CN111763351B - 一种反应型的磷杂菲/亚磷酸酯双基阻燃剂、其制备方法和应用 - Google Patents
一种反应型的磷杂菲/亚磷酸酯双基阻燃剂、其制备方法和应用 Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 94
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Abstract
本发明公开了一种反应型的磷杂菲/亚磷酸酯双基阻燃剂、其制备方法和复合体系在阻燃硬质聚氨酯泡沫中的应用,属于阻燃材料技术领域。本发明采用二醛类化合物、有机亚磷酸酯和DOPO合成出具有双基协同效应的阻燃剂,是一种高效、热稳定性高的环保阻燃剂,其复合体系能够促进硬质聚氨酯泡沫在燃烧时快速成炭,并形成连续、致密的炭层,有效减少热量的释放,使硬质聚氨酯泡沫具有优异的阻燃性能。
Description
技术领域
本发明属于阻燃材料技术领域,具体涉及一种反应型的磷杂菲/亚磷酸酯双基阻燃剂、其制备方法和复合体系在阻燃硬质聚氨酯泡沫中的应用。
背景技术
硬质聚氨酯泡沫具有优良的物理机械性能、电学性能、力学性能以及耐酸耐碱性能,并与多种材料具有很强的粘结力,因而被广泛用于汽车工业、家电工业以及建筑工业等领域。但由于聚氨酯材料在空气中易燃,并分解产生大量有毒烟雾,会引起火灾并造成人员伤亡以及巨大经济损失等,因而限制了聚氨酯泡沫的进一步发展。目前最常应用于聚氨酯泡沫的阻燃剂主要为含磷添加型阻燃剂如亚磷酸酯类阻燃剂,这类阻燃剂主要通过气相阻燃以提高聚氨酯泡沫的阻燃性能,但其大多是液态,具有耐热性差、易析出等缺点,单独使用时会使制备的聚氨酯材料稳定性差。
近年来,研究者们致力于设计并开发阻燃效率好、对基材自身性能影响小的阻燃剂,力求在添加量较低的情况下基材能获得较好的阻燃效果。其中,双基协同阻燃剂受到了研究者们的广泛关注,并在Macromolecules、Polymer、Polymer Degradation andStability、Journal of Applied Polymer Science等诸多期刊上均可见到相关研究成果的发表。另外,一类环境友好型阻燃剂为9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO),因其具有较高的可反应性和良好的阻燃效果,使得近年来以DOPO为原料制备新型高效磷杂菲衍生物阻燃剂成为了阻燃领域的研究热点。
亚磷酸酯类阻燃剂和DOPO若以物理共混的形式同时发挥阻燃作用,这样无疑会带来一定的弊端:亚磷酸酯的极性与聚合物基体的极性差别较大且易团聚,容易出现相容性差的问题,同时有机小分子阻燃剂易出现迁移的现象,另外添加量过大会降低材料的机械性能。因此本发明将亚磷酸酯和磷杂菲基团通过化学键结合在一个分子单元内,形成一种反应型的磷杂菲/亚磷酸酯双基阻燃剂,这既解决了上述问题,又增强了二者的双基协同效应,提高了阻燃效率。
发明内容
本发明针对目前存在的问题,提供一种新型的、环境友好的、具有双基协同效应的磷杂菲/亚磷酸酯双基阻燃剂、其制备方法和复合体系在阻燃硬质聚氨酯泡沫中的应用。本发明的一种反应型的磷杂菲/亚磷酸酯双基阻燃剂具有良好的热稳定性,本发明的含磷杂菲/亚磷酸酯双基阻燃剂的复合体系具有较高的阻燃效率,能明显改善硬质聚氨酯泡沫的阻燃性能。
