[go: up one dir, main page]

CN118909420A - Fluorine-free flame-retardant PC (polycarbonate) recycling modified material and preparation method thereof - Google Patents

Fluorine-free flame-retardant PC (polycarbonate) recycling modified material and preparation method thereof Download PDF

Info

Publication number
CN118909420A
CN118909420A CN202411248531.2A CN202411248531A CN118909420A CN 118909420 A CN118909420 A CN 118909420A CN 202411248531 A CN202411248531 A CN 202411248531A CN 118909420 A CN118909420 A CN 118909420A
Authority
CN
China
Prior art keywords
fluorine
free flame
retardant
flame retardant
powder
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.)
Granted
Application number
CN202411248531.2A
Other languages
Chinese (zh)
Other versions
CN118909420B (en
Inventor
黄金彪
肖高基
张湘孟
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.)
Dongguan Guoheng Plastic Science & Technology Co ltd
Original Assignee
Dongguan Guoheng Plastic Science & Technology 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 Dongguan Guoheng Plastic Science & Technology Co ltd filed Critical Dongguan Guoheng Plastic Science & Technology Co ltd
Priority to CN202411248531.2A priority Critical patent/CN118909420B/en
Priority claimed from CN202411248531.2A external-priority patent/CN118909420B/en
Publication of CN118909420A publication Critical patent/CN118909420A/en
Application granted granted Critical
Publication of CN118909420B publication Critical patent/CN118909420B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/267Magnesium carbonate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/20Recycled plastic

Landscapes

  • 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

本申请涉及高分子材料的领域,更具体地说,它涉及一种无氟阻燃PC回收改性料及其制备方法。由以下重量百分比组成:PC回收料60‑87.2%、无氟阻燃复合物12‑21%、抗氧剂0.3‑0.8%、增韧剂0‑20%;所述无氟阻燃复合物由硅PC粉、含磷阻燃剂、纳米级无机填料、聚二甲基硅氧烷组成;纳米级无机填料为菱镁矿粉和/或浮石粉;磷阻燃剂为四苯基双酚A二磷酸酯和/或聚二苯基氧基磷腈。通过硅PC粉、含磷阻燃剂、纳米级无机填料、聚二甲基硅氧烷复配,起到增效作用,进一步提高PC回收改性料的物理性能、阻燃性能以及耐候性,当用于抽烟机等家电产品,使其长期在高温、油烟环境下,保持较佳性能。提高家电产品的耐久性和使用安全性。The present application relates to the field of polymer materials, and more specifically, it relates to a fluorine-free flame-retardant PC recycled modified material and a preparation method thereof. It is composed of the following weight percentages: 60-87.2% PC recycled material, 12-21% fluorine-free flame-retardant compound, 0.3-0.8% antioxidant, and 0-20% toughening agent; the fluorine-free flame-retardant compound is composed of silicon PC powder, phosphorus-containing flame retardant, nano-scale inorganic filler, and polydimethylsiloxane; the nano-scale inorganic filler is magnesite powder and/or pumice powder; the phosphorus flame retardant is tetraphenyl bisphenol A diphosphate and/or polydiphenyloxyphosphazene. The compounding of silicon PC powder, phosphorus-containing flame retardant, nano-scale inorganic filler, and polydimethylsiloxane plays a synergistic role, further improving the physical properties, flame retardant properties, and weather resistance of PC recycled modified materials. When used in household appliances such as smoke extractors, it can maintain better performance in high temperature and oil fume environments for a long time. Improve the durability and safety of household appliances.

Description

一种无氟阻燃PC回收改性料及其制备方法A fluorine-free flame-retardant PC recycled modified material and preparation method thereof

技术领域Technical Field

本申请涉及高分子材料的领域,更具体地说,它涉及一种无氟阻燃PC回收改性料及其制备方法。The present application relates to the field of polymer materials, and more specifically, to a fluorine-free flame-retardant PC recycled modified material and a preparation method thereof.

背景技术Background Art

PC材料是五大工程塑料之一,其具有优异的透明性、耐冲击性、耐温性、耐老化性等特点,因此被广泛应用于电子电器、汽车工业、建筑行业、医疗器械、包装材料、航空航天、体育器材、光学产品等领域。PC material is one of the five major engineering plastics. It has excellent transparency, impact resistance, temperature resistance, aging resistance and other characteristics. Therefore, it is widely used in electronics, automobile industry, construction industry, medical equipment, packaging materials, aerospace, sports equipment, optical products and other fields.

PC是由石油制成的,目前为了减少能源损耗,对PC进行回收再利用;而PC回收料通常加入阻燃剂,生产阻燃PC回收改性料,并应用于家电产品,如抽烟机、烤箱、烘箱、电饭煲、冰箱等的外壳以及其他部件。PC is made from petroleum. Currently, PC is recycled and reused to reduce energy loss. Flame retardants are usually added to PC recycled materials to produce flame-retardant PC recycled modified materials, which are used in household appliances such as the shells and other parts of range hoods, ovens, rice cookers, refrigerators, etc.

但是再生PC来源于多种渠道,包括消费后回收和工业废料,这导致回收料的成分和性质复杂多变,增加了回收和再利用的难度,导致PC回收生产的制品的性能比PC生产的制品的性能低。并且长期在油烟环境中使用,加速材料老化,特别是应用于抽烟机的PC回收料;如饭店中油烟机,在使用过程油烟量大,且长期处于高温和较重的油烟环境,导致PC回收料容易发生老化,降低其性能。However, recycled PC comes from a variety of channels, including post-consumer recycling and industrial waste, which makes the composition and properties of recycled materials complex and variable, increasing the difficulty of recycling and reuse, resulting in lower performance of PC recycled products than PC products. In addition, long-term use in oil fume environments accelerates material aging, especially PC recycled materials used in smoke extractors; such as hotel range hoods, which produce a large amount of oil fume during use and are in a high temperature and heavy oil fume environment for a long time, causing PC recycled materials to age easily and reduce their performance.

目前采用全氟烷基或多氟烷基化合物的含氟阻燃剂,能够使阻燃PC回收料获得较佳的耐候性和阻燃性能,并保持较佳的物理性能。但是全氟烷基或多氟烷基化健康造成风险。Currently, the use of fluorinated flame retardants containing perfluoroalkyl or polyfluoroalkyl compounds can enable flame-retardant PC recycled materials to obtain better weather resistance and flame retardancy, while maintaining better physical properties. However, perfluoroalkyl or polyfluoroalkyl compounds pose health risks.

也有采用非氟系阻燃剂,如氢氧化镁、氢氧化铝等虽然获得较佳的阻燃效果,也能提高PC材料的耐热性,但是加入较大量,才能获得与含氟阻燃剂相近的阻燃效果,加入的量大,也导致PC回收料的物理性能降低,因此需要对无氟阻燃PC回收料的改性进一步研究。Non-fluorine flame retardants such as magnesium hydroxide and aluminum hydroxide are also used. Although they can achieve better flame retardant effects and improve the heat resistance of PC materials, a larger amount must be added to obtain a flame retardant effect similar to that of fluorinated flame retardants. A large amount added will also lead to a decrease in the physical properties of PC recycled materials. Therefore, further research is needed on the modification of fluorine-free flame retardant PC recycled materials.

