CN116875044A - Composite reinforced flame-retardant nylon material for new energy automobile and preparation method thereof - Google Patents
Composite reinforced flame-retardant nylon material for new energy automobile and preparation method thereof Download PDFInfo
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- CN116875044A CN116875044A CN202310925569.8A CN202310925569A CN116875044A CN 116875044 A CN116875044 A CN 116875044A CN 202310925569 A CN202310925569 A CN 202310925569A CN 116875044 A CN116875044 A CN 116875044A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 146
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 239000000463 material Substances 0.000 title claims abstract description 118
- 239000002131 composite material Substances 0.000 title claims abstract description 96
- 239000004677 Nylon Substances 0.000 title claims abstract description 62
- 229920001778 nylon Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 93
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 88
- 239000011347 resin Substances 0.000 claims abstract description 88
- 229920005989 resin Polymers 0.000 claims abstract description 88
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 83
- 239000002135 nanosheet Substances 0.000 claims abstract description 72
- 239000011159 matrix material Substances 0.000 claims abstract description 71
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003365 glass fiber Substances 0.000 claims abstract description 40
- 229920000007 Nylon MXD6 Polymers 0.000 claims abstract description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 31
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 31
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 31
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 28
- 125000000524 functional group Chemical group 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims description 53
- 239000002245 particle Substances 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 21
- 239000002064 nanoplatelet Substances 0.000 claims description 21
- 230000002787 reinforcement Effects 0.000 claims description 16
- 239000003623 enhancer Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 11
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 5
- -1 poly m-xylylene adipamide Chemical compound 0.000 claims description 4
- 238000011161 development Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000000047 product Substances 0.000 description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000003153 chemical reaction reagent Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 238000005406 washing Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 150000001413 amino acids Chemical class 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 238000005576 amination reaction Methods 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 125000001165 hydrophobic group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- C08K7/14—Glass
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Abstract
The invention provides a composite reinforced flame-retardant nylon material for a new energy automobile and a preparation method thereof. The preparation raw materials of the composite reinforced flame-retardant nylon material comprise high-flow nylon 6 matrix resin, a glass fiber reinforcing agent, nylon-MXD 6, a lamellar graphene nano-sheet reinforcing agent, a magnesium hydroxide flame retardant, a red phosphorus flame retardant and a silane coupling agent, wherein the molecular chain of the high-flow nylon 6 matrix resin is provided with a functional group containing nitrogen, and the lamellar graphene nano-sheet reinforcing agent is a lamellar graphene nano-sheet reinforcing agent with the surface organically modified. The composite reinforced flame-retardant nylon material for the new energy automobile is used for the new energy automobile, is suitable for the background condition that the current global automobile industry has increasingly-increased requirements on environmental protection performance, and can make positive contribution to sustainable development of the new energy automobile industry. The invention also provides a preparation method of the composite reinforced flame-retardant nylon material.
Description
Technical Field
The invention belongs to the technical field of flame-retardant materials, and particularly relates to a composite reinforced flame-retardant nylon material for a new energy automobile and a preparation method thereof.
Background
As an important representative of future sustainable development vehicles, new energy automobiles have the advantages of energy conservation, environmental protection, pollution reduction, greenhouse gas emission reduction and the like, and are increasingly receiving wide attention and promotion in the global scope. With the enhancement of awareness of environmental protection and sustainable development, market demands of new energy automobiles are continuously rising, and higher requirements are also put on performance and safety of automobile materials.
The composite material is used as a multiphase combined material, combines the advantages of different materials, avoids respective limitations, and therefore becomes a popular choice in the field of automobile manufacturing. The composite material is light, high in strength, high in rigidity and excellent in flame retardant property, so that the composite material becomes an ideal choice for new energy automobiles. The application of the composite material can obviously reduce the overall weight of the automobile, improve the energy utilization rate, prolong the battery endurance mileage and positively influence the performance and the safety of the whole automobile.
Among the many synthetic polymeric materials, nylon materials are favored for their excellent physical properties, abrasion resistance, and chemical resistance. Nylon 6 is an important nylon material and is widely used for manufacturing automobile parts, such as engine hoods, exhaust pipes, cooling systems, wire and cable bushings and the like. However, as a high-technology product, the new energy automobile has higher requirements on the safety of parts, and particularly needs further improvement in the aspects of fireproof and flame-retardant performance. Because of the molecular structure and chemical property of nylon 6, the flame retardant property of the nylon 6 is poor, and a single nylon 6 material cannot meet the requirement of a new energy automobile on the fireproof property, and in the related technology, the composite nylon 6 material is not ideal. Therefore, there is a need to develop a new flame retardant material suitable for new energy automobiles.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the invention provides the composite reinforced flame-retardant nylon material for the new energy automobile, which has good flame-retardant property and light weight and is suitable for the new energy automobile.
The invention also provides a preparation method of the composite reinforced flame-retardant nylon material for the new energy automobile.
The first aspect of the invention provides a composite reinforced flame-retardant nylon material for a new energy automobile, which is prepared from the following raw materials:
high flow nylon 6 matrix resin: 100 parts of the total weight of the mixture,
glass fiber reinforcing agent: 20 to 40 parts of the components in parts by weight,
nylon-MXD 6:5 to 20 parts of the components,
lamellar graphene nanoplatelet enhancers: 5 to 15 parts of the components,
magnesium hydroxide flame retardant: 2 to 8 parts of the components,
red phosphorus flame retardant: 0.1 to 1.5 parts of a compound,
silane coupling agent: 0.1 to 1.0 part of the total weight of the composition,
the molecular chain of the high-flow nylon 6 matrix resin is provided with a functional group containing nitrogen,
the lamellar graphene nano-sheet reinforcing agent is a lamellar graphene nano-sheet reinforcing agent with the surface organically modified.
The invention relates to one of the technical schemes of composite reinforced flame-retardant nylon materials for new energy automobiles, which has at least the following beneficial effects:
the composite reinforced flame-retardant nylon material for the new energy automobile is optimized for the proportion of different components, and ensures the good balance between the flame retardant property and the mechanical property of the composite material. The reasonable proportion of the high-flow nylon 6 matrix resin, the glass fiber reinforcing agent, the nylon-MXD 6 and the lamellar graphene nano sheet reinforcing agent can enhance the flame retardant property of the material while improving the strength and the rigidity of the material.
