WO2015131631A1 - 一种无卤阻燃聚烯烃复合泡沫材料及其制备方法 - Google Patents

一种无卤阻燃聚烯烃复合泡沫材料及其制备方法 Download PDF

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WO2015131631A1
WO2015131631A1 PCT/CN2014/094868 CN2014094868W WO2015131631A1 WO 2015131631 A1 WO2015131631 A1 WO 2015131631A1 CN 2014094868 W CN2014094868 W CN 2014094868W WO 2015131631 A1 WO2015131631 A1 WO 2015131631A1
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parts
composite
halogen
composite foam
retardant
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PCT/CN2014/094868
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English (en)
French (fr)
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郑玉婴
陈志杰
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福州大学
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Priority to US15/100,944 priority Critical patent/US9856356B2/en
Publication of WO2015131631A1 publication Critical patent/WO2015131631A1/zh

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    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Definitions

  • the invention belongs to the technical field of polymer composite materials, relates to the preparation of polyolefin composite foam materials, and particularly relates to a halogen-free flame-retardant polyolefin composite foam material and a preparation method thereof.
  • Polyolefin composite foams especially ethylene-vinyl acetate copolymer (EVA) composite foams, have the advantages of low density, good elasticity, and impact resistance. However, like most polymers, it is easy to burn and has a large amount of heat, a large amount of smoke, and releases toxic gases. It is derived from petrochemicals and is difficult to degrade in the natural environment, causing tremendous pressure on the environment.
  • EVA ethylene-vinyl acetate copolymer
  • polyolefin composite foam materials need to have the function of halogen-free flame retardant, using halogen-free, low-smoke, low-toxic environmentally-friendly flame retardant.
  • the preparation of composite foams has become a major focus in flame retardant research.
  • the flame retardant According to the method of using the flame retardant, it can be divided into a reaction type and an additive type.
  • the reactive flame retardant has long-lasting flame retardancy and low toxicity, the process is complicated and the cost is high; and the added flame retardant flame retardant polymer has a simple process, a wide range of use, and a wide variety of flame retardants.
  • Intumescent flame retardant system (IFR) in additive flame retardant is a popular halogen-free flame retardant in recent years. Compared with flame retardants such as aluminum hydroxide and magnesium hydroxide, it is characterized by high flame retardant efficiency. Good stability, uniform dispersion, low density, moderate price, low smoke and no dripping when burning.
  • the object of the present invention is to provide a halogen-free flame-retardant polyolefin composite foam material and a preparation method thereof, and the halogen-free flame-retardant polyolefin composite foam material prepared by the invention has good softness, elasticity, impact resistance and the like. There are also advantages of low density, difficulty in compression deformation, and good shock absorption.
  • the present invention adopts the following technical solutions:
  • a halogen-free flame-retardant polyolefin composite foam material comprises the following components in parts by weight:
  • Plasticizer 4.0 ⁇ 5.5 parts
  • the composite flame retardant is composed of the following raw materials, and is divided into 60 to 77 parts of the acid source raw materials, 17 to 22 parts of the carbon source materials, and 8 to 11 parts of the gas source materials.
  • the polyolefin elastomer is an ethylene-octene copolymer, an ethylene-styrene copolymer, a styrene-ethylene-propylene block copolymer, a styrene-ethylene/butylene-styrene copolymer, a styrene-different One or more of the pentadiene-styrene copolymers.
  • the acid source raw material is one or more of ammonium polyphosphate, ammonium polyphosphate, phosphoric acid, boric acid and borate;
  • the raw material of the carbon source is corn starch, tapioca starch, potato starch and mung bean starch.
  • the gas source material is one or more of melamine, charcoal foaming agent and urea;
  • the flame retardant synergist is aluminum hydroxide, zinc hexahydroxystannate, organic montmorillonite One or more of soil and zinc borate.
