CN111138851A - Flame-retardant reinforced micro-foaming nylon material and preparation method thereof - Google Patents

Flame-retardant reinforced micro-foaming nylon material and preparation method thereof Download PDF

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CN111138851A
CN111138851A CN201911306702.1A CN201911306702A CN111138851A CN 111138851 A CN111138851 A CN 111138851A CN 201911306702 A CN201911306702 A CN 201911306702A CN 111138851 A CN111138851 A CN 111138851A
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parts
flame retardant
nylon material
foaming
flame
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CN111138851B (en
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王滨
刘曙阳
陆体超
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Anhui Juxinglong New Material Technology Co ltd
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Nanjing Julong Engineering Plastics Co ltd
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Abstract

The invention relates to a micro-foaming nylon material and a preparation method thereof, in particular to a flame-retardant reinforced micro-foaming nylon material and a preparation method thereof. The material comprises the following components in parts by weight: 40-65 parts of nylon, 30-45 parts of glass fiber, 7-30 parts of flame retardant, 1-10 parts of smoke suppressant, 0.2-5 parts of hydrolysis resistant agent, 0.5-5 parts of foaming agent, 1-10 parts of foaming auxiliary agent, 0.2-1 part of lubricant and 0.2-1 part of stabilizer. The micro-foaming nylon material has the characteristics of flame retardant grade reaching UL 941.6mm V0 grade, excellent mechanical property, high cell density and good apparent quality, and products such as new energy automobile battery shells and the like prepared by the micro-foaming nylon material have the characteristics of high rigidity, drop resistance, high thin-wall forming efficiency, high heat resistance, good dimensional stability, high yield and the like.

Description

Flame-retardant reinforced micro-foaming nylon material and preparation method thereof
Technical Field
The invention relates to a micro-foaming nylon material and a preparation method thereof, in particular to a flame-retardant reinforced micro-foaming nylon material and a preparation method thereof, belonging to the technical field of materials.
Background
Because the unit specific energy of the currently available power battery is greatly different from the unit specific energy of the traditional automobile using liquid fuel, a power system (mainly a battery) usually accounts for 30-40% of the total mass of the whole automobile. This means that the electric vehicle cannot travel long distances by once supplementing energy as the conventional vehicle, at a unit energy consumption (electricity consumption/50 km) equivalent to the conventional vehicle emission. Therefore, the new energy vehicle is more urgent for light weight than the conventional vehicle. The new energy automobile battery shell has the problems of huge volume, warp deformation in the forming process, low assembly performance qualification rate, poor drop resistance and bundling resistance, unstable flame retardant property and the like.
The specific internal microporous structure of the microporous foaming technology can counteract internal stress, not only can reduce the weight of automobile parts by 15-50%, but also can improve the apparent mass of products, and in addition, the microporous foaming technology also has the advantages of higher rigidity, buffer property, heat insulation, sound insulation performance and the like. However, when a nylon material of a large part such as a battery case of a new energy automobile is subjected to micro-foaming, most foaming agents are decomposed at high temperature and high pressure in the material production or forming process to generate water, ammonia, CO2 and other small molecules, nylon degradation is caused, even the performance of the product such as drop resistance is reduced, and the development and application of the reinforced flame-retardant micro-foaming nylon material are limited.
Disclosure of Invention
In order to solve the problems, the invention provides a micro-foaming nylon material, the flame retardant grade of the material reaches UL 941.6mm V0 grade, the mechanical property is excellent, the cell density is high, the apparent quality is good, and products such as new energy automobile battery shells and the like prepared by the material have the characteristics of high rigidity, drop resistance, high thin-wall forming efficiency, high heat resistance, good dimensional stability, high yield and the like; under the condition that the whole product is lightened, the product can pass a product binding force deformation test; moreover, the product also has good long-term thermal aging performance, and meets the long-term thermal oxidation aging use requirement of a host factory at 150 ℃ for 1000 h; in addition, the product process is easy for industrial production.
