WO2019100748A1 - 一种透明薄膜用无卤阻燃pet复合材料及制备方法 - Google Patents

一种透明薄膜用无卤阻燃pet复合材料及制备方法 Download PDF

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WO2019100748A1
WO2019100748A1 PCT/CN2018/098279 CN2018098279W WO2019100748A1 WO 2019100748 A1 WO2019100748 A1 WO 2019100748A1 CN 2018098279 W CN2018098279 W CN 2018098279W WO 2019100748 A1 WO2019100748 A1 WO 2019100748A1
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retardant
halogen
composite material
flame
pet composite
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PCT/CN2018/098279
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English (en)
French (fr)
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陈哲
陈义忠
费建新
葛雷
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南通市东方塑胶有限公司
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Publication of WO2019100748A1 publication Critical patent/WO2019100748A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • 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
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • 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
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to the technical field of preparation of polymer materials, in particular to a halogen-free flame-retardant PET composite material for transparent film and a preparation method thereof.
  • halogen flame retardants mainly play the main role of chlorine, bromine, fluorine and iodine.
  • hydrogen chloride and hydrogen bromide produced by halogen flame retardants can damage the central nervous system and cause dioxin and other carcinogenesis during processing and use.
  • halogen flame retardants are mainly composed of inorganic metal compounds, phosphorus systems, nitrogen systems, Phosphorus and nitrogen, silicon-based composition, this kind of flame retardant does not contain additives harmful to human health, does not contain certain heavy metals, does not produce toxic gases causing environmental pollution, only produces a little white smoke when burning, for human health and environmental safety Less affected.
  • Aluminum hypophosphite is a kind of inorganic-filled flame retardant, which has poor temperature resistance, large addition amount and great influence on material properties; aluminum diethylphosphoric acid aluminum has a large amount of addition, which has a great influence on material properties, and also affects materials.
  • the present invention provides the following technical solution: a halogen-free flame-retardant PET composite material for a transparent film, the halogen-free flame-retardant PET composite material comprising the following composition by weight: 75-85% of PET resin; organic resistance 10-20% of fuel; 0.1-0.4% of heat stabilizer; 0.7-1.5% of glass fiber; 1.5-3% of nano-montmorillonite; 2-4% of antimony trioxide; 0.1-0.4% of antioxidant; compatible
  • the agent is 0.5-1.5%; the dispersing agent is 0.1-0.5%.
  • the organic flame retardant is a phosphorus-based flame retardant having a phosphorus content of 10.8%.
  • the heat stabilizer is 1010.
  • the antioxidant is a phosphite antioxidant, and one or more of 168, S9228 or Revonox 608 is used, of which Revonox 608 is preferred.
  • the compatibilizer is a bisphenol A type epoxy resin having an epoxy equivalent of 500-1000 g/eq, wherein an epoxy equivalent of 800-1000 g/eq is preferred.
  • the dispersing agent is one or more of PETS, montan wax, and microcrystalline wax, of which a montan wax is preferred.
  • the preparation method comprises the following steps:
  • the PET resin is fully dried to ensure that the moisture content is less than 100 ppm;
  • the organic flame retardant is fully dried to ensure that the moisture content is less than 100 ppm;
  • PET resin PET resin; organic flame retardant; heat stabilizer; glass fiber; nano montmorillonite; antimony trioxide; antioxidant; compatibilizer; dispersant fully mixed, wherein the organic flame retardant is weighed by weight loss Afterwards, it is added from the feeding side of the fifth section of the twin-screw extruder or from the main feeding, wherein it is preferably added from the side feeding, and the PET resin and other ingredients are added by the main feeding after the weighing loss, according to the setting. The extrusion process is then blended and granulated by a twin-screw extruder to obtain the desired PET composite.
  • the extrusion process in the step C is as follows: temperature of one zone is 180 ⁇ 5° C. temperature of two zones is 260 ⁇ 5° C. temperature of three zones is 280 ⁇ 5° C. temperature of four zones is 280 ⁇ 5° C. temperature of five zones 280 ⁇ 5°C, six zone temperature 280 ⁇ 5°C, seven zone temperature 280 ⁇ 5°C, eight zone temperature 260 ⁇ 5°C, nine zone temperature 250 ⁇ 5°C, die temperature 270 ⁇ 5°C, screw speed 360- 400r/min.
