WO2020173490A1 - 一种高极性阻燃苯乙烯类组合物、制备方法及其应用 - Google Patents
一种高极性阻燃苯乙烯类组合物、制备方法及其应用 Download PDFInfo
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- WO2020173490A1 WO2020173490A1 PCT/CN2020/077075 CN2020077075W WO2020173490A1 WO 2020173490 A1 WO2020173490 A1 WO 2020173490A1 CN 2020077075 W CN2020077075 W CN 2020077075W WO 2020173490 A1 WO2020173490 A1 WO 2020173490A1
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- flame
- styrene
- retardant
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- polarity
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- 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
- C08K13/02—Organic and inorganic ingredients
-
- 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
-
- 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
- C08K3/32—Phosphorus-containing compounds
-
- 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
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
Definitions
- the invention belongs to the field of polymer materials, and specifically relates to a high-polarity flame-retardant styrene composition suitable for glue-sealing lead-acid battery casings, a preparation method and application thereof.
- Styrene resin is a terpolymer composed of styrene, butadiene, and acrylonitrile. It combines the high fluidity of styrene, the initial rubber properties of butadiene, and the chemical resistance of acrylonitrile. It has excellent processing Performance, low temperature resistance, electrical insulation, chemical resistance, high gloss, and excellent electroplating performance. At the same time, it has good creep resistance, high dimensional stability, and low mold shrinkage. It is used in military, automobile, and electronics Applications in electrical appliances and other fields are very extensive. But on the one hand, the oxygen index of styrene resin is only 18, which is a flammable material. Therefore, flame-retardant modification of styrene resin is a commonly used modification method of styrene resin.
- styrene resin is a sea-island structure with styrene-acrylonitrile copolymer as the continuous phase and butadiene rubber as the dispersed phase.
- the addition of about 15-25% of the flame retardant system partially destroyed the styrene blend.
- the sea-island structure which in turn leads to a substantial decrease in the initial properties of the styrene matrix resin.
- the content, particle size, and distribution of butadiene rubber can effectively control the initial properties of the styrene resin, while adjusting the initial properties of the styrene resin, the adhesive strength of the glue is greatly reduced.
- the housing Due to the particularity of lead-acid batteries, in addition to UL94 V-0@1.5mm, the housing requires effective heating or glue welding for the battery slot and battery cover. Therefore, it is necessary to develop high-efficiency flame retardant and effective A flame-retardant styrene composition that improves its adhesion to glue is an inevitable choice.
- the purpose of the present invention is to provide a highly polar flame-retardant styrenic composition, which has excellent flame retardancy, good impact resistance, and high adhesion to epoxy resin glue, which is particularly suitable Used to prepare plastic-sealed lead-acid battery shell materials.
- a high-polarity flame-retardant styrenic composition including Including the following parts by weight
- the styrenic resin is acrylonitrile-butadiene-styrene graft copolymer (ABS), acrylonitrile-styrene-acrylic acid terpolymer (ASA) or methyl methacrylate-butadiene- Styrene graft copolymer (MBS).
- ABS acrylonitrile-butadiene-styrene graft copolymer
- ASA acrylonitrile-styrene-acrylic acid terpolymer
- MBS methyl methacrylate-butadiene- Styrene graft copolymer
- the brominated flame retardant system is brominated imine, brominated polycarbonate, polybrominated styrene, brominated polystyrene, tris(tribromophenoxy) cyanurate, octabromoether, One or more of decabromodiphenyl ethane, brominated epoxy, tetrabromobisphenol A, tetrabromobisphenol A ether, etc. are combined with antimony trioxide, colloidal antimony pentoxide, sodium antimonate, trichloro One or several compound systems in antimony and antimony pentachloride.
- the blended elastomer is one or more of acrylic rubber, silicone rubber, SBS, SEBS, grafted POE, nitrile rubber, fluorine rubber, butadiene rubber, styrene butadiene rubber and the like.
- the modulus modifier is a linear expansion coefficient for one or more of a ⁇ l X 10_ powder material 6, such as kaolin, calcite, pyrophosphate, pyrophosphate tungstate, and the like.
- the polar modifier is styrene maleimide copolymer, maleic anhydride grafted SEBS, maleic anhydride grafted styrene copolymer, maleic anhydride grafted AS copolymer, ethylene- One or more of butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer and the like.
- the polar modifier is styrene maleimide copolymer, maleic anhydride grafted SEBS, One or more of maleic anhydride grafted styrene copolymer and maleic anhydride grafted AS copolymer; particularly preferred are styrene maleimide copolymer and maleic anhydride grafted SEBS One or two kinds of; the most preferred is maleic anhydride grafted SEBS o
- the antioxidants include hindered phenolic primary antioxidants and phosphite secondary antioxidants.
