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WO2018036398A1 - Agent ignifuge exempt d'halogène pouvant bien conserver les performances du polypropylène et applications correspondantes - Google Patents

Agent ignifuge exempt d'halogène pouvant bien conserver les performances du polypropylène et applications correspondantes Download PDF

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Publication number
WO2018036398A1
WO2018036398A1 PCT/CN2017/097310 CN2017097310W WO2018036398A1 WO 2018036398 A1 WO2018036398 A1 WO 2018036398A1 CN 2017097310 W CN2017097310 W CN 2017097310W WO 2018036398 A1 WO2018036398 A1 WO 2018036398A1
Authority
WO
WIPO (PCT)
Prior art keywords
flame retardant
halogen
free flame
polypropylene
surface treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2017/097310
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English (en)
Chinese (zh)
Inventor
张秀芹
何燕岭
雷玉才
梁荣辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhongshan Complord New Materials Co Ltd
Original Assignee
Zhongshan Complord New Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhongshan Complord New Materials Co Ltd filed Critical Zhongshan Complord New Materials Co Ltd
Publication of WO2018036398A1 publication Critical patent/WO2018036398A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • 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
    • C08L2201/22—Halogen free composition

Definitions

  • the invention belongs to the technical field of halogen-free flame retardants, and particularly relates to a halogen-free flame retardant capable of maintaining the performance of polypropylene and its application.
  • halogen-free phosphorus-nitrogen flame retardants have caused more High attention.
  • ammonium polyphosphate products are favored by people for their low toxicity, environmental protection, high efficiency flame retardant effect and low cost.
  • Traditional high polymerization ammonium polyphosphate products and triazines The carbon-forming agent is used in polyolefin resins and can easily reach UL 94 V-0.
  • the melt index of the injection molded parts is greatly reduced, and the large parts of the injection molding are prone to gas lines and the like.
  • the flame retardant polypropylene of bromine system has good performance in the grinding base, mold scale and performance, which leads to the traditional halogen-free phosphorus-nitrogen flame retardant not replacing most or all of the bromine system.
  • the halogen-free phosphorus-nitrogen flame retardant replaces only a small part of the bromine bismuth system.
  • the performance of the modified flame retardant PP can be compared with the bromine oxime system, and at the same time
  • the glow wire has a greater advantage than bromine, and this system can broaden the application range of halogen-free phosphorus-nitrogen flame retardants, making it possible to rapidly replace the bromine ruthenium system.
  • Step 4 the ammonium polyphosphate, the triazine carbon forming agent and the trishydroxyethyl isocyanurate polymer forming agent in the third step are in a mass ratio of 5:(0.1-0.7):(0.3-0.8) The ratio is mixed to obtain a mixture, and then the mixture is surface-treated with a surface treatment agent to finally obtain a halogen-free flame retardant; the ammonium polyphosphate is crystalline II type ammonium polyphosphate, and the crystalline type II ammonium polyphosphate
  • the degree of polymerization is 1000 or more; the 1% weight loss temperature of the triazine char forming agent is 310 ° C or more; and the mass of the surface treating agent is 0.5% to 2.0% by mass of the mixture.
  • the above-mentioned halogen-free flame retardant capable of maintaining the performance of the polypropylene, characterized in that the curing temperature in the second step is from 130 ° C to 195 ° C for 1 h to 9 h;
  • the above-mentioned halogen-free flame retardant capable of maintaining the properties of the polypropylene is characterized in that the mass ratio of the catalyst to the trishydroxyethyl isocyanurate in the second step is (0.001 to 0.04):1.
  • the above-mentioned halogen-free flame retardant capable of maintaining the properties of polypropylene, characterized in that the water solubility of the trishydroxyethyl isocyanurate polymer forming agent in the third step is 0.1 g to 1.5 g/ In 100 mL of water, the 1% weight loss temperature of the trishydroxyethyl isocyanurate polymer forming agent is 300 ° C or higher.
  • the above-mentioned halogen-free flame retardant capable of maintaining the performance of polypropylene, characterized in that the water solubility of the ammonium polyphosphate in step 4 is less than 0.5 g / 100 ml of water, and the heat of the triazine is 1%
  • the weight loss temperature is 330 ° C or higher, and the triazine char forming agent has a water solubility of less than 0.1 g / 100 ml of water.
  • the trishydroxyethyl isocyanurate polymer-forming agent prepared in the intermediate process of the present invention still has a carbon-forming effect, and the cost is only one-third of that of the triazine-forming carbon, although it is used alone as a charcoal.
  • the use of a triazine-forming agent has a good carbon-forming effect, but can be used in combination with a triazine-forming agent to replace a part of the triazine-forming agent, thereby reducing the cost of the composite flame retardant and achieving the same flame retardancy. Under the circumstances, it will not increase the total amount of flame retardant added.
  • Step 4 mixing ammonium polyphosphate, triazine carbon forming agent and the trishydroxyethyl isocyanurate polymer forming agent in the fourth step according to a mass ratio of 5:0.2:0.8 (steps when mixing)
  • the mass of the trishydroxyethyl isocyanurate polymer forming agent in the third is 666.67 g), and a mixture is obtained, followed by dodecyltrimethoxysilane, octadecyltrimethoxysilane and n-octyl group.
  • the mixture is subjected to surface treatment by triethoxysilane.
  • Step 2 Slowly add 160 g of concentrated sulfuric acid having a mass concentration of 98% to the trishydroxyethyl isocyanurate heated in the first step, and rapidly stir while increasing the flow rate of nitrogen to 2 m 3 / h, until the reactants become thick, the stirring is stopped, the reaction product is removed from the reaction equipment, and after being naturally cooled, it is pulverized by a coarse mill, and then placed in a tray and solidified at a temperature of 120 ° C for 10 hours; the stirring speed is 46 r / Min;
  • Step 4 mixing ammonium polyphosphate, triazine carbon forming agent and the trishydroxyethyl isocyanurate polymer forming agent in the fourth step according to a mass ratio of 5:0.4:0.6 (steps when mixing)
  • the mass of the trishydroxyethyl isocyanurate polymer carbon-forming agent in the third is 500.0 g)
  • the mixture is obtained, and then the mixture is surface-treated with phenyltriethoxysilane, and the surface treatment process is carried out.
  • the present invention applies the halogen-free flame retardants prepared in Examples 1 to 5, Comparative Example 1 and Comparative Example 2 Preparation of flame retardant polypropylene, the specific preparation process is:

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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)
  • Fireproofing Substances (AREA)

Abstract

L'invention concerne un agent ignifuge exempt d'halogène pouvant bien conserver les performances du polypropylène. Un procédé de préparation de l'agent ignifuge exempt halogène consiste à : 1, chauffer de l'acide 1,3,5-tris(2-hydroxyéthyl)cyanurique; 2, permettre à l'acide 1,3,5-tris(2-hydroxyéthyl)cyanurique de subir une réaction de polymérisation sous l'action d'un catalyseur, de manière à obtenir un polymère d'acide 1,3,5-tris(2-hydroxyéthyl)cyanurique; 3, préparer un agent de carbonisation de polymère d'acide 1,3,5-tris(2-hydroxyéthyl)cyanurique; et 4, mélanger du polyphosphate d'ammonium, un agent de carbonisation de type triazine et l'agent de carbonisation du polymère d'acide 1,3,5-tris(2-hydroxyéthyl)cyanurique pour effectuer un traitement de surface, de façon à obtenir finalement l'agent ignifuge exempt d'halogène. De plus, l'invention concerne également l'agent ignifuge exempt d'halogène préparé à l'aide du procédé, destiné à être utilisé dans la préparation de polypropylène ignifuge. Les propriétés du polypropylène ignifuge préparé sont supérieures à celles du polypropylène ignifuge traditionnel d'un système d'agent de carbonisation à base de polyphosphate d'ammonium-triazine. L'agent ignifuge exempt d'halogène obtenu présente une meilleure compatibilité avec la résine de polypropylène, peut être comparable à un système ignifuge à base de brome-antimoine, est supérieur au brome-antimoine en ce qui concerne l'effet ignifuge de filaments incandescents et est plus respectueux de l'environnement et très compétitif en ce qui concerne le coût.
PCT/CN2017/097310 2016-08-23 2017-08-14 Agent ignifuge exempt d'halogène pouvant bien conserver les performances du polypropylène et applications correspondantes Ceased WO2018036398A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610712000.3 2016-08-23
CN201610712000.3A CN106432901A (zh) 2016-08-23 2016-08-23 一种能良好保持聚丙烯性能的无卤阻燃剂及其应用

