CN106317459A - 一种钙霞石‑红磷协同阻燃剂的制备方法 - Google Patents
一种钙霞石‑红磷协同阻燃剂的制备方法 Download PDFInfo
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Abstract
本发明涉及一种钙霞石‑红磷协同阻燃剂的制备方法,所述方法将钙霞石与一定量0.1mol/L的NiCl2溶液混合,在60℃下离子交换30‑180min后,过滤、洗涤、干燥,然后放在石英管反应器中,在400‑450℃下通入氢气30‑120min,之后在410‑440℃下通入磷化氢2‑10h,最后将样品在隔绝空气的反应容器内在260‑290℃下加热保温10‑60min,得到孔道内负载4‑33%(质量比)红磷的钙霞石‑红磷协同阻燃剂。本发明制备工艺较简单,解决了单独使用红磷阻燃剂存在的不足,制备的阻燃剂具有良好的阻燃性能。
Description
技术领域
本发明属于阻燃剂技术领域,具体涉及一种钙霞石分子筛-红磷协同阻燃剂的制备方法。
背景技术
随着人们健康环保意识的增强,寻求环保、低毒、高效、多功能的阻燃剂已成为阻燃剂行业的必然趋势。超细化技术、微胶囊化技术、复配技术、交联技术等阻燃新技术正在不断发展。
在现代阻燃技术中,阻燃剂的复配是极其重要的一个方面。复配就是利用阻燃剂之间的相互作用,以提高阻燃性能,即阻燃剂的协同效应。具有协同效应的阻燃体系阻燃效果好,阻燃性能增强,既可以阻燃又可以抑烟,还具有一些特殊的功能,应用范围广,成本低,能显著提高经济效益,是实现阻燃剂无卤化的有效途径之一。红磷与其他阻燃剂并用时,具有显著的阻燃增效作用。
无机阻燃剂具有稳定性好、无毒或低毒、腐蚀性小、价格低廉等特点,但其阻燃效率低,通常需要大量添加才能有较好的阻燃效果。因此,在提高制品阻燃性能的同时,其加工性能变差,力学性能大幅下降,严重影响产品的质量。研究表明:阻燃剂的粒度越小,在基材中分散度越大,阻燃效果越好。近年来,纳米技术发展迅速,纳米材料得到广泛应用,现在使用的阻燃剂粒径一般在微米级,如果降低到纳米级,阻燃效果将显著提高,阻燃剂的添加量将大幅度降低,可解决材料阻燃性能与力学性能之间的矛盾。
磷系阻燃剂由于其高效、低毒、低烟成为阻燃剂的热门材料,尤其红磷是一种优良的阻燃剂,其阻燃机理为:受热分解,形成具有极强脱水性的偏磷酸,从而使燃烧的聚合物表面炭化,炭化层一方面可减少可燃气体的放出,另一方面还具有吸热作用;另外,红磷与氧形成PO·自由基进入气相后,可捕捉大量H·、HO·自由基。但红磷在使用时,存在以下问题:易燃,易爆炸,与空气长期接触会放出剧毒PH3气体;本身为红色,易使制品着色;容易吸水,与聚合物兼容性差。上述缺点严重限制了红磷的直接应用。将红磷经微胶囊化技术处理,可克服红磷性能上的上述缺点,消除红磷在贮运、生产、加工过程中的隐患:二是可以白度化,以淡化红磷的颜色,拓宽红磷的应用范围;三是可改善与基材的相容性,减小对基材物理力学性能的影响;四是可通过对囊材的选择,实现多种阻燃元素(阻燃剂)的复配,提高阻燃抑烟效能。杜龙超等研究了水滑石和红磷微胶囊对乙烯-醋酸乙烯共聚物的协同阻燃效果(Longchao Du, Baojun Qu and Zhenjin Xu. Flammability characteristics andsynergistic effect of hydrotalcite with microencapsulated red phosphorus inhalogen-free flame retardant EVA composite. Polymer Degradation and Stability91 (2006) 995-1001.)。虽然红磷微胶囊的阻燃效果不错,但是其制备工艺较复杂,阻燃剂颗粒大小不易控制,限制了其广泛的使用。