发明内容Summary of the invention

为了获得较佳的阻燃效果,且减少长期处于高温和较重的油烟环境下,发生老化的现象,本申请提供一种无氟阻燃PC回收改性料及其制备方法。In order to obtain better flame retardant effect and reduce aging phenomenon caused by long-term exposure to high temperature and heavy oil fume environment, the present application provides a fluorine-free flame retardant PC recycled modified material and a preparation method thereof.

第一方面,本申请提供一种无氟阻燃PC回收改性料,由以下重量百分比组成:PC回收料60-87.2%In the first aspect, the present application provides a fluorine-free flame retardant PC recycled modified material, which is composed of the following weight percentages: PC recycled material 60-87.2%

无氟阻燃复合物12-21%Fluorine-free flame retardant compound 12-21%

抗氧剂0.3-0.8%Antioxidant 0.3-0.8%

增韧剂0-20%;Toughener 0-20%;

所述无氟阻燃复合物由硅PC粉、含磷阻燃剂、纳米级无机填料、聚二甲基硅氧烷中多种组成;The fluorine-free flame retardant composite is composed of silicon PC powder, phosphorus-containing flame retardant, nano-scale inorganic filler, and polydimethylsiloxane;

所述纳米级无机填料为菱镁矿粉和/或浮石粉;所述含磷阻燃剂为四苯基双酚A二磷酸酯和/或聚二苯基氧基磷腈。The nanometer-scale inorganic filler is magnesite powder and/or pumice powder; the phosphorus-containing flame retardant is tetraphenyl bisphenol A diphosphate and/or polydiphenyloxyphosphazene.

硅PC粉,即硅共聚聚碳酸酯,是一种通过在聚碳酸酯中引入硅氧烷基团进行共聚得到的高性能工程塑料。与普通PC相比,具有较佳的柔性、耐水解性、耐高低温、阻燃等性能;因此,配合含磷阻燃剂、纳米级无机填料、聚二甲基硅氧烷,使无氟阻燃PC回收改性料获得较佳的物理性能和阻燃性能,并且具有较佳的阻燃稳定性。Silicon PC powder, namely silicon copolymer polycarbonate, is a high-performance engineering plastic obtained by copolymerizing siloxane groups introduced into polycarbonate. Compared with ordinary PC, it has better flexibility, hydrolysis resistance, high and low temperature resistance, flame retardancy and other properties; therefore, with phosphorus-containing flame retardants, nano-scale inorganic fillers, and polydimethylsiloxane, the fluorine-free flame retardant PC recycled modified material has better physical properties and flame retardancy, and has better flame retardant stability.

四苯基双酚A二磷酸酯具有相对分子质量大、热稳定性高、挥发性低等,且耐水分解性好、耐高温,聚二苯基氧基磷腈具有良好的热稳定性和优异的阻燃性能。能够抑制火焰传播和物质燃烧,提高材料的安全性。此外,它还具有良好的电子特性,可以应用于电子器件、导电材料等领域。因此,采用四苯基双酚A二磷酸酯和/或聚二苯基氧基磷腈的含磷阻燃剂,应用高温高湿环境能够减少迁移或者减少阻燃效果降低,从而阻燃PC回收改性料获得较佳的阻燃效果。Tetraphenyl bisphenol A diphosphate has a large relative molecular weight, high thermal stability, low volatility, etc., and has good water decomposition resistance and high temperature resistance. Polydiphenyloxyphosphazene has good thermal stability and excellent flame retardant properties. It can inhibit the spread of flames and the combustion of materials, and improve the safety of materials. In addition, it also has good electronic properties and can be used in electronic devices, conductive materials and other fields. Therefore, the phosphorus-containing flame retardant using tetraphenyl bisphenol A diphosphate and/or polydiphenyloxyphosphazene can reduce migration or reduce the reduction of flame retardant effect in a high temperature and high humidity environment, so that the flame retardant PC recycled modified material obtains a better flame retardant effect.

聚二甲基硅氧烷是一种超高分子量聚二甲基硅氧烷,为固体粉末。作为阻燃剂和加工助剂,同时用于热塑性塑料中,还能起到增韧的作用。聚二甲基硅氧烷还具有表面张力小,能够降低硅PC粉、含磷阻燃剂、纳米级无机填料颗粒之间的相互作用力,从而提高硅PC粉、含磷阻燃剂、纳米级无机填料在阻燃PC回收改性料原料体系中的相容性,从而获得较佳的阻燃性能和冲击韧性。Polydimethylsiloxane is an ultra-high molecular weight polydimethylsiloxane in the form of solid powder. As a flame retardant and processing aid, it is also used in thermoplastics to enhance toughness. Polydimethylsiloxane also has a low surface tension, which can reduce the interaction between silicon PC powder, phosphorus-containing flame retardant, and nano-scale inorganic filler particles, thereby improving the compatibility of silicon PC powder, phosphorus-containing flame retardant, and nano-scale inorganic filler in the flame retardant PC recycled modified material raw material system, thereby obtaining better flame retardant properties and impact toughness.

而菱镁矿粉主要成分为碳酸镁,在加热过程中,菱镁矿粉会释放出结晶水、结构水及二氧化碳,从而降低材料表面火焰的温度,减少可燃气体和氧气的浓度,形成保护层。此外,氧化镁具有催化热氧交联反应的能力,形成炭化膜,进一步增强阻燃效果。浮石粉是一种多孔的火山岩,主要由二氧化硅组成,具有多孔结构和高热性。浮石粉对火焰传播起到的抑制作用,并能配合硅PC粉、含磷阻燃剂、聚二甲基硅氧烷,起到较佳的阻燃效果。The main component of magnesite powder is magnesium carbonate. During the heating process, magnesite powder will release crystal water, structural water and carbon dioxide, thereby reducing the temperature of the flame on the surface of the material, reducing the concentration of combustible gas and oxygen, and forming a protective layer. In addition, magnesium oxide has the ability to catalyze thermal oxygen cross-linking reactions to form a carbonized film, further enhancing the flame retardant effect. Pumice powder is a porous volcanic rock, mainly composed of silicon dioxide, with a porous structure and high thermal properties. Pumice powder has an inhibitory effect on flame propagation, and can be combined with silicon PC powder, phosphorus-containing flame retardants, and polydimethylsiloxane to achieve a better flame retardant effect.

再者菱镁矿粉和/或浮石粉作为纳米级无机填料,除了进一步提高阻燃效果,还起到增韧、耐油湿热等作用,配合硅PC粉、含磷阻燃剂、聚二甲基硅氧烷,对PC回收改性料起到较佳的耐候性能、阻燃性能以及物理性能。Furthermore, magnesite powder and/or pumice powder as nano-scale inorganic fillers, in addition to further improving the flame retardant effect, also play the role of toughening, oil and heat resistance, etc., combined with silicon PC powder, phosphorus-containing flame retardant, polydimethylsiloxane, it has better weather resistance, flame retardant properties and physical properties for PC recycled modified materials.

综上,本申请通过硅PC粉、含磷阻燃剂、纳米级无机填料、聚二甲基硅氧烷复配,起到增效作用,进一步PC回收改性料起到的物理性能、阻燃性能以及耐候性,当用于抽烟机等家电产品,使其在高温、油烟环境下,仍然保持较佳的阻燃效果和物理性能。提高家电产品的耐久性和使用安全性。In summary, the present application uses silicon PC powder, phosphorus-containing flame retardant, nano-scale inorganic filler, and polydimethylsiloxane to compound and enhance the physical properties, flame retardant properties, and weather resistance of PC recycled modified materials. When used in household appliances such as range hoods, they can still maintain good flame retardant effects and physical properties in high temperature and oil smoke environments, thereby improving the durability and safety of household appliances.

