CN111253546B - 一种反应型聚氨酯阻燃剂的制备方法及应用 - Google Patents

一种反应型聚氨酯阻燃剂的制备方法及应用 Download PDF

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CN111253546B
CN111253546B CN202010082370.XA CN202010082370A CN111253546B CN 111253546 B CN111253546 B CN 111253546B CN 202010082370 A CN202010082370 A CN 202010082370A CN 111253546 B CN111253546 B CN 111253546B
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flame retardant
diphosphophosphazene
phosphazene
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CN111253546A (zh
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李忠芳
孙鹏
郭辉
王立开
牛学良
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Shandong University of Technology
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Abstract

本发明涉及一种聚(双磷酸基磷腈)(PDPP)及其衍生物聚(二磷酸盐磷腈)类(MPDPP)(M＝Mg2+,Ca2+,过渡金属离子，稀土离子等)、聚(双(二烷氧基磷酸酯基)磷腈)(PBPP)三者复配制备聚氨酯阻燃剂的方法，由于其复配物中的PDPP中的磷酸基团及MPDPP中的未反应的磷酸基团和磷酸基团中未反应的羟基与异氰酸酯可以发生反应，所以，其阻燃剂为反应型阻燃剂。由于阻燃剂与异氰酸酯的反应，使阻燃剂在聚氨酯中分布均匀，其阻燃效果更好。该阻燃剂含有聚磷腈基团、磷酸酯及磷酸盐多种阻燃组份，由于协同效应使其阻燃性能很好。可以用于各种聚氨酯材料。

Description

一种反应型聚氨酯阻燃剂的制备方法及应用
技术领域
本发明一种反应型阻燃剂，可用于该阻燃剂用于聚氨酯、纺织品、木材、纸张、装饰材料等领域。
技术背景
阻燃剂是使易燃聚合物具有难燃性的功能性助剂，主要是为高分子材料的阻燃设计的；阻燃剂类型有许多，按使用方法分为添加型阻燃剂和反应型阻燃剂。添加型阻燃剂是通过机械混合方法加入到聚合物中，使聚合物具有阻燃的性能，目前添加型阻燃剂主要分为有机阻燃剂和无机阻燃剂，卤系阻燃剂(有机氯、溴化物)和非卤阻燃剂。有机阻燃剂是以溴系、磷氮系、氮系和红磷及化合物等为阻燃剂，无机阻燃剂是以三氧化二锑、氢氧化镁、氢氧化铝，硅系等作为阻燃体系。反应型阻燃剂则是作为反应物参加聚合反应，使聚合物自身具有一定的阻燃成分，优点是对聚合物材料的性能影响较小，阻燃时间更长。