The nylon-MXD 6 is poly m-xylylene adipamide, and the nylon-MXD 6 is added into the system to help improve the wear resistance, reduce the warp deformation, and more mainly control the water absorption of the material and reduce the property attenuation of the material.
According to the composite reinforced flame-retardant nylon material for the new energy automobile, magnesium hydroxide and red phosphorus flame retardants are used, the particle sizes of the magnesium hydroxide and the red phosphorus flame retardants are controlled in the nanoscale range, the nanoscale flame retardants can be more uniformly dispersed in the material, the flame-retardant effect is improved, and meanwhile, the adverse effect on mechanical properties is reduced.
The composite reinforced flame-retardant nylon material for the new energy automobile is introduced with the silane coupling agent, and has the functions of enhancing the interface interaction between different components and improving the interface bonding strength of the composite material. Therefore, the performance loss caused by interfacial peeling of the materials can be effectively prevented, and the flame retardant property of the materials is increased.
The composite reinforced flame-retardant nylon material for the new energy automobile has the advantages that the molecular chain of the high-flow nylon 6 matrix resin is provided with the functional group containing nitrogen, so that the flame retardant property and the thermal stability of the composite reinforced flame-retardant nylon material can be improved, and more environment-friendly and safer material selection is provided for the fields of new energy automobiles and the like. Meanwhile, the high-flow nylon 6 matrix resin can also increase the surface gloss of the material, and has good compatibility with nylon-MXD 6. By carrying out organic modification on the lamellar graphene nano-sheet reinforcing agent, the surface of the multilayer graphene nano-sheet can become more lipophilic, and the compatibility with resin is enhanced, so that the composite material has better mechanical properties.
The composite reinforced flame-retardant nylon material for the new energy automobile is used for the new energy automobile, is suitable for the background condition that the current global automobile industry has increasingly-increased requirements on environmental protection performance, and can make positive contribution to sustainable development of the new energy automobile industry.
According to some embodiments of the present invention, the method for introducing nitrogen-containing functional groups on the molecular chain of the high-flow nylon 6 matrix resin is as follows:
preparing a reaction material:
high flow nylon 6 matrix resin: commercial nylon 6 particles were used.
Amination reagent: suitable amino acids of the amino group-containing compound are selected.
The method comprises the following specific steps:
(1) Mixing high-flow nylon 6 matrix resin and amino acid according to the mass ratio of 100:1-5;
(2) The mixture is added into a reaction kettle and dissolved in a solvent, wherein the solvent comprises N, N-Dimethylformamide (DMF)
Or N-methylpyrrolidone (NMP);
(3) Heating the reaction kettle to a proper reaction temperature in an inert atmosphere (such as nitrogen), wherein the reaction temperature is in the range of 150-250 ℃ and the reaction time is 1-3 hours;
(4) In the reaction process, the amination reagent and the high-flow nylon 6 matrix resin are subjected to polycondensation reaction, and finally, a functional group containing nitrogen is introduced into a nylon 6 molecular chain;
(5) Cooling the reacted product, and washing with solvent to remove unreacted raw material and by-product, wherein the washing solvent can be ethanol or acetone;
(6) And drying the washed product to obtain the modified high-flow nylon 6 matrix resin containing nitrogen.
According to some embodiments of the invention, the high flow nylon 6 matrix resin has a relative molecular mass of 1.0X10 4 -4.0×10 5 Between them.
The relative molecular mass of the high-flow nylon 6 matrix resin is 1.0x10 4 -4.0×10 5 Firstly, the relative molecular mass range can improve the fluidity and the processing performance of the nylon 6 resin, so that the nylon 6 resin is easier to form and process plastics, and is beneficial to producing new energy automobiles with complex shapesA component. Secondly, it also contributes to improving the structural strength and durability of the new energy automobile component. Third, the high flow nylon 6 matrix resin with relative molecular mass range generally has higher melting point and thermal stability, and is beneficial to the application of the new energy automobile parts in high temperature environment. Fourth, the relative molecular mass range can affect the flame retardant properties of the composite reinforced flame retardant nylon material to some extent. The higher the relative molecular mass, the better the dispersibility and effect of the nanoscale flame retardant in the resin.
According to some embodiments of the invention, the glass fiber reinforcement has a length of 10-20mm.
According to some embodiments of the invention, the glass fiber reinforcement has a diameter of 10-20 μm.
The length of the glass fiber reinforcing agent is limited to be in the range of 10-20mm, and the diameter is limited to be in the range of 10-20 mu m, so that the strength and rigidity of the composite material can be increased, the composite material can be used as an effective path for load transmission, and can bear larger tensile stress when being stressed, and the strength and rigidity of the material are enhanced. The impact resistance of the composite material can be improved, the impact energy can be effectively absorbed and dispersed, and the damage degree of the material under impact loading is reduced. The fatigue life of the composite material can be improved, the rigidity and toughness of the composite material are balanced, and fatigue damage caused by stress concentration is reduced. It can also bear friction and reduce the abrasion of the material surface, thereby increasing the service life of the material. In addition, the bonding between the reinforcing agent and the resin is facilitated, so that the mechanical property of the composite material is improved.
According to some embodiments of the invention, the nylon-MXD 6 is poly (m-xylylene adipamide), and the addition of the nylon-MXD 6 in the system is helpful for improving wear resistance, reducing warp deformation, and more importantly, controlling water absorption of the material and reducing material property attenuation.
According to some embodiments of the invention, the lamellar graphene nanoplatelet reinforcing agent has a thickness of 0.5-5nm.
According to some embodiments of the invention, the lamellar graphene nanoplatelet enhancers have a surface area of 200-500m 2 /g。
According to some embodiments of the invention, the lamellar graphene nanoplatelet enhancer is a surface organically modified lamellar graphene nanoplatelet enhancer.