本申请生产的PC回收改性料主要用于抽烟机的外壳、过滤网、油烟管等。也可以用于冰箱外壳、烤箱底部支脚、微波炉底部支脚等。有油烟环境和无油烟环境均可以使用,并在油烟环境下,起到较佳的耐候性,减少其发生老化,提高耐久性和使用安全性。The PC recycled modified material produced in this application is mainly used for the housing, filter screen, oil fume pipe, etc. of the smoke extractor. It can also be used for the refrigerator housing, the bottom legs of the oven, the bottom legs of the microwave oven, etc. It can be used in both oil fume and non-oil fume environments, and in the oil fume environment, it has better weather resistance, reduces aging, and improves durability and safety of use.

所述PC回收料、无氟阻燃复合物、抗氧化剂、增韧剂的的重量百分比总和为100%。The total weight percentage of the PC recycled material, the fluorine-free flame retardant compound, the antioxidant and the toughening agent is 100%.

进一步地,本申请的增韧剂的重量百分比优选为5%。Furthermore, the weight percentage of the toughening agent of the present application is preferably 5%.

优选的,所述纳米级无机填料的粒径为150-300nm。Preferably, the particle size of the nanoscale inorganic filler is 150-300 nm.

以上粒径范围为本申请较佳选择,在该粒径范围下,容易进行分散,并且对PC回收料起到较佳的增韧作用,并配合硅PC粉、含磷阻燃剂、聚二甲基硅氧烷,进一步提高无氟阻燃PC回收改性料的物理性能和阻燃性能。The above particle size range is the best choice for this application. Within this particle size range, it is easy to disperse and has a better toughening effect on PC recycled materials. In combination with silicon PC powder, phosphorus-containing flame retardant, and polydimethylsiloxane, the physical properties and flame retardant properties of fluorine-free flame retardant PC recycled modified materials are further improved.

优选的,所述硅PC粉、含磷阻燃剂、纳米级无机填料、聚二甲基硅氧烷的重量比为(10-15):(1-4):(3-5):1。Preferably, the weight ratio of the silicon PC powder, the phosphorus-containing flame retardant, the nano-scale inorganic filler and the polydimethylsiloxane is (10-15): (1-4): (3-5): 1.

当硅PC粉、含磷阻燃剂、纳米级无机填料、聚二甲基硅氧烷以重量比为(10-15):(1-4):(3-5):1进行复配后,起到较较佳的增效作用,从使得无氟阻燃PC回收改性料获得较佳的物理性能、阻燃性能和耐候性能。本申请中的耐候性能是指在高温的油烟环境下能够保持较佳的性能,减少出现老化等现象,提高家电产品的耐久性和使用安全性。When silicon PC powder, phosphorus-containing flame retardant, nano-scale inorganic filler and polydimethylsiloxane are compounded in a weight ratio of (10-15): (1-4): (3-5): 1, a better synergistic effect is achieved, so that the fluorine-free flame retardant PC recycled modified material obtains better physical properties, flame retardant properties and weather resistance. The weather resistance in this application refers to the ability to maintain better performance in a high-temperature oil fume environment, reduce aging and other phenomena, and improve the durability and safety of home appliances.

优选的,所述菱镁矿粉、浮石粉的重量比为(1-3):1。当采用菱镁矿粉、浮石粉复配后,起到增效作用从使得无氟阻燃PC回收改性料获得较佳的物理性能、阻燃性能以及稳耐候性能。Preferably, the weight ratio of the magnesite powder to the pumice powder is (1-3): 1. When the magnesite powder and the pumice powder are compounded, a synergistic effect is achieved so that the fluorine-free flame-retardant PC recycled modified material obtains better physical properties, flame retardant properties and stable weather resistance.

优选的,所述无氟阻燃复合物为改性无氟阻燃复合物,所述改性无氟阻燃复合物由以下重量百分比的原料制得:Preferably, the fluorine-free flame retardant compound is a modified fluorine-free flame retardant compound, and the modified fluorine-free flame retardant compound is made from the following raw materials in weight percentage:

丙烯酸异冰片酯1-3%Isobornyl acrylate 1-3%

引发剂0.02-0.04%Initiator 0.02-0.04%

含氮硅烷1.5-6.3%Nitrogen-containing silane 1.5-6.3%

丙烯酸酯磷酸酯2-5%Acrylate Phosphate 2-5%

三(2-羟乙基)异氰脲酸三丙烯酸酯0.1-0.5%Tris(2-hydroxyethyl)isocyanurate triacrylate 0.1-0.5%

2,2-乙氧基-1-(三甲基硅基)-1,2-氮硅杂环戊烷0.3-0.8%2,2-ethoxy-1-(trimethylsilyl)-1,2-nitrogen silanol 0.3-0.8%

余量为无氟阻燃复合物。The balance is fluorine-free flame retardant compound.

丙烯酸异冰片酯作为活性稀释单体,含氮硅烷含有氮,能够提高阻燃效果、耐热性等,并且能够提高无机填料与硅PC粉、含磷阻燃剂、纳米级无机填料的相容性,同时,还能与丙烯酸酯磷酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、2,2-乙氧基-1-(三甲基硅基)-1,2-氮硅杂环戊烷进一步反应,形成含有磷、氮、硅的交联网状结构的大分子物质,具有较佳的阻燃性能和耐候性能。同时进一步促进硅PC粉、含磷阻燃剂、纳米级无机填料与PC回收料的分散相容性,使PC回收改性料的原料体系分散均匀,且结合紧密,从而进一步提高PC回收改性料的物理性能、阻燃性能以及耐候性能。Isobornyl acrylate is used as an active diluent monomer, and nitrogen-containing silane contains nitrogen, which can improve the flame retardant effect, heat resistance, etc., and can improve the compatibility of inorganic fillers with silicon PC powder, phosphorus-containing flame retardants, and nano-scale inorganic fillers. At the same time, it can also further react with acrylate phosphate, tris (2-hydroxyethyl) isocyanuric acid triacrylate, and 2,2-ethoxy-1-(trimethylsilyl)-1,2-nitrogen silanol to form a macromolecular substance with a cross-linked network structure containing phosphorus, nitrogen, and silicon, which has better flame retardant and weather resistance. At the same time, it further promotes the dispersion compatibility of silicon PC powder, phosphorus-containing flame retardants, nano-scale inorganic fillers and PC recycled materials, so that the raw material system of PC recycled modified materials is evenly dispersed and tightly combined, thereby further improving the physical properties, flame retardant properties, and weather resistance of PC recycled modified materials.

优选的,所述含氮硅烷为3-(1,3-二甲基丁烯)氨丙基三乙氧基硅烷、N-[3-三甲氧基甲硅基]丙基]-1,6-己二胺、四甲基胍基丙基三甲氧基硅烷中一种或者多种组成。Preferably, the nitrogen-containing silane is one or more of 3-(1,3-dimethylbutylene)aminopropyltriethoxysilane, N-[3-trimethoxymethylsilyl]propyl]-1,6-hexanediamine, and tetramethylguanidinopropyltrimethoxysilane.

