CN103183901A - Housing material for halogen-free flame retardant storage battery and preparation method thereof - Google Patents
Housing material for halogen-free flame retardant storage battery and preparation method thereof Download PDFInfo
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- CN103183901A CN103183901A CN2013101371485A CN201310137148A CN103183901A CN 103183901 A CN103183901 A CN 103183901A CN 2013101371485 A CN2013101371485 A CN 2013101371485A CN 201310137148 A CN201310137148 A CN 201310137148A CN 103183901 A CN103183901 A CN 103183901A
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Abstract
The invention discloses a housing material for a halogen-free flame retardant storage battery and a preparation method thereof. The housing material is characterized in that the material comprises the following components in percentage by weight: 73%-82% of acrylonitrile-butadiene-styrene ternary copolymer, 6.5%-12% of resorcinol-bis-polycondensate, 3%-6.5% of melamine cyanurate, 6.5%-9% of toughening agent, 0.5%-1% of lubricant and 0.2%-1% of antioxidant. The housing material disclosed by the invention has the advantages of excellent flame retardancy and mechanical properties, low smoke production during burning and no generation of toxic corrosive gas, and can solve the problems of poor dispersion and poor compatibility of a phosphorus-nitrogen elemental expansion type flame retardant in the acrylonitrile-butadiene-styrene ternary copolymer and further provide a novel material for the field of domestic storage batteries.
Description
Technical field
The present invention relates to a kind of halogen-free flameproof accumulator housing material and preparation method thereof, belong to the fire retardant material scientific domain.
Background technology
In recent years, reinforcement day by day along with people's energy-conserving and environment-protective consciousness, increasing people selects the trip of the environmental protection vehicles, the use of Xiang Guan power truck auxiliary products store battery also increases day by day therewith, but, the existing storage battery sheating material overwhelming majority adopts non-environmental protection flame retardant material to make, namely adding brominated flame retardant occupies an leading position, the intensity of this material, shock resistance, ageing resistance is relative with flame retardant properties better, but because bromine class fire retardant material amount of being fuming when burning is big, can discharge a large amount of hydrogen halides.And then suction formation has the haloid acid of severe corrosive and causes the secondary public hazards.
Summary of the invention
The objective of the invention is to be intended to overcome existing accumulator housing Flame Retardancy and can go up the defective of existence, a kind of halogen-free flameproof accumulator housing material is provided, this material has good flame retardant resistance and mechanical property, the amount of being fuming is little when burning, do not generate poisonous corrosive gases, and can solve phosphorus-nitrogen simple substance expansion type flame retardant and in acrylonitrile-butadiene-styrene terpolymer, have dispersiveness, the problem of consistency difference.
The technical scheme that realizes the object of the invention is: a kind of halogen-free flameproof accumulator housing material, and the each component of this material and the weight percent of each component are as follows:
Acrylonitrile-butadiene-styrene terpolymer 73% ~ 82%;
Resorcinol-two polycondensates 6.5% ~ 12%;
Melamine cyanurate 3% ~ 6.5%;
Toughner 6.5% ~ 9%;
Lubricant 0.5% ~ 1%;
Oxidation inhibitor 0.2% ~ 1%.
Further, described toughner is chlorinatedpolyethylene.
Further, described lubricant is the two stearyl ester amine of vinyl, perhaps is the mixture of the two stearyl ester amine of vinyl and whiteruss.
Further, described oxidation inhibitor is the positive octadecanol ester of pentaerythritol tetrathioglycollate or propionic acid.
Further, preparation method of the present invention is as follows:
1) add Resorcinol-two polycondensates, melamine cyanurate, toughner, lubricant and oxidation inhibitor in the high-speed mixer in proportion, earlier under the rotating speed of 350 ~ 450r/min, mix 1.5 ~ 2.2min,, under the rotating speed of 950 ~ 1050r/min, mix 0.8 ~ 1.5min then and can prepare phosphorus-nitrogen composite combustion inhibitor;
2) add phosphorus-nitrogen composite combustion inhibitor and acrylonitrile-butadiene-styrene terpolymer in the high-speed mixer in proportion, earlier under the rotating speed of 350 ~ 450r/min, mix 1.5 ~ 2.2min, under the rotating speed of 950 ~ 1050r/min, mix 0.8 ~ 1.5min then and obtain pre-composition, pre-composition is dropped into twin screw extruder carry out extruding pelletization; Wherein the control of twin screw extruder barrel zone temperature is at 180 ~ 220 ℃, twin screw extruder engine speed 1000 ~ 1100r/min, twin screw extruder main frame rotational frequency is 25Hz, and feeding rotating speed 350 ~ 450r/min, extruding pelletization prepare halogen-free flame retardant ABS plastic cement particle;
3) halogen-free flame retardant ABS plastic cement particle is made halogen-free flameproof accumulator housing material by injection moulding machine machine-shaping.