The multi-layered graphene nanoplatelets have excellent properties as reinforcing agents in composites, but their surfaces are often hydrophilic, which may lead to difficulty in good bonding with aqueous resins, affecting the composite properties. Therefore, through organic modification, the surface of the multilayer graphene nano sheet can become more lipophilic, and the compatibility with resin is enhanced, so that the composite material has better mechanical properties.
The method for organically modifying the surface of the lamellar graphene nano-sheet reinforcing agent comprises the following steps:
preparing a reaction material: using commercial multilayer graphene nanoplatelets, the organic modifying agent is a long chain alkane or an organic functional group containing a hydrophobic group.
The long chain alkane may be octadecyltrimethoxysilane or octadecyltriethylaminosilane.
The organofunctional reagent containing hydrophobic groups may be palmitic acid.
The method comprises the following specific steps:
(1) Mixing the multilayer graphene nano-sheets with an organic modifying reagent according to a proportion, wherein the dosage of the organic modifying reagent is 1-5% of the mass of the multilayer graphene nano-sheets;
(2) Dissolving the reactant mixture in a solvent, and fully stirring to uniformly mix the reactant mixture, wherein the solvent is dimethylbenzene or n-heptane and the like;
(3) Reacting the mixture for 1-5 h at 50-150 ℃;
(4) Cooling the reacted product, and washing with a solvent to remove unreacted raw materials and byproducts;
(5) And drying the washed product to obtain the organically modified multilayer graphene nano sheet.
According to some embodiments of the invention, the magnesium hydroxide flame retardant is a nano-sized particle having an average particle size of 50-100nm.
According to some embodiments of the invention, the red phosphorus flame retardant is a nano-sized particle having an average particle size of 10-30nm.
According to some embodiments of the invention, the silane coupling agent is 3-aminopropyl trimethoxysilane.
The second aspect of the invention provides a method for preparing a composite reinforced flame-retardant nylon material for a new energy automobile, which comprises the following steps:
s1: mixing and melting the high-flow nylon 6 matrix resin, the glass fiber reinforcing agent and the nylon MXD6 according to the proportion;
and S2, adding the lamellar graphene nano sheet reinforcing agent, the magnesium hydroxide flame retardant, the red phosphorus flame retardant and the silane coupling agent into the mixture obtained in the step S1, heating, continuously mixing under a melting condition, cooling, and granulating to obtain the composite reinforced flame retardant nylon material for the new energy automobile.
The invention relates to a technical scheme in a preparation method of a composite reinforced flame-retardant nylon material for a new energy automobile, which at least has the following beneficial effects:
the preparation method of the invention does not need expensive equipment and complex process control, has low reaction conditions, easily obtained raw materials, low production cost and easy industrial production.
According to some embodiments of the invention, in step S1, the temperature of the mixed melt is 180 ℃ to 230 ℃.
In the step S1, the temperature of the mixed melting is 180-230 ℃, and the aim is to uniformly disperse the glass fiber reinforcing agent in the high-flow nylon 6 matrix resin and avoid side reactions and excessive thermal decomposition of materials at a lower temperature.
According to some embodiments of the invention, the elevated temperature is 200 ℃ to 250 ℃.
In step S2, the temperature is raised to 200-250 ℃, and the composite material is usually subjected to hot press molding or injection molding, and the pre-mixed material is formed into a desired shape. This step requires a higher temperature range to achieve melt processing, which helps to increase the melt flow of the material, to allow the composite material to fill more easily in the mold and to form the desired shape, and to facilitate efficient bonding between the reinforcing agent and the high flow nylon 6 matrix resin. In this temperature range, intermolecular interaction forces between the reinforcing agent and the resin are enhanced, helping to form a tighter bond. In addition, the higher temperature can also help to completely remove bubbles in the material and improve the compactness and stability of the finished product.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
In some embodiments of the invention, the invention provides a composite reinforced flame-retardant nylon material for a new energy automobile, which is prepared from the following raw materials:
high flow nylon 6 matrix resin: 100 parts of the total weight of the mixture,
glass fiber reinforcing agent: 20 to 40 parts of the components in parts by weight,
nylon-MXD 6:5 to 20 parts of the components,
lamellar graphene nanoplatelet enhancers: 5 to 15 parts of the components,
magnesium hydroxide flame retardant: 2 to 8 parts of the components,
red phosphorus flame retardant: 0.1 to 1.5 parts of a compound,
silane coupling agent: 0.1 to 1.0 part of the total weight of the composition,
the molecular chain of the high-flow nylon 6 matrix resin is provided with a functional group containing nitrogen,
the lamellar graphene nano-sheet reinforcing agent is a lamellar graphene nano-sheet reinforcing agent with the surface organically modified.
It can be understood that the composite reinforced flame-retardant nylon material for the new energy automobile is optimized according to the proportion of different components, and ensures the good balance between the flame-retardant property and the mechanical property of the composite material. The reasonable proportion of the high-flow nylon 6 matrix resin, the glass fiber reinforcing agent, the nylon-MXD 6 and the lamellar graphene nano sheet reinforcing agent can enhance the flame retardant property of the material while improving the strength and the rigidity of the material.
It can also be understood that the composite reinforced flame-retardant nylon material for the new energy automobile uses magnesium hydroxide and red phosphorus flame retardant, and controls the particle size of the magnesium hydroxide and the red phosphorus flame retardant in a nanoscale range, so that the nanoscale flame retardant can be more uniformly dispersed in the material, the flame-retardant effect is improved, and the adverse effect on mechanical properties is reduced.
It can also be understood that the composite reinforced flame-retardant nylon material for the new energy automobile is introduced with the silane coupling agent, and has the functions of enhancing the interface interaction between different components and improving the interface bonding strength of the composite material. Therefore, the performance loss caused by interfacial peeling of the materials can be effectively prevented, and the flame retardant property of the materials is increased.
Furthermore, the composite reinforced flame-retardant nylon material for the new energy automobile has the functional groups containing nitrogen on the molecular chain of the high-flow nylon 6 matrix resin, so that the flame retardant property and the thermal stability of the composite reinforced flame-retardant nylon material can be improved, and more environment-friendly and safer material selection is provided for the fields of new energy automobiles and the like. By carrying out organic modification on the lamellar graphene nano-sheet reinforcing agent, the surface of the multilayer graphene nano-sheet can become more lipophilic, the compatibility with resin is enhanced, and the mechanical property of the composite material is better.