  • the composite blowing agent is one or more of azodicarbonamide, azobisisobutyronitrile, sodium hydrogencarbonate, 1,3-benzenedisulfonyl hydrazide, p-toluenesulfonylhydrazide;
  • the crosslinking agent is dicumyl peroxide;
  • the plasticizer is a mixture of two or more of glycerin, citric acid, ethanol, and polyvinyl alcohol.
  • the surface treatment agent is one or more of a silane coupling agent, a titanate coupling agent, a phosphate coupling agent, and an aluminum-titanium composite coupling agent;
  • the compatibilizer is ethylene-acrylic acid.
  • the inorganic filler is one or two of talc, bentonite and kaolin.
  • the other auxiliary agent is 0.1 to 0.6 parts by weight of stearic acid, 0.5 to 1.0 part by weight of zinc stearate, and 1 to 3 parts by weight of zinc oxide.
  • the preparation method comprises the following steps:
  • the significant advantage of the present invention is that the base material used in the halogen-free flame-retardant polyolefin composite foam of the present invention is ethylene-vinyl acetate copolymer (EVA) having good compatibility, and high density polyethylene/low density is added.
  • EVA ethylene-vinyl acetate copolymer
  • Polyethylene, polyolefin elastomer, compatibilizer, etc. improve the compatibility and bonding force between the organism and the inorganic body (powder), avoiding the phenomenon of easy pore breakage during the foaming process, due to the added powder Insufficient reduction in melt strength caused by many.
  • the composite flame retardant adopts an intumescent flame retardant system (IFR) which has the advantages of high flame retardant efficiency, low smoke during combustion, no melt dripping, and the like, wherein the carbon source raw material starch has complete degradation characteristics, so that the invention is environmentally friendly. advantage.
  • the inorganic filler is a commonly used filler, and its function is to improve the dimensional stability and increase the strength of the polyolefin, and to some extent reduce the production cost. Therefore, the halogen-free flame-retardant polyolefin composite foam of the invention has the advantages of good flame retardant property, mechanical property, impact resistance and environmental friendliness, and has wide market prospect and remarkable social and economic benefits.
  • the polyolefin elastomer is an ethylene-octene copolymer (POE); the acid source, the carbon source, and the gas source are respectively ammonium polyphosphate, tapioca starch, and melamine; and the flame retardant synergist is organic montmorillonite and Zinc borate (1:1 ratio); composite blowing agent is azodicarbonamide; crosslinking agent is dicumyl peroxide; plasticizer is glycerin and citric acid (3:4 ratio); surface treatment The agent is a silane coupling agent (KH570); the compatibilizer is an ethylene-acrylic acid copolymer (EAA); the inorganic filler is talc; the other additives are stearic acid, zinc stearate, and zinc oxide.
  • POE ethylene-octene copolymer
  • the acid source, the carbon source, and the gas source are respectively ammonium polyphosphate, tapioca starch, and melamine
  • the preparation process of the halogen-free flame-retardant polyolefin composite foam is as follows:
  • Step 1 Surface treatment of the acid source raw material: ammonium polyphosphate and KH570 were placed in a high-speed kneader, stirred at high speed for 5 min, and then placed in an oven at 60 ° C for 8 h for use.
  • Step 2 plasticizing treatment of the carbon source raw material: the tapioca starch and the plasticizer are placed in a high-speed kneading machine, stirred at a high speed for 10 minutes, and then placed in a sealed bag for 36 hours, and used.
  • Step 3 mixing treatment of the mixed flame retardant: firstly mixing the acid source raw material and the carbon source raw material, adding the gas source raw material, stirring uniformly, and placing it in a sealed bag for use.
  • Step 4 first add EVA, HDPE/LDPE, POE to the mixer for preheating for 5 min, then add the remaining raw materials such as composite flame retardant, flame retardant synergist, inorganic filler, and melt blending at 100 ° C for 12 min. material.
  • step 5 the material after the step 4 is quickly moved to an open mill with a temperature control at 80 ° C for 3 to 5 times, and then broken in a fast breaking machine.
  • Step 6 Weigh the appropriate amount of the material after the step 5 is added to the preheated mold, and vulcanize and foam for 9 minutes under the condition of 170 ° C and 12 MPa of the flat vulcanizer, that is, the halogen-free flame retardant polyolefin is obtained.
