CN115785663A - Halogen-free flame-retardant nylon material for battery pack shell and preparation method thereof - Google Patents
Halogen-free flame-retardant nylon material for battery pack shell and preparation method thereof Download PDFInfo
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- 239000004677 Nylon Substances 0.000 title claims abstract description 66
- 229920001778 nylon Polymers 0.000 title claims abstract description 66
- 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 62
- 239000003063 flame retardant Substances 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920000388 Polyphosphate Polymers 0.000 claims abstract description 41
- 239000001205 polyphosphate Substances 0.000 claims abstract description 41
- 235000011176 polyphosphates Nutrition 0.000 claims abstract description 41
- 150000007974 melamines Chemical class 0.000 claims abstract description 36
- 239000003365 glass fiber Substances 0.000 claims abstract description 27
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims abstract description 22
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004970 Chain extender Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000012745 toughening agent Substances 0.000 claims abstract description 14
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical group O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 238000007605 air drying Methods 0.000 claims 1
- -1 alcohol stearates Chemical class 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- 239000011152 fibreglass Substances 0.000 claims 1
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 239000011257 shell material Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 9
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 9
- 229920002292 Nylon 6 Polymers 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000011208 reinforced composite material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 210000001320 hippocampus Anatomy 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a halogen-free flame-retardant nylon material for a battery pack shell and a preparation method thereof, wherein the halogen-free flame-retardant nylon material comprises the following raw materials in parts by weight: 40-67 parts of nylon, 20-30 parts of glass fiber, 5-10 parts of modified melamine polyphosphate, 4-10 parts of diethyl aluminum hypophosphite, 0.1-0.5 part of flame-retardant chain extender, 3-8 parts of toughening agent and 1-2 parts of other auxiliary agents; according to the invention, through surface coating modification of melamine polyphosphate, better dispersion and interface combination are realized in a nylon matrix, and the synergistic effect of the melamine polyphosphate, the aluminum diethylhypophosphite and the flame-retardant chain extender can improve the density and strength of a carbon layer formed in the combustion process of the material, so that the flame retardant property and the mechanics of the nylon composite material are obviously improved by using a smaller addition amount.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an environment-friendly halogen-free flame-retardant nylon material for a battery pack shell and a preparation method thereof.
Background
The new energy automobile is used as a new generation of transportation tool for automobile industry development, has great advantages in the aspects of energy conservation, emission reduction and reduction of dependence on traditional petroleum resources, and the battery pack is a bearing body of the battery module in the new energy automobile and plays a key role in safety protection of the battery module. The traditional battery pack shell for the vehicle is cast by materials such as steel plates and aluminum alloys, the mass is heavier, and along with the development of light weight of an automobile section, the battery pack shell material is made of various light-weight materials such as glass fiber reinforced composite materials, SMC sheet materials and carbon fiber reinforced composite materials. The glass fiber reinforced nylon is one of the most applied engineering plastics at present, and has higher mechanical property and heat distortion temperature. But the glass fiber wick effect makes the material easier to burn, and the flame retardant property can not meet the requirement of new energy vehicles, thereby limiting the wider application of the material. Therefore, further research on enhancing the flame retardant performance of nylon materials to make the nylon materials have more excellent safety and environmental protection indexes is a hot spot which is widely concerned by researchers in recent years.
The halogen-free flame-retardant system material has the advantages of less harmful substances generated in the combustion process, low smoke generation amount and the like, and is one of important directions for the development of flame-retardant polyamide in recent years. CN112409785B uses MCA as flame retardant, nano-silica as synergistic combustion improver, exerts the nano-effect of nano-silica, and acts together with MCA flame retardant to accelerate the carbonization speed of nylon, thus preparing the halogen-free flame retardant nylon material. In patent CN113248912B, the flame retardant effect of the nylon material can be effectively improved by preparing the microcapsule-coated red phosphorus master batch flame retardant and the coordination effect of hydrotalcite and zinc oxide. However, MCA melamine salt is mainly suitable for flame retardation of PA6 (nylon 6) and PA66 (nylon 66) without filler, and always generates a phenomenon of precipitation in a heating process. The compatibility problem of the red phosphorus master batch flame retardant and nylon resin easily causes the reduction of the mechanical property of the nylon material.