After having adopted technique scheme, the present invention has following beneficial effect:
1, existing bittern-free flame-proof material is in order to prevent and reduce a certain amount of anti-dripping agent of the most adding of generation of molten drop phenomenon, can not accomplish truly " Halogen ", the present invention is not adding under the situation of anti-dripping agent, adopted acrylonitrile-butadiene-styrene terpolymer, it is nontoxic, tasteless that acrylonitrile-butadiene-styrene terpolymer has, and the characteristic of not having the fusion drip phenomenon during burning produces molten drop when it can prevent from burning.
2, adopt the mixed phosphorus-nitrogen composite combustion inhibitor that gets of Resorcinol-two polycondensates, melamine cyanurate, toughner, lubricant and oxidation inhibitor, phosphorus-nitrogen composite combustion inhibitor has Heat stability is good, and the characteristics good with resin compatible, solved the phosphorus-dispersiveness of nitrogen simple substance expansion type flame retardant in acrylonitrile-butadiene-styrene terpolymer, the shortcoming of consistency difference.
3, product is when burning, and showing at resin of phosphorus-nitrogen composite combustion inhibitor burning forms one deck porous foam carbon-coating, and this charcoal layer is the amorphous carbon structure, its essence is the crystallite of carbon, in case form, itself does not fire, and can stop thermal conduction between plastics and thermal source, reduce the pyrolysis temperature of plastics; In addition, gaseous diffusion and external oxygen that the porous charcoal layer can stop pyrolysis to produce simultaneously are diffused into not cracking frosting, make the plastics of burning can not get enough oxygen and heat energy and put out certainly, and can prevent molten drop.
4, phosphorus-nitrogen composite combustion inhibitor also can suppress the smog generation, does not generate poisonous or corrosive gases.
Embodiment
Content of the present invention is easier to be expressly understood that the present invention is further detailed explanation according to specific embodiment below in order to make.
Embodiment one
A kind of halogen-free flameproof accumulator housing material is made up of 82% acrylonitrile-butadiene-styrene copolymer (ABS), Resorcinol-two (diphenyl phosphoester) polycondensate (SOL-DP) of 6.5%, 3% melamine cyanurate (SMA), 7.7% chlorinatedpolyethylene (toughening agent C PE), 0.5% two stearyl ester amine (lubricant EBS) of vinyl, 0.1% whiteruss and 0.2% pentaerythritol tetrathioglycollate (antioxidant 1010).Resorcinol with 6.5%-two (diphenyl phosphoester) polycondensate (SOL-DP), 3% melamine cyanurate (SMA), 7.7% chlorinatedpolyethylene (toughening agent C PE), 0.5% two stearyl ester amine (lubricant EBS) of vinyl, 0.1% whiteruss and 0.2% pentaerythritol tetrathioglycollate (antioxidant 1010) drop in the high-speed mixer, earlier under the rotating speed of 350 r/min, mix 2.2min, after mixing 1.5min under the rotating speed of 950 r/min, prepare phosphorus-nitrogen composite combustion inhibitor then; The acrylonitrile-butadiene-styrene copolymer (ABS) of phosphorus-nitrogen composite combustion inhibitor and 82% is added in the high-speed mixer, earlier under the rotating speed of 350 r/min, mix 2.2min, after mixing 1.5min under the rotating speed of 950 r/min, prepare pre-composition then, pre-composition is added twin screw extruder carry out extruding pelletization, the control of twin screw extruder barrel zone temperature is at 180 ℃, engine speed 1000 r/min, the main frame rotational frequency is 25Hz, feeding rotating speed 350r/min.Extruding pelletization is prepared halogen-free flame retardant ABS plastic cement particle; Halogen-free flame retardant ABS plastic cement particle is made halogen-free flameproof accumulator housing material by injection moulding machine machine-shaping.
