CN103562348B - 稳定剂的用于制造无卤素的含有聚磷酸铵的防火涂层组合物的用途 - Google Patents

稳定剂的用于制造无卤素的含有聚磷酸铵的防火涂层组合物的用途 Download PDF

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CN103562348B
CN103562348B CN201280011873.1A CN201280011873A CN103562348B CN 103562348 B CN103562348 B CN 103562348B CN 201280011873 A CN201280011873 A CN 201280011873A CN 103562348 B CN103562348 B CN 103562348B
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托马斯·施塔费尔
于尔根·斯特劳布
迈克尔·施密特
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Abstract

本发明涉及一种稳定剂的用途，该稳定剂明显地改善结合剂（聚合物分散体）与液态的聚磷酸铵（简称为APP）在防火涂层组合物中的相容性。液态的聚磷酸铵在这种防火涂层组合物中作为活性阻燃剂起作用。该防火涂层组合物良好地适用于各种种类的纺织品，但是也适用于纸张、皮革以及纤维材料。防火剂用于延迟可燃的材料的，如塑料、纺织品或木材的点燃并且延缓或者完全防止火焰扩散。

Description

稳定剂的用于制造无卤素的含有聚磷酸铵的防火涂层组合物的用途
技术领域
本发明涉及一种稳定剂的用途，该稳定剂明显地改善结合剂（聚合物分散体）与液态的聚磷酸铵（简称为APP）在防火涂层组合物中的相容性。液态的聚磷酸铵在这种防火涂层组合物中起作为活性阻燃剂的作用。该防火涂层组合物良好地适用于各种种类的纺织品，但是也适用于纸张、皮革以及纤维材料。防火剂用于延迟可燃的材料的，如塑料、纺织品或木材的点燃并且延缓或者完全防止火焰扩散。
这涉及到在例如在电视机和电脑的塑料壳体中、家居纺织品中、绝缘泡沫和装配泡沫中的不同的化学化合物。
背景技术
在现有技术中有以下类型的防火剂：
·卤化防火剂
·氮基防火剂
·有机磷防火剂
·无机防火剂
燃着的纺织品是常见的现象，例如在设有地毯、家具或家用纺织品的住宅中。但是服装，特别是消防员、儿童或者还有厨房工作人员的服装，也非常常见地暴露在火焰的危险下。在许多工业方法中，纺织品扮演着重要的角色，这些纺织品必须是耐火上浆的。还有在公共交通工具中，座椅套和垫子以及地板面的耐火性是非常重要的安全性要求。
在制止已经陷于火灾中的纺织材料的时候，有一些可能性来避免进一步的火灾，即，可以简单地通过水或者通过沙子或者还有盖子或者通过所谓的干粉灭火器扑灭，在干粉灭火器中常见地设有二氧化碳压力下的碳酸氢钠。在此，灭火器的机理在于通过释放的二氧化碳熄灭火焰，二氧化碳通过碳酸氢钠的热分解形成。通过含磷的防火剂产生的防火效果主要通过形成覆盖层和在凝聚相中脱水来产生。含有粉状聚磷酸铵的膨胀型防火涂料，主要通过形成对于热绝缘的泡沫起作用。在现有技术中公知了用于防火涂层的组合物，这些防火涂层用于如以上所谈到的纺织品或材料。这些组合物在例如含卤素的活性防火剂之外含有结合剂。结合剂通常是水状的聚合物分散体，其例如由聚合物：聚氨酯、聚丙烯酸酯或氯乙烯共聚物组成。作为其他的组成部分，这种组合物含有助剂，如交联剂、泡沫稳定剂、增稠剂、活性阻燃介质如例如有机溴和/或氯化合物。这种介质，首先是含溴的防火剂有时是有生态问题的，多溴联苯醚（PBDE）、四溴双酚A（TBBPA）和六溴环十二烷（HBCD）属于含溴的防火剂。其长期以来使用在环境中，但是是难于化学降解的，并且部分是生物积累的，也就是说，这些含溴的防火剂在生物中富集。TBBPA和HBCD是对水生生物有毒的。已经在人类的母乳和血液中检测到了TBBPA和HBCD。TBBPA和HBCD被怀疑具有长期性的毒性效果。开始了多项法令，以便把这种试剂从市场上替换出去。