In order to solve the technical problems, the invention adopts the following technical scheme:
the flame-retardant reinforced micro-foaming nylon material comprises the following components in parts by weight:
40-65 parts of nylon
10-20 parts of polyphenylene sulfide
30-45 parts of glass fiber
7-30 parts of flame retardant
1-10 parts of smoke suppressant
0.2-5 parts of hydrolysis resistant agent
0.5-5 parts of foaming agent
1-10 parts of foaming auxiliary agent
0.2 to 1 portion of lubricant
0.2 to 1 portion of stabilizer
According to a further technical scheme, the nylon material is a blend of nylon 66 and nylon 12, and the mass ratio of the nylon material to the nylon 12 is 3: 1. the polyphenylene sulfide is polyphenylene sulfide with molecular weight of 15000-20000, and is preferably polyphenylene sulfide with molecular weight of 20000.
Further technical scheme, the glass fiber is alkali-free glass fiber, the diameter is 6-20um, 6-10um hydrolysis-resistant glass fiber, and 10um hydrolysis-resistant glass fiber is preferred.
According to a further technical scheme, the flame retardant is one or two of silicon flame retardant, nitrogen flame retardant, phosphorus flame retardant, inorganic mineral flame retardant and boron flame retardant, preferably, the silicon flame retardant and the boron flame retardant are compounded, and the preferable mass ratio is 2: 1 brominated polystyrene grafted polydimethylsiloxane and zinc borate complex.
The smoke suppressant is one or two of magnesium oxide, aluminum oxide, zinc oxide, ferric oxide, dibasic lead phosphite, tribasic lead sulfate and montmorillonite, preferably a compound of ferric oxide and tribasic lead sulfate.
In a further technical scheme, the hydrolysis resistant agent is one or two of calcium chloride, anhydrous copper sulfate, cellulose, chitosan and polyacrylic acid polyvalent metal salt, and calcium chloride is preferably selected.
According to a further technical scheme, the foaming agent is one of carbonate, azo compounds, hydrazide compounds and nitroso compounds, preferably hydrazide compounds, such as BSH, OBSH, BDSH and the like;
the foaming auxiliary agent is one of superfine ferrocene, superfine barium sulfate, superfine zinc sulfide, nano attapulgite and nano kaolin, and superfine zinc sulfide is preferably selected.
According to a further technical scheme, the stabilizer is one or two of 1098, 168, H10 and H318, preferably H10;
the lubricant is one of EBS, erucamide, stearic acid, oxidized PE wax and ethylene bis fatty acid amide, preferably ethylene bis fatty acid amide (TAF).
A preparation method of a flame-retardant reinforced micro-foaming nylon material comprises the following steps:
(1) 40-65 parts of nylon, 10-20 parts of polyphenylene sulfide, 7-30 parts of flame retardant, 1-10 parts of smoke suppressant, 0.2-5 parts of hydrolysis resistant agent, 1-10 parts of foaming auxiliary agent, 0.2-1 part of lubricant and 0.2-1 part of stabilizer are mixed according to parts by weight to prepare a mixture, the mixture is put into a high-speed mixer to be mixed for 1-3min, the mixture is added into a double-screw extruder through a hopper, 30-45 parts of glass fiber is added through a side feeding port, and the mixture is subjected to extrusion, bracing, traction and granulation at the temperature of 380 ℃ of 220-;
(2) and mixing the premixed composite master batch and a foaming agent in a mixer according to a certain weight part, and performing injection molding to obtain the flame-retardant reinforced micro-foamed nylon material or product.
Advantageous effects
Compared with the prior art, the invention has the following remarkable advantages:
1. according to the invention, by selecting the foaming agent with low decomposed water content and the hydrolysis resistant agent for compounding, small molecular substances such as water and ammonia generated by decomposition of the foaming agent and easy to degrade a nylon matrix are eliminated, and a modified nylon system is scientifically designed, so that decomposition and degradation of the nylon matrix in a flame-retardant reinforced nylon micro-foaming process are systematically solved, the realization of product performance is ensured, meanwhile, the reinforced flame-retardant nylon micro-foaming material reaches the V0 grade of more than UL941.6 mm, the glow wire ignition temperature exceeds 750 ℃, and the flame-retardant performance requirements of new energy automobile battery shells/frames and the like are met. On the other hand, the long carbon chain nylon and the polyphenylene sulfide with proper molecular weight are adopted, the processing formability is ensured, meanwhile, the product has excellent toughness and heat resistance, and the anti-falling performance of the product is further improved due to the existence of micropores.
2. The battery case/frame product of the micro-foaming new energy automobile prepared by the invention also has the characteristics of low warpage, easy thin-wall forming, high rigidity, good dimensional stability and the like, and the product completely passes tests such as binding force and the like, so that the qualification rate is high; the whole weight of the actual product is reduced by more than 18 percent; moreover, the product also has good long-term thermal aging performance, and meets the long-term thermal oxidation aging use requirement of a host factory at 150 ℃ for 1000 h.