  • Composite foam

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  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开了一种无卤阻燃聚烯烃复合泡沫材料及其制备方法，所述的复合泡沫材料包括以下组分（按重量份计）：乙烯-醋酸乙烯酯共聚物80~125份、高密度聚乙烯或低密度聚乙烯8~13份、聚烯烃弹性体15~25份、复合阻燃剂85~110份、阻燃增效剂1~8份、复合发泡剂5.5~8份、交联剂0.7~1.0份、增塑剂4.0~5.5份、表面处理剂0.5~1.6份、增容剂20~35份、无机填料6~14份、其他助剂1.6~4.6份。本发明制得的无卤阻燃聚烯烃复合泡沫材料具有良好的柔软性、弹性、耐冲击性等特性，还有密度小、不易压缩变形、减震性好等优点。由于采用了酸源、炭源、气源原料复合的阻燃剂，使得复合泡沫材料具有良好的阻燃性能，同时也大大改善了复合泡沫材料的机械加工性能和物理力学性能，提高复合泡沫材料的应用性能。

Description

一种无卤阻燃聚烯烃复合泡沫材料及其制备方法 技术领域
本发明属于高分子复合材料技术领域，涉及聚烯烃复合泡沫材料的制备，具体涉及一种无卤阻燃聚烯烃复合泡沫材料及其制备方法。
背景技术
聚烯烃复合泡沫材料，尤其是乙烯-醋酸乙烯酯共聚物(EVA)复合泡沫材料具有密度低、弹性好、耐冲击等优点。但是同大多数聚合物一样，容易燃烧且放热量大、发烟量大，并释放有毒气体并且其来源于石油化工，在自然环境中难以降解，对环境造成了巨大的压力。
目前，随着社会进步以及人们对生命财产安全的重视、环境保护意识的不断增强，聚烯烃复合泡沫材料需要具有无卤阻燃的功能，采用无卤、低烟、低毒的环保型阻燃剂来制备复合泡沫材料已经成为阻燃研究中的一大重点。
按照阻燃剂的使用方法不同可分为反应型和添加型。其中反应型阻燃剂虽然阻燃性持久、毒性较低，但工艺过程复杂，成本高；而添加型阻燃剂阻燃聚合物的工艺简单，使用范围广泛，可选择的阻燃剂种类多。添加型阻燃剂中的膨胀型阻燃体系(IFR)是近年来研究热门的无卤阻燃剂，与氢氧化铝、氢氧化镁等阻燃剂相比，其特点是阻燃效率高、稳定性好、分散均匀、密度小、价格适中，燃烧时低烟、无熔融滴落。
发明内容
本发明的目的在于提供一种无卤阻燃聚烯烃复合泡沫材料及其制备方法，本发明制得的无卤阻燃聚烯烃复合泡沫材料具有良好的柔软性、弹性、耐冲击性等特性，还有密度小、不易压缩变形、减震性好等优点。
为实现上述目的，本发明采用如下技术方案：
一种无卤阻燃聚烯烃复合泡沫材料包括以下组分，按重量份计：
乙烯-醋酸乙烯酯共聚物 80～125份；
高密度聚乙烯或低密度聚乙烯 8～13份；
聚烯烃弹性体 15～25份；
复合阻燃剂 85～110份；
阻燃增效剂 1～8份；
复合发泡剂 5.5～8份；
交联剂 0.7～1.0份；
增塑剂 4.0～5.5份；
表面处理剂 0.5～1.6份；
增容剂 20～35份；
无机填料 6～14份；
其他助剂 1.6～4.6份；
所述的复合阻燃剂是由以下原料复合而成，按重量份计：酸源原料60～77份，炭源原料17～22份，气源原料8～11份。
所述的聚烯烃弹性体为乙烯-辛烯共聚物、乙烯-苯乙烯共聚物、苯乙烯-乙烯-丙烯嵌段共聚物、苯乙烯-乙烯/丁烯-苯乙烯共聚物、苯乙烯-异戊二烯-苯乙烯共聚物中的一种或多种。
所述的酸源原料为聚磷酸铵、多聚磷酸铵、磷酸、硼酸、硼酸盐中的一种或多种；所述的炭源原料为玉米淀粉、木薯淀粉、马铃薯淀粉、绿豆淀粉中的一种；所述的气源原料为三聚氰胺、成炭发泡剂、尿素中的一种或多种；所述的阻燃增效剂为氢氧化铝、六羟基锡酸锌、有机蒙脱土、硼酸锌中的一种或多种。
所述的复合发泡剂为偶氮二甲酰胺、偶氮二异丁腈、碳酸氢钠、1,3-苯二磺酰肼、对甲苯磺酰肼中的一种或多种；所述的交联剂为过氧化二异丙苯；所述的增塑剂为甘油、柠檬酸、乙醇、聚乙烯醇中的两种或两种以上的复配物。
所述的表面处理剂为硅烷类偶联剂、钛酸酯偶联剂、磷酸酯偶联剂、铝钛复合偶联剂中的一种或多种；所述的增容剂为乙烯-丙烯酸、马来酸酐接枝高密度聚乙烯、甲基丙烯酸甲酯、丙烯酸丁酯共聚物中的一种或多种；所述的无机填料为滑石粉、膨润土、高岭土中的一种或两种。
所述的其他助剂，按重量份计为硬脂酸0.1～0.6份、硬脂酸锌0.5～1.0份、氧化锌1～3份。
制备方法包括以下步骤：
(1)将酸源原料和表面处理剂高速搅拌3～5min后，40～60℃干燥8～10h；
(2)将炭源原料和增塑剂高速搅拌5～15min后，装于密封袋中24～48h；
(3)先将酸源原料和炭源原料充分混合后，加入气源原料，搅拌均匀后置于密封袋中，即为所述的复合阻燃剂；
(4)先将乙烯-醋酸乙烯酯共聚物、高密度聚乙烯或低密度聚乙烯和聚烯烃弹性体加入 密炼机中预热5～8min，然后加入复合阻燃剂、阻燃增效剂、复合发泡剂、交联剂、增容剂、无机填料和其他助剂，在90～120℃下熔融共混10～15min后出料；