阻燃剂发挥阻燃作用的机理由很多，并且大多数阻燃剂通过几种机理共同发挥作用起到阻燃的作用。(1)吸热作用：燃烧反应在一定的时间内放出有限的热量，阻燃剂能及时吸收反应放出的一部分热量，使温度降低，使燃烧表面和可燃分子吸收的热量减少，从而抑制燃烧的进行。高温反应条件下，阻燃剂可发挥吸热作用，吸收反应的热量，使可燃物表面温度降低，阻止可燃气体的生成，从而起到阻燃的作用。(2)覆盖作用：阻燃剂能够在在高温的条件下形成一定形状的覆盖层，使可燃物隔绝空气，起到隔氧、隔热、阻止气体外泄，从而起到阻燃的作用。(3)抑制链反应：由链反应可知，燃烧反应进行还需一定的自由基。阻燃剂可以捕捉气相燃烧反应时的自由基，阻止燃烧的传播，使燃烧的反应速率下降直到燃烧终止。(4)不燃气体窒息作用：阻燃剂受热可分解出不燃的气体，使可燃性气体的浓度下降并且能够稀释氧气的浓度，从而使燃烧窒息，起到阻燃的目的。
阻燃材料就是把阻燃剂加入到材料里面重新混炼做阻燃处理。阻燃材料的特点是一种保护材料，提高了着火点，燃烧速度减缓，从而阻止燃烧并且自己不易燃烧。阻燃材料应用较广泛，可制成多种工业用品，主要可分为阻燃织物、阻燃化学纤维、阻燃塑料、阻燃橡胶、防火涂料、阻燃木质材料及阻燃纸、无机不燃填充材料等7大类。
阻燃科学技术的发展是为了适应社会安全生产和生活的需要，对预防火灾的发生，保护人民生命财产具有非常重要的意义。它的研究主要包括阻燃机理的研究、阻燃剂的制备工艺、阻燃体系的选择、阻燃处理及其制品的开发、阻燃处理技术以及阻燃效果的评价。同时为了适应社会对阻燃材料的需求及推广的必须，还要研究制订相关的技术标准、规范和管理法规，并大量开展阻燃材料制品的应用研究。现在，人们日益认识到，合理使用一定的阻燃材料是减少火灾的战略措施之一，而且阻燃和抑烟、减毒是可以同时实现的。所以，在这种对阻燃剂的研究就显得尤为重要。阻燃材料不仅要求具有良好的阻燃的效果，还要不生成有毒或不寻常的燃烧产物。这样通过合理安全的防火设计并采用阻燃制品，完全有可能防止燃烧的发生，这对推动防火安全设计的发展也具有重要的意义。
C·H·小波威尔等报道了(CN 201280013371.2)用环上溴代的芳香族化合物的二酯二醇用于软质聚氨酯泡沫的反应性阻燃剂。该阻燃剂属于含卤型的反应型阻燃剂，反应的活性基团为羟基。范浩军等报道了(CN 201410704651.9)二氨基-1,3,5-三嗪衍生物的取代基磷酸酯类作为水基聚氨酯用反应性膨胀型阻燃剂。K·卢迪等报道了(CN201480045154.0)含磷醇作为反应性阻燃剂。寿崇琦等报道了(CN 201610804469.X)超支化阻燃剂的制备方法及在聚氨酯中的应用，如，含磷型超支化阻燃剂，可以把端羟基超支化聚合物中的羟基被含磷基团取代得到应用。S.鲍尔比戈特等(CN 201280011035.4)报道了一种反应型阻燃剂用于聚氨酯阻燃剂，其是用三聚氰胺与磷酸形成的盐及其混合物的磷酸盐组分。这种阻燃剂的无机磷酸和三聚氰胺的胺基分别作为反应型阻燃剂的活性基团，但是，其磷酸和三聚氰胺是分别与异氰酸酯反应，二者是孤立的，反应后二者无法起到协同作用。这些固体颗粒对聚合物具有不良影响，尤其是对聚氨酯泡沫的性质具有不良影响。
分别按照标准GB/T 2406-1993、GB/T 2408-2008，制备试样并测定其阻燃性能如极限氧指数、垂直燃烧试验，按照标准QB/T 4197-2011，制备试样并测定其机械性能如拉伸强度，断裂伸长率。
发明内容：
本发明是利用聚(二氯磷腈)高分子中P-Cl之间的强极性键，与亚磷酸酯反应得到聚(二磷酸酯磷腈)，在浓盐酸中水解得到聚(二磷酸磷腈)，与水溶性的高价过渡金属离子反应得到不溶性的聚(二磷酸盐磷腈)聚合物。具体的操作步骤及反应过程如下：
(1)阻燃剂各组分的制备