Publications (1)

Publication Number Publication Date
WO2018036398A1 true WO2018036398A1 (fr) 2018-03-01

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Country Status (2)

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CN (1) CN106432901A (fr)
WO (1) WO2018036398A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210395477A1 (en) * 2018-09-28 2021-12-23 Sekisui Chemical Co., Ltd. Foamed polyolefin-based-resin sheet
CN118325215A (zh) * 2024-04-26 2024-07-12 北方民族大学 阻燃低密度聚乙烯复合材料及其制备方法和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106432901A (zh) * 2016-08-23 2017-02-22 中山康诺德新材料有限公司 一种能良好保持聚丙烯性能的无卤阻燃剂及其应用
CN114015060B (zh) * 2021-12-07 2022-11-22 什邡市长丰化工有限公司 一种聚磷酸铵阻燃剂、其制备方法及应用
CN117165249B (zh) * 2023-08-12 2024-05-10 江苏明昊新材料科技股份有限公司 一种光伏组件阻燃型密封胶及其制备方法

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WO2008079998A1 (fr) * 2006-12-21 2008-07-03 Dow Global Technologies Inc. Compositions de tpo chargées, procédés de fabrication de celles-ci et articles préparés à partir de celles-ci
CN101550249A (zh) * 2008-04-02 2009-10-07 上海化工研究院 一种无卤膨胀型阻燃玻纤增强聚丙烯材料及其制备方法
CN101550242A (zh) * 2008-04-02 2009-10-07 上海化工研究院 一种深色无卤膨胀聚烯烃阻燃剂及其制备方法
CN105732971A (zh) * 2016-01-21 2016-07-06 中山康诺德新材料有限公司 一种无卤环保成炭剂制备方法以及应用
CN106432901A (zh) * 2016-08-23 2017-02-22 中山康诺德新材料有限公司 一种能良好保持聚丙烯性能的无卤阻燃剂及其应用

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CN102276888B (zh) * 2011-07-22 2013-08-14 上海安凸塑料添加剂有限公司 用于动态硫化聚烯烃弹性体的无卤阻燃母粒及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008079998A1 (fr) * 2006-12-21 2008-07-03 Dow Global Technologies Inc. Compositions de tpo chargées, procédés de fabrication de celles-ci et articles préparés à partir de celles-ci
CN101550249A (zh) * 2008-04-02 2009-10-07 上海化工研究院 一种无卤膨胀型阻燃玻纤增强聚丙烯材料及其制备方法
CN101550242A (zh) * 2008-04-02 2009-10-07 上海化工研究院 一种深色无卤膨胀聚烯烃阻燃剂及其制备方法
CN105732971A (zh) * 2016-01-21 2016-07-06 中山康诺德新材料有限公司 一种无卤环保成炭剂制备方法以及应用
CN106432901A (zh) * 2016-08-23 2017-02-22 中山康诺德新材料有限公司 一种能良好保持聚丙烯性能的无卤阻燃剂及其应用

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210395477A1 (en) * 2018-09-28 2021-12-23 Sekisui Chemical Co., Ltd. Foamed polyolefin-based-resin sheet
US12060470B2 (en) * 2018-09-28 2024-08-13 Sekisui Chemical Co., Ltd. Foamed polyolefin-based-resin sheet
CN118325215A (zh) * 2024-04-26 2024-07-12 北方民族大学 阻燃低密度聚乙烯复合材料及其制备方法和应用

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