3-(1,3-二甲基丁烯)氨丙基三乙氧基硅烷、N-[3-三甲氧基甲硅基]丙基]-1,6-己二胺、四甲基胍基丙基三甲氧基硅烷均能起到增效作用,能够引入氮硅,提高阻燃性能和耐热,同时又能促进无氟阻燃PC回收改性料的相容性,使其原料体系结合紧密,减少出现迁移、热解等可能性,提高PC回收改性料的耐候性。3-(1,3-dimethylbutylene)aminopropyltriethoxysilane, N-[3-trimethoxysilyl]propyl]-1,6-hexanediamine, and tetramethylguanidinylpropyltrimethoxysilane can all play a synergistic role, introduce nitrogen silicon, improve flame retardancy and heat resistance, and promote the compatibility of fluorine-free flame retardant PC recycled modified materials, making the raw material system tightly combined, reducing the possibility of migration and pyrolysis, and improving the weather resistance of PC recycled modified materials.

当将3-(1,3-二甲基丁烯)氨丙基三乙氧基硅烷、N-[3-三甲氧基甲硅基]丙基]-1,6-己二胺、四甲基胍基丙基三甲氧基硅烷进行复配,起到协同作用,并与丙烯酸酯磷酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、2,2-乙氧基-1-(三甲基硅基)-1,2-氮硅杂环戊烷进复合反应,形成的交联网状结构的大分子物质与硅PC粉、含磷阻燃剂、纳米级无机填料、聚二甲基硅氧烷共混改性后,得到改性无氟阻燃复合物具有较佳的增韧、阻燃以及耐候等作用。进一步提高PC回收改性料的物理性能、阻燃性能以及耐候性能。当其生产的家电产品,在高温、烟油环境下使用,能够减少出现老化现象,提高其耐久性和使用安全性。When 3-(1,3-dimethylbutylene)aminopropyl triethoxysilane, N-[3-trimethoxysilyl]propyl]-1,6-hexanediamine, and tetramethylguanidopropyl trimethoxysilane are compounded to play a synergistic role, and react with acrylate phosphate, tri(2-hydroxyethyl)isocyanuric acid triacrylate, and 2,2-ethoxy-1-(trimethylsilyl)-1,2-nitrosilanol, the macromolecular substance with a cross-linked network structure is blended and modified with silicon PC powder, phosphorus-containing flame retardant, nano-scale inorganic filler, and polydimethylsiloxane to obtain a modified fluorine-free flame retardant composite with better toughening, flame retardancy, and weather resistance. Further improve the physical properties, flame retardancy, and weather resistance of PC recycled modified materials. When the home appliances produced by it are used in high temperature and smoke oil environments, they can reduce aging phenomena and improve their durability and safety of use.

优选,所述丙烯酸酯磷酸酯为烷基丙烯酸酯磷酸酯和/或2-羟乙基甲基丙烯酸酯磷酸酯。Preferably, the acrylate phosphate is alkyl acrylate phosphate and/or 2-hydroxyethyl methacrylate phosphate.

烷基丙烯酸酯磷酸酯和2-羟乙基甲基丙烯酸酯磷酸酯均含有磷和丙烯酸酯基,与含氮硅烷、2-乙氧基-1-(三甲基硅基)-1,2-氮硅杂环戊烷、三(2-羟乙基)异氰脲酸三丙烯酸酯进一步反应后,得到交联网状的大分子物质,能够与无氟阻燃复合物共混改性后,进一步提高PC回收改性料的阻燃性能、物理性能以及耐候性。Alkyl acrylate phosphate and 2-hydroxyethyl methacrylate phosphate both contain phosphorus and acrylate groups. After further reaction with nitrogen-containing silane, 2-ethoxy-1-(trimethylsilyl)-1,2-nitrogen silanol, and tri(2-hydroxyethyl)isocyanuric acid triacrylate, a cross-linked network of macromolecular substances is obtained. After being blended and modified with fluorine-free flame retardant compounds, the flame retardancy, physical properties and weather resistance of PC recycled modified materials are further improved.

优选的,所述改性无氟阻燃复合物,由以下方法制得:Preferably, the modified fluorine-free flame retardant composite is prepared by the following method:

称取丙烯酸异冰片酯、引发剂、含氮硅烷、丙烯酸酯磷酸酯、2,2-乙氧基-1-(三甲基硅基)-1,2-氮硅杂环戊烷加热反应,再加入三(2-羟乙基)异氰脲酸三丙烯酸酯混合均匀,继续反应,再加入无氟阻燃复合物,混合均匀,得到改性无氟阻燃复合物。Weigh isobornyl acrylate, initiator, nitrogen-containing silane, acrylate phosphate, and 2,2-ethoxy-1-(trimethylsilyl)-1,2-nitrogen silanol and heat to react, then add tris(2-hydroxyethyl)isocyanuric acid triacrylate and mix evenly, continue to react, then add fluorine-free flame retardant compound and mix evenly to obtain a modified fluorine-free flame retardant compound.

通过含氮硅烷、丙烯酸酯磷酸酯、2,2-乙氧基-1-(三甲基硅基)-1,2-氮硅杂环戊烷进行反应后,再加入三(2-羟乙基)异氰脲酸三丙烯酸酯继续其物料进一步交联反应后,与无氟阻燃复合物进一步进行共混改性,进一步得到改性无氟阻燃复合物的物理性能、阻燃性能以及耐候性能,第二方面,本申请提供一种如权利要求所述的无氟阻燃PC回收改性料,由以下方法制得:After nitrogen-containing silane, acrylate phosphate, and 2,2-ethoxy-1-(trimethylsilyl)-1,2-nitrogen silanol are reacted, tris(2-hydroxyethyl)isocyanuric acid triacrylate is added to continue the further cross-linking reaction of the materials, and then further blended and modified with the fluorine-free flame retardant composite to further obtain the physical properties, flame retardant properties and weather resistance of the modified fluorine-free flame retardant composite. In a second aspect, the present application provides a fluorine-free flame retardant PC recycled modified material as claimed in claim 1, which is prepared by the following method:

称取纳米级无机填料、聚二甲基硅氧烷混合均匀,得到混合物A;称取硅PC粉、含磷阻燃剂混合,研磨,得到混合物B;将混合物A与混合物B混合均匀,得到无氟阻燃复合料;Weigh nano-scale inorganic filler and polydimethylsiloxane and mix them evenly to obtain a mixture A; weigh silicon PC powder and phosphorus-containing flame retardant and mix them, grind them to obtain a mixture B; mix the mixture A and the mixture B evenly to obtain a fluorine-free flame retardant composite;

按照重量百分比计,称取PC回收料、无氟阻燃复合料、抗氧剂混合均匀,熔融挤出,冷却,烘干,造粒,得到PC回收改性料。According to the weight percentage, the PC recycled material, the fluorine-free flame retardant composite material and the antioxidant are weighed and mixed evenly, melt-extruded, cooled, dried and granulated to obtain the PC recycled modified material.