在氮气保护下，向装搅拌器，冷凝管的的三口烧瓶中分别加入氨基磺酸(0.52mmol，0.05g)、六氯环三磷腈(HCCP)(14.4mmol，5g)、溶剂二苯醚(15～30mL)，通氮气20～40min后，搅拌、升温至210～250℃下进行开环聚合反应，当溶液变粘稠时，停止加热，冷却，倒入盛有40～60mL石油醚烧杯中，以除去未反应的原料HCCP，用石油醚洗涤三次，抽滤将得到的固体产物在真空干燥箱中，70～90℃下干燥4～8h得到聚(二氯磷腈)(PDCP)；将得到的聚(二氯磷腈)与过量的(50～60mL)亚磷酸三乙酯，在100～120℃下反应5～7h，冷却，用适量石油醚洗涤3～4次，以除去过量的未反应的亚磷酸三乙酯，抽滤，固体在真空干燥箱内60～100℃干燥，得到聚(双(二乙氧基磷酸酯基)磷腈)(PBPP)；将得到的聚(双(二乙氧基磷酸酯基)磷腈)(PBPP)加入60～90mL浓盐酸，在搅拌下，110～150℃下水解至溶液变澄清，在110～140℃下，浓缩至近干，以除去反应产物和过量的浓盐酸，用30～50mL的乙酸乙酯萃取3～4次，以除去未水解完全的PBPP，剩余的液体放入真空干燥箱110～130℃烘干，得到聚(双磷酸基磷腈)(PDPP)，其反应过程的方程式如下。
Figure GDA0003158278900000031
将得到的聚(双磷酸基磷腈)(PDPP)白色固体2.07g溶于一定的去离子水中，并将1.61g的氧氯化锆溶于水中，待两者各自溶解完全，边搅拌边把氧氯化锆溶液逐滴加入到聚(双磷酸基磷腈)(PDPP)水溶液中，滴加完毕，搅拌24h，抽滤水洗至中性后，放入真空干燥箱中80～90℃烘干，得到白色固体ZrPDPP(0.78)(其质量百分比为氯氧化锆：PDPP＝0.78)1.93g，产率为76.44％。按此方法可得到不同比例的ZrPDPP。
Figure GDA0003158278900000041
不同配比的MgPDPP，CaPDPP等金属的盐的制备方法同上，只是将其它金属的可溶性盐替代氧氯化锆即可。
Figure GDA0003158278900000042
上述反应方程式中的M可以是+4价，也可以是+2、+3价。
(2)阻燃剂的复配工艺研究
MPDPP，PDPP及PBPP三者按照一定的比例复配得到反应型聚氨酯阻燃剂，聚(双(二烷氧基磷酸酯基)磷腈)，聚(双磷酸基磷腈)和聚(二磷酸盐磷腈)三者进行复配，三者的质量比为6:1:1～1:3:4；复配工艺为：首先研磨聚(二磷酸盐磷腈)1～2h，再按照比例加入聚(双磷酸基磷腈)继续研磨0.5～2h，等研磨均匀后加入聚(双(二烷氧基磷酸酯基)磷腈)及适当溶剂研磨0.5～2h
(3)复配后的阻燃剂的与异氰酸酯的反应
(a)PDPP与异氰酸酯的反应
在聚氨酯的A、B两种原料混合制备聚氨酯过程中，PDPP中的磷酸基团与异氰酸酯可以反应，得到由聚磷腈磷酸酯参与的聚氨酯，阻燃剂组份与聚氨酯可以充分混合且存在于聚氨酯中，可以有效阻止聚氨酯的燃烧，所以，其阻燃性能可以达到最佳。反应方程式如下：
Figure GDA0003158278900000051
(b)MPDPP与异氰酸酯的反应
在聚氨酯的A、B两种原料混合制备聚氨酯过程中，MPDPP中未与金属离子反应的磷酸基团或剩余的磷酸基团中的羟基与异氰酸酯可以反应，得到由MPDPP参与的聚氨酯，阻燃剂组份与聚氨酯可以充分混合且存在于聚氨酯中，可以有效阻止聚氨酯的燃烧，所以，其阻燃性能可以达到最佳。反应方程式如下：
Figure GDA0003158278900000061
(c)由于PBPP是疏水性的化合物，与聚氨酯互溶性好，可以直接掺杂到聚氨酯中起到阻燃效果。
(4)使用方法研究