Disclosure of Invention
The invention aims to provide a halogen-free flame-retardant nylon material for a battery pack shell and a preparation method thereof, and the halogen-free flame-retardant nylon material has the characteristics of good flame-retardant effect, good high temperature resistance, good mechanical properties, high impact strength and the like.
The invention adopts the following technical scheme that:
the invention relates to a halogen-free flame-retardant nylon material for a battery pack shell, which is characterized by comprising the following raw materials in parts by weight: 40-67 parts of nylon, 20-30 parts of glass fiber, 5-10 parts of modified melamine polyphosphate, 4-10 parts of diethyl aluminum hypophosphite, 0.1-0.5 part of flame-retardant chain extender, 3-8 parts of toughening agent and 1-2 parts of other auxiliary agents;
the nylon is PA6, PA66 or a mixture thereof, the relative viscosity is 2.5-2.9, and the preferred relative viscosity is 2.7;
the modified melamine polyphosphate is SiO through a sol-gel method 2 The melamine polyphosphate is prepared by surface coating;
the glass fiber is untwisted chopped glass fiber, the diameter of a single filament is 10-15um, and the length of the single filament is 3-4.5mm;
the average particle size (D50) of the diethyl aluminum hypophosphite is 10-20um.
The flame-retardant chain extender is triglycidyl isocyanurate.
The toughening agent is maleic anhydride grafted POE (POE-g-MAH), and the grafting rate is 1-2%;
the processing aid includes but is not limited to one or two of an antioxidant and a lubricant.
The preparation method of the halogen-free flame-retardant nylon material for the battery pack shell comprises the following steps: adding the nylon resin, the modified melamine polyphosphate, the diethyl aluminum hypophosphite, the flame-retardant chain extender, the toughening agent and other auxiliaries into a high-speed mixer, and mixing for 15-20min to obtain a mixed raw material; and adding the mixed raw materials into a main feeding port of a co-rotating double-screw extruder for feeding, feeding the chopped glass fibers from a side feeding port, extruding after melt blending, cooling, and pelletizing to obtain the halogen-free flame-retardant nylon material for the battery pack shell.
Compared with the prior art, the invention has the advantages that:
the invention uses a sol-gel method to prepare SiO 2 The modified melamine polyphosphate MPP obviously improves the surface performance, realizes good interface bonding property and dispersibility of mMPP particles in a nylon matrix, has high thermal decomposition temperature and long decomposition time, and is beneficial to the exertion of the flame retardant effect of the MPP in a PA6 matrix and the improvement of the mechanical performance of a PA6 composite material. Under the condition of compounding diethyl aluminum hypophosphite, the flame retardant grade of the material reaches UL 94V-0 by using a small addition amount, and the mechanical property is obviously improved. Triglycidyl isocyanurate TGIC has reactive epoxy groups, can perform high-density crosslinking with terminal carboxyl groups and amino groups of a PA6 material, so that nylon forms more compact carbon after combustion, the content of flame-retardant elements in a carbon layer is increased, a flame-retardant effect is exerted in a gas phase and a condensed phase, and the flame-retardant effect is enhanced.
Detailed Description
The following are commercially available or commercially available materials specifically used in the examples and comparative examples of the present invention, but are not limited to the following: nylon 66EPR27: hippocampus engineering plastics, inc., relative viscosity of 2.7; glass fiber ESC10-03-568H/A: china giant Stone Ltd, diameter 10um, length 3mm; melamine polyphosphate EPFR-MPP300 with an average particle size (D50) of 5um for Pusofufur Chemicals, inc.; diethyl aluminum hypophosphite ADP, suzhou diandrogenic refinement Industrial science, inc., with an average particle size (D50) of 10-20um; triglycidyl isocyanurate, suzhou sailing Biotech Ltd, molecular weight 297.264; POE-g-MAH: N413A, ningbo energy optical new materials science and technology Limited, functional group content 0.4-0.8 wt%; the auxiliary agents are antioxidant 1098 German Basff, antioxidant 168 Beijing extremely easy chemical industry Co., ltd and lubricant EBS Japan flower king.