有机含磷防火剂，例如以下所列出的典型的磷酸的芳香族酯和脂肪族酯，也是有关于环境的问题的。下面列出了几个代表。
·TCEP（三（氯乙基）磷酸酯）
·TCPP（三（氯丙基）磷酸酯）
·TDCPP（三（二氯异丙基）磷酸酯）
·TPP（磷酸三苯酯）
·TEHP（三（2-乙基己基）磷酸酯）
·TKP（磷酸三甲苯酯）
·ITP（异丙基化磷酸三苯酯）不同异丙基化程度的单、双、和三（异丙基苯基）磷酸酯
·RDP（间苯二酚双（磷酸二苯酯））
·BDP（双酚A双（磷酸二苯酯））
这种防火剂例如应用在软质和硬质聚氨酯泡沫的情况下，如在软垫家具、车辆座椅或建筑材料中。
属于已知的无机防火剂的例如有：
·氢氧化铝（Al(OH)3），世界上最广泛使用的防火剂（也被称为ATH“三羟基铝”）。通过脱水，氢氧化铝冷却性地和气体稀释性地起作用，但是必须以大的份额（直至60%）混入。
·氢氧化镁（Mg(OH)2，MDH，“二羟基镁”）是带有比ATH更高的耐温性的矿物性防火剂，但是作用方式相同。
·硫酸铵（(NH4)2SO4）和磷酸铵（(NH4)3PO4）通过脱出氨气（NH3）在火焰中稀释气体，氨气燃烧成水和不同的氮氧化物，并且由此消耗掉火焰的氧气。同时硫酸铵和磷酸铵通过产生的硫酸（H2SO4）或磷酸（H3PO4）导致形成保护层，硫酸或磷酸的功能之一是可以打断自由基链反应。此外酸是不可燃的、强烈吸湿的并且拥有高沸点。因此酸在火焰的较冷区域中凝聚并且凝聚到材料上。磷酸通过脱水额外地构成偏磷酸和聚磷酸，其拥有更高的沸点。
·红磷在表面上构成由磷酸和聚磷酸形成的层，并且可以让这个层隆起（膨胀）。这个层起隔离作用并且保护材料不禁受氧气进入。在这里形成的磷酸酯具有与源自磷酸铵的聚磷酸铵相同的性能。
·三氧化二锑（Sb2O3）仅作为增效剂，与卤化防火剂一同起作用。缺点是在火灾中生成二恶英时的催化效果。
·五氧化二锑（Sb2O5）与Sb2O3相似地作为增效剂起作用。
·硼酸锌（参见硼酸盐）此外通过硼酸的输水，起冷却和稀释气体的作用。但是锌化合物也可以起协同增效的作用并且部分地替代更危险的三氧化二锑。
·熟石灰（Ca(OH)2）在二战时期作为用于屋顶架的木材的防火剂。熟石灰首先在脱水的情况下与空气中的二氧化碳化合，并且转变为碳酸钙（CaCO3）。其作为覆层使侵入变得困难。
聚磷酸铵溶液作为活性防火剂也是已知的。
在DE102008021027中介绍了聚磷酸铵溶液。这种溶液非常良好地适用于上述目的，亦即，给各种种类的纺织品耐火上浆。可是单独以水溶液施加于纺织品，聚磷酸铵溶液不能足够深入地渗透到纤维中，并且此外，当纺织品被如此处理时，这种纺织品变得非常僵硬和沉重，该纺织品变成有污渍的并且由此具有差的穿着性能。随着时间的推移，聚磷酸铵将通过洗涤被从纺织品结构中洗脱。
因此，必须对于基材（如纺织品）的处理始终应用适当的防火涂层组合物，除其他外包括结合剂（聚合物分散体）和液态的聚磷酸铵。
在结合剂（聚合物分散体）中，含有不同的化合物：
主要初始原料为塑料单体、保护性胶体和/或乳化剂、引发剂。通过单体的聚合获得相应的、聚合物分散体形式的结合剂。这种结合剂对改善基材上的防火涂层组合物的附着力负责。
然而基于聚氨酯、醋酸乙烯酯或聚丙烯酸酯的结合剂（聚合物分散体）与液态的聚磷酸铵是不相容的，常常形成不可逆的凝聚或絮凝。这种凝聚也许是由于由保护性胶体和乳化剂构成的稳定剂系统的损坏而发生的。
发明内容
因此，本发明的任务是找到一种可能性，来克服这两种组成部分的，亦即液态的聚磷酸铵与结合剂（聚合物分散体）的这种不相容性。
令人吃惊地发现，在使用烷基苯磺酸盐时，该烷基苯磺酸盐添加到结合剂（聚合物分散体）中，凝聚或絮凝现象不再发生，聚合物分散体可以良好地操作并且由此制造的防火涂层组合物永久地均匀地涂覆到各种基材上。本发明通过在此列出的权利要求更详细地指明：
