CN114773670B - 一种含有多组分相容剂的甲基八溴醚阻燃母粒及其阻燃聚苯乙烯泡沫材料 - Google Patents

一种含有多组分相容剂的甲基八溴醚阻燃母粒及其阻燃聚苯乙烯泡沫材料 Download PDF

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CN114773670B
CN114773670B CN202210442811.1A CN202210442811A CN114773670B CN 114773670 B CN114773670 B CN 114773670B CN 202210442811 A CN202210442811 A CN 202210442811A CN 114773670 B CN114773670 B CN 114773670B
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retardant
maleic anhydride
compatilizer
methyl octabromoether
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CN114773670A (zh
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王靖宇
钱立军
辛晓华
赵震
王盛海
王光禹
杨木森
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Shandong Brother Sci&tech Co ltd
Shandong Golden Bay New Material Technology Co ltd
Beijing Technology and Business University
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Shandong Golden Bay New Material Technology Co ltd
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Abstract

本发明公开了一种含有多组分相容剂的甲基八溴醚阻燃母粒及其阻燃聚苯乙烯泡沫材料，是制备用于聚苯乙烯泡沫材料的阻燃母粒的技术；具体是首先将马来酸酐‑四溴双酚A类化合物的共聚物和马来酸酐接枝聚苯乙烯组成多组份相容剂，再将甲基八溴醚与多组份相容剂制备成阻燃母粒，实现甲基八溴醚与马来酸酐‑四溴双酚A类化合物的共聚物、马来酸酐接枝聚苯乙烯的良好分散；并提高了甲基八溴醚的热稳定性；制备的颗粒化母粒解决了甲基八溴醚阻燃粉体在加工和运输过程中产生的粉尘和污染等问题；该阻燃体系获得的阻燃聚苯乙烯泡沫材料成型发泡工艺性能良好，在较低的阻燃剂添加量下使挤出发泡聚苯乙烯(XPS)实现良好的阻燃性能，并且保持材料的物理机械性能和产品外观颜色。