上述工艺操作简单,生产效率高通过混合形成的混合物A和混合物B,再将其进行混合,有利于提高无氟阻燃复合料混合均匀性。而通过PC回收料、无氟阻燃复合料、抗氧剂进行混合均匀后,进行熔融挤出,经过冷却、干燥、烘干、造粒后,得到的PC回收改性料的原料体系中各个原料充分混合均匀,且具有较佳的物理性能、阻燃性能以及耐候性,当其用于油烟机的配件生产,起到较佳的耐高温性、耐油烟性,并具有较佳的物理性能和阻燃性能。The above process is simple to operate and has high production efficiency. The mixture A and mixture B formed by mixing are then mixed, which is beneficial to improving the mixing uniformity of the fluorine-free flame retardant composite material. After the PC recycled material, fluorine-free flame retardant composite material and antioxidant are evenly mixed, melt extruded, cooled, dried, baked and granulated, the raw materials in the raw material system of the obtained PC recycled modified material are fully mixed and uniform, and have better physical properties, flame retardant properties and weather resistance. When it is used in the production of range hood accessories, it has better high temperature resistance, oil fume resistance, and better physical properties and flame retardant properties.

综上所述,本申请具有以下有益效果:In summary, this application has the following beneficial effects:

1、本申请通过硅PC粉、含磷阻燃剂、纳米级无机填料、聚二甲基硅氧烷复配,起到增效作用,进一步PC回收改性料起到的物理性能、阻燃性能以及耐候性,当用于抽烟机等家电产品,使其在高温、油烟环境下,仍然保持较佳的阻燃效果和物理性能。提高家电产品的耐久性和使用安全性。1. This application uses silicon PC powder, phosphorus-containing flame retardant, nano-scale inorganic filler, and polydimethylsiloxane to compound to enhance the physical properties, flame retardant properties, and weather resistance of PC recycled modified materials. When used in household appliances such as smoke extractors, they can still maintain better flame retardant effects and physical properties in high temperature and oil fume environments. Improve the durability and safety of household appliances.

2、通过含氮硅烷、丙烯酸酯磷酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、2,2-乙氧基-1-(三甲基硅基)-1,2-氮硅杂环戊烷反应后,形成含有磷、氮、硅的交联网状结构的大分子物质,具有较佳的阻燃性能和耐候性能,同时进一步促进硅PC粉、含磷阻燃剂、纳米级无机填料与PC回收料的分散相容性,使PC回收改性料的原料体系分散均匀,且结合紧密,从而进一步提高PC回收改性料的物理性能、阻燃性能以及耐候性能。2. Through the reaction of nitrogen-containing silane, acrylate phosphate, tris(2-hydroxyethyl)isocyanuric acid triacrylate, and 2,2-ethoxy-1-(trimethylsilyl)-1,2-nitrogen silanol, a macromolecular substance with a cross-linked network structure containing phosphorus, nitrogen, and silicon is formed, which has better flame retardant and weather resistance. At the same time, it further promotes the dispersion compatibility of silicon PC powder, phosphorus-containing flame retardant, nano-scale inorganic filler and PC recycled materials, so that the raw material system of PC recycled modified materials is evenly dispersed and tightly combined, thereby further improving the physical properties, flame retardant properties and weather resistance of PC recycled modified materials.

具体实施方式DETAILED DESCRIPTION

以下结合实施例对本申请作进一步详细说明。The present application is further described in detail below with reference to the embodiments.

部分原料的介绍:Introduction of some raw materials:

表1部分原料的介绍Table 1 Introduction of some raw materials

实施例Example

实施例1Example 1

一种无氟阻燃PC回收改性料的制备,由以下方法制得:A preparation method of a fluorine-free flame-retardant PC recycled modified material is prepared by the following method:

以重量比称取纳米级无机填料、聚二甲基硅氧烷混合均匀,得到混合物A;称取硅PC粉、含磷阻燃剂混合后,再放入研磨机中进行研磨,过筛800目,得到混合物B;将混合物A与混合物B混合均匀,得到无氟阻燃复合料。Nano-scale inorganic filler and polydimethylsiloxane are weighed in weight ratio and mixed evenly to obtain mixture A; silicon PC powder and phosphorus-containing flame retardant are weighed and mixed, then put into a grinder for grinding, and sieved through 800 mesh to obtain mixture B; mixture A and mixture B are mixed evenly to obtain a fluorine-free flame retardant composite material.

称取PC回收料78.7kg、无氟阻燃复合料21kg、抗氧剂0.3kg加热至熔融,在转速20r/min下,搅拌30min,再转移至双螺杆挤出机中进行混合,加热至熔融并挤出,螺杆转速为400转/min,双螺杆挤出机设定温度为240℃、250℃、260℃、270℃、280℃、265℃、255℃,挤出后进入冷水槽进行冷却,再进入150℃的烘箱中进行干燥5s,再进入造粒机中进行造粒,得到阻燃PC回收改性料。Weigh 78.7 kg of PC recycled material, 21 kg of fluorine-free flame retardant composite material, and 0.3 kg of antioxidant, heat them until they are melted, stir them at a speed of 20 r/min for 30 min, and then transfer them to a twin-screw extruder for mixing, heat them until they are melted and extrude them. The screw speed is 400 rpm, and the set temperatures of the twin-screw extruder are 240°C, 250°C, 260°C, 270°C, 280°C, 265°C, and 255°C. After extrusion, they enter a cold water tank for cooling, and then enter an oven at 150°C for drying for 5 seconds, and then enter a granulator for granulation to obtain a flame retardant PC recycled modified material.

无氟阻燃复合料由PC粉、含磷阻燃剂、纳米级无机填料、聚二甲基硅氧烷以重量比15:1:3:1组成,其中纳米级无机填料为菱镁矿粉,该纳米级无机填料的粒径为150-300nm。含磷阻燃剂为四苯基双酚A二磷酸酯;抗氧剂为抗氧剂1010。The fluorine-free flame retardant composite material is composed of PC powder, phosphorus-containing flame retardant, nano-scale inorganic filler and polydimethylsiloxane in a weight ratio of 15:1:3:1, wherein the nano-scale inorganic filler is magnesite powder, and the particle size of the nano-scale inorganic filler is 150-300nm. The phosphorus-containing flame retardant is tetraphenyl bisphenol A diphosphate; and the antioxidant is antioxidant 1010.

实施例2-3Example 2-3

实施例2-3与实施例1的不同之处在于:原料的用量不同,具体如表2所示:The difference between Example 2-3 and Example 1 is that the amount of raw materials used is different, as shown in Table 2:

表2实施例1-3的原料用量(kg)Table 2 Raw material dosage of Examples 1-3 (kg)

原料raw material 实施例1Example 1 实施例2Example 2 实施例3Example 3 PC回收料PC recycled material 78.778.7 8080 87.287.2 无氟阻燃复合物Fluorine-free flame retardant compound 21twenty one 19.519.5 1212 抗氧剂Antioxidants 0.30.3 0.50.5 0.80.8

实施例4Example 4

实施例4与实施例2的不同之处在于:无氟阻燃复合料由PC粉、含磷阻燃剂、纳米级无机填料、聚二甲基硅氧烷以重量比10:4:5:1组成。The difference between Example 4 and Example 2 is that the fluorine-free flame retardant composite material is composed of PC powder, phosphorus-containing flame retardant, nano-scale inorganic filler, and polydimethylsiloxane in a weight ratio of 10:4:5:1.

实施例5Example 5

实施例5与实施例4的不同之处在于:磷阻燃剂由四苯基双酚A二磷酸酯和聚二苯基氧基磷腈以重量比为1:1组成。The difference between Example 5 and Example 4 is that the phosphorus flame retardant is composed of tetraphenyl bisphenol A diphosphate and polydiphenyloxyphosphazene in a weight ratio of 1:1.