3. The preparation method of the material provided by the invention has the advantages of controllable process, low production cost, high efficiency and easiness in realization of industrialization.
Detailed Description
The present invention will be described in further detail with reference to examples.
Examples
A preparation method of a flame-retardant reinforced micro-foaming nylon material comprises the following steps:
(1) 40-65 parts of nylon, 10-20 parts of polyphenylene sulfide, 7-30 parts of flame retardant, 1-10 parts of smoke suppressant, 0.2-5 parts of hydrolysis resistant agent, 1-10 parts of foaming auxiliary agent, 0.2-1 part of lubricant and 0.2-1 part of stabilizer are mixed according to parts by weight to prepare a mixture, the mixture is put into a high-speed mixer to be mixed for 1-3min, the mixture is added into a double-screw extruder through a hopper, 30-45 parts of glass fiber is added through a side feeding port, and the mixture is subjected to extrusion, bracing, traction and granulation at the temperature of 380 ℃ of 220-;
(2) and mixing the premixed composite master batch and a foaming agent in a mixer according to a certain weight part, and performing injection molding to obtain the flame-retardant reinforced micro-foamed nylon material or product.
The nylon material is a blend of nylon 66 and nylon 12, and the mass ratio of the nylon material to the nylon 12 is 3: 1. the polyphenylene sulfide is polyphenylene sulfide with molecular weight of 15000-20000, and is preferably polyphenylene sulfide with molecular weight of 20000.
The glass fiber is alkali-free glass fiber, and has a diameter of 6-20um, 6-10um hydrolysis-resistant glass fiber, preferably 10um hydrolysis-resistant glass fiber.
The flame retardant is one or two of silicon flame retardant, nitrogen flame retardant, phosphorus flame retardant, inorganic mineral flame retardant and boron flame retardant, preferably, the silicon flame retardant and the boron flame retardant are compounded, and the preferable mass ratio is 2: 1 brominated polystyrene grafted polydimethylsiloxane and zinc borate complex.
The smoke suppressant is one or two of magnesium oxide, aluminum oxide, zinc oxide, ferric oxide, dibasic lead phosphite, tribasic lead sulfate and montmorillonite, preferably a compound of ferric oxide and tribasic lead sulfate.
The hydrolysis resisting agent is one or two of calcium chloride, anhydrous copper sulfate, cellulose, chitosan and polyacrylic acid polyvalent metal salt, preferably calcium chloride.
The foaming agent is one of carbonate, azo compounds, hydrazide compounds and nitroso compounds, preferably hydrazide compounds, such as BSH, OBSH, BDSH and the like;
the foaming auxiliary agent is one of superfine ferrocene, superfine barium sulfate, superfine zinc sulfide, nano attapulgite and nano kaolin, and superfine zinc sulfide is preferably selected.
The stabilizer is one or two of 1098, 168, H10 and H318, preferably H10;
the lubricant is one of EBS, erucamide, stearic acid, oxidized PE wax and ethylene bis fatty acid amide, preferably ethylene bis fatty acid amide (TAF).
According to the method, 4 flame-retardant reinforced micro-foaming nylon materials and comparative examples are prepared by adjusting the specific components and parts, and the specific formula is shown in the following table 1.
