree and lacks the rigid functional groups, so that the comprehensive strength of the composite material in the comparative example 1 is reduced; the branched nylon prepared from the hexamethylene diamine adipate has lower viscosity and better processing fluidity, so that the elongation at break of the composite material is improved, and the reduction of the notch impact strength is slowed down;
compared with the comparative example 1, the glass fiber in the comparative example 2 is modified by impregnation; compared with the comparative example 2, the impregnation solution of the comparative example 3 is replaced by siloxane, and POSS is not added for modification; compared with the comparative example 3, the impregnating solution of the comparative example 4 is modified without adding epoxy resin; compared with the comparative example 4, the impregnating solution of the comparative example 5 is modified without adding caprolactam; compared with the comparative example 5, the impregnating solution of the comparative example 6 is modified by gamma-aminopropyltriethoxysilane; the tensile strength, the bending strength and the notch impact strength of the material are all reduced to some extent; therefore, the glass fiber modification process and the glass fiber modification material can improve the comprehensive strength of the prepared composite material;
compared with the comparative example 1, the glass fibers in the comparative examples 2 to 6 are all subjected to impregnation modification; the notch impact strength is obviously reduced; the reason is that: the glass fiber is subjected to impregnation modification, and materials are coated on the surface of the glass fiber to form a coating layer, so that mechanical and chemical bonding is realized; however, the bonding performance between the coating layer and the glass fiber is not the same as that of the comparative example 1, so that when the prepared composite material is impacted, the damage occurs to the coating layer firstly, the interface performance 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, herein, relational terms such as first and second, and the like may be 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. Furthermore, 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: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A processing technology of a high-strength nylon 66 composite material is characterized by comprising the following steps: the processing technology comprises the following steps:
(1) preparation of branched nylon:
taking hexamethylenediamine and 1,3, 5-triglycidyl-S-triazine trione to react to obtain a poly amino compound;
taking 1,3, 5-tri (4-phenyl formate) benzene and a poly amino compound to react to obtain amine salt;
taking caprolactam, amine salt and lysine, and heating for reaction to obtain branched nylon;
(2) preparing a composite material: and mixing nylon 66, glass fiber, branched nylon, an antioxidant and a lubricant, extruding and injection molding to obtain the composite material.
2. The processing technology of the high-strength nylon 66 composite material as claimed in claim 1, wherein the processing technology comprises the following steps: the (1) comprises the following processes:
adding hexamethylene diamine into tetrahydrofuran, heating to 40-70 ℃, slowly adding 1,3, 5-triglycidyl-S-triazinetrione, and reacting for 20-60 min; cooling, washing and drying to obtain a polyamino compound;
adding 1,3, 5-tri (4-phenyl formate) benzene into deionized water, heating to 40-50 ℃ in a nitrogen atmosphere, and stirring and mixing; adding a molten polyamino compound until the pH value of the system is 7.2-7.5, and keeping the temperature for 30-40 min; cooling, washing the precipitate, and drying to obtain amine salt;
mixing caprolactam, amine salt, lysine and deionized water, heating to 240-250 ℃ in a nitrogen atmosphere, and maintaining the pressure for 150-200 min; heating to 260-270 ℃, reacting for 80-100 min, cooling to 255-265 ℃, reacting for 80-100 min, cooling to 250-260 ℃, reacting for 60-75 min, cooling to 245-255 ℃, and reacting for 60-90 min; vacuumizing and standing for 3-5 min, extracting for 36h at 97-100 ℃, and drying to obtain the branched nylon.
3. The processing technology of the high-strength nylon 66 composite material as claimed in claim 2, wherein the processing technology comprises the following steps: the molar ratio of the 1,3, 5-triglycidyl-S-triazine trione to the hexamethylene diamine is 1 (1.05-1.10);
the mass ratio of caprolactam, amine salt, lysine and deionized water is (20-50): (0.5-1.0): 6.0-8.5).