Description

一种含有多组分相容剂的甲基八溴醚阻燃母粒及其阻燃聚苯 乙烯泡沫材料
技术领域
本发明涉及一种含有多组份相容剂的甲基八溴醚阻燃母粒及其阻燃聚苯乙烯泡沫材料及其制备方法，属于在聚苯乙烯中添加特定阻燃成分获得阻燃聚苯乙烯泡沫材料的技术领域。
背景技术
聚苯乙烯(PS)树脂是五大通用塑料之一，是制备挤塑型聚苯乙烯保温板(XPS)的主要原料；XPS以经济、高机械强度和优良的隔热性能等优点，广泛的应用于商用和民用外墙保温材料中；但是PS极易燃烧且产烟量巨大，由此引发了大量的建筑和住宅火灾；因此，对XPS进行阻燃改性，使其遇火不燃或者离火自熄，已经成为其在建筑领域安全应用的研究重点。
在过去的几十年里，XPS主要采用六溴环十二烷(HBCD)作为阻燃剂，但该助剂由于具有持久性有机污染已经被列入斯德哥尔摩国际公约禁用名单，并已在我国全面禁用；因此，目前国内建筑节能领域急需应用于XPS中的绿色环保替代型阻燃剂，这对国家实现建设环境友好型和资源节约型社会的目标极为关键；当前阻燃XPS市场中，甲基八溴醚是替代HBCD的主要产品；而在采用甲基八溴醚替代HBCD生产XPS的生产中，发现甲基八溴醚与PS基体相容性低于HBCD，导致挤出过程难以均匀分散，且制品泡孔不稳定，影响了制品的质量。另外甲基八溴醚含有活泼的溴化脂肪烃，它会在加工温度范围内分解并释放溴化氢，腐蚀设备的同时也会影响XPS的发泡和阻燃性能，并导致产品变色；因此在以甲基八溴醚为阻燃剂生产XPS材料的过程中必须改善甲基八溴醚与聚苯乙烯的相容性并引入匹配的热稳定体系，从而保证XPS的加工性能和发泡材料的成型稳定性和阻燃性能。
目前，甲基八溴醚的合成开展了一定规模的研究，如甲基八溴醚的专利申请CN109796315A、CN109336746A，以上研究致力于在合成过程中减少游离溴的产生，从而提高阻燃剂的热稳定性；但是甲基八溴醚熔点低、与PS基体相容性差，难以在热加工过程中与基体形成良好的分散体系，不可避免的影响相应聚苯乙烯发泡材料的成型性能，致其阻燃的XPS材料加工性能和力学性能明显下降，难以满足对材料性能要求越来越高的工业需求；另外甲基八溴醚在运输和应用过程中产生的粉尘问题也亟需解决；通常情况下，阻燃母粒化是解决阻燃剂粉体产生粉尘污染的有效手段，而选用适当的载体也有望同时解决阻燃剂与聚合物基体相容性差的问题，并且在阻燃剂母粒化的过程中，也可以同时引进热稳定剂以稳定甲基八溴醚含有的溴化脂肪烃，从而可以实现阻燃母粒的多功能化。因此发展与聚苯乙烯高相容的甲基八溴醚阻燃母粒，对推广高性能的阻燃聚苯乙烯泡沫材料的应用具有重要的支撑作用。
发明内容
本发明针对目前存在的问题，提供了一种含有多组份相容剂的甲基八溴醚阻燃母粒及其阻燃聚苯乙烯泡沫材料；该阻燃母粒是由甲基八溴醚加入多组份相容剂、热稳定剂和抗氧剂共同组成，其中多组份相容剂是由与甲基八溴醚和聚苯乙烯结构相近的马来酸酐-四溴双酚A类化合物的共聚物和马来酸酐接枝聚苯乙烯组成；将甲基八溴醚阻燃母粒与聚苯乙烯、滑石粉和发泡剂等通过熔融塑化发泡，挤出获得阻燃聚苯乙烯发泡材料。
本发明涉及的甲基八溴醚，以及马来酸酐-四溴双酚A类化合物的共聚物中的代表例—马来酸酐-(四溴双酚A-双(烯2-甲基丙基)醚)共聚物的分子式如下所示，
马来酸酐-(四溴双酚A-双(烯2-甲基丙基)醚)共聚物的分子式所用原料：甲基八溴醚、马来酸酐-四溴双酚A类化合物的共聚物(马来酸酐-四溴双酚A共聚物、马来酸酐-(四溴双酚A-双烯丙基醚)共聚物和马来酸酐-(四溴双酚A-双(烯2-甲基丙基)醚)共聚物，是以自由基引发剂引发马来酸酐与四溴双酚A、四溴双酚A丙烯醚或异丙烯醚等烯烃醚化物发生自由基聚合反应获得马来酸酐与四溴双酚A的共聚物或马来酸酐与四溴双酚A烯烃醚化物的共聚物)、马来酸酐接枝聚苯乙烯、硬脂酸盐(选自硬脂酸钙、硬脂酸锌、硬脂酸钡中的一种或几种)、滑石粉、聚苯乙烯(选自通用聚苯乙烯、回收聚苯乙烯)、发泡剂(选自氟利昂、乙醇、水、二氧化碳中的一种或几种)、抗氧剂(选自1010和168中的一种或几种)。
第一步，将马来酸酐-四溴双酚A类化合物的共聚物和马来酸酐接枝聚苯乙烯组成多组份相容剂，再将多组份相容剂与甲基八溴醚、热稳定剂和抗氧剂进行熔融共混，制得甲基八溴醚阻燃母粒；
优选的，所述的多组份相容剂中来马来酸酐-四溴双酚A类化合物的共聚物和马来酸酐接枝聚苯乙烯的质量比例为1:99.5～99.5:1。
优选的，所述的甲基八溴醚与多组份相容剂质量比例为1:99.5～99.5:1。
优选的，所述的马来酸酐接枝聚苯乙烯中马来酸酐的接枝率为0.05％-3.0％。
优选的，热稳定剂由硬脂酸钙、硬脂酸锌、硬脂酸钡的一种或几种混合组成；优选的，抗氧剂由1010和168混合组成。
优选的，所述的热稳定剂占甲基八溴醚和多组份相容剂之和的质量比例为0.5％～20％，抗氧剂占甲基八溴醚和多组份相容剂之和的质量比例为0.1％～4％。
第二步，将第一步制得的甲基八溴醚阻燃母粒0.1-50质量份、滑石粉0-5质量份、聚苯乙烯100质量份在熔融共混过程中，加入发泡剂氟利昂、乙醇、水、二氧化碳中的一种或几种的混合物，制得阻燃发泡聚苯乙烯材料。