本发明选用具有不同阻燃机理的阻燃剂,通过复配使用使其产生良好的协同效应,获得更为显著的阻燃效果,提高产品的安全性能。磷杂菲/亚磷酸酯双基阻燃剂同时具有羟基基团和阻燃基团,在与聚氨酯中的异氰酸酯基团反应过程中,其中的磷杂菲基团和亚磷酸酯基团连接到聚氨酯分子结构的主链上而阻碍其燃烧。此外,可膨胀石墨(EG)受热分解后会在基体表面形成蠕虫状炭层,从而发挥优异的凝聚相阻隔作用。这两种反应过程一直在不断进行,使阻燃RPUF的炭层外表面形成一层致密的磷酸类化合物保护层,增加了表面炭层的致密性,以隔绝氧气和热量。
本发明采用以下技术方案:
一种反应型的磷杂菲/亚磷酸酯双基阻燃剂,其结构通式如下式所示:
其中,R和R’均为烷基或芳基。
本发明还公开了所述一种反应型的磷杂菲/亚磷酸酯双基阻燃剂的合成方法,合成路线如下:
(1)
(2)
其具体制备方法,包括如下步骤:
(1)a.将二醛类化合物和有机溶剂加入反应容器中,并使其在50℃下搅拌溶解,然后向溶液中加入一定量的碱性催化剂;b.将溶解于适量有机溶剂的有机亚磷酸酯溶液以一定速度滴加到烧瓶中,滴加完毕后使体系上升至一定温度下反应一定时间。
(2)随后将DOPO加入步骤(1)获得的反应体系继续反应8-12h。反应结束后,冷却至室温,经减压蒸馏和干燥得到一种反应型的磷杂菲/亚磷酸酯双基阻燃剂。
上述技术方案中,优选的,步骤(1)中所述的二醛类化合物和有机亚磷酸酯的摩尔比为1:1-1:3,优先选择1:1-1:1.5;所述的二醛类化合物为对苯二甲醛、丙二醛、丁二醛、3,3-二苯基戊二醛、己二醛、庚二醛中的一种;
优选的,步骤(1)a、b中所述的有机溶剂为甲醇、乙醇、丙醇、***、二丙二醇二甲醚中的一种或多种组合;有机溶剂的用量:a中为5-30ml(更优选7-20ml)溶剂/1g二醛类化合物、b中为5-50ml(更优选10-35ml)溶剂/1g有机亚磷酸酯;
优选的,步骤(1)中所述的碱性催化剂为三乙胺、乙醇钠、氢氧化钠、氢氧化钾、碳酸氢钠、碳酸氢钾、吡啶、4-二甲氨基吡啶、N,N-二异丙基乙胺中的一种;催化剂的用量为有机亚磷酸酯与催化剂的摩尔比为1:1-1:3,更优选1:1-1:2.5;
优选的,步骤(1)中所述的有机亚磷酸酯为亚磷酸二甲酯、亚磷酸二乙酯、亚磷酸二正丙酯、亚磷酸二苯酯、亚磷酸二苄酯中的一种;有机亚磷酸酯溶液的滴加速度为0.2-5ml/min,更优选0.5-3ml/min;有机亚磷酸酯溶液滴加完毕后使体系上升至一定温度下反应一定时间为:温度上升至60-120℃反应5-15h,更优选70-90℃反应10-15h;
优选的,步骤(2)中所述的DOPO和步骤(1)中所述的有机亚磷酸酯的摩尔比为1:1-1:3,优先选择1:1-1:1.5。
本发明还提供一种含有磷杂菲/亚磷酸酯双基阻燃剂的无卤复合阻燃体系,该复合体系的成分包括:上述的磷杂菲/亚磷酸酯双基阻燃剂和可膨胀石墨。
上述技术方案中,优选的,复合体系中磷杂菲/亚磷酸酯双基阻燃剂:可膨胀石墨的质量比为3:1-1:1。
本发明还提供一种阻燃硬质聚氨酯泡沫,其制备方法如下:
(1)将聚醚多元醇、水、发泡剂、泡沫稳定剂、催化剂和上述的无卤复合阻燃剂混合,并在常温下机械搅拌3~5min直至原料混合均匀;
(2)将多异氰酸酯加入上述体系中,搅拌后倒入准备好的模具中自然发泡,泡沫熟化后即可得到阻燃硬质聚氨酯泡沫。
所述的多异氰酸酯与步骤(1)中聚醚多元醇的质量比为1-1.6:1。
本发明的有益效果在于:
1.本发明的一种反应型的磷杂菲/亚磷酸酯双基阻燃剂将磷杂菲基团和有机亚磷酸酯通过化学键结合在同一分子单元内,形成双基协同效应,磷杂菲基团和亚磷酸酯基团通过反应连接到聚氨酯分子结构的主链上而阻碍其燃烧,提高阻燃效率。
2.本发明的一种反应型的磷杂菲/亚磷酸酯双基阻燃剂具有高的热稳定性、抗吸湿性和基体相容性,是一种高效、热稳定性高的环保阻燃剂,其复合体系能够促进硬质聚氨酯泡沫在燃烧时快速成炭,并形成连续、完整、致密的炭层,有效减少热量的释放,使硬质聚氨酯泡沫具有优异的阻燃性能。