多孔材料可以应用到阻燃剂中提高阻燃剂的性能,尤其是对高分子材料热稳定性的提高尤为明显。目前,已有一些科研工作者开展了对该类阻燃剂性能的研究。叶蕾等研究了多壁碳纳米管和氢氧化镁对乙烯-醋酸乙烯酯共聚物的协同阻燃效果,当多壁碳纳米管的添加量为2%时,可以明显降低乙烯-醋酸乙烯酯共聚物的热释放速率,质量损失率达到50%-60%,使阻燃剂的氧指数提高5%(Lei Ye, Qianghua Wu and Baojun Qu. Synergisticeffects and mechanism of multiwalled carbon nanotubes with magnesiumhydroxide in halogen-free flame retardant EVA/MH/MWNT nanocomposites. PolymerDegradation and Stability 94 (2009) 751–756.)。
钙霞石分子式为Na8(Si6Al6O24)( H0.88(CO3)1.44(H2O)2)。钙霞石的晶体具有十二元环孔道,孔道尺寸为0.59 nm × 0.59 nm。孔道内的金属离子具有离子交换能力,作为无机材料也具有一定的阻燃性能。
本发明的目的就是将红磷阻燃性能好、超细钙霞石的优势和阻燃剂的复配协同增效集中于一体,既解决单独使用红磷阻燃剂存在的几方面不足,又可以制备颗粒大小为亚微米、粒径均匀的阻燃剂。该阻燃剂保留了红磷阻燃剂高效、低烟、低毒的优点,又发挥了钙霞石对红磷阻燃的协同增强作用,还能有效控制阻燃剂颗粒大小,超细阻燃剂还可以改善与有机材料的兼容性,有助于提高阻燃复合材料的力学性能和热稳定性。本发明制备的钙霞石负载红磷超细阻燃剂在有机涂层和高分子薄膜材料阻燃领域具有广阔的应用前景。
发明内容
本发明采用的技术方案是:一种钙霞石-红磷协同阻燃剂的制备方法,本发明以超细钙霞石、磷化氢为主要原料,先在钙霞石孔道内负载Ni,然后使磷化氢在钙霞石孔道内被Ni催化分解生成黄磷,黄磷再转化为红磷,即可制得超细钙霞石-红磷协同阻燃剂。包括以下步骤:
(1)将钙霞石与一定量0.1mol/L的NiCl2溶液混合,在60℃下离子交换一定时间后,过滤、洗涤、干燥,得到孔道内负载Ni2+的钙霞石;
(2)将(1)制备的样品放在石英管反应器中,在一定温度下通入氢气还原一定时间,得到孔道内负载Ni的钙霞石;
(3)将(2)制备的负载Ni的钙霞石在石英管反应器中,在一定温度下通入磷化氢一定时间,使磷化氢在钙霞石孔道内分解为黄磷;
(4)将(3)制备的样品在隔绝空气的反应容器内加热至一定温度,保温一定时间,将黄磷转换为红磷,得到孔道内负载红磷的钙霞石-红磷协同阻燃剂。
在优选实施方式中,所述钙霞石粒径为0.5-1μm。
在优选实施方式中,所述钙霞石与0.1mol/L的NiCl2溶液混合,在60℃下离子交换的时间为30-180min。
在优选实施方式中,所述钙霞石孔道内负载的Ni2+在氢气中还原的温度为400-450℃,时间为30-120min。
在优选实施方式中,所述磷化氢在钙霞石孔道内分解的温度为410-440℃,时间为2-10h。
在优选实施方式中,所述黄磷转换为红磷的加热温度为260-290℃,时间为10-60min。
本发明所制备产品红磷含量为4-33%(质量比)。
本发明所制备阻燃剂的优点是解决了单独使用红磷阻燃剂存在的不足,可以制备亚微米尺寸、粒径均匀的阻燃剂。该阻燃剂保留了红磷阻燃剂高效、低烟、低毒的优点,又发挥了钙霞石对红磷阻燃的协同增强作用,还能有效控制阻燃剂颗粒大小,超细阻燃剂还可以改善与有机材料的兼容性,有助于提高阻燃复合材料的力学性能和热稳定性。本发明制备技术可有效控制磷化氢气体在钙霞石孔道内分解,能够控制高效阻燃成分红磷仅进入钙霞石孔道内部,而不会在钙霞石表面沉积,制备工艺较简单。本发明还为次磷酸钠工业副产品磷化氢气体的资源化利用提供了新途径。