The composite reinforced flame-retardant nylon material for the new energy automobile is used for the new energy automobile, is suitable for the background condition that the current global automobile industry has increasingly-increased requirements on environmental protection performance, and can make positive contribution to sustainable development of the new energy automobile industry.
In some embodiments of the invention, the high flow nylon 6 matrix resin has nitrogen-containing functional groups on the molecular chain.
In some embodiments of the present invention, the method for introducing nitrogen-containing functional groups into the molecular chain of the high-flow nylon 6 matrix resin is as follows:
preparing a reaction material:
high flow nylon 6 matrix resin: commercial nylon 6 particles were used.
Amination reagent: suitable amino acids of the compound containing amino and phosphate groups are selected.
The method comprises the following specific steps:
(1) Mixing high-flow nylon 6 matrix resin and amino acid according to the mass ratio of 100:1-5;
(2) The mixture is added into a reaction kettle and dissolved in a solvent, wherein the solvent comprises N, N-Dimethylformamide (DMF)
Or N-methylpyrrolidone (NMP);
(3) Heating the reaction kettle to a proper reaction temperature in an inert atmosphere (such as nitrogen), wherein the reaction temperature is in the range of 150-250 ℃ and the reaction time is 1-3 hours;
(4) In the reaction process, the phosphoramidation reagent and the high-flow nylon 6 matrix resin undergo a polycondensation reaction, and finally, a functional group containing nitrogen is introduced into a nylon 6 molecular chain;
(5) Cooling the reacted product, and washing with solvent to remove unreacted raw material and by-product, wherein the washing solvent can be ethanol or acetone;
(6) And drying the washed product to obtain the modified high-flow nylon 6 matrix resin containing nitrogen.
In some embodiments of the invention, the high flow nylon 6 matrix resin has a relative molecular mass of 1.0X10 4 -4.0×10 5 Between them.
The relative molecular mass of the high-flow nylon 6 matrix resin is 1.0x10 4 -4.0×10 5 Firstly, the relative molecular mass range can improve the fluidity and the processing performance of the nylon 6 resin, so that the nylon 6 resin is easier to mold and process plastic, and is beneficial to producing new energy automobile parts with complex shapes. Secondly, it also contributes to improving the structural strength and durability of the new energy automobile component. Third, the high flow nylon 6 matrix resin with relative molecular mass range generally has higher melting point and thermal stability, and is beneficial to the application of the new energy automobile parts in high temperature environment. Fourth, the relative molecular mass range can affect the flame retardant properties of the composite reinforced flame retardant nylon material to some extent. The higher the relative molecular mass, the better the dispersibility and effect of the nanoscale flame retardant in the resin.
In some embodiments of the invention, the length of the glass fiber reinforcement is 10-20mm.
In some embodiments of the invention, the glass fiber reinforcement has a diameter of 10-20 μm.
The length of the glass fiber reinforcing agent is limited to be in the range of 10-20mm, and the diameter is limited to be in the range of 10-20 mu m, so that the strength and rigidity of the composite material can be increased, the composite material can be used as an effective path for load transmission, and can bear larger tensile stress when being stressed, and the strength and rigidity of the material are enhanced. The impact resistance of the composite material can be improved, the impact energy can be effectively absorbed and dispersed, and the damage degree of the material under impact loading is reduced. The fatigue life of the composite material can be improved, the rigidity and toughness of the composite material are balanced, and fatigue damage caused by stress concentration is reduced. It can also bear friction and reduce the abrasion of the material surface, thereby increasing the service life of the material. In addition, the bonding between the reinforcing agent and the resin is facilitated, so that the mechanical property of the composite material is improved.
In some embodiments of the invention, nylon-MXD 6 is poly (m-xylylene adipamide), and the addition of nylon-MXD 6 to the system helps to improve wear resistance, reduce warp deformation, and more importantly, control water absorption of the material and reduce material property attenuation.
In some embodiments of the invention, the thickness of the layered graphene nanoplatelet enhancer is from 0.5 to 5nm.
In some embodiments of the invention, the lamellar graphene nanoplatelet enhancers have a surface area of 200-500m 2 /g。
In some embodiments of the invention, the lamellar graphene nanoplatelet enhancer is a surface organically modified lamellar graphene nanoplatelet enhancer.
The multi-layered graphene nanoplatelets have excellent properties as reinforcing agents in composites, but their surfaces are often hydrophilic, which may lead to difficulty in good bonding with aqueous resins, affecting the composite properties. Therefore, through organic modification, the surface of the multilayer graphene nano sheet can become more lipophilic, the compatibility with resin is enhanced, and the mechanical property of the composite material is better.
The method for organically modifying the surface of the lamellar graphene nano-sheet reinforcing agent comprises the following steps:
preparing a reaction material: using commercial multilayer graphene nanoplatelets, the organic modifying agent is a long chain alkane or an organic functional group containing a hydrophobic group.
The long chain alkane may be octadecyltrimethoxysilane or octadecyltriethylaminosilane.
The organofunctional reagent containing hydrophobic groups may be palmitic acid.
The method comprises the following specific steps:
(1) Mixing the multilayer graphene nano-sheets with an organic modifying reagent according to a proportion, wherein the dosage of the organic modifying reagent is 1-5% of the mass of the multilayer graphene nano-sheets;
(2) Dissolving the reactant mixture in a solvent, and fully stirring to uniformly mix the reactant mixture, wherein the solvent is dimethylbenzene or n-heptane and the like;
(3) Reacting the mixture for 1-5 h at 50-150 ℃;
(4) Cooling the reacted product, and washing with a solvent to remove unreacted raw materials and byproducts;
(5) And drying the washed product to obtain the organically modified multilayer graphene nano sheet.
In some embodiments of the invention, the magnesium hydroxide flame retardant is a nano-sized particle having an average particle size of 50-100nm.
In some embodiments of the invention, the red phosphorus flame retardant is a nano-sized particle having an average particle size of 10-30nm.
