WO2020215700A1 - Matériau de polypropylène ignifuge sans halogène pour parties de contact électrique de véhicules électriques conformément à gb17761-2018 et son procédé de moulage par injection - Google Patents

Matériau de polypropylène ignifuge sans halogène pour parties de contact électrique de véhicules électriques conformément à gb17761-2018 et son procédé de moulage par injection Download PDF

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Publication number
WO2020215700A1
WO2020215700A1 PCT/CN2019/118496 CN2019118496W WO2020215700A1 WO 2020215700 A1 WO2020215700 A1 WO 2020215700A1 CN 2019118496 W CN2019118496 W CN 2019118496W WO 2020215700 A1 WO2020215700 A1 WO 2020215700A1
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Prior art keywords
polypropylene
parts
retardant
halogen
free flame
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PCT/CN2019/118496
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English (en)
Chinese (zh)
Inventor
杜祥波
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台州市黄岩广环工贸有限公司
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Publication of WO2020215700A1 publication Critical patent/WO2020215700A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/009—Use of pretreated compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/017—Additives being an antistatic agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

  • the invention relates to a halogen-free flame-retardant polypropylene material for electric vehicle electrical contacts in compliance with GB17761-2018 and its injection molding process.
  • Polypropylene is one of the lightest varieties of all plastics at present. It is particularly stable to water, with a water absorption rate of only 0.01% in water and does not react with most chemicals. It has good mechanical properties. Except for impact resistance, other mechanical properties are better than polyethylene, and the molding processability is better. However, polypropylene products are susceptible to aging and combustibility due to light, heat and oxygen in use.
  • the purpose of the present invention is to solve the above problems and provide a halogen-free flame-retardant polypropylene material for electric vehicle electrical contacts that meets GB17761-2018.
  • Another object of the present invention is to provide an injection molding process of halogen-free flame-retardant polypropylene material for electric vehicle electrical contacts in compliance with GB17761-2018.
  • a halogen-free flame-retardant polypropylene material for electric vehicle electrical contacts in accordance with GB17761-2018, in parts by weight, composed of the following raw materials: 87-95 parts of polypropylene, 15-25 parts of polypropylene elastomer, flame-retardant and anti-aging 10-40 parts of filler and 0.1-0.7 parts of foaming agent.
  • the polypropylene elastomer is composed of 80-95 parts by weight of polypropylene and 0.4-1 parts of vinyl acetate , 0.6-1.2 parts of peroxy compound free radical initiator.
  • the flame-retardant and aging-resistant filler is calculated in parts by weight, consisting of 40-60 parts of nano-hydrogen with a grain size of 5-25nm. Alumina, 50 to 70 parts of carbon black with a particle size of 10 to 50 nm, 70 to 80 parts of absolute ethanol, and 5 to 8 parts of coupling agent.
  • the polypropylene is polypropylene with a melt flow rate of not less than 3g/10 minutes at 230°C and a load of 2.16kg Homopolymer.
  • halogen-free flame-retardant polypropylene material for electric vehicle electrical contacts in accordance with GB17761-2018, it is characterized in that the polypropylene elastomer is uniformly mixed by polypropylene and vinyl acetate through a high mixer and then passed through the main feed
  • the hopper is added to the twin-screw extruder for melt blending, and the vinyl acetate is injected into the twin-screw extruder at a uniform speed through the side feeding port at a barrel temperature of 200-220°C, and dried for 3 ⁇ 3 after extrusion and granulation.
  • the flame-retardant and anti-aging filler is fully mixed with nano aluminum hydroxide, carbon black and absolute ethanol, and then coupled with The agent is prepared after coupling treatment.
  • the melt flow rate at 230°C and a load of 2.16kg is not less than 35g/10 minutes, in the test of GB/T5169.16 Under the conditions, the combustion category is not less than V-1.
  • An injection molding process of halogen-free flame-retardant polypropylene material for electric vehicle electrical contacts in accordance with GB17761-2018 includes the following process steps:
  • the barrel temperature of the twin-screw extruder is 180°C ⁇ 210°C
  • the screw speed is 200 ⁇ 240r/min
  • the fuel and aging resistant filler is fed at a uniform speed by a liquid pump.
  • the barrel temperature of the injection molding machine is 190-210°C
  • the injection pressure is 15-30 MPa
  • the injection speed is 70-100 mm/s.
  • the material of the present invention meets the flame retardant performance standard of GB17761-2018, and makes full use of the excellent properties of polypropylene, which is light in weight and waterproof. Compared with the existing polypropylene material, the material of the present invention has a high melt flow rate, low raw material cost and simple process.