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting.
Example 1
A halogen-free flame-retardant nylon material for a battery pack shell comprises the following raw materials in parts by weight: 67 parts of nylon, 20 parts of glass fiber, 5 parts of modified melamine polyphosphate, 4 parts of diethyl aluminum hypophosphite, 0.1 part of flame-retardant chain extender, 3 parts of flexibilizer, 0.3 part of antioxidant 1098, 0.2 part of antioxidant 168 and 0.5 part of EBS;
the preparation method of the modified melamine polyphosphate comprises the following steps: adding 200ml of ethyl orthosilicate and 300ml of ethanol, mechanically stirring for 10min, slowly adding 200g of MPP, adding 0.2g of glacial acetic acid as a catalyst, mechanically stirring for 1h, washing, filtering, drying and crushing to obtain modified melamine polyphosphate mMPP powder.
The preparation method comprises the following steps:
adding nylon resin, modified melamine polyphosphate, diethyl aluminum hypophosphite, a flame-retardant chain extender, a toughening agent and other auxiliaries into a high-speed mixer, and uniformly mixing for 15min to obtain a mixture; and adding the mixture into a main feeding port of a co-rotating double-screw extruder for feeding, feeding the glass fiber from a side feeding port, controlling the rotating speed of a screw at 240-265 ℃, melting, blending, extruding, cooling and granulating to obtain the halogen flame-retardant nylon material.
Example 2
A halogen-free flame-retardant nylon material for a battery pack shell comprises the following raw materials in parts by weight: 62 parts of nylon, 20 parts of glass fiber, 8 parts of modified melamine polyphosphate, 4 parts of diethyl aluminum hypophosphite, 0.2 part of flame-retardant chain extender, 5 parts of flexibilizer, 0.3 part of antioxidant 1098, 0.2 part of antioxidant 168 and 0.5 part of EBS;
the preparation method of the modified melamine polyphosphate comprises the following steps: adding 200ml of ethyl orthosilicate and 300ml of ethanol, mechanically stirring for 10min, slowly adding 200g of MPP, adding 0.2g of glacial acetic acid as a catalyst, mechanically stirring for 1h, washing, filtering, drying and crushing to obtain modified melamine polyphosphate mMPP powder.
The preparation method comprises the following steps:
adding nylon resin, modified melamine polyphosphate, diethyl aluminum hypophosphite, a flame-retardant chain extender, a toughening agent and other auxiliaries into a high-speed mixer, and uniformly mixing for 15min to obtain a mixture; and adding the mixture into a main feeding port of a co-rotating double-screw extruder for feeding, feeding the glass fiber from a side feeding port, controlling the rotating speed of a screw at 240-265 ℃, melting, blending, extruding, cooling and granulating to obtain the halogen flame-retardant nylon material.
Example 3
A halogen-free flame-retardant nylon material for a battery pack shell comprises the following raw materials in parts by weight: 62 parts of nylon, 20 parts of glass fiber, 8 parts of modified melamine polyphosphate, 4 parts of diethyl aluminum hypophosphite, 0.2 part of flame-retardant chain extender, 5 parts of flexibilizer, 0.3 part of antioxidant 1098, 0.2 part of antioxidant 168 and 0.5 part of EBS;
the preparation method of the modified melamine polyphosphate comprises the following steps: adding 200ml of tetraethoxysilane and 500ml of ethanol, mechanically stirring for 10min, slowly adding 300g of MPP, adding 0.15g of glacial acetic acid as a catalyst, mechanically stirring for 1h, washing, filtering, drying and crushing to obtain modified melamine polyphosphate mMPP powder.