In some embodiments of the invention, the silane coupling agent is 3-aminopropyl trimethoxysilane.
In other embodiments of the present invention, the present invention provides a method for preparing a composite reinforced flame retardant nylon material for a new energy automobile, comprising the steps of:
s1: mixing and melting high-flow nylon 6 matrix resin, glass fiber reinforcing agent and nylon-MXD 6 according to the proportion;
s2: and (2) adding the lamellar graphene nano sheet reinforcing agent, the magnesium hydroxide flame retardant, the red phosphorus flame retardant and the silane coupling agent into the mixture obtained in the step (S1), heating, continuously mixing under a melting condition, cooling, and granulating to obtain the composite reinforced flame retardant nylon material for the new energy automobile.
It can be understood that the preparation method of the invention does not need expensive equipment and complex process control, has harsh reaction conditions, easily obtained raw materials, low production cost and easy industrial production.
In some embodiments of the invention, in step S1, the temperature of the mixed melt is 180 ℃ to 230 ℃.
In step S1, the temperature of mixing and melting is 180-230 ℃, and the aim is to uniformly disperse the glass fiber reinforcing agent in the high-flow nylon 6 matrix resin and avoid side reactions and excessive thermal decomposition of materials at lower temperature.
In some embodiments of the invention, the elevated temperature is 200 ℃ to 250 ℃.
In step S2, the temperature is raised to 200-250 ℃, and the composite material is usually subjected to hot press molding or injection molding, and the pre-mixed material is formed into a desired shape. This step requires a higher temperature range to achieve melt processing, which helps to increase the melt flow of the material, to allow the composite material to fill more easily in the mold and to form the desired shape, and to facilitate efficient bonding between the reinforcing agent and the high flow nylon 6 matrix resin. In this temperature range, intermolecular interaction forces between the reinforcing agent and the resin are enhanced, helping to form a tighter bond. In addition, the higher temperature can also help to completely remove bubbles in the material and improve the compactness and stability of the finished product.
The technical solution of the present invention will be better understood in conjunction with the following specific examples.
In the examples and comparative examples, the raw materials used were commercially available.
Wherein, the high-flow nylon 6 matrix resin is purchased from Ningbo plastic new material Co.
nylon-MXD 6 was purchased from shanghai curing company, inc.
Example 1
The embodiment provides a composite reinforced flame-retardant nylon material for new energy automobiles, which is prepared from the following raw materials:
high flow nylon 6 matrix resin: 100 parts of the total weight of the mixture,
glass fiber reinforcing agent: 20 parts of a mixture of two or more components,
nylon-MXD 6:20 parts of a mixture of two or more components,
lamellar graphene nanoplatelet enhancers: 5 parts of the components in parts by weight,
magnesium hydroxide flame retardant: 2 parts of the components are mixed together,
red phosphorus flame retardant: 0.1 part of the total weight of the composition,
silane coupling agent: 0.1 part.
Wherein, the molecular chain of the high-flow nylon 6 matrix resin is provided with a functional group containing nitrogen.
The method for introducing nitrogen-containing functional groups into the molecular chain of the high-flow nylon 6 matrix resin comprises the following steps:
(1) Mixing high-flow nylon 6 matrix resin and amino acid according to a mass ratio of 100:5;
(2) Adding the mixture into a reaction kettle, and dissolving in DMF;
(3) Heating the reaction kettle to about 200 ℃ under the condition of nitrogen, and reacting for 2 hours;
(4) In the reaction process, the amination reagent and the high-flow nylon 6 matrix resin are subjected to polycondensation reaction, and finally, a functional group containing nitrogen is introduced into a nylon 6 molecular chain;
(5) Cooling the reacted product, and washing with ethanol;
(6) And drying the washed product to obtain the modified high-flow nylon 6 matrix resin containing nitrogen.
The length of the glass fiber reinforcement is about 15 mm.
The diameter of the glass fiber reinforcement is about 15 μm.
nylon-MXD 6 is poly (m-xylylenediamine) adipamide.
The thickness of the lamellar graphene nano-sheet reinforcing agent is about 3 nm.
The surface area of the lamellar graphene nano-sheet reinforcing agent is 300m 2 About/g.
The lamellar graphene nano-sheet reinforcing agent is a lamellar graphene nano-sheet reinforcing agent with the surface organically modified.
The method for organically modifying the surface of the lamellar graphene nano-sheet reinforcing agent comprises the following steps:
the method comprises the following specific steps:
(1) Mixing the multilayer graphene nano-sheets and octadecyltrimethoxysilane according to a proportion, wherein the dosage of the organic modifying reagent is 5% of the mass of the multilayer graphene nano-sheets;
(2) Dissolving the reactant mixture in xylene and stirring thoroughly to mix homogeneously;
(3) Reacting the mixture at 100 ℃ for 3 hours;
(4) Cooling the reacted product, and washing with a solvent to remove unreacted raw materials and byproducts;
(5) And drying the washed product to obtain the organically modified multilayer graphene nano sheet.
The magnesium hydroxide flame retardant is nano-sized particles with an average particle size of about 80 nm.
The red phosphorus flame retardant is nano-grade particles, and the average particle diameter is about 20 nm.
The silane coupling agent is 3-aminopropyl trimethoxy silane.
The preparation method of the composite reinforced flame-retardant nylon material for the new energy automobile comprises the following steps:
s1: mixing and melting high-flow nylon 6 matrix resin, glass fiber reinforcing agent and nylon-MXD 6 according to the proportion;
s2: and (2) adding the lamellar graphene nano sheet reinforcing agent, the magnesium hydroxide flame retardant, the red phosphorus flame retardant and the silane coupling agent into the mixture obtained in the step (S1), heating, continuously mixing under a melting condition, cooling, and granulating to obtain the composite reinforced flame retardant nylon material for the new energy automobile.
In step S1, the temperature of the mixed melt was 200 ℃.
In step S2, the temperature of the temperature rise is 230 ℃.