实施例6Example 6

实施例6与实施例5的不同之处在于:纳米级无机填料由菱镁矿粉和浮石粉以重量比为3:1组成。The difference between Example 6 and Example 5 is that the nano-scale inorganic filler is composed of magnesite powder and pumice powder in a weight ratio of 3:1.

实施例7Example 7

实施例7与实施例5的不同之处在于:纳米级无机填料由菱镁矿粉和浮石粉以重量比为1:1组成。The difference between Example 7 and Example 5 is that the nano-scale inorganic filler is composed of magnesite powder and pumice powder in a weight ratio of 1:1.

实施例8Example 8

实施例8与实施例7的不同之处在于:无氟阻燃复合物为改性无氟阻燃复合物,改性无氟阻燃复合物由以下方法制得。The difference between Example 8 and Example 7 is that the fluorine-free flame retardant compound is a modified fluorine-free flame retardant compound, and the modified fluorine-free flame retardant compound is prepared by the following method.

以重量百分比,称取1%丙烯酸异冰片酯、0.04%引发剂、6.3%含氮硅烷、2%丙烯酸酯磷酸酯、0.3%2,2-乙氧基-1-(三甲基硅基)-1,2-氮硅杂环戊烷放入反应釜中混合均匀,加热至70℃,反应70min,再加入0.5%三(2-羟乙基)异氰脲酸三丙烯酸酯,反应1h,再加入89.86%无氟阻燃复合物,混合均匀,得到改性无氟阻燃复合物。In terms of weight percentage, 1% isobornyl acrylate, 0.04% initiator, 6.3% nitrogen-containing silane, 2% acrylate phosphate, and 0.3% 2,2-ethoxy-1-(trimethylsilyl)-1,2-nitrogen silanol were weighed and put into a reaction kettle and mixed evenly. The mixture was heated to 70° C. and reacted for 70 min. Then, 0.5% tris(2-hydroxyethyl)isocyanurate triacrylate was added and reacted for 1 h. Then, 89.86% fluorine-free flame retardant compound was added and mixed evenly to obtain a modified fluorine-free flame retardant compound.

该氟阻燃复合料由PC粉、含磷阻燃剂、纳米级无机填料、聚二甲基硅氧烷以重量比10:4:5:1组成,;含氮硅烷为3-(1,3-二甲基丁烯)氨丙基三乙氧基硅烷;丙烯酸酯磷酸酯为2-羟乙基甲基丙烯酸酯磷酸酯;引发剂为过氧化-3,5,5-三甲基己酸叔丁酯。The fluorine flame retardant composite material is composed of PC powder, phosphorus-containing flame retardant, nano-scale inorganic filler and polydimethylsiloxane in a weight ratio of 10:4:5:1; the nitrogen-containing silane is 3-(1,3-dimethylbutylene)aminopropyltriethoxysilane; the acrylate phosphate is 2-hydroxyethyl methacrylate phosphate; and the initiator is peroxy-3,5,5-trimethylhexanoic acid tert-butyl ester.

实施例9-10Examples 9-10

实施例9-10与实施例8的不同之处在于:该改性无氟阻燃复合物的原料用量不同,具体如表3所示:The difference between Example 9-10 and Example 8 is that the amount of raw materials used in the modified fluorine-free flame retardant composite is different, as shown in Table 3:

表3实施例8-10的原料用量(%)Table 3 Raw material dosage of Examples 8-10 (%)

实施例11Embodiment 11

实施例11与实施例9的不同之处在于:含氮硅烷为3-(1,3-二甲基丁烯)氨丙基三乙氧基硅烷、N-[3-三甲氧基甲硅基]丙基]-1,6-己二胺、四甲基胍基丙基三甲氧基硅烷以重量比为2:2:1。The difference between Example 11 and Example 9 is that the nitrogen-containing silane is 3-(1,3-dimethylbutylene)aminopropyltriethoxysilane, N-[3-trimethoxysilyl]propyl]-1,6-hexanediamine, and tetramethylguanidinylpropyltrimethoxysilane in a weight ratio of 2:2:1.

实施例12Example 12

实施例12与实施例9的不同之处在于:丙烯酸酯磷酸酯由烷基丙烯酸酯磷酸酯和2-羟乙基甲基丙烯酸酯磷酸酯以重量比为1:1组成。The difference between Example 12 and Example 9 is that the acrylate phosphate is composed of alkyl acrylate phosphate and 2-hydroxyethyl methacrylate phosphate in a weight ratio of 1:1.

实施例13Embodiment 13

实施例13与实施例8的不同之处在于:2,2-乙氧基-1-(三甲基硅基)-1,2-氮硅杂环戊烷等量替换成丙烯酸酯磷酸酯。The difference between Example 13 and Example 8 is that an equal amount of 2,2-ethoxy-1-(trimethylsilyl)-1,2-nitrogen silanol is replaced by acrylate phosphate.

实施例14Embodiment 14

实施例14与实施例8的不同之处在于:三(2-羟乙基)异氰脲酸三丙烯酸酯等量替换成丙烯酸酯磷酸酯。The difference between Example 14 and Example 8 is that an equal amount of tris(2-hydroxyethyl)isocyanurate triacrylate is replaced by acrylate phosphate.

实施例15Embodiment 15

实施例15与实施例8的不同之处在于:丙烯酸酯磷酸酯等量替换成含氮硅烷。The difference between Example 15 and Example 8 is that the acrylate phosphate is replaced by nitrogen-containing silane in equal amounts.

实施例16Example 16

实施例16与实施例12的不同之处在于:还包括增韧剂,增韧剂为MBS(韩国LGEM505),该阻燃PC再生料中的PC回收料、无氟阻燃复合料、亚磷酸三(十三烷基)酯、增韧剂75kg、19.5kg、0.5kg、5kg。The difference between Example 16 and Example 12 is that: it also includes a toughening agent, and the toughening agent is MBS (South Korea LGEM505). The flame retardant PC recycled material includes PC recycled material, fluorine-free flame retardant composite material, tri(tridecyl) phosphite, and toughening agent 75kg, 19.5kg, 0.5kg, and 5kg.

对比例Comparative Example

对比例1Comparative Example 1

对比例1与实施例1的不同之处在于:纳米级无机填料等量替换成硅PC粉。The difference between Comparative Example 1 and Example 1 is that the nano-scale inorganic filler is replaced by silicon PC powder in equal amounts.

对比例2Comparative Example 2

对比例2与实施例1的不同之处在于:无氟阻燃复合物为氢氧化铝。The difference between Comparative Example 2 and Example 1 is that the fluorine-free flame retardant compound is aluminum hydroxide.

性能检测试验Performance testing

将实施例1-16和对比例1-2得到的无氟阻燃PC回收改性料经过注塑成型后,注塑的温度为275℃,得到若干个测试样品,再采用相应的测试样品进行阻燃性能和冲击韧性,具体数据详见表4。The fluorine-free flame-retardant PC recycled modified materials obtained in Examples 1-16 and Comparative Examples 1-2 were injection molded at a temperature of 275° C. to obtain several test samples, and then the corresponding test samples were used to test the flame retardancy and impact toughness. The specific data are shown in Table 4.