  • the flame-retardant and anti-aging filler used in the material of the present invention is based on the flame-retardant filler, and comprehensively utilizes the effects of aluminum hydroxide in smoke suppression and carbon black in anti-aging, anti-static, and foaming, and does not require additional anti-aging. Oxygen, nucleating agent, and at the same time enhance the mechanical properties of polypropylene.
  • the polypropylene elastomer used in the material of the present invention uses isotactic polypropylene as a matrix to avoid compatibility or precipitation problems during the modification of traditional polypropylene elastomers, and the process is simple and industrialization is possible.
  • the raw materials involved in the present invention include:
  • Polypropylene homopolymer No. 1 Sinopec, brand T30S, melt flow rate of 3.0g/10min (230°C, 2.16Kg); referred to as PP-1.
  • Polypropylene homopolymer No. 2 Zhongyuan Petrochemical, brand Z11G, melt flow rate of 25g/10min (230°C, 2.16Kg); referred to as PP-2.
  • Polypropylene homopolymer No. 3 American Ineos, brand 100-GA35, melt flow rate is 35g/10min (230°C, 2.16Kg); referred to as PP-3.
  • polypropylene is polypropylene homopolymer; vinyl acetate (CAS number: 108-05-4), selected from Jinan Liyang Chemical Co., Ltd.; peroxy compound radical initiators include alkylated peroxy esters Compounds and hydrogen peroxide compounds, such as tert-butyl peroxybenzoate, di-tert-butyl peroxytrimethyladipate, cumene hydroperoxide, etc.
  • peroxy compound radical initiator used in the present invention It is selected from the tert-butyl peroxybenzoate produced by Tianjin Hangu Polymer Chemical Auxiliary Co., Ltd.
  • Nano aluminum hydroxide is selected from Guangzhou Huigu Chemical Co., Ltd.
  • carbon black is selected from Seiko Epson Co., Ltd.
  • absolute ethanol is selected from Changzhou Qidi Chemical Co., Ltd.
  • coupling agent is selected from Shanghai Yiji Industrial Co., Ltd. Silane Coupling Agent KH-500.
  • the foaming agent can be one or more of inorganic chemical foaming agents, and the foaming agent used in the present invention is selected from ammonium bicarbonate produced by Zhejiang Shuntai Rubber Technology Co., Ltd.
  • test methods used in the present invention include:
  • Flame retardant performance According to the test of GB/T 5196.16, the test condition is the vertical burning test;
  • the notched impact strength of the cantilever beam is tested according to ASTM D-256, and the test condition is 1/4 inch;
  • the heat distortion temperature is tested according to ISO75A-1, -2, and the test condition is 1.80MPa, without annealing.
  • Foaming ratio It is calculated by measuring the thickness of the bottom after injection molding and dividing it by the cavity gap in the closed state of the mold.
  • Polypropylene elastomer A In parts by weight, it is made of 80 parts of polypropylene, 0.4 parts of vinyl acetate, and 0.6 parts of peroxy compound free radical initiator, referred to as elastomer A.
  • Polypropylene elastomer B In parts by weight, it is made of 95 parts of polypropylene, 1 part of vinyl acetate, and 1.2 parts of peroxy compound free radical initiator, referred to as elastomer B.
  • Flame-retardant and anti-aging filler A In parts by weight, it consists of 40 parts of nano aluminum hydroxide with a grain size of 5-25nm, 50 parts of carbon black with a particle size of 10-50nm, 70 parts of absolute ethanol, 5 parts of even It is made of coupling agent, referred to as filler A.
  • Flame-retardant and anti-aging filler B in parts by weight, composed of 60 parts of nano aluminum hydroxide with a grain size of 5-25nm, 70 parts of carbon black with a particle size of 10-50nm, 80 parts of absolute ethanol, 8 parts of even It is made of coupling agent, referred to as filler B.
  • the barrel temperature of the twin-screw extruder of Comparative Example 7 is lower than 180°C, the screw speed is lower than 200r/min, the barrel temperature of the injection molding machine is lower than 190°C, the injection pressure is lower than 15MPa, and the injection speed Lower than 70mm/s;
  • Comparative Example 8 compared with Example 1, the injection molding machine barrel temperature is lower than 190°C, the injection pressure is lower than 15MPa, and the injection speed is lower than 70mm/s;
  • Comparative Example 9 is compared with Example 1, The barrel temperature of the twin-screw extruder is higher than 210°C, the screw speed is higher than 240r/min, the barrel temperature of the injection molding machine is higher than 210°C, the injection pressure is higher than 30MPa, and the injection speed is higher than 100mm/s; Comparative Example 10 and
  • Comparative Example 12 has a twin-screw extruder.
  • the barrel temperature is higher than 210°C
  • the screw speed is higher than 240r/min
  • the injection molding machine barrel temperature is higher than 210°C
  • the injection pressure is higher than 30MPa
  • the injection speed is higher than 100mm/s.