4. The processing technology of the high-strength nylon 66 composite material as claimed in claim 1, wherein the processing technology comprises the following steps: the (2) comprises the following processes:
2.1. extruding:
mixing nylon 66, glass fiber, branched nylon, an antioxidant and a lubricant at a high speed for 3-5 min; double-screw extrusion, wherein the extrusion process comprises the following steps: the temperature is 260-280 ℃, and the rotating speed of the screw is 300-400 r/min; drawing, cooling, granulating, and drying at 100 ℃ for 4-5 hours to obtain granules;
2.2. injection molding:
taking the granules for injection molding, wherein the injection molding process comprises the following steps: and (3) keeping the temperature at 260-280 ℃, setting the injection molding speed at 60mm/s and the injection molding pressure at 80MPa, keeping the pressure and cooling for 15s, and standing and cooling for 24h to obtain the composite material.
5. The processing technology of the high-strength nylon 66 composite material as claimed in claim 1, wherein the processing technology comprises the following steps: the glass fiber is modified, and the modification process comprises the following steps:
(1) mixing deionized water, methanol and formic acid, adding gamma-glycidyl ether oxypropyl trimethoxy silane, stirring for dissolving, adding glass fiber, heating to 65-75 ℃, and stirring for reacting for 3-5 hours; 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 benzyltriethylammonium chloride, and heating to 140-150 ℃ in a nitrogen atmosphere to stir and react for 24 hours; carrying out suction filtration, washing and drying to obtain glass fiber B;
(2) mixing the glass fiber B, adipic acid and deionized water, adding a catalyst triphenylphosphine, heating to 100-130 ℃, and reacting for 5-24 hours to obtain a 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; carrying out suction filtration, washing and drying to obtain glass fiber D;
(4) taking epoxy resin, n-butanol and triphenylphosphine serving as a catalyst, stirring and mixing, heating to 130-140 ℃, adding glass fiber D, and reacting for 5-6 hours; filtering, washing and drying to obtain the modified glass fiber.
6. The processing technology of the high-strength nylon 66 composite material as claimed in claim 5, wherein the processing technology comprises the following steps: the mass ratio of the deionized water, the methanol and the formic acid in the step (1) is 100 (7.0-7.5) to (0.1-0.5); the mass ratio of the glass fiber to the gamma-glycidyl ether oxypropyl trimethoxysilane is 100 (0.5-3); the mass ratio of the gamma-glycidoxypropyltrimethoxysilane 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).
7. A high strength nylon 66 composite produced by the process according to any one of claims 1 to 6 wherein: comprises the following components 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.
8. The high strength nylon 66 composite of claim 7, wherein: the glass fiber is cylindrical, the diameter of the cross section of the glass fiber is 8-10 mu m, and the length of the glass fiber is 2.7-3.0 mm.
9. The high strength nylon 66 composite of claim 7, wherein: the antioxidant comprises 1.2-1.5 parts of antioxidant 1010 and 0.8-1.0 part of antioxidant 168.
10. The high strength nylon 66 composite of claim 7, wherein: the lubricant is one or more of paraffin, polypropylene wax, polyethylene wax, amide wax, pentaerythritol stearate, polyacrylamide and silicone resin.
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| CN115521078A (en) * | 2022-11-08 | 2022-12-27 | 株洲时代新材料科技股份有限公司 | Glass fiber grafting modification method and application |
| CN116041949A (en) * | 2022-12-02 | 2023-05-02 | 苏州优利金新材料有限公司 | Preparation process of high-strength carbon nanotube modified nylon 6 composite material |
| CN116606544A (en) * | 2023-04-03 | 2023-08-18 | 常州逸冠塑料制品有限公司 | Heat-resistant impact-resistant polyamide plastic and preparation method thereof |
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| CN115521078A (en) * | 2022-11-08 | 2022-12-27 | 株洲时代新材料科技股份有限公司 | Glass fiber grafting modification method and application |
| 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 |
| CN116041949A (en) * | 2022-12-02 | 2023-05-02 | 苏州优利金新材料有限公司 | Preparation process of high-strength carbon nanotube modified nylon 6 composite material |
| 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 |
| CN116606544A (en) * | 2023-04-03 | 2023-08-18 | 常州逸冠塑料制品有限公司 | Heat-resistant impact-resistant polyamide plastic and preparation method thereof |
| 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 |
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