检测方法/试验方法Detection method/test method

阻燃性能:参考ASTMD2863标准进行测试氧指数;Flame retardant performance: refer to ASTMD2863 standard to test oxygen index;

冲击韧性:按照ASTM D256进行,测试条件为2mmV型缺口,温度为25℃,测试样品的厚度为3mm。Impact toughness: carried out in accordance with ASTM D256, the test conditions are 2mm V-notch, temperature is 25℃, and the thickness of the test sample is 3mm.

耐候性实验:将测试样品测试放入耐候实验测试装置中7天,测试条件:温度150℃,并连续通入蒸汽,蒸汽由水蒸汽和油蒸汽以流量比1:1混合形成,蒸汽流量为200L/h,油蒸汽是由猪油、花生油、菜籽油以重量比1:1:1混合后在高温下形成。Weathering test: The test sample was placed in a weathering test device for 7 days. The test conditions were: temperature 150°C, and steam was continuously introduced. The steam was formed by mixing water vapor and oil vapor in a flow ratio of 1:1. The steam flow rate was 200L/h. The oil vapor was formed by mixing lard, peanut oil, and rapeseed oil in a weight ratio of 1:1:1 at high temperature.

以上实验数据见表4;The above experimental data are shown in Table 4;

表4实施例1-16和对比例1-2的实验数据Table 4 Experimental data of Examples 1-16 and Comparative Examples 1-2

结合实施例1和对比例1-2并结合表4可以看出,实施例1的氧指数、冲击韧性、氧指数残率、冲击韧性均高于对比例1-2,说明采用本申请硅PC粉、含磷阻燃剂、纳米级无机填料、聚二甲基硅氧烷复配,起到较佳的增效作用,并使得无氟阻燃PC回收改性料获得较佳的阻燃性能、物理性能以及耐候性。Combining Example 1 and Comparative Examples 1-2 and Table 4, it can be seen that the oxygen index, impact toughness, oxygen index residual rate, and impact toughness of Example 1 are all higher than those of Comparative Examples 1-2, indicating that the compounding of the silicon PC powder, phosphorus-containing flame retardant, nanoscale inorganic filler, and polydimethylsiloxane of the present application has a better synergistic effect, and enables the fluorine-free flame retardant PC recycled modified material to obtain better flame retardant properties, physical properties, and weather resistance.

结合实施例5和实施例7并结合表4可以看出,实施例6的氧指数、冲击韧性、氧指数残率、冲击韧性均高于对比例5,说明书采用菱镁矿粉和浮石粉起到协同作用,并配合硅PC粉、含磷阻燃剂、聚二甲基硅氧烷起到较佳的增效作用,从而使得PC回收改性料获得较佳的物理性能、阻燃性能以及耐候性能。Combining Example 5 and Example 7 with Table 4, it can be seen that the oxygen index, impact toughness, oxygen index residual rate and impact toughness of Example 6 are all higher than those of Comparative Example 5. The specification uses dolomite powder and pumice powder to play a synergistic role, and cooperates with silicon PC powder, phosphorus-containing flame retardant and polydimethylsiloxane to play a better synergistic role, so that the PC recycled modified material obtains better physical properties, flame retardant properties and weather resistance.

结合实施例7和实施例8并结合表4可以看出,实施例8的氧指数、冲击韧性、氧指数残率、冲击韧性均高于实施例7,说明书通过含氮硅烷、丙烯酸酯磷酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、2,2-乙氧基-1-(三甲基硅基)-1,2-氮硅杂环戊烷反应后,形成的交联网状结构的大分子物质,与硅PC粉、含磷阻燃剂、纳米级无机填料共混改性,得到改性无氟阻燃复合物与PC回收改性料的原料体系中,进一步提高PC回收改性料的物理性能、阻燃性能以及耐候性能。Combining Example 7 and Example 8 and Table 4, it can be seen that the oxygen index, impact toughness, oxygen index residual rate and impact toughness of Example 8 are all higher than those of Example 7. The specification discloses that a macromolecular substance with a cross-linked network structure is formed by reacting nitrogen-containing silane, acrylate phosphate, tris(2-hydroxyethyl)isocyanurate triacrylate and 2,2-ethoxy-1-(trimethylsilyl)-1,2-nitrogen silanol, and is blended and modified with silicon PC powder, phosphorus-containing flame retardant and nano-scale inorganic filler to obtain a modified fluorine-free flame retardant composite and a raw material system of PC recycled modified material, thereby further improving the physical properties, flame retardant properties and weather resistance of PC recycled modified material.

结合实施例8和实施例13-15并结合表4可以看出,实施例13-15的氧指数、冲击韧性、氧指数残率、冲击韧性均低于实施例8,说明本申请采用含氮硅烷、丙烯酸酯磷酸酯、2,2-乙氧基-1-(三甲基硅基)-1,2-氮硅杂环戊烷、三(2-羟乙基)异氰脲酸三丙烯酸酯复配反应,起到较佳的增效作用,并与硅PC粉、含磷阻燃剂、纳米级无机填料、聚二甲基硅氧烷共混改性后,得到的改性无氟阻燃复合物用于PC回收改性料的原料体系中,使PC回收改性料兼备较佳的物理性能、阻燃性能以及耐候性能。Combining Example 8 and Example 13-15 and Table 4, it can be seen that the oxygen index, impact toughness, oxygen index residual rate and impact toughness of Example 13-15 are lower than those of Example 8, indicating that the present application adopts nitrogen-containing silane, acrylate phosphate, 2,2-ethoxy-1-(trimethylsilyl)-1,2-nitrogen silanol, tris(2-hydroxyethyl)isocyanuric acid triacrylate for compounding reaction, which has a better synergistic effect, and after blending and modifying with silicon PC powder, phosphorus-containing flame retardant, nanoscale inorganic filler and polydimethylsiloxane, the modified fluorine-free flame retardant composite is used in the raw material system of PC recycled modified material, so that the PC recycled modified material has better physical properties, flame retardant properties and weather resistance.

本具体实施例仅仅是对本申请的解释,其并不是对本申请的限制,本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改,但只要在本申请的权利要求范围内都受到专利法的保护。This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims (10)