Embodiment two
A kind of halogen-free flameproof accumulator housing material is made up of 73% acrylonitrile-butadiene-styrene copolymer (ABS), Resorcinol-two (diphenyl phosphoester) polycondensate (SOL-DP) of 12%, 6.5% melamine cyanurate (SMA), 7.5% chlorinatedpolyethylene (toughening agent C PE), 0.8% two stearyl ester amine (lubricant EBS) of vinyl and 0.2% the positive octadecanol ester of propionic acid (antioxidant 1076).In Resorcinol with 12%-two (diphenyl phosphoester) polycondensate (SOL-DP), 6.5% melamine cyanurate (SMA), 7.5% chlorinatedpolyethylene (toughening agent C PE), 0.8% two stearyl ester amine (lubricant EBS) of vinyl and 0.2% the positive octadecanol ester of propionic acid (antioxidant 1076) the input high-speed mixer, earlier under the rotating speed of 350 r/min, mix 2min, after mixing 1min under the rotating speed of 1000 r/min, prepare phosphorus-nitrogen composite combustion inhibitor then; The acrylonitrile-butadiene-styrene copolymer (ABS) of phosphorus-nitrogen composite combustion inhibitor and 73% is added in the high-speed mixer, earlier under the rotating speed of 350 r/min, mix 2min, after mixing 1min under the rotating speed of 1000 r/min, prepare pre-composition then, pre-composition is added twin screw extruder carry out extruding pelletization, the control of twin screw extruder barrel zone temperature is at 190 ℃, engine speed 1000 r/min, the main frame rotational frequency is 25Hz, feeding rotating speed 400 r/min.Extruding pelletization is prepared halogen-free flame retardant ABS plastic cement particle; Halogen-free flame retardant ABS plastic cement particle is made halogen-free flameproof accumulator housing material by injection moulding machine machine-shaping; Wherein oxidation inhibitor also can be the positive octadecanol ester of propionic acid (antioxidant 1076) and composite the making of GW-540 (oxidation inhibitor 168).
Embodiment three
A kind of halogen-free flameproof accumulator housing material is made up of 79% acrylonitrile-butadiene-styrene copolymer (ABS), Resorcinol-two (diphenyl phosphoester) polycondensate (SOL-DP) of 6.5%, 6% melamine cyanurate (SMA), 7.5% chlorinatedpolyethylene (toughening agent C PE), 0.5% two stearyl ester amine (lubricant EBS) of vinyl and 0.5% the positive octadecanol ester of propionic acid (antioxidant 1076).In Resorcinol with 6.5%-two (diphenyl phosphoester) polycondensate (SOL-DP), 6% melamine cyanurate (SMA), 7.5% chlorinatedpolyethylene (toughening agent C PE), 0.5% two stearyl ester amine (lubricant EBS) of vinyl and 0.5% the positive octadecanol ester of propionic acid (antioxidant 1076) the input high-speed mixer, earlier under the rotating speed of 450r/min, mix 1.5min, after mixing 0.8min under the rotating speed of 1050 r/min, prepare phosphorus-nitrogen composite combustion inhibitor then; The acrylonitrile-butadiene-styrene copolymer (ABS) of phosphorus-nitrogen composite combustion inhibitor and 79% is added in the high-speed mixer, earlier under the rotating speed of 450r/min, mix 1.5min, after mixing 0.8min under the rotating speed of 1050 r/min, prepare pre-composition then, pre-composition is added twin screw extruder carry out extruding pelletization, the control of twin screw extruder barrel zone temperature is at 200 ℃, engine speed 1100r/min, the main frame rotational frequency is 25Hz, feeding rotating speed 450r/min.Extruding pelletization is prepared halogen-free flame retardant ABS plastic cement particle; Halogen-free flame retardant ABS plastic cement particle is made halogen-free flameproof accumulator housing material by injection moulding machine machine-shaping.