  • the invention has the beneficial effects that the halogen-free flame-retardant PET composite prepared by the invention has good transparency and excellent flame retardancy, and can meet the requirement of 10 um thickness film flame retardant VTM-0.
  • the added nano montmorillonite has excellent high temperature resistance and flame retardant property, and further improves the flame retardancy of the composite material; the added glass fiber can further improve the toughness of the composite material.
  • tensile properties; the addition of antimony trioxide can lower the combustion temperature. At high temperature, the antimony trioxide is vaporized, diluting the oxygen concentration in the air, thereby exerting a flame retarding effect and improving the flame retardancy of the composite material.
  • a halogen-free flame-retardant PET composite material for a transparent film comprises the following composition of weight percentage: PET resin 75-85%; organic flame retardant 10-20 %; heat stabilizer 0.1-0.4%; glass fiber 0.7-1.5%; nano-montmorillonite 1.5-3%; antimony trioxide 2-4%; antioxidant 0.1-0.4%; compatibilizer 0.5-1.5% ; dispersant 0.1-0.5%; wherein the PET resin has an intrinsic viscosity of more than 0.8 dl / g, preferably a PET resin having an intrinsic viscosity of more than 0.85 dl / g; the PET resin is preferably a PET resin containing only terephthalic acid groups;
  • the agent is a phosphorus-based flame retardant having a phosphorus content of 10.8%, a glass transition temperature of about 105 ° C, and a heat stabilizer of 1010.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • the halogen-free flame-retardant PET composite comprises the following composition by weight: 75% of PET resin; 20% of organic flame retardant; 0.1% of heat stabilizer; 0.7% of glass fiber; 1.5% of nano-montmorillonite; %; antioxidant 0.1%; compatibilizer 0.5%; dispersant 0.1%.
  • the antioxidant is a phosphite-based antioxidant, and 168 is used.
  • the compatibilizer is a bisphenol A type epoxy resin having an epoxy equivalent of 500 g/eq.
  • the dispersant is PETS.
  • the PET resin is fully dried to ensure that the moisture content is less than 100 ppm;
  • the organic flame retardant is fully dried to ensure that the moisture content is less than 100 ppm;
  • PET resin PET resin; organic flame retardant; heat stabilizer; glass fiber; nano montmorillonite; antimony trioxide; antioxidant; compatibilizer; dispersant fully mixed, wherein the organic flame retardant is weighed by weight loss Afterwards, it is added from the feeding side of the fifth section of the twin-screw extruder or from the main feeding, wherein it is preferably added from the side feeding, and the PET resin and other ingredients are added by the main feeding after the weighing loss, according to the setting. The extrusion process is then blended and granulated by a twin-screw extruder to obtain the desired PET composite.
  • the extrusion process in step C is as follows: one zone temperature 175 ° C, two zone temperature 255 ° C, three zone temperature 275 ° C, four zone temperature 275 ° C, five zone temperature 275 ° C, six zone temperature 275 ° C
  • the temperature in the seven zones is 275 ° C
  • the temperature in the eight zones is 255 ° C
  • the temperature in the nine zones is 245 ° C
  • the temperature of the die is 265 ° C
  • the screw speed is 360 r / min.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • the halogen-free flame-retardant PET composite comprises the following composition by weight: 85% of PET resin; 10% of organic flame retardant; 0.1% of heat stabilizer; 0.7% of glass fiber; 1.5% of nano-montmorillonite; %; antioxidant 0.1%; compatibilizer 0.5%; dispersant 0.1%.
  • the antioxidant is a phosphite-based antioxidant, and one or more of 168, S9228 or Revonox 608 is used.
  • the compatibilizer is a bisphenol A type epoxy resin having an epoxy equivalent of 1000 g/eq.
  • the dispersing agent is a microcrystalline wax.