Example 2
The embodiment provides a composite reinforced flame-retardant nylon material for new energy automobiles, which is prepared from the following raw materials:
high flow nylon 6 matrix resin: 100 parts of the total weight of the mixture,
glass fiber reinforcing agent: 40 parts of a powder for injection,
nylon-MXD 6:5 parts of the components in parts by weight,
lamellar graphene nanoplatelet enhancers: 15 parts of a mixture of two or more components,
magnesium hydroxide flame retardant: 8 parts of the components in parts by weight,
red phosphorus flame retardant: 1.5 parts of the total weight of the mixture,
silane coupling agent: 1.0 parts.
Wherein, the molecular chain of the high-flow nylon 6 matrix resin is provided with a functional group containing nitrogen.
The method for introducing nitrogen-containing functional groups into the molecular chain of the high-flow nylon 6 matrix resin comprises the following steps:
(1) Mixing high-flow nylon 6 matrix resin and amino acid according to a mass ratio of 100:5;
(2) Adding the mixture into a reaction kettle, and dissolving in DMF;
(3) Heating the reaction kettle to about 200 ℃ under the condition of nitrogen, and reacting for 2 hours;
(4) In the reaction process, the amination reagent and the high-flow nylon 6 matrix resin are subjected to polycondensation reaction, and finally, a functional group containing nitrogen is introduced into a nylon 6 molecular chain;
(5) Cooling the reacted product, and washing with ethanol;
(6) And drying the washed product to obtain the modified high-flow nylon 6 matrix resin containing nitrogen.
The length of the glass fiber reinforcement is about 15 mm.
The diameter of the glass fiber reinforcement is about 15 μm.
nylon-MXD 6 is poly (m-xylylenediamine) adipamide.
The thickness of the lamellar graphene nano-sheet reinforcing agent is about 3 nm.
The surface area of the lamellar graphene nano-sheet reinforcing agent is 300m 2 About/g.
The lamellar graphene nano-sheet reinforcing agent is a lamellar graphene nano-sheet reinforcing agent with the surface organically modified.
The method for organically modifying the surface of the lamellar graphene nano-sheet reinforcing agent comprises the following steps:
the method comprises the following specific steps:
(1) Mixing the multilayer graphene nano-sheets and octadecyltrimethoxysilane according to a proportion, wherein the dosage of the organic modifying reagent is 5% of the mass of the multilayer graphene nano-sheets;
(2) Dissolving the reactant mixture in xylene and stirring thoroughly to mix homogeneously;
(3) Reacting the mixture at 100 ℃ for 3 hours;
(4) Cooling the reacted product, and washing with a solvent to remove unreacted raw materials and byproducts;
(5) And drying the washed product to obtain the organically modified multilayer graphene nano sheet.
The magnesium hydroxide flame retardant is nano-sized particles with an average particle size of about 80 nm.
The red phosphorus flame retardant is nano-grade particles, and the average particle diameter is about 20 nm.
The silane coupling agent is 3-aminopropyl trimethoxy silane.
The preparation method of the composite reinforced flame-retardant nylon material for the new energy automobile comprises the following steps:
s1: mixing and melting high-flow nylon 6 matrix resin, glass fiber reinforcing agent and nylon-MXD 6 according to the proportion;
s2: and (2) adding the lamellar graphene nano sheet reinforcing agent, the magnesium hydroxide flame retardant, the red phosphorus flame retardant and the silane coupling agent into the mixture obtained in the step (S1), heating, continuously mixing under a melting condition, cooling, and granulating to obtain the composite reinforced flame retardant nylon material for the new energy automobile.
In step S1, the temperature of the mixed melt was 200 ℃.
In step S2, the temperature of the temperature rise is 230 ℃.
Example 3
The embodiment provides a composite reinforced flame-retardant nylon material for new energy automobiles, which is prepared from the following raw materials:
high flow nylon 6 matrix resin: 100 parts of the total weight of the mixture,
glass fiber reinforcing agent: 30 parts of the total weight of the mixture,
nylon-MXD 6:10 parts of a powder for injection,
lamellar graphene nanoplatelet enhancers: 10 parts of a powder for injection,
magnesium hydroxide flame retardant: 5 parts of the components in parts by weight,
red phosphorus flame retardant: 1 part of the total weight of the mixture,
silane coupling agent: 0.5 part.
Wherein, the molecular chain of the high-flow nylon 6 matrix resin is provided with a functional group containing nitrogen.
The method for introducing nitrogen-containing functional groups into the molecular chain of the high-flow nylon 6 matrix resin comprises the following steps:
(1) Mixing high-flow nylon 6 matrix resin and amino acid according to a mass ratio of 100:5;
(2) Adding the mixture into a reaction kettle, and dissolving in DMF;
(3) Heating the reaction kettle to about 200 ℃ under the condition of nitrogen, and reacting for 2 hours;
(4) In the reaction process, the amination reagent and the high-flow nylon 6 matrix resin are subjected to polycondensation reaction, and finally, a functional group containing nitrogen is introduced into a nylon 6 molecular chain;
(5) Cooling the reacted product, and washing with ethanol;
(6) And drying the washed product to obtain the modified high-flow nylon 6 matrix resin containing nitrogen.
The length of the glass fiber reinforcement is about 15 mm.
The diameter of the glass fiber reinforcement is about 15 μm.
nylon-MXD 6 is poly (m-xylylenediamine) adipamide.
The thickness of the lamellar graphene nano-sheet reinforcing agent is about 3 nm.
The surface area of the lamellar graphene nano-sheet reinforcing agent is 300m 2 About/g.
The lamellar graphene nano-sheet reinforcing agent is a lamellar graphene nano-sheet reinforcing agent with the surface organically modified.
The method for organically modifying the surface of the lamellar graphene nano-sheet reinforcing agent comprises the following steps:
the method comprises the following specific steps:
(1) Mixing the multilayer graphene nano-sheets and octadecyltrimethoxysilane according to a proportion, wherein the dosage of the organic modifying reagent is 5% of the mass of the multilayer graphene nano-sheets;
(2) Dissolving the reactant mixture in xylene and stirring thoroughly to mix homogeneously;
(3) Reacting the mixture at 100 ℃ for 3 hours;
(4) Cooling the reacted product, and washing with a solvent to remove unreacted raw materials and byproducts;
(5) And drying the washed product to obtain the organically modified multilayer graphene nano sheet.