Embodiment four
A kind of halogen-free flameproof accumulator housing material is made up of 77% acrylonitrile-butadiene-styrene copolymer (ABS), Resorcinol-two (diphenyl phosphoester) polycondensate (SOL-DP) of 10%, 4.5% melamine cyanurate (SMA), 7% chlorinatedpolyethylene (toughening agent C PE), 0.7% two stearyl ester amine (lubricant EBS) of vinyl, 0.1% whiteruss and 0.7% pentaerythritol tetrathioglycollate (antioxidant 1010).Resorcinol with 10%-two (diphenyl phosphoester) polycondensate (SOL-DP), 4.5% melamine cyanurate (SMA), 7% chlorinatedpolyethylene (toughening agent C PE), 0.7% two stearyl ester amine (lubricant EBS) of vinyl, 0.1% whiteruss and 0.7% pentaerythritol tetrathioglycollate (antioxidant 1010) drop in the high-speed mixer, earlier under the rotating speed of 400r/min, mix 2min, after mixing 1min under the rotating speed of 1000 r/min, prepare phosphorus-nitrogen composite combustion inhibitor then; The acrylonitrile-butadiene-styrene copolymer (ABS) of phosphorus-nitrogen composite combustion inhibitor and 77% is added in the high-speed mixer, earlier under the rotating speed of 400r/min, mix 2min, after mixing 1min under the rotating speed of 1000 r/min, prepare pre-composition then, pre-composition is added twin screw extruder carry out extruding pelletization, the control of twin screw extruder barrel zone temperature is at 220 ℃, engine speed 1050r/min, the main frame rotational frequency is 25Hz, feeding rotating speed 400 r/min.Extruding pelletization is prepared halogen-free flame retardant ABS plastic cement particle; Halogen-free flame retardant ABS plastic cement particle is made halogen-free flameproof accumulator housing material by injection moulding machine machine-shaping; Wherein oxidation inhibitor also can be pentaerythritol tetrathioglycollate (antioxidant 1010) and composite the making of GW-540 (oxidation inhibitor 168).
The Performance Detection of embodiment one ~ embodiment four is reported as follows:
As can be known from the above table, the oxygen index of embodiment one ~ embodiment four can reach 34%, combustionproperty is V-0, heat-drawn wire can reach 84 ℃, the result shows, the present invention has good thermostability and flame retardant properties, has solved the phosphorus-dispersiveness of nitrogen simple substance expansion type flame retardant in acrylonitrile-butadiene-styrene terpolymer, the problem of consistency difference; The density of embodiment one ~ embodiment four can reach 1.09g/cm3, and tensile strength can reach 42 Mpa, and modulus in flexure can reach 2610 Mpa, and simple beam impact strength (breach) can reach 25 KJ/m2, and the result shows that the present invention has good mechanical property.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. halogen-free flameproof accumulator housing material, it is characterized in that: the each component of this material and the weight percent of each component are as follows:
Acrylonitrile-butadiene-styrene terpolymer 73% ~ 82%;
Resorcinol-two polycondensates 6.5% ~ 12%;
Melamine cyanurate 3% ~ 6.5%;
Toughner 6.5% ~ 9%;
Lubricant 0.5% ~ 1%;
Oxidation inhibitor 0.2% ~ 1%.
2. halogen-free flameproof accumulator housing material according to claim 1, it is characterized in that: described toughner is chlorinatedpolyethylene.
3. halogen-free flameproof accumulator housing material according to claim 1 and 2 is characterized in that: described lubricant is the two stearyl ester amine of vinyl, perhaps be the mixture of vinyl pair stearyl ester amine and whiteruss.
4. halogen-free flameproof accumulator housing material according to claim 1 and 2, it is characterized in that: described oxidation inhibitor is the positive octadecanol ester of pentaerythritol tetrathioglycollate or propionic acid.
5. halogen-free flameproof accumulator housing material according to claim 3, it is characterized in that: described oxidation inhibitor is the positive octadecanol ester of pentaerythritol tetrathioglycollate or propionic acid.