(5)将步骤(4)混炼后的物料快速移到温度控制在78-85℃的开炼机中进行塑炼3～5遍，然后进行破碎；
(6)称量破碎后的物料加入到预热后的模具中，在平板硫化仪160～175℃、10～13MPa条件下保压8～10min进行硫化发泡，即得所述的无卤阻燃聚烯烃复合泡沫材料。
本发明的显著优点在于：本发明无卤阻燃聚烯烃复合泡沫材料采用的基体原料为具有良好相容性的乙烯-醋酸乙烯酯共聚物(EVA)，并加入了高密度聚乙烯/低密度聚乙烯、聚烯烃弹性体、增容剂等，提高了有机体和无机体(粉料)的相容性和结合力，可避免了发泡过程中易破孔的现象、因加入的粉料过多而造成的熔体强度降低等不足。复合阻燃剂采用了具有阻燃效率高、燃烧时低烟、无熔融滴落等优点的膨胀型阻燃体系(IFR)，其中炭源原料淀粉具有完全降解的特点，使得本发明具有环保的优点。而无机填料为常用的填料，其作用是对聚烯烃的性能起到改善了尺寸稳定性、增加强度的作用，也一定程度上降低了生产成本。故本发明无卤阻燃聚烯烃复合泡沫材料具有良好的阻燃性能、力学性能、耐冲击、环境友好等优点，有着广泛的市场前景和显著的社会经济效益。
具体实施方式
为了进一步阐述本发明的具体内容，下面将列出具体实施例，但未限于所列出的实施例。
实施例1～3如下表：
表1 无卤阻燃聚烯烃复合泡沫材料实施例1～3配方(按重量份计)
Figure PCTCN2014094868-appb-000001
表1中，聚烯烃弹性体为乙烯-辛烯共聚物(POE)；酸源、炭源、气源原料分别为聚磷酸铵、木薯淀粉、三聚氰胺；阻燃增效剂为有机蒙脱土和硼酸锌(比例为1:1)；复合发泡剂为偶氮二甲酰胺；交联剂为过氧化二异丙苯；增塑剂为甘油和柠檬酸(比例为3:4)；表面处理剂为硅烷类偶联剂(KH570)；增容剂为乙烯-丙烯酸共聚物(EAA)；无机填料为滑石粉；其他助剂分别为硬脂酸、硬脂酸锌、氧化锌。
无卤阻燃聚烯烃复合泡沫材料制备工艺如下：
步骤一，酸源原料的表面处理：将聚磷酸铵和KH570置于高速捏合机中，高速搅拌5min后置于60℃烘箱中干燥8h，备用。
步骤二，炭源原料的增塑处理：将木薯淀粉和增塑剂置于高速捏合机中，高速搅拌10min后装于密封袋中36h，备用。
步骤三，混合阻燃剂的混合处理：先将酸源原料和炭源原料充分混合后，加入气源原料，搅拌均匀后置于密封袋中，备用。
步骤四，先将EVA、HDPE/LDPE、POE加入密炼机中预热5min，然后加入复合阻燃剂、阻燃增效剂、无机填料等余下原料，在100℃下熔融共混12min后出料。
步骤五，将步骤四混炼后的物料快速移到温度控制在80℃左后的开炼机中进行薄塑炼3～5遍，然后在快速破粹机里进行破粹。
步骤六，称量适量的经步骤五破粹后的物料加入到预热后的模具中，在平板硫化仪170℃、12MPa条件下保压9min进行硫化发泡，即得无卤阻燃聚烯烃复合泡沫材料。
以上实施例(1、2、3)所制备得的无卤阻燃聚烯烃复合泡沫材料的部分性能与adidas PO-EVA00049标准比较结果如下表所示：
表2 部分性能比较结果
Figure PCTCN2014094868-appb-000002
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (7)

  1. 一种无卤阻燃聚烯烃复合泡沫材料，其特征在于：包括以下组分，按重量份计：
    乙烯-醋酸乙烯酯共聚物80～125份；
    高密度聚乙烯或低密度聚乙烯8～13份；
    聚烯烃弹性体15～25份；
    复合阻燃剂85～110份；
    阻燃增效剂1～8份；
    复合发泡剂5.5～8份；
    交联剂0.7～1.0份；
    增塑剂4.0～5.5份；
    表面处理剂0.5～1.6份；
    增容剂20～35份；
    无机填料6～14份；
    其他助剂1.6～4.6份；
    所述的复合阻燃剂是由以下原料复合而成，按重量份计：酸源原料60～77份，炭源原料17～22份，气源原料8～11份。
  2. 根据权利要求1所述的无卤阻燃聚烯烃复合泡沫材料，其特征在于：所述的聚烯烃弹性体为乙烯-辛烯共聚物、乙烯-苯乙烯共聚物、苯乙烯-乙烯-丙烯嵌段共聚物、苯乙烯-乙烯/丁烯-苯乙烯共聚物、苯乙烯-异戊二烯-苯乙烯共聚物中的一种或多种。
  3. 根据权利要求1所述的无卤阻燃聚烯烃复合泡沫材料，其特征在于：所述的酸源原料为聚磷酸铵、多聚磷酸铵、磷酸、硼酸、硼酸盐中的一种或多种；所述的炭源原料为玉米淀粉、木薯淀粉、马铃薯淀粉、绿豆淀粉中的一种；所述的气源原料为三聚氰胺、成炭发泡剂、尿素中的一种或多种；所述的阻燃增效剂为氢氧化铝、六羟基锡酸锌、有机蒙脱土、硼酸锌中的一种或多种。
  4. 根据权利要求1所述的无卤阻燃聚烯烃复合泡沫材料，其特征在于：所述的复合发泡剂为偶氮二甲酰胺、偶氮二异丁腈、碳酸氢钠、1,3-苯二磺酰肼、对甲苯磺酰肼中的一种或多种；所述的交联剂为过氧化二异丙苯；所述的增塑剂为甘油、柠檬酸、乙醇、聚乙烯醇中的两种或两种以上的复配物。