- the light stabilizers include one or more of benzophenones, benzotriazoles, triazines, substituted acrylonitriles, oxamides, and hindered amines.
- the processing aid is one or a mixture of stearamide lubricants such as EBS, silicone oil and white mineral oil.
- the above mixture is conveyed to the twin-screw extruder through a precisely metered feeding device.
- the temperature of the screws in each section of the extruder is controlled between 170 ⁇ 230 ° C, and the aspect ratio of the twin-screw extruder is 20 ⁇ 40, The screw speed is 200-800 rpm.
- the materials Under the shearing, mixing and conveying of the screw, the materials can be fully melted and compounded, and then extruded, granulated and dried to obtain a highly polar flame-retardant styrene composition particle;
- the above-mentioned high-polarity flame-retardant styrene composition particles are added to an injection molding machine to be processed into the required splines.
- the injection conditions are: barrel temperature 180-220 ° C, mold temperature 50-70 ° C, Injection pressure is 6-10MPa.
- an application of the high-polarity flame-retardant styrenic composition is also provided, specifically it is used as a lead-acid battery shell material welded by epoxy resin glue.
- the high-polarity flame-retardant styrene composition of the present invention prepares sample strips according to the standard, and performs the performance tests listed in Table 1 below.
- the equipment used in the present invention includes:
- the twin-screw extruder used to prepare the highly polar flame-retardant styrene composition is SHJ-30 produced by Nanjing Ruiya Polymer Equipment Co., Ltd.
- the injection molding machine used to prepare the test strips of the high-polarity flame-retardant styrene composition is the B-920 model produced by Zhejiang Haitian Injection Molding Machine Co., Ltd.
- the instrument used to test the melt flow rate is the ZR21452 melt flow rate meter produced by Meister Industrial Systems (China) Co., Ltd.
- the impact testing machine used to test the impact strength is the T92 type produced by Tinius Olsenis, USA.
- the universal testing machine for testing tensile strength and adhesion is H10K-S produced by Hounsfield.
- the Vicat heat distortion tester used to test the heat distortion temperature is the 40-197 type produced by COESFELD in Germany.
- the UL-94 vertical combustion instrument used to test the combustion performance is the HVUL-2 type produced by ATLAS in the United States.
- the provided raw materials can be purchased from the market.
- styrene resin is selected from Taiwan Taihua's styrene AG15A1
- ASA resin is selected from Japan UMG ASA A600N;
- the brominated flame retardant is FR-245 of Israel Dead Sea Bromine Company, and the 8010 of Albemarle, USA;
- the antimony flame retardant is S-05N of Yunnan Muli Antimony Industry Co., Ltd.;
- Acrylic rubber is selected from DuPont’s EA101, silicone rubber is from Japan’s Zhongyuan’s MR-01, SBS is from South Korea’s LG503N, butadiene rubber is from South Korea’s Kumho HR181;
- Calcium pyrophosphate is selected from Nanjing Songguan, China, and kaolin is selected from US HG90;
- Polar modifier adopts Taiwan Rubber's maleic anhydride grafted SEBS-7131, Nippon Electrochemical's styrene-maleimide copolymer MS-NB, and Shenyang Ketong's maleic anhydride grafted styrene copolymer KT-2, maleic anhydride grafted AS copolymer S601N of Japan UMG;
- the antioxidants are Irganox 1010 and Irganox 168 made from Qiba refined;
- the light stabilizer is selected from Qiba refined 770 and UV-P;
- Example 1-4 Comparative Example 1-4 According to the parts by weight listed in Table 2, each component was added to a high-speed mixer for uniform mixing, and then the above mixture was fed into a twin-screw extruder for mixing and extrusion ⁇ Stretching, water cooling, pelletizing; Among them, the length to diameter ratio of the twin-screw extruder is 20-40; the screw barrel temperature is set as: the temperature of the first zone is 180°C, the temperature of the second zone is 190°C, and the temperature of the third zone is 200 °C, four zone temperature 210°C, five zone temperature 220°C, six zone temperature 220°C, seven zone temperature 220°C, eight zone temperature 220°C, nine zone temperature 220°C, ten zone temperature 220° C, the head temperature is 230°C; the screw speed is 200-800 revolutions/#