The preparation method comprises the following steps:
adding nylon resin, modified melamine polyphosphate, diethyl aluminum hypophosphite, a flame-retardant chain extender, a toughening agent and other auxiliaries into a high-speed mixer, and uniformly mixing for 15min to obtain a mixture; and adding the mixture into a main feeding port of a co-rotating double-screw extruder for feeding, feeding the glass fiber from a side feeding port, controlling the rotating speed of a screw at 240-265 ℃, melting, blending, extruding, cooling and granulating to obtain the halogen flame-retardant nylon material.
Example 4
A halogen-free flame-retardant nylon material for a battery pack shell comprises the following raw materials in parts by weight: 62 parts of nylon, 20 parts of glass fiber, 8 parts of modified melamine polyphosphate, 4 parts of diethyl aluminum hypophosphite, 0.3 part of flame-retardant chain extender, 6 parts of flexibilizer, 0.3 part of antioxidant 1098, 0.2 part of antioxidant 168 and 0.5 part of EBS;
the preparation method of the modified melamine polyphosphate comprises the following steps: adding 200ml of ethyl orthosilicate and 300ml of ethanol, mechanically stirring for 10min, slowly adding 200g of MPP, adding 0.2g of glacial acetic acid as a catalyst, mechanically stirring for 1h, washing, filtering, drying and crushing to obtain modified melamine polyphosphate mMPP powder.
The preparation method comprises the following steps:
adding nylon resin, modified melamine polyphosphate, diethyl aluminum hypophosphite, a flame-retardant chain extender, a toughening agent and other auxiliaries into a high-speed mixer, and uniformly mixing for 15min to obtain a mixture; and adding the mixture into a main feeding port of a co-rotating double-screw extruder for feeding, feeding the glass fiber from a side feeding port, controlling the rotating speed of a screw at 240-265 ℃, melting, blending, extruding, cooling and granulating to obtain the halogen flame-retardant nylon material.
Example 5
A halogen-free flame-retardant nylon material for a battery pack shell comprises the following raw materials in parts by weight: 40 parts of nylon, 30 parts of glass fiber, 10 parts of modified melamine polyphosphate, 10 parts of diethyl aluminum hypophosphite, 0.5 part of flame-retardant chain extender, 8 parts of flexibilizer, 0.6 part of antioxidant 1098, 0.4 part of antioxidant 168 and 1 part of EBS;
the preparation method of the modified melamine polyphosphate comprises the following steps: adding 200ml of ethyl orthosilicate and 300ml of ethanol, mechanically stirring for 10min, slowly adding 200g of MPP, adding 0.2g of glacial acetic acid as a catalyst, mechanically stirring for 1h, washing, filtering, drying and crushing to obtain modified melamine polyphosphate mMPP powder.
The preparation method comprises the following steps:
adding nylon resin, modified melamine polyphosphate, diethyl aluminum hypophosphite, a flame-retardant chain extender, a toughening agent and other auxiliaries into a high-speed mixer, and uniformly mixing for 15min to obtain a mixture; and adding the mixture into a main feeding port of a co-rotating double-screw extruder for feeding, feeding the glass fiber from a side feeding port, controlling the rotating speed of a screw at 240-265 ℃, melting, blending, extruding, cooling and granulating to obtain the halogen flame-retardant nylon material.
Comparative example 1
Comparative example 1 is a comparative example of example 2, comprising the following raw materials in parts by weight: 62 parts of nylon, 20 parts of glass fiber, 8 parts of unmodified melamine polyphosphate, 4 parts of diethyl aluminum hypophosphite, 0.2 part of flame-retardant chain extender, 5 parts of flexibilizer, 0.3 part of antioxidant 1098, 0.2 part of antioxidant 168 and 0.5 part of EBS; the specific preparation method is the same as that of example 1.