  5. 根据权利要求1所述的无卤阻燃聚烯烃复合泡沫材料，其特征在于：所述的表面处理剂为硅烷类偶联剂、钛酸酯偶联剂、磷酸酯偶联剂、铝钛复合偶联剂中的一种或多种；所述的增容剂为乙烯-丙烯酸、马来酸酐接枝高密度聚乙烯、甲基丙烯酸甲酯、丙烯酸丁酯共聚物中的一种或多种；所述的无机填料为滑石粉、膨润土、高岭土中的一种或两种。
  6. 根据权利要求1所述的无卤阻燃聚烯烃复合泡沫材料，其特征在于：所述的其他助剂，按重量份计为硬脂酸0.1～0.6份、硬脂酸锌0.5～1.0份、氧化锌1～3份。
  7. 一种制备如权利要求1所述的无卤阻燃聚烯烃复合泡沫材料的方法，其特征在于：包括以下步骤：
    (1)将酸源原料和表面处理剂高速搅拌3～5min后，40～60℃干燥8～10h；
    (2)将炭源原料和增塑剂高速搅拌5～15min后，装于密封袋中24～48h；
    (3)先将酸源原料和炭源原料充分混合后，加入气源原料，搅拌均匀后置于密封袋中，即为所述的复合阻燃剂；
    (4)先将乙烯-醋酸乙烯酯共聚物、高密度聚乙烯或低密度聚乙烯和聚烯烃弹性体加入密炼机中预热5～8min，然后加入复合阻燃剂、阻燃增效剂、复合发泡剂、交联剂、增容剂、无机填料和其他助剂，在90～120℃下熔融共混10～15min后出料；
    (5)将步骤(4)混炼后的物料快速移到温度控制在78-85℃的开炼机中进行塑炼3～5遍，然后进行破碎；
    (6)称量破碎后的物料加入到预热后的模具中，在平板硫化仪160～175℃、10～13MPa条件下保压8～10min进行硫化发泡，即得所述的无卤阻燃聚烯烃复合泡沫材料。
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106397963A (zh) * 2016-10-08 2017-02-15 南京理工大学 一种膨胀型无卤阻燃eva基复合材料及其制备方法
CN114591557A (zh) * 2022-04-21 2022-06-07 北方民族大学 一种阻燃低密度聚乙烯复合材料及其制备方法
US11395931B2 (en) 2017-12-02 2022-07-26 Mighty Fire Breaker Llc Method of and system network for managing the application of fire and smoke inhibiting compositions on ground surfaces before the incidence of wild-fires, and also thereafter, upon smoldering ambers and ashes to reduce smoke and suppress fire re-ignition
US11400324B2 (en) 2017-12-02 2022-08-02 Mighty Fire Breaker Llc Method of protecting life, property, homes and businesses from wild fire by proactively applying environmentally-clean anti-fire (AF) chemical liquid spray in advance of wild fire arrival and managed using a wireless network with GPS-tracking
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CN105175856B (zh) * 2015-08-28 2018-06-29 河南胜华电缆集团有限公司 再生聚烯烃无卤阻燃环保发泡塑料及其生产方法
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US10947371B2 (en) * 2016-03-15 2021-03-16 Nike, Inc. Foam compositions and uses thereof
CN105694323A (zh) * 2016-04-11 2016-06-22 苏州甫众塑胶有限公司 一种防火保温节能复合板材的制备方法
CN107057166A (zh) * 2017-05-31 2017-08-18 三斯达（江苏）环保科技有限公司 一种无味pe发泡材料及其制造方法
CN107189190A (zh) * 2017-07-07 2017-09-22 三斯达（江苏）环保科技有限公司 一种用于汽车座垫的新型透气孔eva发泡材料及其制备
CN107474408A (zh) * 2017-08-25 2017-12-15 东莞市同亿橡塑制品有限公司 一种cpe发泡配方及其制备方法
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CN107746680A (zh) * 2017-09-26 2018-03-02 上海和和热熔胶有限公司 一种用于金属件与塑料件粘合的热熔胶膜及制备方法