Table 1 comparative and 4 example formulations
Comparative example 1 Example 1 Example 2 Example 3 Example 4
Nylon 66 40 45 65 40 40
Nylon 12 15 5
Polyphenylene sulfide 10 15 12 20
Brominated polystyrene grafted polydimethylsiloxane 12
Zinc borate 6 10
Red phosphorus 7
Melamine pyrophosphate 30 30 18
Glass fiber 30 30 35 40 45
Alumina oxide 5
Tribasic lead sulfate 2
Ferric oxide 2 10
Zinc oxide 1
Calcium chloride 2
Anhydrous cupric sulfate 5
Cellulose, process for producing the same, and process for producing the same 3
Chitosan 0.2
Azobisisobutyronitrile 0.5
OBSH 2 3
Aluminum carbonate 5
Superfine ferrocene 10
Superfine zinc sulfide 1 5
Nano concave-convex rod 4
1098 0.5 0.8
H10 0.3 0.2 1
Oxidized PE wax 0.2 1
TAF 0.5 0.5 0.6
The performance results of the above comparative and example examples are shown in the following table
Performance tables of comparative examples and examples of the products of the invention
Detecting items Standard of merit Comparative example 1 Example 1 Example 2 Example 3 Example 4
Density/g/cm3 ISO 1183 1.42 1.10 1.12 1.15 1.20
Tensile strength/MPa ISO 527 138 145 138 142 150
Flexural modulus/MPa ISO 178 6800 8950 8620 8310 7850
Notched Izod impact Strength/kJ/m2（23℃） ISO 179 8.9 11.6 12.3 13.7 14.8
Heat distortion temperature/. degree.C ISO 75 240 255 262 259 266
Flame retardant rating UL94 1.6mm V0/Large Smoke formation V0/less fuming V0/less fuming V0/less fuming V0/less fuming
Shrinkage ratio/% JL method 0.59 0.32 0.36 0.33 0.23
From the above results, it can be seen that, compared with comparative example 1, example 2, example 3, example 4, the weight is reduced by at least 15% or more, and the product weight reduction effect is obvious; and all reach V0 grade of more than UL941.6mm; after micro-foaming, the material strength meets the use requirement, the shrinkage rate is reduced to be within 0.4% from 0.59%, the dimensional stability is obviously improved, and the requirement of a host factory on the performance of the new energy automobile battery shell/frame material is met.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any equivalent changes or modifications made by those skilled in the art according to the spirit of the present invention should be covered within the scope of the present invention.

Claims (10)

1. The flame-retardant reinforced micro-foaming nylon material is characterized by comprising the following components in parts by weight:
40-65 parts of nylon
10-20 parts of polyphenylene sulfide
30-45 parts of glass fiber
7-30 parts of flame retardant
1-10 parts of smoke suppressant
0.2-5 parts of hydrolysis resistant agent
0.5-5 parts of foaming agent
1-10 parts of foaming auxiliary agent
0.2 to 1 portion of lubricant
0.2-1 part of stabilizer.
2. The flame retardant reinforced microcellular foamed nylon material according to claim 1, wherein: the nylon material is prepared from the following raw materials in a mass ratio of 3: nylon 66 of 1 and nylon 12 blend.
3. The flame retardant reinforced microcellular foamed nylon material according to claim 1, wherein: the polyphenylene sulfide is polyphenylene sulfide with the molecular weight of 15000-20000;
the glass fiber is alkali-free glass fiber with the diameter of 6-20 um;
the flame retardant is one or two of silicon flame retardant, nitrogen flame retardant, phosphorus flame retardant, inorganic mineral flame retardant and boron flame retardant.
4. The flame retardant reinforced microcellular foamed nylon material according to claim 3, wherein:
the polyphenylene sulfide is polyphenylene sulfide with molecular weight of 20000;
the glass fiber is 6-10um hydrolysis-resistant glass fiber;
the flame retardant is a compound of a silicon flame retardant and a boron flame retardant.
5. The flame retardant reinforced microcellular foamed nylon material according to claim 4, wherein: the glass fiber is 10um hydrolysis-resistant glass fiber;
the flame retardant is prepared from the following components in percentage by mass: 1 brominated polystyrene grafted polydimethylsiloxane and zinc borate complex.
6. The flame retardant reinforced microcellular foamed nylon material according to claim 1, wherein: the smoke suppressant is one or two of magnesium oxide, aluminum oxide, zinc oxide, ferric oxide, dibasic lead phosphite, tribasic lead sulfate and montmorillonite;
the hydrolysis resistant agent is one or two of calcium chloride, anhydrous copper sulfate, cellulose, chitosan and polyacrylic acid polyvalent metal salt;
the foaming agent is one of carbonate, azo compounds, hydrazide compounds and nitroso compounds;
the foaming auxiliary agent is one of superfine ferrocene, superfine barium sulfate, superfine zinc sulfide, nano attapulgite and nano kaolin.
7. The flame retardant reinforced microcellular foamed nylon material according to claim 6, wherein: the smoke suppressant is a compound of ferric oxide and tribasic lead sulfate;
the hydrolysis-resistant agent is calcium chloride;
the foaming agent is a hydrazide compound, and the hydrazide compound is one of BSH, OBSH and BDSH;
the foaming auxiliary agent is superfine zinc sulfide.