Comparative example 2
Comparative example 2 is a comparative example of example 2, comprising the following raw materials in parts by weight: 62 parts of nylon, 20 parts of glass fiber, 8 parts of modified melamine polyphosphate, 0.2 part of flame-retardant chain extender, 5 parts of flexibilizer, 0.3 part of antioxidant 1098, 0.2 part of antioxidant 168 and 0.5 part of EBS; the specific preparation method is the same as that of example 2.
Comparative example 3
Comparative example 3 is a comparative example to example 4, comprising the following raw materials in parts by weight: 62 parts of nylon, 20 parts of glass fiber, 8 parts of modified melamine polyphosphate, 4 parts of diethyl aluminum hypophosphite, 6 parts of toughening agent, 0.3 part of antioxidant 1098, 0.2 part of antioxidant 168 and 0.5 part of EBS; the specific preparation method is the same as example 4.
Comparative example 4
Comparative example 4 is a comparative example to example 5, comprising the following raw materials in parts by weight: 40 parts of nylon, 30 parts of glass fiber, 10 parts of modified melamine polyphosphate, 8 parts of toughening agent, 10980.6 parts of antioxidant, 168.4 parts of antioxidant and 1 part of EBS; the specific preparation method is the same as example 5.
The halogen-free flame retardant nylon materials for battery pack cases prepared in the above examples 1 to 5 and comparative examples 1 to 4 were dried in a forced air oven at 100 to 110 ℃ for 6 to 8 hours, and then the dried particles were injection molded on an injection molding machine to prepare a sample. The tensile strength, flexural modulus, notched impact strength and flame retardant property were measured according to ISO standard, and the results are shown in Table 1.
TABLE 1 test results of examples 1 to 5 and comparative examples 1 to 4
As can be seen from Table 1, compared with comparative example 1, examples 2-3 show that the flame retardant property and the mechanical property of the nylon material are both obviously improved after the melamine polyphosphate is modified, and the modification effect of example 2 is better. Compared with the comparative example 2, the example 2 has the synergistic flame retardant effect by compounding the diethyl aluminum hypophosphite and the modified melamine polyphosphate. Compared with comparative examples 3-4, examples 4-5 show that the flame retardant chain extender improves the flame retardant effect and the mechanical property.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The halogen-free flame-retardant nylon material for the battery pack shell and the preparation method thereof are characterized by comprising the following raw materials in parts by weight: 40-67 parts of nylon, 20-30 parts of glass fiber, 5-10 parts of modified melamine polyphosphate, 4-10 parts of diethyl aluminum hypophosphite, 0.1-0.5 part of flame-retardant chain extender, 3-8 parts of toughening agent and 1-2 parts of other auxiliary agents;
the nylon is PA6, PA66 or a mixture thereof, and the relative viscosity is 2.5-2.9;
the modified melamine polyphosphate is SiO through a sol-gel method 2 The melamine polyphosphate is prepared by surface coating.
2. The halogen-free flame retardant nylon material for battery pack case according to claim 1, wherein the glass fiber is untwisted chopped glass fiber, and the monofilament diameter is 10-15um.
3. The halogen-free flame retardant nylon material for battery pack cases according to claim 1, wherein the preparation method of the modified melamine polyphosphate comprises the following steps: adding ethyl orthosilicate and a proper amount of ethanol according to a certain proportion, heating to 100 ℃, slowly adding MPP, adding glacial acetic acid as a catalyst, and washing, filtering, drying and crushing to obtain mMPP powder.
4. The halogen-free flame retardant nylon material for battery pack case according to claim 1, wherein the diethyl aluminum hypophosphite has an average particle size (D50) of 10-20um.
5. The halogen-free flame retardant nylon material for battery pack case according to claim 1, wherein the flame retardant chain extender is triglycidyl isocyanurate.
6. The halogen-free flame retardant nylon material for battery pack case as claimed in claim 1, wherein the toughening agent is at least one of POE-g-MAH, SEBS-g-MAH, PE-g-MAH.
7. The halogen-free flame retardant nylon material for battery pack cases according to claim 1, wherein the other auxiliary agents comprise antioxidants and/or lubricants.