WO2019108362A1 (en) * 2017-11-28 2019-06-06 Corning Research & Development Corporation Cable component including a halogen-free flame retardant composition
CN108034368B (zh) * 2017-12-15 2020-09-08 中国科学院长春应用化学研究所 一种无voc汽车用热熔胶膜及其制备方法
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CN114163713B (zh) * 2022-01-05 2022-08-16 宿迁荣诚新材料有限公司 一种高缓冲阻燃高粘泡棉及其制备方法
CN114456477B (zh) * 2022-02-15 2022-08-12 广东安拓普聚合物科技有限公司 一种低毒高阻燃的低烟无卤材料及其制备方法
CN115160692B (zh) * 2022-07-14 2023-11-17 江苏金发科技新材料有限公司 一种无卤阻燃可吸塑聚丙烯合金材料及其制备方法与应用
CN116987333A (zh) * 2023-04-03 2023-11-03 上海马环新材料科技集团有限公司 一种用于板材的环保阻燃材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06271700A (ja) * 1993-03-22 1994-09-27 Sekisui Chem Co Ltd 発泡性難燃樹脂組成物
CN101724194A (zh) * 2009-12-11 2010-06-09 东北林业大学 无卤膨胀阻燃复合材料
CN102558659A (zh) * 2010-12-21 2012-07-11 深圳市沃尔核材股份有限公司 无卤阻燃烯烃类发泡体及其制备方法
CN103804775A (zh) * 2014-03-06 2014-05-21 福州大学 一种无卤阻燃聚烯烃复合泡沫材料及其制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6287692B1 (en) * 1999-06-11 2001-09-11 Judd Wire, Inc. Melt-processable, crosslinkable coating compositions
KR100648519B1 (ko) * 2005-10-21 2006-11-27 주식회사 컴테크케미칼 사출성형성이 우수한 저경도 에틸렌 비닐 아세테이트계발포체 및 그의 제조방법
CN100549082C (zh) * 2006-08-02 2009-10-14 福州大学 Eva/pe/淀粉复合发泡材料的制备方法
CN101792602A (zh) * 2010-03-11 2010-08-04 四川大学 无卤膨胀型阻燃热塑性树脂组合物
CN101899183B (zh) * 2010-09-02 2012-05-23 中国科学技术大学 一种辐照交联耐水阻燃聚烯烃纳米复合材料及其制备方法
JP5594330B2 (ja) * 2012-07-25 2014-09-24 日立金属株式会社 ハロゲンフリー難燃性樹脂組成物、絶縁電線及びケーブル
CN103275354B (zh) * 2013-06-13 2014-04-16 西北师范大学 生物质成炭阻燃剂的制备及其应用
CN103421241B (zh) * 2013-07-23 2016-09-07 中国科学院宁波材料技术与工程研究所 一种阻燃聚烯烃类复合物
CN103360674B (zh) * 2013-07-26 2015-10-14 福州大学 一种木粉复合发泡材料及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06271700A (ja) * 1993-03-22 1994-09-27 Sekisui Chem Co Ltd 発泡性難燃樹脂組成物
CN101724194A (zh) * 2009-12-11 2010-06-09 东北林业大学 无卤膨胀阻燃复合材料
CN102558659A (zh) * 2010-12-21 2012-07-11 深圳市沃尔核材股份有限公司 无卤阻燃烯烃类发泡体及其制备方法
CN103804775A (zh) * 2014-03-06 2014-05-21 福州大学 一种无卤阻燃聚烯烃复合泡沫材料及其制备方法