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un matériau de polypropylène ignifuge sans halogène pour des parties de contact électrique de véhicules électriques conformément à GB17761-2018, et un procédé de moulage par injection de celui-ci. Le matériau est composé des matières premières suivantes en parties en poids : 87 à 95 parties d'un polypropylène, 15 à 25 parties d'un élastomère de polypropylène, 10 à 40 parties d'une charge ignifuge et résistant au vieillissement, et 0,1 à 0,7 parties d'un agent moussant. Le matériau utilise pleinement les performances supérieures de légèreté et de résistance à l'eau du polypropylène, sur la base de la norme de performance de résistance au feu de GB17761-2018. Par rapport aux matériaux de polypropylène existants, le matériau présente un indice de fluidité élevé, un faible coût de matière première, et un processus simple.
PCT/CN2019/118496 2019-04-23 2019-11-14 Matériau de polypropylène ignifuge sans halogène pour parties de contact électrique de véhicules électriques conformément à gb17761-2018 et son procédé de moulage par injection WO2020215700A1 (fr)

Applications Claiming Priority (2)

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CN201910327422.2A CN110092981A (zh) 2019-04-23 2019-04-23 符合gb17761-2018的电动车电气接触件无卤阻燃聚丙烯材料及其注塑工艺
CN201910327422.2 2019-04-23

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WO2020215700A1 true WO2020215700A1 (fr) 2020-10-29

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110092981A (zh) * 2019-04-23 2019-08-06 台州市黄岩广环工贸有限公司 符合gb17761-2018的电动车电气接触件无卤阻燃聚丙烯材料及其注塑工艺

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002026879A1 (fr) * 2000-09-29 2002-04-04 Compco Pty Ltd Composition polymere ne contenant pas d'halogene
CN1786065A (zh) * 2005-11-14 2006-06-14 天津市润生塑胶制品有限公司 烯烃类树脂及烯烃类热塑性弹性体高阻燃发泡体及制造方法
US20080081869A1 (en) * 2006-09-29 2008-04-03 Randal Howard Kerstetter Thermoplastic elastomer compositions, methods of making and articles made from the same
WO2010026230A1 (fr) * 2008-09-05 2010-03-11 Thor Gmbh Composition retardatrice de flamme renfermant un dérivé de l'acide phosphonique
CN102321285A (zh) * 2011-07-30 2012-01-18 江苏安格特新材料科技有限公司 柔软型低烟无卤阻燃弹性体改性材料及其制备方法
CN102367312A (zh) * 2011-09-26 2012-03-07 广州市聚赛龙工程塑料有限公司 一种阻燃低发泡聚丙烯材料及其制备方法
CN102807707A (zh) * 2012-08-12 2012-12-05 深圳市沃尔核材股份有限公司 一种无卤阻燃聚丙烯发泡体及其制备方法
CN110092981A (zh) * 2019-04-23 2019-08-06 台州市黄岩广环工贸有限公司 符合gb17761-2018的电动车电气接触件无卤阻燃聚丙烯材料及其注塑工艺

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002026879A1 (fr) * 2000-09-29 2002-04-04 Compco Pty Ltd Composition polymere ne contenant pas d'halogene
CN1786065A (zh) * 2005-11-14 2006-06-14 天津市润生塑胶制品有限公司 烯烃类树脂及烯烃类热塑性弹性体高阻燃发泡体及制造方法
US20080081869A1 (en) * 2006-09-29 2008-04-03 Randal Howard Kerstetter Thermoplastic elastomer compositions, methods of making and articles made from the same
WO2010026230A1 (fr) * 2008-09-05 2010-03-11 Thor Gmbh Composition retardatrice de flamme renfermant un dérivé de l'acide phosphonique
CN102321285A (zh) * 2011-07-30 2012-01-18 江苏安格特新材料科技有限公司 柔软型低烟无卤阻燃弹性体改性材料及其制备方法
CN102367312A (zh) * 2011-09-26 2012-03-07 广州市聚赛龙工程塑料有限公司 一种阻燃低发泡聚丙烯材料及其制备方法
CN102807707A (zh) * 2012-08-12 2012-12-05 深圳市沃尔核材股份有限公司 一种无卤阻燃聚丙烯发泡体及其制备方法
CN110092981A (zh) * 2019-04-23 2019-08-06 台州市黄岩广环工贸有限公司 符合gb17761-2018的电动车电气接触件无卤阻燃聚丙烯材料及其注塑工艺

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