The magnesium hydroxide flame retardant is nano-sized particles with an average particle size of about 80 nm.
The red phosphorus flame retardant is nano-grade particles, and the average particle diameter is about 20 nm.
The silane coupling agent is 3-aminopropyl trimethoxy silane.
The preparation method of the composite reinforced flame-retardant nylon material for the new energy automobile comprises the following steps:
s1: mixing and melting high-flow nylon 6 matrix resin, glass fiber reinforcing agent and nylon-MXD 6 according to the proportion;
s2: and (2) adding the lamellar graphene nano sheet reinforcing agent, the magnesium hydroxide flame retardant, the red phosphorus flame retardant and the silane coupling agent into the mixture obtained in the step (S1), heating, continuously mixing under a melting condition, cooling, and granulating to obtain the composite reinforced flame retardant nylon material for the new energy automobile.
In step S1, the temperature of the mixed melt was 200 ℃.
In step S2, the temperature of the temperature rise is 230 ℃.
Comparative example 1
This comparative example provides a composite reinforced flame retardant nylon material, differing from example 1 in that no nylon-MXD 6 component is added to the system.
The preparation raw materials are as follows:
high flow nylon 6 matrix resin: 100 parts of the total weight of the mixture,
glass fiber reinforcing agent: 20 parts of a mixture of two or more components,
lamellar graphene nanoplatelet enhancers: 5 parts of the components in parts by weight,
magnesium hydroxide flame retardant: 2 parts of the components are mixed together,
red phosphorus flame retardant: 0.1 part of the total weight of the composition,
silane coupling agent: 0.1 part.
The length of the glass fiber reinforcement is about 15 mm.
The diameter of the glass fiber reinforcement is about 15 μm.
The thickness of the lamellar graphene nano-sheet reinforcing agent is about 3 nm.
The surface area of the lamellar graphene nano-sheet reinforcing agent is 300m 2 About/g.
The lamellar graphene nano-sheet reinforcing agent is a lamellar graphene nano-sheet reinforcing agent with the surface organically modified.
The method for organically modifying the surface of the lamellar graphene nano-sheet reinforcing agent comprises the following steps:
the method comprises the following specific steps:
(1) Mixing the multilayer graphene nano-sheets and octadecyltrimethoxysilane according to a proportion, wherein the dosage of the organic modifying reagent is 5% of the mass of the multilayer graphene nano-sheets;
(2) Dissolving the reactant mixture in xylene and stirring thoroughly to mix homogeneously;
(3) Reacting the mixture at 100 ℃ for 3 hours;
(4) Cooling the reacted product, and washing with a solvent to remove unreacted raw materials and byproducts;
(5) And drying the washed product to obtain the organically modified multilayer graphene nano sheet.
The magnesium hydroxide flame retardant is nano-sized particles with an average particle size of about 80 nm.
The red phosphorus flame retardant is nano-grade particles, and the average particle diameter is about 20 nm.
The silane coupling agent is 3-aminopropyl trimethoxy silane.
The preparation method of the composite reinforced flame-retardant nylon material for the new energy automobile of the comparative example comprises the following steps:
s1: mixing and melting high-flow nylon 6 matrix resin and a glass fiber reinforcing agent according to a proportion;
s2: and (2) adding the lamellar graphene nano sheet reinforcing agent, the magnesium hydroxide flame retardant, the red phosphorus flame retardant and the silane coupling agent into the mixture obtained in the step (S1), heating, continuously mixing under a melting condition, cooling, and granulating to obtain the composite reinforced flame retardant nylon material for the new energy automobile.
In step S1, the temperature of the mixed melt was 200 ℃.
In step S2, the temperature of the temperature rise is 230 ℃.
Comparative example 2
The comparative example provides a composite reinforced flame retardant nylon material, which is different from example 1 in that the surface of the lamellar graphene nanoplatelet reinforcing agent is not organically modified.
The preparation raw materials are as follows:
high flow nylon 6 matrix resin: 100 parts of the total weight of the mixture,
glass fiber reinforcing agent: 20 parts of a mixture of two or more components,
nylon-MXD 6:20 parts of a mixture of two or more components,
lamellar graphene nanoplatelet enhancers: 5 parts of the components in parts by weight,
magnesium hydroxide flame retardant: 2 parts of the components are mixed together,
red phosphorus flame retardant: 0.1 part of the total weight of the composition,
silane coupling agent: 0.1 part.
Wherein, the molecular chain of the high-flow nylon 6 matrix resin is provided with a functional group containing nitrogen.
The method for introducing nitrogen-containing functional groups into the molecular chain of the high-flow nylon 6 matrix resin comprises the following steps:
(1) Mixing high-flow nylon 6 matrix resin and amino acid according to a mass ratio of 100:5;
(2) Adding the mixture into a reaction kettle, and dissolving in DMF;
(3) Heating the reaction kettle to about 200 ℃ under the condition of nitrogen, and reacting for 2 hours;
(4) In the reaction process, the amination reagent and the high-flow nylon 6 matrix resin are subjected to polycondensation reaction, and finally, a functional group containing nitrogen is introduced into a nylon 6 molecular chain;
(5) Cooling the reacted product, and washing with ethanol;
(6) And drying the washed product to obtain the modified high-flow nylon 6 matrix resin containing nitrogen.
The length of the glass fiber reinforcement is about 15 mm.
The diameter of the glass fiber reinforcement is about 15 μm.
nylon-MXD 6 is poly (m-xylylenediamine) adipamide.
The thickness of the lamellar graphene nano-sheet reinforcing agent is about 3 nm.
The surface area of the lamellar graphene nano-sheet reinforcing agent is 300m 2 About/g.
The magnesium hydroxide flame retardant is nano-sized particles with an average particle size of about 80 nm.
The red phosphorus flame retardant is nano-grade particles, and the average particle diameter is about 20 nm.
The silane coupling agent is 3-aminopropyl trimethoxy silane.