  • the PET resin is fully dried to ensure that the moisture content is less than 100 ppm;
  • the organic flame retardant is fully dried to ensure that the moisture content is less than 100 ppm;
  • PET resin PET resin; organic flame retardant; heat stabilizer; glass fiber; nano montmorillonite; antimony trioxide; antioxidant; compatibilizer; dispersant fully mixed, wherein the organic flame retardant is weighed by weight loss Afterwards, it is added from the feeding side of the fifth section of the twin-screw extruder or from the main feeding, wherein it is preferably added from the side feeding, and the PET resin and other ingredients are added by the main feeding after the weighing loss, according to the setting. The extrusion process is then blended and granulated by a twin-screw extruder to obtain the desired PET composite.
  • the extrusion process in step C is specifically as follows: one zone temperature 185 ° C, two zone temperature 265 ° C, three zone temperature 285 ° C, four zone temperature 285 ° C, five zone temperature 285 ° C, six zone temperature 285 ° C
  • the temperature in the seven zones is 285 ° C
  • the temperature in the eight zones is 265 ° C
  • the temperature in the nine zones is 255 ° C
  • the temperature of the die is 275 ° C
  • the screw speed is 400 r / min.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • the halogen-free flame-retardant PET composite comprises the following composition by weight: 78% of PET resin; 13.5% of organic flame retardant; 0.4% of heat stabilizer; 1.5% of glass fiber; 1.5% of nano-montmorillonite; %; antioxidant 0.1%; compatibilizer 0.5%; dispersant 0.5%.
  • the antioxidant is a phosphite antioxidant, and a mixture of 168 and S9228 is used.
  • the compatibilizer is a bisphenol A type epoxy resin having an epoxy equivalent of 600 g/eq.
  • the dispersant is a mixture of PETS and microcrystalline wax.
  • the PET resin is fully dried to ensure that the moisture content is less than 100 ppm;
  • the organic flame retardant is fully dried to ensure that the moisture content is less than 100 ppm;
  • PET resin PET resin; organic flame retardant; heat stabilizer; glass fiber; nano montmorillonite; antimony trioxide; antioxidant; compatibilizer; dispersant fully mixed, wherein the organic flame retardant is weighed by weight loss Afterwards, it is added from the feeding side of the fifth section of the twin-screw extruder or from the main feeding, wherein it is preferably added from the side feeding, and the PET resin and other ingredients are added by the main feeding after the weighing loss, according to the setting. The extrusion process is then blended and granulated by a twin-screw extruder to obtain the desired PET composite.
  • the extrusion process in step C is as follows: one zone temperature 182 ° C, two zone temperature 264 ° C, three zone temperature 278 ° C, four zone temperature 284 ° C, five zone temperature 282 ° C, six zone temperature 276 ° C
  • the temperature in the seven zones is 284 ° C
  • the temperature in the eight zones is 258 ° C
  • the temperature in the nine zones is 252 ° C
  • the temperature of the die is 274 ° C
  • the screw speed is 390 r / min.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • the halogen-free flame-retardant PET composite comprises the following composition by weight: 80% of PET resin; 11.6% of organic flame retardant; 0.2% of heat stabilizer; 1% of glass fiber; 2% of nano-montmorillonite; %; antioxidant 0.2%; compatibilizer 1.5%; dispersant 0.5%.
  • the antioxidant is a phosphite-based antioxidant, and Revonox 608 is used.
  • the compatibilizer is a bisphenol A type epoxy resin having an epoxy equivalent of 800 g/eq.
  • the dispersant is a montan wax.
  • the PET resin is fully dried to ensure that the moisture content is less than 100 ppm;
  • the organic flame retardant is fully dried to ensure that the moisture content is less than 100 ppm;
  • PET resin PET resin; organic flame retardant; heat stabilizer; glass fiber; nano montmorillonite; antimony trioxide; antioxidant; compatibilizer; dispersant fully mixed, wherein the organic flame retardant is weighed by weight loss Afterwards, it is added from the feeding side of the fifth section of the twin-screw extruder or from the main feeding, wherein it is preferably added from the side feeding, and the PET resin and other ingredients are added by the main feeding after the weighing loss, according to the setting. The extrusion process is then blended and granulated by a twin-screw extruder to obtain the desired PET composite.