8. The flame retardant reinforced microcellular foamed nylon material according to claim 1, wherein: the stabilizer is one or two of 1098, 168, H10 and H318;
the lubricant is one of EBS, erucamide, stearic acid, oxidized PE wax and ethylene bis fatty acid amide TAF.
9. The flame retardant reinforced microcellular foamed nylon material according to claim 8, wherein: the stabilizer is H10;
the lubricant is ethylene bis fatty acid amide (TAF).
10. A method for preparing a flame-retardant reinforced microcellular foamed nylon material according to any one of claims 1 to 9, which is characterized in that: the method comprises the following steps:
(1) 40-65 parts of nylon, 10-20 parts of polyphenylene sulfide, 7-30 parts of flame retardant, 1-10 parts of smoke suppressant, 0.2-5 parts of hydrolysis resistant agent, 1-10 parts of foaming auxiliary agent, 0.2-1 part of lubricant and 0.2-1 part of stabilizer are mixed according to parts by weight to prepare a mixture, the mixture is put into a high-speed mixer to be mixed for 1-3min, the mixture is added into a double-screw extruder through a hopper, 30-45 parts of glass fiber is added through a side feeding port, and the mixture is subjected to extrusion, bracing, traction and granulation at the temperature of 380 ℃ of 220-;
(2) and mixing the premixed composite master batch and a foaming agent in a mixer according to a certain weight part, and performing injection molding to obtain the flame-retardant reinforced micro-foamed nylon material or product.
CN201911306702.1A 2019-12-18 2019-12-18 Flame-retardant reinforced micro-foaming nylon material and preparation method thereof Active CN111138851B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114213838A (en) * 2021-12-03 2022-03-22 上海金发科技发展有限公司 Flame-retardant nylon composite material with low pungent smell and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010229205A (en) * 2009-03-26 2010-10-14 Sekisui Plastics Co Ltd Expandable thermoplastic resin particle, process for producing the same, prefoamed particle and foam molded product
CN103849144A (en) * 2012-12-03 2014-06-11 合肥杰事杰新材料股份有限公司 Polyphenylene sulfide/nylon alloy material and preparation method thereof
WO2014104592A1 (en) * 2012-12-26 2014-07-03 영보화학 주식회사 Flame-retardant foam insulating material based on electron beam cross-linked polyvinyl chloride and method for producing same
CN106633880A (en) * 2015-11-04 2017-05-10 常州市法沃森塑胶科技有限公司 High-strength and high-toughness polyphenylene sulfide composite material and preparation method thereof
CN107903620A (en) * 2017-11-09 2018-04-13 南京聚隆科技股份有限公司 A kind of automobile engine cover fretting map nylon material and preparation method thereof
CN109181290A (en) * 2018-09-30 2019-01-11 金旸（厦门）新材料科技有限公司 A kind of fire-retardant nylon/polyphenylene sulfide alloy material and its preparation method and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010229205A (en) * 2009-03-26 2010-10-14 Sekisui Plastics Co Ltd Expandable thermoplastic resin particle, process for producing the same, prefoamed particle and foam molded product
CN103849144A (en) * 2012-12-03 2014-06-11 合肥杰事杰新材料股份有限公司 Polyphenylene sulfide/nylon alloy material and preparation method thereof
WO2014104592A1 (en) * 2012-12-26 2014-07-03 영보화학 주식회사 Flame-retardant foam insulating material based on electron beam cross-linked polyvinyl chloride and method for producing same
CN106633880A (en) * 2015-11-04 2017-05-10 常州市法沃森塑胶科技有限公司 High-strength and high-toughness polyphenylene sulfide composite material and preparation method thereof
CN107903620A (en) * 2017-11-09 2018-04-13 南京聚隆科技股份有限公司 A kind of automobile engine cover fretting map nylon material and preparation method thereof
CN109181290A (en) * 2018-09-30 2019-01-11 金旸（厦门）新材料科技有限公司 A kind of fire-retardant nylon/polyphenylene sulfide alloy material and its preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114213838A (en) * 2021-12-03 2022-03-22 上海金发科技发展有限公司 Flame-retardant nylon composite material with low pungent smell and preparation method and application thereof
CN114213838B (en) * 2021-12-03 2024-03-15 上海金发科技发展有限公司 Flame-retardant nylon composite material with low pungent smell and preparation method and application thereof

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