6. halogen-free flameproof accumulator housing preparation methods as claimed in claim 1 is characterized in that the step of this method is as follows:
1) add Resorcinol-two polycondensates, melamine cyanurate, toughner, lubricant and oxidation inhibitor in the high-speed mixer in proportion, earlier under the rotating speed of 350 ~ 450r/min, mix 1.5 ~ 2.2min,, under the rotating speed of 950 ~ 1050r/min, mix 0.8 ~ 1.5min then and can prepare phosphorus-nitrogen composite combustion inhibitor;
2) add phosphorus-nitrogen composite combustion inhibitor and acrylonitrile-butadiene-styrene terpolymer in the high-speed mixer in proportion, earlier under the rotating speed of 350 ~ 450r/min, mix 1.5 ~ 2.2min, under the rotating speed of 950 ~ 1050r/min, mix 0.8 ~ 1.5min then and obtain pre-composition, pre-composition is dropped into twin screw extruder carry out extruding pelletization; Wherein the control of twin screw extruder barrel zone temperature is at 180 ~ 220 ℃, twin screw extruder engine speed 1000 ~ 1100r/min, twin screw extruder main frame rotational frequency is 25Hz, and feeding rotating speed 350 ~ 450r/min, extruding pelletization prepare halogen-free flame retardant ABS plastic cement particle;
3) halogen-free flame retardant ABS plastic cement particle is made halogen-free flameproof accumulator housing material by injection moulding machine machine-shaping.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2013101371485A CN103183901A (en) | 2013-04-19 | 2013-04-19 | Housing material for halogen-free flame retardant storage battery and preparation method thereof |
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| CN2013101371485A CN103183901A (en) | 2013-04-19 | 2013-04-19 | Housing material for halogen-free flame retardant storage battery and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881287A (en) * | 2014-04-18 | 2014-06-25 | 常州润邦新材料科技有限公司 | Environment-friendly flame-retardant ABS (Acrylonitrile Butadiene Styrene) material and preparation method thereof |
| CN105086336A (en) * | 2015-08-31 | 2015-11-25 | 无锡市嘉邦电力管道厂 | Storage battery shell material and preparation method thereof |
| CN105086335A (en) * | 2015-08-31 | 2015-11-25 | 无锡市嘉邦电力管道厂 | Storage battery shell material and preparation method thereof |
| CN104371203B (en) * | 2014-10-15 | 2016-10-05 | 超威电源有限公司 | A kind of heat sealability high temperature battery shell resin alloy and preparation method thereof |
| CN111253916A (en) * | 2020-03-13 | 2020-06-09 | 南通融盛智能科技有限公司 | High-thermal-conductivity shaped composite phase change energy storage material and application thereof |
| CN114316500A (en) * | 2021-12-02 | 2022-04-12 | 金发科技股份有限公司 | Halogen-free flame-retardant ABS material and preparation method thereof |
| CN117487308A (en) * | 2023-12-05 | 2024-02-02 | 广东沃欧电子科技股份有限公司 | Reinforced halogen-free flame-retardant battery shell material and preparation method thereof |
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| CN101759949A (en) * | 2008-11-21 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Halogen-free flame-retardant ABS composition |
| EP2505607A1 (en) * | 2011-04-01 | 2012-10-03 | Lg Chem, Ltd. | Thermoplastic ABS resin compositions having excellent resistance to flame retardancy |
| CN102731958A (en) * | 2012-07-13 | 2012-10-17 | 北京理工大学 | Halogen-free flame-retardant ABS (Acrylonitrile Butadiene Styrene) resin and preparation method thereof |
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| CN101759949A (en) * | 2008-11-21 | 2010-06-30 | 上海普利特复合材料股份有限公司 | Halogen-free flame-retardant ABS composition |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881287A (en) * | 2014-04-18 | 2014-06-25 | 常州润邦新材料科技有限公司 | Environment-friendly flame-retardant ABS (Acrylonitrile Butadiene Styrene) material and preparation method thereof |
| CN104371203B (en) * | 2014-10-15 | 2016-10-05 | 超威电源有限公司 | A kind of heat sealability high temperature battery shell resin alloy and preparation method thereof |
| CN105086336A (en) * | 2015-08-31 | 2015-11-25 | 无锡市嘉邦电力管道厂 | Storage battery shell material and preparation method thereof |
| CN105086335A (en) * | 2015-08-31 | 2015-11-25 | 无锡市嘉邦电力管道厂 | Storage battery shell material and preparation method thereof |
| CN111253916A (en) * | 2020-03-13 | 2020-06-09 | 南通融盛智能科技有限公司 | High-thermal-conductivity shaped composite phase change energy storage material and application thereof |
| CN114316500A (en) * | 2021-12-02 | 2022-04-12 | 金发科技股份有限公司 | Halogen-free flame-retardant ABS material and preparation method thereof |
| CN114316500B (en) * | 2021-12-02 | 2024-01-26 | 金发科技股份有限公司 | Halogen-free flame-retardant ABS material and preparation method thereof |
| CN117487308A (en) * | 2023-12-05 | 2024-02-02 | 广东沃欧电子科技股份有限公司 | Reinforced halogen-free flame-retardant battery shell material and preparation method thereof |
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Application publication date: 20130703 |