  • the extrusion process in step C is as follows: one zone temperature 180 ° C, two zone temperature 260 ° C, three zone temperature 280 ° C, four zone temperature 280 ° C, five zone temperature 280 ° C, six zone temperature 280 ° C
  • the temperature in the seven zones is 280 ° C
  • the temperature in the eight zones is 260 ° C
  • the temperature in the nine zones is 250 ° C
  • the temperature of the die is 270 ° C
  • the screw speed is 380 r / min.
  • the halogen-free flame-retardant PET composite prepared by the invention has good transparency and excellent flame retardancy, can meet the requirement of 10 um thick film flame retardant VTM-0, and has excellent toughness and workability; among them, adding The nano montmorillonite has excellent high temperature resistance and flame retardant property, and further improves the flame retardancy of the composite material; the added glass fiber can further improve the toughness and tensile properties of the composite material; the added antimony trioxide can reduce the combustion temperature. At high temperature, the antimony trioxide is vaporized, diluting the oxygen concentration in the air, thereby exerting a flame retarding effect and improving the flame retardancy of the composite material.

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Abstract

本发明公开了一种透明薄膜用无卤阻燃PET复合材料及制备方法，该无卤阻燃PET复合材料包含如下重量百分比的配方组成：PET树脂75-85％；有机阻燃剂10-20％；热稳定剂0.1-0.4％；玻璃纤维0.7-1.5％；纳米蒙脱土1.5-3％；三氧化二锑2-4％；抗氧剂0.1-0.4％；相容剂0.5-1.5％；分散剂0.1-0.5％。本发明制备的无卤阻燃PET复合材料，具有良好的透明性和优异的阻燃性，可达到10um厚度薄膜阻燃VTM-0的要求，同时具有优异的韧性和可加工性。

Description

[根据细则26改正22.08.2018]　一种透明薄膜用无卤阻燃PET复合材料及制备方法 技术领域
本发明涉及高分子材料制备技术领域，具体为一种透明薄膜用无卤阻燃PET复合材料及制备方法。
背景技术