1.一种烷基苯化合物的用途，所述烷基苯化合物在无卤素的、含有液态聚磷酸铵的防火涂层组合物中，用作结合剂稳定剂，通式为[R-苯-SO3]Me，其中，R=C3到C9，是支链或直链的烷基基团，Me=Na和/或K和/或NH4，其特征在于，所述烷基苯磺酸化合物是对异丙苯磺酸的钠盐和/或钾盐和/或铵盐，其在所述组合物中的含量为相对于所述结合剂（聚合物分散体）由1:10到1:30。
2.根据权利要求1所述的用途，其特征在于，在所述分散体中所述结合剂（聚合物分散体）相对所述液态聚磷酸铵（APP）的比例为1.3:1到1:5。
3.根据权利要求1所述的用途，其特征在于，所述液态聚磷酸铵（APP）是能够获得的，方式为，将组成为Hn+2PnO3n+1，其中n=1到50，并且由P1到P3的磷酸根离子分布直至20重量%，而P4到P50的磷酸根离子分布为从70重量%到90重量%的聚磷酸与10重量%到30重量%的氨的水溶液，和/或与氨气在最高60℃下混合，并且直至达到由6.5到7.5的pH值范围，把如此获得的溶液冷却到室温，从而得出澄清的液态聚磷酸铵，其分子式为(NH4PO3)n，其中n=1到50并且带有直至50重量%的固体成份，带有由6.5到7.5的pH值，以及1.1g/ml到1.3g/ml密度，并且P4到P50的份额为由60重量%到90重量%，优选70重量%到80重量%。
4.根据权利要求1至3所述的防火涂层组合物的用途，其特征在于，这种组合物通过浸润、喷洒、浸泡、浸渍和包覆以由10g/m2到500g/m2的量涂覆到基材上。
这种化合物是可以商业化地获得的。
在本发明的范畴中，液态的聚磷酸铵仅被理解作这些以液态形式制造的化合物，也就是说，不通过在水中溶解粉状的、固态的聚磷酸铵产生溶液，因为粉状的聚磷酸铵的水溶解性非常微小，仅仅只有为约1%。
这种烷基苯磺酸盐在防火涂层组合物中抗凝聚地稳定结合剂（聚合物分散体）。通过这种组合物处理的纺织品基材首先是具有几乎不变的柔软的手感。这还决定了由此制造的衣服的良好的穿着性能或者纺织品的良好的可加工性，例如在车辆或家具的套子的制造中。本发明普遍性地涉及各种种类的纺织品的上浆，如织物，针织物，针织面料，基于天然纤维的无卷曲织物和无纺布：如植物纤维、纤维素纤维、植物蛋白纤维、纸浆造纸纤维、橡胶纤维和海藻酸盐纤维，以及动物纤维：如羊毛和毛发、皮革和皮革纤维，基于化学纤维的纤维：聚合纤维，缩聚纤维和加聚纤维。
根据本发明优选地，对异丙苯磺酸在防火涂层组合物中以它的Na盐和/或K盐的形式作为用于结合剂（聚合物分散体）的稳定剂。
具体实施方式
根据本发明的配方
在下列表1到表2中表明了实验室燃烧试验的结果。
试验1
由棉织物构成的同样大小的带子通过不同的溶液浸润，并且在之后干燥。干燥的带子暴露在温度超过500℃的强烈的燃气火焰下并且在约450℃到600℃的情况下在燃气燃烧器火焰保持中约一分钟。
浸渍的棉织物，大小2cm×20cm，重量约180g/m2
覆层量 燃烧特性 织物破坏程度
液态聚磷酸铵 60g/m2（干燥） 从火焰中取出时熄灭 织物烧焦，但是组织完好
配方1 125/m2（干燥） 从火焰中取出时熄灭 织物烧焦，但是组织完好
配方2 120g/m2（干燥） 从火焰中取出时熄灭 织物烧焦，但是组织完好
配方3 125g/m2（干燥） 从火焰中取出时熄灭 织物烧焦，但是组织完好
试验2
浸渍的聚乙烯针织物，大小3cm×20cm，重量约365g/m2
覆层量 燃烧特性 针织物破坏程度
液态聚磷酸铵 130g/m2（干燥） 从火焰中取出时熄灭 针织物熔化
配方1 220/m2（干燥） 从火焰中取出时熄灭 针织物熔化
配方2 220g/m2（干燥） 从火焰中取出时熄灭 针织物熔化
配方3 230g/m2（干燥） 从火焰中取出时熄灭 针织物熔化
结果总结
为了防火上浆把液态聚磷酸铵与结合剂（聚合物分散体）组合，而不导致凝聚形式的结合剂损坏的问题，可以通过添加异丙苯磺酸钠得到解决。
液态聚磷酸铵的阻燃性能由此不受影响。该系统由液态APP、结合剂以及根据本发明的稳定剂，例如异丙苯磺酸钠构成，该系统可以卓越地加入到防火涂层组合物中或者这种组合物可以然后均匀地并且毫无问题地涂覆到基材上。