3.本发明的磷杂菲/亚磷酸酯双基阻燃剂及其复合体系制备的高效、环保阻燃硬质聚氨酯泡沫塑料,原料来源充足以及成本低廉,制备方法简单、工业条件易控制,适于工业化生产。
附图说明
构成本发明的一部分的附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限制。在附图中:
图1为实施例1中制备的一种磷杂菲/亚磷酸酯双基阻燃剂的核磁共振碳谱图;
图2为实施例1中制备的一种磷杂菲/亚磷酸酯双基阻燃剂的红外谱图;
图3为实施例1中阻燃RPUF的锥形量热测试后残炭照片。
具体实施方式
下面结合实施例和附表对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1
将21.48g对苯二甲醛和120ml乙醇加入反应容器中,并使其在50℃下搅拌溶解,然后向溶液中加入24ml三乙胺;将22.10g亚磷酸二乙酯溶解于300ml乙醇,燃后将亚磷酸二乙酯溶液以1ml/min的速度滴加到烧瓶中,滴加完毕后使体系上升至90℃下反应8h;随后将34.56g DOPO加入反应体系15h;反应结束后,冷却至室温,经减压蒸馏和干燥得到一种反应型的磷杂菲/亚磷酸酯双基阻燃剂;按质量计,将72份聚醚多元醇、48份磷杂菲/亚磷酸酯双基阻燃剂和22份可膨胀石墨、0.9份水、9份发泡剂、2.2份泡沫稳定剂、2.8份催化剂加入600mL的塑料烧杯中,用电动搅拌机搅拌3~5min至原料混合均匀,然后将108份多异氰酸酯快速加入烧杯中,同时使用电动搅拌机快速搅拌10s,然后将所得到的混合物料快速倒入准备好的模具中自然发泡,泡沫熟化后即可得到阻燃硬质聚氨酯泡沫。
实施例2
将22.47g对苯二甲醛和150ml丙醇加入反应容器中,并使其在50℃下搅拌溶解,然后向溶液中加入20ml乙醇钠;将26.42g亚磷酸二正丙酯溶解于300ml丙醇,燃后将亚磷酸二正丙酯溶液以1.5ml/min的速度滴加到烧瓶中,滴加完毕后使体系上升至90℃下反应10h;随后将38.88g DOPO加入反应体系12h;反应结束后,冷却至室温,经减压蒸馏和干燥得到一种反应型的磷杂菲/亚磷酸酯双基阻燃剂;按质量计,将80份聚醚多元醇、40份磷杂菲/亚磷酸酯双基阻燃剂和20份可膨胀石墨、0.6份水、10份发泡剂、2.5份泡沫稳定剂、2.5份催化剂加入600mL的塑料烧杯中,用电动搅拌机搅拌3~5min至原料混合均匀,然后将120份多异氰酸酯快速加入烧杯中,同时使用电动搅拌机快速搅拌10s,然后将所得到的混合物料快速倒入准备好的模具中自然发泡,泡沫熟化后即可得到阻燃硬质聚氨酯泡沫。
实施例3
将11.53g己二醛和100ml***加入反应容器中,并使其在50℃下搅拌溶解,然后向溶液中加入18ml N,N-二异丙基乙胺;将37.47g亚磷酸二苯酯溶解于350ml***,燃后将亚磷酸二苯酯溶液以2ml/min的速度滴加到烧瓶中,滴加完毕后使体系上升至90℃下反应12h;随后将41.04g DOPO加入反应体系15h;反应结束后,冷却至室温,经减压蒸馏和干燥得到一种反应型的磷杂菲/亚磷酸酯双基阻燃剂;按质量计,将70份聚醚多元醇、30份磷杂菲/亚磷酸酯双基阻燃剂和20份可膨胀石墨、0.8份水、8份发泡剂、3份泡沫稳定剂、2份催化剂按比例加入600mL的塑料烧杯中,用电动搅拌机搅拌3~5min至原料混合均匀,然后将105份多异氰酸酯快速加入烧杯中,同时使用电动搅拌机快速搅拌10s,然后将所得到的混合物料快速倒入准备好的模具中自然发泡,泡沫熟化后即可得到阻燃硬质聚氨酯泡沫。
对照例