与通常的直接采用甲基八溴醚作为阻燃剂应用于聚苯乙烯泡沫材料相比，本发明创造性的采用了与甲基八溴醚和聚苯乙烯结构相近且相容的马来酸酐-四溴双酚A类化合物的共聚物和马来酸酐接枝聚苯乙烯组成多组分相容剂，再与甲基八溴醚制备阻燃母粒，从而增加了甲基八溴醚母粒在聚苯乙烯中的分散和相容，并且在甲基八溴醚母粒化的过程中，并入了热稳定剂体系，相比于纯阻燃剂体系，甲基八溴醚阻燃母粒的1wt％分解温度最高提高了50℃达到275℃，相比于210℃的阻燃剂变色温度，甲基八溴醚阻燃母粒在260℃之前不变色，所制备的XPS板材保持白色状态，且XPS板材的发泡倍率可以达到50倍；其中含50wt.％的甲基八溴醚阻燃母粒添加量为1％时，获得阻燃XPS材料的极限氧指数(LOI)值高达25.9％；添加量为6％时，LOI值高达34.3％，获得的XPS泡沫板的表观密度为29.1kg/m3，导热系数为0.031W/m·k，压缩强度为334kPa；作为对比，直接采用甲基八溴醚作为阻燃剂，添加量为3％时，获得阻燃XPS材料的极限氧指数(LOI)值仅为31.1％；获得的XPS泡沫板的表观密度为30.2kg/m3，导热系数为0.039W/m·k，压缩强度为302kPa。以上对比结果表明，含有多组份相容剂的甲基八溴醚阻燃母粒能够显著的提高阻燃XPS的阻燃和物理机械性能。
附图说明
图1高热稳定的甲基八溴醚阻燃母粒与纯甲基八溴醚的热失重对比曲线；
图2阻燃XPS材料的扫描电镜图；
具体实施方式
实施例1
将100g甲基八溴醚、100g多组份相容剂(2g马来酸酐-(四溴双酚A-双(烯2-甲基丙基)醚)共聚物和98g马来酸酐接枝聚苯乙烯)，2.5g硬脂酸钙、1.5g硬脂酸锌、0.5g抗氧剂1010熔融制备成甲基八溴醚阻燃母粒，甲基八溴醚阻燃母粒1wt％分解温度269℃且在250℃不变色，再将以上共0.6kg甲基八溴醚阻燃母粒与0.02kg滑石粉和9.38kg通用聚苯乙烯在双螺杆机组中连续熔融共混，并采用氟利昂/CO2/乙醇/水组合发泡剂进行挤塑发泡。获得的含6％甲基八溴醚阻燃母粒质量分数(含3％甲基八溴醚)阻燃XPS材料，如图2所示，阻燃XPS材料的泡孔尺寸稳定，大小基本一致。阻燃XPS材料的LOI高达34.3％，表观密度为29.1kg/m3、导热系数为0.031W/m·k、压缩强度为334kPa，XPS板材白色。而获得的含3％甲基八溴醚阻燃XPS材料(即直接采用甲基八溴醚作为阻燃剂)，其泡孔尺寸大小相差较大(图2)。并且其LOI仅为31.1％；表观密度上升到30.2kg/m3，导热系数升高到0.039W/m·k，压缩强度降低至302kPa。
实施例2
将300g甲基八溴醚、100g多组份相容剂(25g马来酸酐-四溴双酚A共聚物、25g马来酸酐-(四溴双酚A-双(烯2-甲基丙基)醚)共聚物和50g马来酸酐接枝聚苯乙烯)、10g硬脂酸钙、0.5g抗氧剂168熔融制备成甲基八溴醚阻燃母粒，甲基八溴醚阻燃母粒1wt％分解温度250℃且在240℃不变色，再将以上共0.6kg甲基八溴醚阻燃母粒与0.1kg滑石粉和19.3kg通用聚苯乙烯在双螺杆机组中连续熔融共混，并采用CO2/乙醇/水组合发泡剂进行挤塑发泡；获得的含3.0％甲基八溴醚阻燃母粒质量分数(含2.25％甲基八溴醚)的阻燃XPS材料的LOI为29.6％，表观密度为29.4kg/m3、导热系数为0.032W/m·k、压缩强度为325kpa,，XPS板材近白色。
实施例3
将1000g甲基八溴醚、1000g多组份相容剂(30g马来酸酐-四溴双酚A共聚物、30g马来酸酐-(四溴双酚A-双烯丙基醚)共聚物、40g马来酸酐-(四溴双酚A-双(烯2-甲基丙基)醚)共聚物和900g马来酸酐接枝聚苯乙烯)、50g硬脂酸钙和3g抗氧剂168熔融共混获得甲基八溴醚阻燃母粒，甲基八溴醚阻燃母粒1wt％热分解温度260℃且在250℃不变色，再将以上共0.2kg甲基八溴醚阻燃母粒与0.1kg滑石粉和19.7kg通用聚苯乙烯在双螺杆机组中连续熔融共混，并采用CO2/乙醇/水组合发泡剂进行挤塑发泡。获得的含1.0％甲基八溴醚阻燃母粒质量分数(含0.5％甲基八溴醚)的阻燃XPS材料的LOI为25.9％，表观密度为29.1kg/m3、导热系数为0.031W/m·k、压缩强度为335kpa,，XPS板材近白色。
实施例4
将950g甲基八溴醚、50g多组份相容剂(20g马来酸酐-四溴双酚A共聚物、20g马来酸酐-(四溴双酚A-双烯丙基醚)共聚物和10g马来酸酐接枝聚苯乙烯)、1.5g硬脂酸钙、1.5g硬脂酸锌、0.6g抗氧剂1010、0.4g抗氧剂168熔融制备成甲基八溴醚阻燃母粒，甲基八溴醚阻燃母粒1wt％分解温度245℃且在225℃不变色，再将以上0.8kg甲基八溴醚阻燃母粒和9.12kg通用聚苯乙烯在双螺杆机组中连续熔融共混，并采用氟利昂/乙醇/水组合发泡剂进行挤塑发泡。获得的含8％甲基八溴醚阻燃母粒质量分数(含7.6％甲基八溴醚)的阻燃XPS材料的LOI为37.9％，表观密度为30.3kg/m3、导热系数为0.035W/m·k、压缩强度为319kpa，XPS板材近白色。
实施例5
将200g甲基八溴醚、800g多组份相容剂(60g马来酸酐-(四溴双酚A-双烯丙基醚)共聚物和740g马来酸酐接枝聚苯乙烯)、4.0g硬脂酸钙、2.0g硬脂酸锌与0.6g抗氧剂1010熔融制备成甲基八溴醚阻燃母粒，甲基八溴醚阻燃母粒1wt％热分解温度275℃且在260℃不变色，再将以上共1.0kg甲基八溴醚阻燃母粒与0.08kg滑石粉和8.92kg通用聚苯乙烯在双螺杆机组中连续熔融共混，并采用氟利昂/乙醇/水组合发泡剂进行挤塑发泡。获得的含10％甲基八溴醚阻燃母粒质量分数(含2.0％甲基八溴醚)的阻燃XPS材料的LOI为29.1％，表观密度为30.2kg/m3、导热系数为0.034W/m·k、压缩强度为327kpa，XPS板材近白色。
上述实施例用来解释说明本发明，而不是对本发明进行限制，在本发明的精神和权利要求的保护范围内，对本发明作出的任何修改和改变，都适用于本发明的保护范围。
表1部分甲基八溴醚阻燃母粒阻燃XPS泡沫材料的阻燃和物理机械性能结果
表2甲基八溴醚阻燃母粒与甲基八溴醚阻燃XPS泡沫材料的平行对比结果