8. The halogen-free flame retardant nylon material for battery pack case according to claim 7, wherein the antioxidant is at least one of hindered phenols, amines, and phosphates; the lubricant is at least one of stearamides, alcohol stearates, stearates and long-chain saturated linear carboxylates.
9. The preparation method of the halogen-free flame retardant nylon material for the battery pack case according to any one of claims 1 to 8, characterized by comprising the steps of:
1) Adding ethyl orthosilicate and a proper amount of ethanol according to a certain proportion, heating to 100 ℃, slowly adding MPP, adding glacial acetic acid as a catalyst, and washing, filtering, drying and crushing to obtain modified melamine polyphosphate mMPP;
2) Adding the nylon resin, the modified melamine polyphosphate obtained in the step 1, diethyl aluminum hypophosphite, a flame-retardant chain extender, a toughening agent and other auxiliaries into a high-speed mixer, mixing for 15-20min, and uniformly mixing to obtain a mixed raw material;
3) And (3) adding the mixed raw materials obtained in the step (2) into a co-rotating double-screw extruder for extrusion granulation, adopting a melt blending extrusion process, adding the mixed raw materials from a main feeding port, adding glass fibers into a side feeding port, and after melt blending, cooling, air drying and granulating to obtain the glass fiber reinforced plastic composite material.
10. The preparation method of the halogen-free flame retardant nylon material for battery pack case according to claim 8, wherein the temperature of each zone of the twin-screw extruder is as follows: the temperature of a first area is 150-230 ℃, the temperature of a second area is 180-265 ℃, the temperature of a third area is 190-275 ℃, the temperature of a fourth area is 200-280 ℃, the temperature of a fifth area is 200-280 ℃, the temperature of a sixth area is 200-280 ℃, and the temperature of a machine head is 200-280 ℃; the vacuum is turned on at a speed of 250-350 rpm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060226404A1 (en) * | 2005-04-08 | 2006-10-12 | Clariant Produkte (Deutschland) Gmbh | Stabilized flame retardant |
| CN110776733A (en) * | 2019-10-16 | 2020-02-11 | 广东省石油与精细化工研究院 | In-situ reaction compatibilization halogen-free flame-retardant nylon 6 and preparation method thereof |
| CN112646366A (en) * | 2020-12-22 | 2021-04-13 | 江苏集萃先进高分子材料研究所有限公司 | Halogen-free environment-friendly flame-retardant master batch of long glass fiber reinforced nylon composite material and preparation method thereof |
| CN114874612A (en) * | 2022-06-23 | 2022-08-09 | 青岛科技大学 | Flame-retardant polyamide foam and preparation process thereof |
| CN114921043A (en) * | 2022-05-11 | 2022-08-19 | 林淑红 | High-flame-retardancy resin film and preparation method thereof |
-
2022
- 2022-12-23 CN CN202211663185.5A patent/CN115785663A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060226404A1 (en) * | 2005-04-08 | 2006-10-12 | Clariant Produkte (Deutschland) Gmbh | Stabilized flame retardant |
| CN110776733A (en) * | 2019-10-16 | 2020-02-11 | 广东省石油与精细化工研究院 | In-situ reaction compatibilization halogen-free flame-retardant nylon 6 and preparation method thereof |
| CN112646366A (en) * | 2020-12-22 | 2021-04-13 | 江苏集萃先进高分子材料研究所有限公司 | Halogen-free environment-friendly flame-retardant master batch of long glass fiber reinforced nylon composite material and preparation method thereof |
| CN114921043A (en) * | 2022-05-11 | 2022-08-19 | 林淑红 | High-flame-retardancy resin film and preparation method thereof |
| CN114874612A (en) * | 2022-06-23 | 2022-08-09 | 青岛科技大学 | Flame-retardant polyamide foam and preparation process thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘策 等: "阻燃玻纤增强尼龙 6 复合材料的制备及性能研究", 《矿冶工程》, vol. 37, no. 4, pages 124 - 131 * |
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