具体实施方式
实施例1
将20g 中位粒径为0.5μm的钙霞石与500mL 0.1mol/L的NiCl2溶液混合,在60℃下搅拌180min,过滤、洗涤、干燥后,置于石英管反应器中,450℃下通入氢气120min后,440℃下通入磷化氢,反应10h,冷却后,将样品在隔绝空气的反应容器内加热至290℃,保温60min,得到红磷含量为33%的钙霞石孔道内负载红磷的阻燃剂,该阻燃剂与聚乙烯混合制备的阻燃材料的氧指数为33.2。
实施例2
将20g 中位粒径为1μm的钙霞石与500mL 0.1mol/L的NiCl2溶液混合,在60℃下搅拌30min,过滤、洗涤、干燥后,置于石英管反应器中,400℃下通入氢气30min后,410℃下通入磷化氢,反应2h,冷却后,将样品在隔绝空气的反应容器内加热至260℃,保温10min,得到红磷含量为4%的钙霞石孔道内负载红磷的阻燃剂,该阻燃剂与聚乙烯混合制备的阻燃材料的氧指数为28.1。
实施例3
将20g 中位粒径为0.75μm的钙霞石与500mL 0.1mol/L的NiCl2溶液混合,在60℃下搅拌105min,过滤、洗涤、干燥后,置于石英管反应器中,425℃下通入氢气75min后,425℃下通入磷化氢,反应6h,冷却后,将样品在隔绝空气的反应容器内加热至275℃,保温35min,得到红磷含量为17%的钙霞石孔道内负载红磷的阻燃剂,该阻燃剂与聚乙烯混合制备的阻燃材料的氧指数为31.4。
实施例4
将20g 中位粒径为0.5μm的钙霞石与500mL 0.1mol/L的NiCl2溶液混合,在60℃下搅拌180min,过滤、洗涤、干燥后,置于石英管反应器中,450℃下通入氢气30min后,440℃下通入磷化氢,反应10h,冷却后,将样品在隔绝空气的反应容器内加热至290℃,保温60min,得到红磷含量为10%的钙霞石孔道内负载红磷的阻燃剂,该阻燃剂与聚乙烯混合制备的阻燃材料的氧指数为29.5。
实施例5
将20g 中位粒径为0.5μm的钙霞石与500mL 0.1mol/L的NiCl2溶液混合,在60℃下搅拌180min,过滤、洗涤、干燥后,置于石英管反应器中,450℃下通入氢气120min后,440℃下通入磷化氢,反应6h,冷却后,将样品在隔绝空气的反应容器内加热至290℃,保温60min,得到红磷含量为28%的钙霞石孔道内负载红磷的阻燃剂,该阻燃剂与聚乙烯混合制备的阻燃材料的氧指数为32.6。
氧指数(阻燃性能)测试实验:
将上述实施例1、2、3、4和5制备的阻燃剂和聚乙烯混合(其中阻燃剂占30%),在120℃下双辊混炼10min,制成厚度为1mm的薄片状样品。氧指数测试按照GB/T2406—1993进行。
Claims (1)
1.一种钙霞石-红磷协同阻燃剂的制备方法,其特征在于,包括以下步骤:以亚微米钙霞石、磷化氢为主要原料,将钙霞石与一定量0.1mol/L的NiCl2溶液混合,在60℃下离子交换一定时间后,过滤、洗涤、干燥,得到孔道内负载Ni2+的钙霞石,然后放在石英管反应器中,在一定温度下通入氢气,得到孔道内负载Ni的钙霞石,之后在一定温度下通入磷化氢,使磷化氢在钙霞石孔道内分解为黄磷,将其在隔绝空气的反应容器内加热至一定温度,将黄磷转换为红磷,得到孔道内负载红磷的钙霞石-红磷协同阻燃剂;钙霞石的粒径为0.5-1μm;钙霞石与NiCl2溶液离子交换的时间为30-180min;钙霞石孔道内负载的Ni2+在氢气中还原的温度为400-450℃,时间为30-120min;磷化氢在钙霞石孔道内分解温度为410-440℃,时间为2-10h;黄磷转换为红磷的加热温度为260-290℃,时间为10-60min;制备的阻燃剂红磷含量为4-33%(质量比)。
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