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US11697039B2 (en) 2017-12-02 2023-07-11 Mighty Fire Breaker Llc Wireless communication network, GPS-tracked back-pack spraying systems and command center configured for proactively spraying environmentally-safe anti-fire chemical liquid on property surfaces to inhibit fire ignition and flame spread in the presence of wild fire
US11730987B2 (en) 2017-12-02 2023-08-22 Mighty Fire Breaker Llc GPS tracking and mapping wildfire defense system network for proactively defending homes and neighborhoods against threat of wild fire by spraying environmentally-safe anti-fire chemical liquid on property surfaces to inhibit fire ignition and flame spread in the presence of wild fire
US11794044B2 (en) 2017-12-02 2023-10-24 Mighty Fire Breaker Llc Method of proactively forming and maintaining GPS-tracked and mapped environmentally-clean chemical firebreaks and fire protection zones that inhibit fire ignition and flame spread in the presence of wild fire
US11633636B2 (en) 2017-12-02 2023-04-25 Mighty Fire Breaker Llc Wireless neighborhood wildfire defense system network supporting proactive protection of life and property in a neighborhood through GPS-tracking and mapping of environmentally-clean anti-fire (AF) chemical liquid spray applied to the property before wild fires reach the neighborhood
US11638844B2 (en) 2017-12-02 2023-05-02 Mighty Fire Breaker Llc Method of proactively protecting property from wild fire by spraying environmentally-clean anti-fire chemical liquid on property surfaces prior to wild fire arrival using remote sensing and GPS-tracking and mapping enabled spraying
US11642555B2 (en) 2017-12-02 2023-05-09 Mighty Fire Breaker Llc Wireless wildfire defense system network for proactively defending homes and neighborhoods against wild fires by spraying environmentally-clean anti-fire chemical liquid on property and buildings and forming GPS-tracked and mapped chemical fire breaks about the property
US11654313B2 (en) 2017-12-02 2023-05-23 Mighty Fire Breaker Llc Wireless communication network, GPS-tracked ground-based spraying tanker vehicles and command center configured for proactively spraying environmentally-safe anti-fire chemical liquid on property surfaces to inhibit fire ignition and flame spread in the presence of wild fire