Claims (3)

1.一种烷基苯化合物的用途，所述烷基苯化合物在无卤素的、含有液态聚磷酸铵的防火涂层组合物中用作结合剂稳定剂，通式为[R-苯-SO3]Me，其中，R＝C3到C9，是支链或直链的烷基基团，Me＝Na和/或K和/或NH4，其特征在于，具有通式[R-苯-SO3]Me的烷基苯磺酸化合物是对异丙苯磺酸的钠盐和/或钾盐和/或铵盐，其在所述组合物中的含量为相对于所述结合剂由1:10到1:30，其中，
所述液态聚磷酸铵是能够获得的，方式为，将组成为Hn+2PnO3n+1，其中n＝1到50，并且由P1到P3的磷酸根离子分布为直至20重量％，而P4到P50的磷酸根离子分布为从70重量％到90重量％的聚磷酸与10重量％到30重量％的氨的水溶液，和/或与氨气在最高60℃下混合，并且直至达到由6.5到7.5的pH值范围，把如此获得的溶液冷却到室温，从而得出澄清的液态聚磷酸铵，其分子式为(NH4PO3)n，其中n＝1到50并且带有直至50重量％的固体成分，带有由6.5到7.5的pH值，以及1.1g/ml到1.3g/ml密度，并且P4到P50的份额为由60重量％到90重量％。
2.根据权利要求1所述的用途，其特征在于，在所述组合物中所述结合剂相对于所述液态聚磷酸铵的比例为1.3:1到1:5。
3.根据权利要求1至2中任一项所述的用途，其特征在于，防火涂层组合物通过浸润、喷洒、浸泡、浸渍和包覆以由10g/m2到500g/m2的量涂覆到基材上。
CN201280011873.1A 2011-03-05 2012-02-29 稳定剂的用于制造无卤素的含有聚磷酸铵的防火涂层组合物的用途 Expired - Fee Related CN103562348B (zh)

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