上述阻燃剂复配物按照聚氨酯的配方和不同用量加入到聚氨酯的A配料中。聚氨酯的原料由A、B两组分组成，按质量份计包括：A组分(组合聚醚组分)：聚醚多元醇50～100份；聚合物多元醇0～50份；催化剂0.2～5份；发泡剂1～8份；泡沫稳定剂0.2～3；交联剂0.2～6份；开孔剂0～10；反应型阻燃剂(本发明涉及的)0.1～20份；B组分(异氰酸酯组分)：多异氰酸酯，可以用TDI、MDI、聚合MDI或改性MDI及其混合物；
A∶B质量比为100∶30～100∶80。
其中，聚氨酯的配方中所指的聚醚多元醇官能度为3，相对分子质量为4000～9000，端羟基中伯羟基含量大于65％；聚合物多元醇为聚醚多元醇与苯乙烯丙烯腈的接枝共聚物；所述催化剂为叔胺或仲胺类；所述发泡剂为去离子水、多元伯胺、季铵碳酸盐中的一种或几种的混合物；所述泡沫稳定剂为聚硅氧烷聚醚共聚物；所述交联剂为醇胺类化合物；所述开孔剂为EO含量≥50％的聚醚多元醇。
(5)阻燃剂的阻燃性能研究
阻燃剂加入到聚氨酯中，值得的产品其阻燃性能检测分别按照标准GB/T 2406-1993、GB/T 2408-2008，制备试样并测定其阻燃性能如极限氧指数、垂直燃烧试验，按照标准QB/T 4197-2011，制备试样并测定其机械性能如拉伸强度，断裂伸长率。
本发明的阻燃剂的特点分析及创新点：
1)阻燃剂复配物各组份分子中均含有阻燃的无机的聚磷腈基团和磷酸基团，有聚合的多磷酸镁等盐类的阻燃成分。
2)阻燃剂中阻燃的氮、磷两种元素，可以产生氮、磷的协同阻燃效果。阻燃性能更好。
3)组份中的PBPP中的多磷酸基团和MPDPP盐中未反应的磷酸基团或磷酸基团中未反应的羟基可以与异氰酸酯发生反应，使其阻燃剂的阻燃基团连接到聚氨酯中，不但可以混合均匀，而且可以使阻燃发生在未燃烧时刻。可以达到很好的阻燃效果。
4)阻燃剂的PDPP磷酸酯组份，可以混合到聚氨酯材料中起到阻燃效果。
5)MPDPP，PDPP及PBPP三者按照一定质量比和复配工艺制备的阻燃剂，其阻燃基团、阻燃成分更多，可以有更好的阻燃效果。
具体实施方式
[实施例1]：聚(二氯磷腈)的制备
在氮气保护下，向装搅拌器，冷凝管的的三口烧瓶中分别加入氨基磺酸(0.52mmol，0.05g)、六氯环三磷腈(HCCP)(14.4mmol，5g)、溶剂二苯醚(15～30mL)，通氮气20～40min后，搅拌、升温至210～250℃下进行开环聚合反应，当溶液变粘稠时，停止加热，冷却，倒入盛有40～60mL石油醚烧杯中，以除去未反应的原料HCCP，用石油醚洗涤三次，抽滤将得到的固体产物在真空干燥箱中，70～90℃下干燥4～8h得到聚(二氯磷腈)(PDCP)，得到的PDCP产率70％，粘均分子量6～8万
采用上述方法只是把二苯醚换成其它溶剂(芳烃溶剂油，环丁砜，三乙酸甘油酯，季戊四醇四乙酸酯，多聚乙二醇二乙酸酯，液体石蜡，甲基萘油中的一种或几种的混合液)，也可以控制温度在210～250℃，有的甚至可以控制更高的反应温度，也可以得到开环聚合的产物，只是去除溶剂时要用对该溶剂溶解性能更好低沸点的溶剂清洗。
用不同溶剂进行开环聚合反应的产率在40％～80％范围内，粘均分子量在4～10万范围内。
[实施例2]：聚(双(二烷氧基磷酸酯基)磷腈)(PBPP)的制备
将得到的聚(二氯磷腈)20g与过量的(50～60mL)亚磷酸三乙酯，在100～120℃下反应5～7h，冷却，用适量石油醚洗涤3～4次，以除去过量的未反应的亚磷酸三乙酯，抽滤，固体在真空干燥箱内60～100℃干燥，得到聚(双(二乙氧基磷酸酯基)磷腈)(PBPP)；将得到的聚(双(二乙氧基磷酸酯基)磷腈)(PBPP)产率83％。