目前，实现PET树脂阻燃的阻燃剂主要有两类：卤素类和非卤素类。卤素阻燃剂主要是氯、溴、氟、碘元素起到主要作用，但卤素阻燃剂产生的氯化氢、溴化氢等在加工与使用过程中能破坏人体中枢神经且产生二恶英等致癌物等有毒有害物质，同时在燃烧时产生大量的有毒黑浓烟，侵蚀破坏设备及环境安全卫生，延长与阻碍消防救援工作；卤阻燃剂主要是由无机金属化合物、磷系、氮系、磷氮系、硅系组成，该类阻燃剂不含有害于人类健康的添加剂，不含某些重金属，不产生有毒气体引起环境污染，燃烧时只产生少许淡白烟，对人类健康及环境安全影响较小。
现在市场上用于PET树脂的无卤阻燃剂主要有以下几种：次磷酸铝，二乙基次磷酸铝，磷腈阻燃剂。次磷酸铝属无机填充型阻燃剂，耐温性较差，添加量大，对材料的性能影响大；二乙基次磷酸铝添加量较大，对材料性能影响较大，也会影响材料的透明性；磷腈阻燃剂虽然添加量不大，但阻燃效果差，不能充分满足薄膜的阻燃要求。
发明内容
本发明的目的在于提供一种透明薄膜用无卤阻燃PET复合材料及制备方法，以解决上述背景技术中提出的问题。
为实现上述目的，本发明提供如下技术方案：一种透明薄膜用无卤阻燃PET复合材料,该无卤阻燃PET复合材料包含如下重量百分比的配方组成：PET树脂 75-85％；有机阻燃剂10-20％；热稳定剂0.1-0.4％；玻璃纤维0.7-1.5％；纳米蒙脱土1.5-3％；三氧化二锑2-4％；抗氧剂0.1-0.4％；相容剂0.5-1.5％；分散剂0.1-0.5％。
优选的，所述有机阻燃剂为磷系阻燃剂，其磷含量为10.8％。
优选的，所述的热稳定剂为1010。
优选的，所述的抗氧剂为亚磷酸酯系抗氧化剂，采用168、S9228或Revonox 608中的一种或几种，其中优选Revonox 608。
优选的，所述的相容剂为双酚A型环氧树脂，环氧当量500-1000g/eq，其中优选环氧当量800-1000g/eq。
优选的，所述的分散剂为PETS、蒙旦蜡、微晶蜡中的一种或几种，其中优选蒙旦蜡。
优选的，其制备方法包括以下步骤：
A、将PET树脂充分烘干，保证水分含量小于100ppm；
B、将有机阻燃剂充分烘干，保证水分含量小于100ppm；
C、将PET树脂；有机阻燃剂；热稳定剂；玻璃纤维；纳米蒙脱土；三氧化二锑；抗氧剂；相容剂；分散剂充分混合，其中有机阻燃剂经失重称计量后由双螺杆挤出机第五段侧喂料处加入或从主喂料加入，其中优选从侧喂料加入，PET树脂及其他配料经失重称计量后由主喂料加入，根据设定的挤出工艺，然后经双螺杆挤出机共混挤出造粒，得到所需的PET复合材料。
优选的，所述步骤C中的挤出工艺具体如下：一区温度180±5℃，二区温度260±5℃，三区温度280±5℃，四区温度280±5℃，五区温度280±5℃，六区温度280±5℃，七区温度280±5℃，八区温度260±5℃，九区温度250±5℃，模头温度270±5℃，螺杆转速为360-400r/min。
与现有技术相比，本发明的有益效果是：本发明制备的无卤阻燃PET复合材料，具有良好的透明性和优异的阻燃性，可达到10um厚度薄膜阻燃VTM-0的要求，同时具有优异的韧性和可加工性；其中，添加的纳米蒙脱土具有优异的耐高温、阻燃性能，进一步提高了复合材料的阻燃性能；添加的玻璃纤维能够进一步提高复合材料的韧性和抗拉性能；添加的三氧化二锑能够降低燃烧温度。在高温状态下三氧化二锑被气化，稀释了空气中氧浓度，从而起到阻燃作用，提高了复合材料的阻燃性能。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供如下技术方案：一种透明薄膜用无卤阻燃PET复合材料,该无卤阻燃PET复合材料包含如下重量百分比的配方组成：PET树脂75-85％；有机阻燃剂10-20％；热稳定剂0.1-0.4％；玻璃纤维0.7-1.5％；纳米蒙脱土1.5-3％；三氧化二锑2-4％；抗氧剂0.1-0.4％；相容剂0.5-1.5％；分散剂0.1-0.5％；其中，PET树脂特性粘度大于0.8dl/g,优选特性粘度大于0.85dl/g的PET树脂；PET树脂优选只含有对苯二甲酸基团的PET树脂；有机阻燃剂为磷系阻燃剂，其磷含量为10.8％，玻璃化转变温度约105℃；热稳定剂为1010。
实施例一：
无卤阻燃PET复合材料包含如下重量百分比的配方组成：PET树脂75％；有机阻燃剂20％；热稳定剂0.1％；玻璃纤维0.7％；纳米蒙脱土1.5％；三氧化二锑2％；抗氧剂0.1％；相容剂0.5％；分散剂0.1％。