US11654314B2 (en) 2017-12-02 2023-05-23 Mighty Fire Breaker Llc Method of managing the proactive spraying of environment ally-clean anti-fire chemical liquid on GPS-specified property surfaces so as to inhibit fire ignition and flame spread in the presence of wild fire
US11400324B2 (en) 2017-12-02 2022-08-02 Mighty Fire Breaker Llc Method of protecting life, property, homes and businesses from wild fire by proactively applying environmentally-clean anti-fire (AF) chemical liquid spray in advance of wild fire arrival and managed using a wireless network with GPS-tracking
US11395931B2 (en) 2017-12-02 2022-07-26 Mighty Fire Breaker Llc Method of and system network for managing the application of fire and smoke inhibiting compositions on ground surfaces before the incidence of wild-fires, and also thereafter, upon smoldering ambers and ashes to reduce smoke and suppress fire re-ignition
US11697040B2 (en) 2017-12-02 2023-07-11 Mighty Fire Breaker Llc Wild fire defense system network using a command center, spraying systems and mobile computing systems configured to proactively defend homes and neighborhoods against threat of wild fire by spraying environmentally-safe anti-fire chemical liquid on property surfaces before presence of wild fire
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US11865390B2 (en) 2017-12-03 2024-01-09 Mighty Fire Breaker Llc Environmentally-clean water-based fire inhibiting biochemical compositions, and methods of and apparatus for applying the same to protect property against wildfire
US11865394B2 (en) 2017-12-03 2024-01-09 Mighty Fire Breaker Llc Environmentally-clean biodegradable water-based concentrates for producing fire inhibiting and fire extinguishing liquids for fighting class A and class B fires
US11826592B2 (en) 2018-01-09 2023-11-28 Mighty Fire Breaker Llc Process of forming strategic chemical-type wildfire breaks on ground surfaces to proactively prevent fire ignition and flame spread, and reduce the production of smoke in the presence of a wild fire
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