采用相同反应步骤，以不同亚磷酸酯或在不同条件进行反应的产率汇总如表1所示：
表1不同亚磷酸酯反应制备PBPP的反应条件及产率
Figure GDA0003158278900000081
[实施例3]：聚(双磷酸基磷腈)的制备
将25g的PBPP加入60～90mL浓盐酸，在搅拌下，110～150℃下水解至溶液变澄清，在110～140℃下，浓缩至近干，以除去反应产物和过量的浓盐酸，用30～50mL的乙酸乙酯萃取3～4次，以除去未水解完全的PBPP，剩余的液体放入真空干燥箱110～130℃烘干，得到聚(双磷酸基磷腈)(PDPP)，产率89％
采用相同反应步骤，只是用二氯甲烷、苯、甲苯或石油醚萃取，产率分别为87％，83％，81％和85％。
采用相同的反应步骤，在浓盐酸中回流24h，在70℃下减压蒸馏，用乙酸乙酯萃取，产率为84％。
不同酯基的PBPP水解反应结果如表2所示。
表2不同酯基的PBPP水解制备PDPP的产率
Figure GDA0003158278900000091
[实施例4]：MPDPP的制备
将得到的聚(双磷酸基磷腈)(PDPP)白色固体2.07g溶于一定的去离子水中，并将1.61g的氧氯化锆溶于稀盐酸中，待两者各自溶解完全，边搅拌边把氧氯化锆溶液逐滴加入到聚(双磷酸基磷腈)(PDPP)水溶液中，滴加完毕，室温下搅拌反应24h，抽滤、水洗至中性后，放入真空干燥箱中80～90℃烘干，得到白色固体ZrPDPP(0.78)1.93g，产率为76.44％。
MPDPP的制备采用上述制备ZrPDPP相同的方法进行制备，只是将其中的锆盐溶液换成其它金属的可溶性盐的溶液即可。通过调控PDPP与金属盐的配比可以得到不同质量配比的MPDPP，其制备工艺及产品的性能结果见表3所示。
[实施例5]：阻燃剂的复配工艺
MPDPP，PDPP及PBPP三者按照一定的比例复配得到反应型聚氨酯阻燃剂，聚(双(二烷氧基磷酸酯基)磷腈)，聚(双磷酸基磷腈)和聚(二磷酸盐磷腈)三者进行复配，三者的质量比为6:1:1～1:3:4；复配工艺为：首先研磨聚(二磷酸盐磷腈)1～2h，再按照比例加入聚(双磷酸基磷腈)继续研磨0.5～2h，等研磨均匀后加入聚(双(二烷氧基磷酸酯基)磷腈)及适当溶剂研磨0.5～2h
[实施例6]：阻燃剂在聚氨酯中的使用方法和聚氨酯产品的制备工艺
把实施例5中的阻燃剂按照加入的比例份数加入到已经配好的聚氨酯配方A中。聚氨酯的原料由A、B两组分组成，按质量份计包括：A组分(组合聚醚组分)：聚醚多元醇50～100份；聚合物多元醇0～50份；催化剂0.2～5份；发泡剂1～8份；泡沫稳定剂0.2～3；交联剂0.2～6份；开孔剂0～10；反应型阻燃剂(本发明涉及的)0.1～20份；B组分(异氰酸酯组分)：多异氰酸酯，可以用TDI、MDI、聚合MDI或改性MDI及其混合物；A∶B质量比为100∶30～100∶80。
其中，聚氨酯的配方中所指的聚醚多元醇官能度为3，相对分子质量为4000～9000，端羟基中伯羟基含量大于65％；聚合物多元醇为聚醚多元醇与苯乙烯丙烯腈的接枝共聚物；所述催化剂为叔胺或仲胺类；所述发泡剂为去离子水、多元伯胺、季铵碳酸盐中的一种或几种的混合物；所述泡沫稳定剂为聚硅氧烷聚醚共聚物；所述交联剂为醇胺类化合物；所述开孔剂为EO含量≥50％的聚醚多元醇。
制备的添加新型阻燃剂的聚氨酯产品，按照标准GB/T 2406-1993、GB/T 2408-2008，制备试样并测定其阻燃性能如极限氧指数、垂直燃烧试验，按照标准QB/T 4197-2011，制备试样并测定其机械性能如拉伸强度，断裂伸长率。其结果见表4。