本实施例中，抗氧剂为亚磷酸酯系抗氧化剂，采用168。
本实施例中，相容剂为双酚A型环氧树脂，环氧当量500g/eq。
本实施例中，分散剂为PETS。
本实施例的制备方法包括以下步骤：
A、将PET树脂充分烘干，保证水分含量小于100ppm；
B、将有机阻燃剂充分烘干，保证水分含量小于100ppm；
C、将PET树脂；有机阻燃剂；热稳定剂；玻璃纤维；纳米蒙脱土；三氧化二锑；抗氧剂；相容剂；分散剂充分混合，其中有机阻燃剂经失重称计量后由双螺杆挤出机第五段侧喂料处加入或从主喂料加入，其中优选从侧喂料加入，PET树脂及其他配料经失重称计量后由主喂料加入，根据设定的挤出工艺，然后经双螺杆挤出机共混挤出造粒，得到所需的PET复合材料。
本实施例中，步骤C中的挤出工艺具体如下：一区温度175℃，二区温度255℃，三区温度275℃，四区温度275℃，五区温度275℃，六区温度275℃，七区温度275℃，八区温度255℃，九区温度245℃，模头温度265℃，螺杆转速为360r/min。
实施例二：
无卤阻燃PET复合材料包含如下重量百分比的配方组成：PET树脂85％；有机阻燃剂10％；热稳定剂0.1％；玻璃纤维0.7％；纳米蒙脱土1.5％；三氧化二锑2％；抗氧剂0.1％；相容剂0.5％；分散剂0.1％。
本实施例中，抗氧剂为亚磷酸酯系抗氧化剂，采用168、S9228或Revonox 608中的一种或几种。
本实施例中，相容剂为双酚A型环氧树脂，环氧当量1000g/eq。
本实施例中，分散剂为微晶蜡。
本实施例的制备方法包括以下步骤：
A、将PET树脂充分烘干，保证水分含量小于100ppm；
B、将有机阻燃剂充分烘干，保证水分含量小于100ppm；
C、将PET树脂；有机阻燃剂；热稳定剂；玻璃纤维；纳米蒙脱土；三氧化二锑；抗氧剂；相容剂；分散剂充分混合，其中有机阻燃剂经失重称计量后由双螺杆挤出机第五段侧喂料处加入或从主喂料加入，其中优选从侧喂料加入，PET树脂及其他配料经失重称计量后由主喂料加入，根据设定的挤出工艺，然后经双螺杆挤出机共混挤出造粒，得到所需的PET复合材料。
本实施例中，步骤C中的挤出工艺具体如下：一区温度185℃，二区温度265℃，三区温度285℃，四区温度285℃，五区温度285℃，六区温度285℃，七区温度285℃，八区温度265℃，九区温度255℃，模头温度275℃，螺杆转速为400r/min。
实施例三：
无卤阻燃PET复合材料包含如下重量百分比的配方组成：PET树脂78％；有机阻燃剂13.5％；热稳定剂0.4％；玻璃纤维1.5％；纳米蒙脱土1.5％；三氧化二锑4％；抗氧剂0.1％；相容剂0.5％；分散剂0.5％。
本实施例中，抗氧剂为亚磷酸酯系抗氧化剂，采用168、S9228混合物。
本实施例中，相容剂为双酚A型环氧树脂，环氧当量600g/eq。
本实施例中，分散剂为PETS、微晶蜡混合物。
本实施例的制备方法包括以下步骤：
A、将PET树脂充分烘干，保证水分含量小于100ppm；
B、将有机阻燃剂充分烘干，保证水分含量小于100ppm；
C、将PET树脂；有机阻燃剂；热稳定剂；玻璃纤维；纳米蒙脱土；三氧化 二锑；抗氧剂；相容剂；分散剂充分混合，其中有机阻燃剂经失重称计量后由双螺杆挤出机第五段侧喂料处加入或从主喂料加入，其中优选从侧喂料加入，PET树脂及其他配料经失重称计量后由主喂料加入，根据设定的挤出工艺，然后经双螺杆挤出机共混挤出造粒，得到所需的PET复合材料。
本实施例中，步骤C中的挤出工艺具体如下：一区温度182℃，二区温度264℃，三区温度278℃，四区温度284℃，五区温度282℃，六区温度276℃，七区温度284℃，八区温度258℃，九区温度252℃，模头温度274℃，螺杆转速为390r/min。
实施例四：
无卤阻燃PET复合材料包含如下重量百分比的配方组成：PET树脂80％；有机阻燃剂11.6％；热稳定剂0.2％；玻璃纤维1％；纳米蒙脱土2％；三氧化二锑3％；抗氧剂0.2％；相容剂1.5％；分散剂0.5％。
本实施例中，抗氧剂为亚磷酸酯系抗氧化剂，采用Revonox 608。
本实施例中，相容剂为双酚A型环氧树脂，环氧当量800g/eq。
本实施例中，分散剂为蒙旦蜡。
本实施例的制备方法包括以下步骤：