- the high-polarity flame-retardant styrene composition particles prepared by the method described above are tested according to the standard preparation samples listed in Table 1. Record the
- each component was added to a high-speed mixer according to the weight parts listed in Table 3 for uniform mixing, and then the above-mentioned mixture was fed into a twin-screw extruder for mixing, extruding, drawing, and Water cooling and pelletizing;
- the length-to-diameter ratio of the twin-screw extruder is 20-40;
- the temperature of the screw barrel is set as: 180°C in the first zone, 190°C in the second zone, 200°C in the third zone, and four Zone temperature 210°C, five zone temperature 220°C, six zone temperature 220°C, seven zone temperature 220°C, eight zone temperature 220°C, nine zone temperature 220°C, ten zone temperature 220°C, machine head
- the temperature is 230°C;
- the screw speed is 200-800 rpm/#
- the high-polarity flame-retardant styrene composition prepared by the method described above is tested according to the standard preparation samples listed in Table 1 and the data is recorded
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
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Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910149332.9 | 2019-02-28 | ||
| CN201910149332.9A CN109897331A (zh) | 2019-02-28 | 2019-02-28 | 一种高极性阻燃苯乙烯类组合物、制备方法及其应用 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2020173490A1 true WO2020173490A1 (zh) | 2020-09-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2020/077075 Ceased WO2020173490A1 (zh) | 2019-02-28 | 2020-02-28 | 一种高极性阻燃苯乙烯类组合物、制备方法及其应用 |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109897331A (zh) |
| WO (1) | WO2020173490A1 (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897331A (zh) * | 2019-02-28 | 2019-06-18 | 金发科技股份有限公司 | 一种高极性阻燃苯乙烯类组合物、制备方法及其应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0060824A2 (en) * | 1981-03-17 | 1982-09-22 | Monsanto Company | Flame-retardant molding compositions comprising a copolymer of a vinylaromatic monomer and an unsaturated dicarboxylic acid anhydride, polyvinyl chloride and a graft polymer |
| JPS60184546A (ja) * | 1984-03-05 | 1985-09-20 | Denki Kagaku Kogyo Kk | 発泡成形用熱可塑性樹脂組成物 |
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| CN109897331A (zh) * | 2019-02-28 | 2019-06-18 | 金发科技股份有限公司 | 一种高极性阻燃苯乙烯类组合物、制备方法及其应用 |
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| AR033368A1 (es) * | 2000-05-19 | 2003-12-17 | Bayer Ag | Mezclas de polimeros que contienen poliamida, y polimeros modificados con caucho, uso de las mezclas de polimeros en la produccion de cuerpos moldeados, y cuerpos moldeados, partes de gabinetes, placas de cubierta y piezas para el sector automotriz obtenibles a partir de las mezclas de polimeros |
-
2019
- 2019-02-28 CN CN201910149332.9A patent/CN109897331A/zh active Pending
-
2020
- 2020-02-28 WO PCT/CN2020/077075 patent/WO2020173490A1/zh not_active Ceased
Patent Citations (19)
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|---|---|---|---|---|
| EP0060824A2 (en) * | 1981-03-17 | 1982-09-22 | Monsanto Company | Flame-retardant molding compositions comprising a copolymer of a vinylaromatic monomer and an unsaturated dicarboxylic acid anhydride, polyvinyl chloride and a graft polymer |
| JPS60184546A (ja) * | 1984-03-05 | 1985-09-20 | Denki Kagaku Kogyo Kk | 発泡成形用熱可塑性樹脂組成物 |
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| CN104403258A (zh) * | 2014-12-17 | 2015-03-11 | 天津金发新材料有限公司 | 一种阻燃增强abs复合材料及其制备方法 |
| CN105331038A (zh) * | 2015-11-03 | 2016-02-17 | 浙江理工大学 | 一种玄武岩纤维增强的环保阻燃abs复合材料及其制备方法 |
| CN105462157A (zh) * | 2015-12-28 | 2016-04-06 | 江苏金发科技新材料有限公司 | 高流动、耐划伤、耐低温溴系阻燃abs/tpu合金材料及其制备方法与应用 |
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| CN107523002A (zh) * | 2017-08-03 | 2017-12-29 | 长兴天晟能源科技有限公司 | 一种蓄电池外壳专用的高耐油高性能abs合金材料 |
| CN107828176A (zh) * | 2017-11-08 | 2018-03-23 | 天津金发新材料有限公司 | 一种阻燃抗菌abs复合物及其制备方法与应用 |
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| CN107936888A (zh) * | 2017-11-08 | 2018-04-20 | 天津金发新材料有限公司 | 一种阻燃abs复合物及其制备方法与应用 |
| CN108219351A (zh) * | 2017-12-28 | 2018-06-29 | 金发科技股份有限公司 | 低内应力、高抗冲阻燃abs组合物及其制备方法和应用 |
| CN109897331A (zh) * | 2019-02-28 | 2019-06-18 | 金发科技股份有限公司 | 一种高极性阻燃苯乙烯类组合物、制备方法及其应用 |
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