表3 MPDPP类化合物的制备工艺条件
Figure GDA0003158278900000111
表4 PBPP、PDPP和MPDPP复配阻燃剂用于聚氨酯的阻燃性能
Figure GDA0003158278900000121
注：RTHP：酯类，Me-甲基；Et-乙基；Pr-丙基等

Claims (7)

1.一种反应型聚氨酯阻燃剂的制备方法，其特征在于：该阻燃剂是以聚(二磷酸盐磷腈)、聚(双(二烷氧基磷酸酯基)磷腈)及聚(双磷酸基磷腈)三者进行复配得到的复配物作为聚氨酯阻燃剂；其制备方法如下：
(1)以六氯环三磷腈为原料，在沸点高于220℃且对六氯环三磷腈和聚(二氯磷腈)稳定的高沸点的溶剂中，加热开环聚合得到聚(二氯磷腈)，聚(二氯磷腈)与亚磷酸三酯反应，得到聚(双(二烷氧基磷酸酯基)磷腈)；聚(双(二烷氧基磷酸酯基)磷腈)在浓盐酸中水解得到聚(双磷酸基磷腈)，聚(双磷酸基磷腈)与金属离子中的一种或多种发生聚合而得到聚(二磷酸盐磷腈)：六氯环三磷腈210～250℃下开环聚合得到聚(二氯磷腈)；聚(二氯磷腈)与亚磷酸三酯在100～120℃下反应得到聚(双(二烷氧基磷酸酯基)磷腈)；将聚(双(二烷氧基磷酸酯基)磷腈)浓盐酸中水解得到聚(双磷酸基磷腈)；聚(双磷酸基磷腈)与金属离子溶液反应得到不同配比的聚(二磷酸盐磷腈)；
(2)聚(二磷酸盐磷腈)，聚(双磷酸基磷腈)及聚(双(二烷氧基磷酸酯基)磷腈)三者按照一定的比例复配得到反应型聚氨酯阻燃剂，该阻燃剂用于聚氨酯。
2.根据权利要求1所述的一种反应型聚氨酯阻燃剂的制备方法，其特征在于：高沸点的溶剂选用：芳烃溶剂油，二苯醚，环丁砜，三乙酸甘油酯，季戊四醇四乙酸酯，多聚乙二醇二乙酸酯，液体石蜡，甲基萘油中的一种或几种的混合液。
3.根据权利要求1所述的一种反应型聚氨酯阻燃剂的制备方法，其特征在于：其亚磷酸三酯选用：亚磷酸三甲酯、亚磷酸三乙酯、亚磷酸三丙酯或亚磷酸三异丙酯中的一种或几种的混合物。
4.根据权利要求1所述的一种反应型聚氨酯阻燃剂的制备方法，其特征在于：所述的金属离子选用：Mg2+、Ca2+、过渡金属离子或稀土离子中的一种或多种，所述的金属离子的盐可溶于水，溶液中能电离出金属离子，所述的金属离子的盐为醋酸盐、盐酸盐、硝酸盐中的一种或几种。
5.根据权利要求1所述的一种反应型聚氨酯阻燃剂的制备方法，其特征在于：金属离子与聚(双磷酸基磷腈)的质量比为2:5～3:2。
6.根据权利要求1中所述的一种反应型聚氨酯阻燃剂的制备方法，其特征在于：聚(双(二烷氧基磷酸酯基)磷腈)，聚(双磷酸基磷腈)和聚(二磷酸盐磷腈)三者进行复配，上述三者的质量比为6:1:1～1:3:4；复配工艺为：首先研磨聚(二磷酸盐磷腈)1～2h，再按照比例加入聚(双磷酸基磷腈)继续研磨0.5～2h，等研磨均匀后加入聚(双(二烷氧基磷酸酯基)磷腈)及溶剂研磨0.5～2h。
7.根据权利要求1中所述的一种反应型聚氨酯阻燃剂的制备方法，其特征在于：聚氨酯的原料由A、B两组分组成，复配得到的阻燃剂按照不同质量比加入到A组分中，A组分含有：聚醚多元醇、聚合物多元醇、催化剂、发泡剂、泡沫稳定剂、交联剂、开孔剂、反应型阻燃剂组成，阻燃剂占的质量分数为1～20份；B组分：多异氰酸酯，包括：TDI、MDI、聚合MDI或改性MDI及其混合物；A∶B质量比为100∶30～100∶80。
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