Claims (4)

1.一种含有多组分相容剂的甲基八溴醚阻燃母粒，其特征在于，所述含多组份相容剂的甲基八溴醚阻燃母粒是由马来酸酐-四溴双酚A类化合物的共聚物和马来酸酐接枝聚苯乙烯组成多组分相容剂，再与甲基八溴醚混合，加入热稳定剂和抗氧剂后通过熔融共混制得；所述的马来酸酐-四溴双酚A类化合物的共聚物由马来酸酐-（四溴双酚A-双烯丙基醚）共聚物和马来酸酐-（四溴双酚A-双（烯2-甲基丙基）醚）共聚物中的一种或几种混合组成；所述的多组份相容剂中马来酸酐-四溴双酚A类化合物的共聚物和马来酸酐接枝聚苯乙烯的质量比例为1:99.5~99.5:1，甲基八溴醚与多组份相容剂质量比例为1:99.5~99.5:1；所述的热稳定剂占甲基八溴醚和多组份相容剂之和的质量比例为0.5%~20%，抗氧剂占甲基八溴醚和多组份相容剂之和的质量比例为0.1%~4%。
2.如权利要求1所述的一种含有多组份相容剂的甲基八溴醚阻燃母粒，其特征在于，所述的马来酸酐接枝聚苯乙烯中马来酸酐的接枝率为0.05%-3.0%。
3.如权利要求1所述的一种含有多组份相容剂的甲基八溴醚阻燃母粒，其特征在于，所述热稳定剂由硬脂酸钙、硬脂酸锌、硬脂酸钡中的一种或几种混合组成；所述抗氧剂由1010和168中的一种或几种混合组成。
4.一种含有多组份相容剂的甲基八溴醚阻燃母粒阻燃聚苯乙烯泡沫材料，其特征在于，将如权利要求1所述的甲基八溴醚阻燃母粒0.1-50质量份、滑石粉0-5质量份、聚苯乙烯100质量份在熔融共混过程中，加入发泡剂氟利昂、乙醇、水、二氧化碳中的一种或几种的混合物，制得阻燃聚苯乙烯泡沫材料。
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