对所述的实施例1中由磷杂菲/亚磷酸酯双基阻燃剂和可膨胀石墨制备的阻燃硬质聚氨酯泡沫进行了阻燃性能测试,并将纯RPUF作为对照例,用于与实施例1的阻燃样品作对比。具体测试结果见表1和图3。
表1为实施例1和对照例的锥形量热测试结果,其中RPUF为对照例的锥形量热测试结果,PDEP/EG/RPUF为实施例1的锥形量热测试结果。图3为实施例1锥形量热测试后残炭的宏观照片。
表1对照例和实施例1的锥形量热测试结果
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思的前提下,做出若干等同替代或明显变型,而且性能或用途相同,都应当视为属于本发明的保护范围。
Claims (10)
2.一种权利要求1所述的磷杂菲/亚磷酸酯双基阻燃剂的制备方法,其特征在于,包括如下步骤:
(1)a.将二醛类化合物和有机溶剂加入反应容器中,并使其在50℃下搅拌溶解,然后向溶液中加入一定量的碱性催化剂;b.将溶解于适量有机溶剂的有机亚磷酸酯溶液以一定速度滴加到烧瓶中,滴加完毕后使体系上升至一定温度下反应一定时间;
(2)随后将DOPO加入步骤(1)获得的反应体系继续反应8-12h,反应结束后,冷却至室温,经减压蒸馏和干燥得到一种反应型的磷杂菲/亚磷酸酯双基阻燃剂。
3.根据权利要求2所述的磷杂菲/亚磷酸酯双基阻燃剂的制备方法,其特征在于:步骤(1)中所述的二醛类化合物和有机亚磷酸酯的摩尔比为1:1-1:3;所述的二醛类化合物为对苯二甲醛、丙二醛、丁二醛、3,3-二苯基戊二醛、己二醛、庚二醛中的一种。
4.根据权利要求2所述的磷杂菲/亚磷酸酯双基阻燃剂的制备方法,其特征在于:步骤(1)a、b中所述的有机溶剂选自甲醇、乙醇、丙醇、***、二丙二醇二甲醚中的一种或多种组合;有机溶剂的用量:a中为5-30ml溶剂/1g二醛类化合物,b中为5-50ml溶剂/1g有机亚磷酸酯。
5.根据权利要求2所述的磷杂菲/亚磷酸酯双基阻燃剂的制备方法,其特征在于:步骤(1)中所述的碱性催化剂为三乙胺、乙醇钠、氢氧化钠、氢氧化钾、碳酸氢钠、碳酸氢钾、吡啶、4-二甲氨基吡啶、N,N-二异丙基乙胺中的一种;有机亚磷酸酯与催化剂的摩尔比为1:1-1:3。
6.根据权利要求2所述的磷杂菲/亚磷酸酯双基阻燃剂的制备方法,其特征在于:步骤(1)中所述的有机亚磷酸酯为亚磷酸二甲酯、亚磷酸二乙酯、亚磷酸二正丙酯、亚磷酸二苯酯、亚磷酸二苄酯中的一种;有机亚磷酸酯溶液的滴加速度为0.2-5ml/min;有机亚磷酸酯溶液滴加完毕后使体系温度上升至60-120℃反应5-15h。
7.根据权利要求2所述的磷杂菲/亚磷酸酯双基阻燃剂的制备方法,其特征在于:步骤(2)中所述的DOPO和步骤(1)中所述的有机亚磷酸酯的摩尔比为1:1-1:3。
8.一种无卤复合阻燃体系,其特征在于,包括如权利要求1所述的反应型的磷杂菲/亚磷酸酯双基阻燃剂或如权利要求2-7任一项方法制备的磷杂菲/亚磷酸酯双基阻燃剂和可膨胀石墨。
9.根据权利要求8所述的一种无卤复合阻燃体系,其特征在于,所述的磷杂菲/亚磷酸酯双基阻燃剂与可膨胀石墨的质量比为3:1-1:1。
10.一种阻燃硬质聚氨酯泡沫,其特征在于,采用如权利要求9所述的无卤复合阻燃体系制得,具体的制备方法如下:
(1)将聚醚多元醇、水、发泡剂、泡沫稳定剂、催化剂和无卤复合阻燃剂混合,并在常温下机械搅拌直至原料混合均匀;
(2)将多异氰酸酯加入上述体系中,所述的多异氰酸酯与步骤(1)中聚醚多元醇的质量比为1-1.6:1,搅拌后倒入模具中自然发泡,泡沫熟化后即得到阻燃硬质聚氨酯泡沫。
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