The preparation method of the composite reinforced flame-retardant nylon material for the new energy automobile of the comparative example comprises the following steps:
s1: mixing and melting high-flow nylon 6 matrix resin, glass fiber reinforcing agent and nylon-MXD 6 according to the proportion;
s2: and (2) adding the lamellar graphene nano sheet reinforcing agent, the magnesium hydroxide flame retardant, the red phosphorus flame retardant and the silane coupling agent into the mixture obtained in the step (S1), heating, continuously mixing under a melting condition, cooling, and granulating to obtain the composite reinforced flame retardant nylon material for the new energy automobile.
In step S1, the temperature of the mixed melt was 200 ℃.
In step S2, the temperature of the temperature rise is 230 ℃.
Performance testing
The mechanical properties and flame retardant properties of the composite reinforced flame retardant nylon materials of examples 1 to 3 and comparative examples 1 and 2 were tested. The results are shown in Table 1.
TABLE 1
In table 1, the flame retardant test is based on the following criteria: UL94-5VA.
The tensile strength is based on the following criteria: ISO527.
The criteria for flexural strength are: ISO178.
The Izod impact strength is based on the following criteria: ISO180.
The odor class is based on the criteria: VDA270.
According to the embodiment and the comparative example, the composite reinforced flame-retardant nylon material for the new energy automobile is optimized according to the proportion of different components, so that the good balance between the flame-retardant property and the mechanical property of the composite material is ensured. The reasonable proportion of the high-flow nylon 6 matrix resin, the glass fiber reinforcing agent, the nylon-MXD 6 and the lamellar graphene nano sheet reinforcing agent can improve the strength and rigidity of the material, reduce the water absorption of the material, reduce the performance attenuation of the material and enhance the flame retardant property of the material. Wherein, the high-flow nylon 6 matrix resin can make the material show more luster and has good compatibility with nylon-MXD 6. The magnesium hydroxide and the red phosphorus flame retardant are used, the particle sizes of the magnesium hydroxide and the red phosphorus flame retardant are controlled in the nanoscale range, the nanoscale flame retardant can be more uniformly dispersed in the material, the flame retardant effect is improved, and meanwhile, the adverse effect on the mechanical property is reduced. The silane coupling agent is introduced, so that the interface interaction between different components is enhanced, and the interface bonding strength of the composite material is improved. Therefore, the performance loss caused by interfacial peeling of the materials can be effectively prevented, and the flame retardant property of the materials is increased. The molecular chain of the high-flow nylon 6 matrix resin is provided with a functional group containing nitrogen, so that the flame retardant property and the thermal stability of the composite reinforced flame retardant nylon material can be improved, and more environment-friendly and safer material selection is provided for the fields of new energy automobiles and the like. By carrying out organic modification on the lamellar graphene nano-sheet reinforcing agent, the surface of the multilayer graphene nano-sheet can become more lipophilic, and the compatibility with resin is enhanced, so that the composite material has better mechanical properties.
Finally, the composite reinforced flame-retardant nylon material for the new energy automobile is used for the new energy automobile, is suitable for the background condition that the current global automobile industry has increasingly-increased requirements on environmental protection performance, and can make positive contribution to sustainable development of the new energy automobile industry.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. The composite reinforced flame-retardant nylon material for the new energy automobile is characterized by comprising the following preparation raw materials:
high flow nylon 6 matrix resin: 100 parts of the total weight of the mixture,
glass fiber reinforcing agent: 20 to 40 parts of the components in parts by weight,
nylon-MXD 6:5 to 20 parts of the components,
lamellar graphene nanoplatelet enhancers: 5 to 15 parts of the components,
magnesium hydroxide flame retardant: 2 to 8 parts of the components,
red phosphorus flame retardant: 0.1 to 1.5 parts of a compound,
silane coupling agent: 0.1 to 1.0 part of the total weight of the composition,
the molecular chain of the high-flow nylon 6 matrix resin is provided with a functional group containing nitrogen,
the lamellar graphene nano-sheet reinforcing agent is a lamellar graphene nano-sheet reinforcing agent with the surface organically modified.
2. The composite reinforced flame retardant nylon material for new energy automobiles according to claim 1, wherein the length of the glass fiber reinforcement is 10-20mm.
3. The composite reinforced flame retardant nylon material for new energy automobiles according to claim 1, wherein the glass fiber reinforcement has a diameter of 10-20 μm.
4. The composite reinforced flame retardant nylon material for new energy automobiles according to claim 1, wherein the nylon-MXD 6 is poly m-xylylene adipamide.
5. The composite reinforced flame-retardant nylon material for the new energy automobile according to claim 1, wherein the thickness of the lamellar graphene nano sheet reinforcing agent is 0.5-5nm; and/or the surface area of the lamellar graphene nano-sheet reinforcing agent is 200-500m 2 /g。
6. The composite reinforced flame-retardant nylon material for new energy automobiles according to claim 1, wherein the magnesium hydroxide flame retardant is nano-sized particles with an average particle diameter of 50-100nm.
7. The composite reinforced flame-retardant nylon material for new energy automobiles according to claim 1, wherein the red phosphorus flame retardant is nano-sized particles with an average particle size of 10-30nm.
8. The composite reinforced flame-retardant nylon material for new energy automobiles according to claim 1, wherein the silane coupling agent is 3-aminopropyl trimethoxysilane.
9. A method for preparing the composite reinforced flame retardant nylon material for the new energy automobile according to any one of claims 1 to 8, which is characterized by comprising the following steps:
s1: mixing and melting the high-flow nylon 6 matrix resin, the glass fiber reinforcing agent and the nylon-MXD 6 according to the proportion;
s2: and (2) adding the lamellar graphene nano sheet reinforcing agent, the magnesium hydroxide flame retardant, the red phosphorus flame retardant and the silane coupling agent into the mixture obtained in the step (S1), heating, continuously mixing under a melting condition, cooling, and granulating to obtain the composite reinforced flame retardant nylon material for the new energy automobile.
10. The method according to claim 9, wherein in step S1, the temperature of the mixed melting is 180 ℃ to 230 ℃; and/or, in the step S2, the temperature of the heating is 180-230 ℃.
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