A、将PET树脂充分烘干，保证水分含量小于100ppm；
B、将有机阻燃剂充分烘干，保证水分含量小于100ppm；
C、将PET树脂；有机阻燃剂；热稳定剂；玻璃纤维；纳米蒙脱土；三氧化二锑；抗氧剂；相容剂；分散剂充分混合，其中有机阻燃剂经失重称计量后由双螺杆挤出机第五段侧喂料处加入或从主喂料加入，其中优选从侧喂料加入，PET树脂及其他配料经失重称计量后由主喂料加入，根据设定的挤出工艺，然后经双螺杆挤出机共混挤出造粒，得到所需的PET复合材料。
本实施例中，步骤C中的挤出工艺具体如下：一区温度180℃，二区温度260℃，三区温度280℃，四区温度280℃，五区温度280℃，六区温度280℃，七区温度280℃，八区温度260℃，九区温度250℃，模头温度270℃，螺杆转速为380r/min。
实验例：
采用本发明各实施例制得的复合材料进行试验，得到数据如下表：
Figure PCTCN2018098279-appb-000001
本发明制备的无卤阻燃PET复合材料，具有良好的透明性和优异的阻燃性，可达到10um厚度薄膜阻燃VTM-0的要求，同时具有优异的韧性和可加工性；其中，添加的纳米蒙脱土具有优异的耐高温、阻燃性能，进一步提高了复合材料的阻燃性能；添加的玻璃纤维能够进一步提高复合材料的韧性和抗拉性能；添加的三氧化二锑能够降低燃烧温度。在高温状态下三氧化二锑被气化，稀释了空气中氧浓度，从而起到阻燃作用，提高了复合材料的阻燃性能。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。

Claims (8)

  1. 一种透明薄膜用无卤阻燃PET复合材料,其特征在于：该无卤阻燃PET复合材料包含如下重量百分比的配方组成：PET树脂75-85％；有机阻燃剂10-20％；热稳定剂0.1-0.4％；玻璃纤维0.7-1.5％；纳米蒙脱土1.5-3％；三氧化二锑2-4％；抗氧剂0.1-0.4％；相容剂0.5-1.5％；分散剂0.1-0.5％。
  2. 根据权利要求1所述的一种透明薄膜用无卤阻燃PET复合材料,其特征在于：所述有机阻燃剂为磷系阻燃剂，其磷含量为10.8％。
  3. 根据权利要求1所述的一种透明薄膜用无卤阻燃PET复合材料,其特征在于：所述的热稳定剂为1010。
  4. 根据权利要求1所述的一种透明薄膜用无卤阻燃PET复合材料,其特征在于：所述的抗氧剂为亚磷酸酯系抗氧化剂，采用168、S9228或Revonox 608中的一种或几种，其中优选Revonox 608。
  5. 根据权利要求1所述的一种透明薄膜用无卤阻燃PET复合材料,其特征在于：所述的相容剂为双酚A型环氧树脂，环氧当量500-1000g/eq，其中优选环氧当量800-1000g/eq。
  6. 根据权利要求1所述的一种透明薄膜用无卤阻燃PET复合材料,其特征在于：所述的分散剂为PETS、蒙旦蜡、微晶蜡中的一种或几种，其中优选蒙旦蜡。
  7. 实现权利要求1所述的一种透明薄膜用无卤阻燃PET复合材料的制备方法,其特征在于：其制备方法包括以下步骤：
    A、将PET树脂充分烘干，保证水分含量小于100ppm；
    B、将有机阻燃剂充分烘干，保证水分含量小于100ppm；
    C、将PET树脂；有机阻燃剂；热稳定剂；玻璃纤维；纳米蒙脱土；三氧化二锑；抗氧剂；相容剂；分散剂充分混合，其中有机阻燃剂经失重称计量后由双螺杆挤出机第五段侧喂料处加入或从主喂料加入，其中优选从侧喂料加入， PET树脂及其他配料经失重称计量后由主喂料加入，根据设定的挤出工艺，然后经双螺杆挤出机共混挤出造粒，得到所需的PET复合材料。
  8. 根据权利要求7所述的一种透明薄膜用无卤阻燃PET复合材料的制备方法,其特征在于：所述步骤C中的挤出工艺具体如下：一区温度180±5℃，二区温度260±5℃，三区温度280±5℃，四区温度280±5℃，五区温度280±5℃，六区温度280±5℃，七区温度280±5℃，八区温度260±5℃，九区温度250±5℃，模头温度270±5℃，螺杆转速为360-400r/min。
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