1. The fluorine-free flame-retardant PC recycling modified material is characterized by comprising the following components in percentage by weight:
PC reclaimed material 60-87.2%
Fluorine-free flame-retardant compound 12-21%
Antioxidant 0.3-0.8%
0-20% Of toughening agent;
the fluorine-free flame retardant composite consists of silicon PC powder, a phosphorus-containing flame retardant, nanoscale inorganic filler and polydimethylsiloxane;
the nano-scale inorganic filler is magnesite powder and/or pumice powder; the phosphorus-containing flame retardant is tetraphenyl bisphenol A diphosphate and/or polydiphenyloxyphosphine.
2. The fluorine-free flame-retardant PC recycling modified material according to claim 1, wherein: the weight ratio of the silicon PC powder to the phosphorus-containing flame retardant to the nanoscale inorganic filler to the polydimethylsiloxane is (10-15): (1-4): (3-5): 1.
3. The fluorine-free flame-retardant PC recycling modified material according to claim 1, wherein: the particle size of the nano-scale inorganic filler is 150-300nm.
4. The fluorine-free flame-retardant PC recycling modified material according to claim 1, wherein: the weight ratio of the magnesite powder to the pumice powder is (1-3): 1.
5. The fluorine-free flame-retardant PC recycling modified material according to claim 1, wherein: the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant 2246 and antioxidant 168.
6. The fluorine-free flame retardant PC recycling modified material according to claim 1, wherein the fluorine-free flame retardant compound is a modified fluorine-free flame retardant compound, and the modified fluorine-free flame retardant compound is prepared from the following raw materials in percentage by weight:
Isobornyl acrylate 1-3%
Initiator 0.02-0.04%
1.5 To 6.3 percent of nitrogen-containing silane
Acrylic ester phosphate 2-5%
0.1 To 0.5 percent of tri (2-hydroxyethyl) isocyanurate triacrylate
2, 2-Ethoxy-1- (trimethylsilyl) -1, 2-azasilacyclopentane 0.3-0.8%
The balance being fluorine-free flame-retardant compound.
7. The fluorine-free flame-retardant PC recycling modified material according to claim 6, wherein: the nitrogen-containing silane is one or more of 3- (1, 3-dimethylbutene) aminopropyl triethoxysilane, N- [ 3-trimethoxysilyl ] propyl ] -1, 6-hexamethylenediamine and tetramethyl guanidine propyl trimethoxy silane.
8. The fluorine-free flame-retardant PC recycling modified material according to claim 6, wherein: the acrylic ester phosphate is alkyl acrylic ester phosphate and/or 2-hydroxyethyl methacrylate phosphate.
9. The fluorine-free flame retardant PC recycling modified material according to any of claims 6-8, wherein the modified fluorine-free flame retardant composite is prepared by the following method:
According to weight percentage, weighing isobornyl acrylate, an initiator, nitrogen-containing silane, acrylic ester phosphate and 2, 2-ethoxy-1- (trimethylsilyl) -1, 2-azacyclopentane, heating for reaction, adding tri (2-hydroxyethyl) isocyanurate triacrylate, mixing uniformly, continuing to react, adding the fluorine-free flame-retardant compound, and mixing uniformly to obtain the modified fluorine-free flame-retardant compound.
10. A method for preparing the fluorine-free flame retardant PC recycling modified material according to any one of claims 1-9, which is characterized by comprising the following steps:
Weighing nanoscale inorganic filler and polydimethylsiloxane, and uniformly mixing to obtain a mixture A; weighing silicon PC powder and a phosphorus-containing flame retardant, mixing and grinding to obtain a mixture B; uniformly mixing the mixture A and the mixture B to obtain a fluorine-free flame-retardant composite material;
and weighing the PC reclaimed material, the fluorine-free flame-retardant composite material and the antioxidant according to the weight percentage, uniformly mixing, melting, extruding, cooling, drying and granulating to obtain the PC reclaimed modified material.
CN202411248531.2A 2024-09-06 A fluorine-free flame-retardant PC recycled modified material and preparation method thereof Active CN118909420B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202411248531.2A CN118909420B (en) 2024-09-06 A fluorine-free flame-retardant PC recycled modified material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202411248531.2A CN118909420B (en) 2024-09-06 A fluorine-free flame-retardant PC recycled modified material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN118909420A true CN118909420A (en) 2024-11-08
CN118909420B CN118909420B (en) 2025-04-04

Family

ID=

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105849171A (en) * 2014-01-14 2016-08-10 沙特基础工业全球技术有限公司 Interior train components having low smoke and low heat release, and methods of their manufacture
CN110157174A (en) * 2019-05-30 2019-08-23 深圳华力兴新材料股份有限公司 A kind of the fire-retardant polycarbonate composite material and preparation method and application of glass fiber reinforcement
CN111205617A (en) * 2020-02-25 2020-05-29 广东圆融新材料有限公司 Polycarbonate composition and preparation method thereof
CN112646343A (en) * 2020-12-23 2021-04-13 上海品诚控股集团有限公司 Low-smoke-density flame-retardant PC composition
CN115322552A (en) * 2022-08-29 2022-11-11 南京聚隆科技股份有限公司 Low-smoke low-heat-release polycarbonate material for rail transit interior decoration

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105849171A (en) * 2014-01-14 2016-08-10 沙特基础工业全球技术有限公司 Interior train components having low smoke and low heat release, and methods of their manufacture
CN110157174A (en) * 2019-05-30 2019-08-23 深圳华力兴新材料股份有限公司 A kind of the fire-retardant polycarbonate composite material and preparation method and application of glass fiber reinforcement
CN111205617A (en) * 2020-02-25 2020-05-29 广东圆融新材料有限公司 Polycarbonate composition and preparation method thereof
CN112646343A (en) * 2020-12-23 2021-04-13 上海品诚控股集团有限公司 Low-smoke-density flame-retardant PC composition
CN115322552A (en) * 2022-08-29 2022-11-11 南京聚隆科技股份有限公司 Low-smoke low-heat-release polycarbonate material for rail transit interior decoration

Similar Documents

Publication Publication Date Title
CN103013105A (en) Conducting halogen-free flame-retardant PA6 (polyamide 6) composite material and preparation method thereof
CN107236273B (en) A kind of PC/ABS plastic alloys of halogen-free flameproof and preparation method thereof
CN104086970B (en) A kind of efficient fire-retardant weather polycarbonate composite material of bromine silicon and preparation method thereof
CN101184810A (en) Products treated with flame retardant resin
CN102731920B (en) A compound flame-retardant polystyrene composition and its preparation method
CN104479353A (en) Novel halogen-free flame-retardant composition, halogen-free flame-retardant PBT engineering plastic composite material and preparation method thereof
CN107955368B (en) Heat-conducting nylon with improved heat resistance and preparation method thereof
CN113930044B (en) A kind of flame retardant ABS composite material, preparation method and use thereof
CN110511554A (en) Halogen-free flameproof nitrogen phosphorus Si modification graphene/polycarbonate/ABS alloy material and preparation method thereof
CN102558790B (en) Transparent and fire-retardant polyester and resin composition and preparation method thereof
CN102775754A (en) Halogen-free composite flame retardant poly carbonates (PC)/acrylonitrile butadiene styrene copolymers (ABS) alloy and preparation method thereof
CN114806156B (en) Nylon composite material with both flame retardancy, smoke suppression and reinforcement and preparation method thereof
CN102382439B (en) A kind of modified polycarbonate and preparation method thereof
CN107189393A (en) A kind of halogen-free flameproof enhancing PC/AES alloys and preparation method thereof
CN118909420A (en) Fluorine-free flame-retardant PC (polycarbonate) recycling modified material and preparation method thereof
CN118909420B (en) A fluorine-free flame-retardant PC recycled modified material and preparation method thereof
CN104910601B (en) High-gloss high-heat-resistance and high-fluidity halogen-free flame-retardant glass fiber reinforced PC material and preparation method thereof
CN1807506A (en) Self-extinguishing type halogen-free flame-retardant PC/ABS alloy and its preparation process
CN105331038A (en) Basalt fiber enhanced environment-friendly flame-retardant ABS composite material and preparation method thereof
CN110577716A (en) Preparation method of high-impact-resistance polystyrene special material for television shell
CN101864137A (en) High-impact-resistance anti-smoldering polystyrene resin composition and preparation method thereof
CN105237997A (en) Halogen-free flame-retardant PC/ABS alloy and preparation method thereof
CN100506914C (en) Smoke suppression type halogen-free flame retardant polycarbonate
CN106554605A (en) A kind of phosphorus bromine synergistic highly expanded flame-retardant PET material and preparation method thereof
CN103881347B (en) Polycarbonate composition and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant