CN110799564A - 溴化阻燃剂及其在聚氨酯泡沫中的应用 - Google Patents

溴化阻燃剂及其在聚氨酯泡沫中的应用 Download PDF

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CN110799564A
CN110799564A CN201880043672.7A CN201880043672A CN110799564A CN 110799564 A CN110799564 A CN 110799564A CN 201880043672 A CN201880043672 A CN 201880043672A CN 110799564 A CN110799564 A CN 110799564A
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polyurethane foam
polyol
formulation
amount
polyurethane foams
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T-C.吴
A.C.伊贝
J.M.奥代
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Albemarle Corp
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Albemarle Corp
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Abstract

本发明提供了含有溴化阻燃剂的聚氨酯泡沫。还提供了用于制备含有溴化阻燃剂的聚氨酯泡沫的配方和方法。

Description

溴化阻燃剂及其在聚氨酯泡沫中的应用
技术领域
本发明涉及可在柔性和硬质聚氨酯泡沫中用作阻燃剂的溴化短链醇。
背景技术
耐火性是聚氨酯泡沫的重要性能。各种化合物或其混合物已被有效地使用以满足适用的消防安全标准。磷酸三(1-氯-2-丙基)酯(TCPP)是聚氨酯泡沫中广泛使用的阻燃剂。然而，TCPP是聚氨酯泡沫形成中的非反应性化合物，因此可能会从泡沫中浸出或迁移。这导致健康和环境问题。
已被公开作为阻燃剂的溴化异氰酸酯反应性化合物是2，3-二溴丁烯-1，4-二醇(例如，美国专利第4,002,580号)。然而，2，3-二溴丁烯-1，4-二醇(DBBD)是具有高熔点的固体，需要额外的步骤进行预溶解才能在聚氨酯泡沫应用中使用。
因此，期望具有在加工条件下为液体并且具有低粘度以使得加工(混合和泵送)容易进行的阻燃剂。除了作为阻燃剂的有效性外，还期望提供与聚氨酯泡沫制造工艺相容并且不会随时间迁移出聚氨酯泡沫从而减轻对健康和环境的影响的化合物。
发明内容
本发明提供了用于生产阻燃性聚氨酯泡沫的配方和工艺。更具体地，本发明提供了可用于聚氨酯泡沫中的异氰酸酯反应性溴化阻燃化合物。特别地，本发明涉及2，3-二溴-2-丙烯-1-醇(2，3-二溴烯丙基醇或DBAA)在聚氨酯泡沫(包括开孔喷涂泡沫、闭孔喷涂泡沫、硬质面板泡沫和柔性泡沫)中的应用。
本发明的实施方案是由包含DBAA的成分形成的聚氨酯泡沫。
还提供了可用于制备阻燃性聚氨酯泡沫的配方。
本发明的其它实施方案包括用于形成聚氨酯泡沫的工艺。
本发明的进一步详述
本文通篇使用的短语“反应性溴化阻燃剂”与“异氰酸酯反应性溴化阻燃剂”具有相同的含义。
聚氨酯泡沫通常是通过使两种主要的液体组分，即多异氰酸酯(A侧)和多元醇(B侧)接触来生产的。期望含有除多异氰酸酯以外的所有组分的B侧(在此为本发明的配方)为液体形式。如本文所用，术语“液体”意指该配方在B侧配方被使用的条件下为液态。有关聚氨酯泡沫形成的更多信息，请参见例如美国专利第3,954,684号；第4,209,609号；第5,356,943号；第5,563,180号；和第6,121,338号。
本发明涉及用二溴烯丙基醇(DBAA)阻燃的聚氨酯泡沫。这些泡沫由包含DBAA、至少一种多元醇、至少一种发泡剂、至少一种催化剂和至少一种表面活性剂的配方形成，所述配方与多异氰酸酯接触。
异氰酸酯反应性溴化阻燃剂含有至少一个这样的官能团，该官能团可用于并且能够在聚氨酯形成过程中与另一种聚氨酯形成组分反应，使得所得聚氨酯含有化学结合形式的反应性溴化阻燃剂。据认为，在制备聚氨酯泡沫期间，反应性溴化阻燃剂的官能团与异氰酸酯基团反应；通常，反应性溴化阻燃剂中的官能团(反应性基团)是羟基。
在本发明的实践中使用的异氰酸酯反应性溴化阻燃剂2，3-二溴-丙-2-烯-1-醇是一种已知的分子(在本文中也称为二溴烯丙基醇或DBAA)，其
Figure BDA0002341235890000031
注册号为7228-11-7(化学文摘社)。DBAA不可商购获得，但是已知在室温下在溶剂中由炔丙醇(2-丙炔-1-醇)和元素溴(Br2)合成DBAA。过去，DBAA被用作制备磷化合物的中间体(请参见美国专利第3,950,457号)。
DBAA可用于形成柔性聚氨酯泡沫和硬质聚氨酯泡沫。DBAA是一种反应性组分，其成为聚氨酯泡沫的一部分。这提供了DBAA不会从泡沫中迁移出来的优点。另一个优点是DBAA的溴含量高(74重量％)。可以与DBAA一起包含在聚氨酯泡沫中的其它阻燃剂包括四溴邻苯二甲酸酐与二甘醇和丙二醇的混合酯、磷酸三(1-氯-2-丙基)酯，或者磷酸三(1-氯-2-丙基)酯和四溴邻苯二甲酸酐与二甘醇和丙二醇的混合酯两者。
可以在形成聚氨酯泡沫的工艺中用作B侧的本发明配方包含DBAA、多元醇、发泡剂、催化剂和表面活性剂。
在形成本发明的聚氨酯泡沫时，使用了阻燃量的DBAA。阻燃量是指获得所需水平的阻燃性所需的DBAA的量。基于配方(B侧组分)的总重量，阻燃量通常在约1重量％至约25重量％，优选约3重量％至约20重量％，更优选约3重量％至约18重量％的范围内。
在本发明的实践中形成聚氨酯泡沫所使用的一种或多种多元醇可以是通常用于生产柔性聚氨酯泡沫或硬质聚氨酯泡沫的任何多元醇。常常使用多元醇的混合物，选择特定的多元醇是因为它们对所形成的聚氨酯泡沫的性能有影响。
当形成柔性聚氨酯泡沫时，多元醇通常是羟基数高达约150mgKOH/g，优选在约5mgKOH/g至约150mgKOH/g，更优选约10mgKOH/g至约100mgKOH/g，甚至更优选约20mgKOH/g至约75mgKOH/g的范围内的多元醇或多元醇的混合物。当使用聚合多元醇时，它们通常具有在约2,000至约10,000，优选约3,000至约8,000的范围内的分子量。
当形成硬质聚氨酯泡沫时，多元醇通常是羟基数在约100mgKOH/g至约850mgKOH/g的范围内，优选在约110mgKOH/g至约600mgKOH/g的范围内的多元醇或多元醇的混合物。当使用聚合多元醇时，它们通常具有在约250至约5000的范围内，常常在约400至约3000的范围内的分子量。
用于形成聚氨酯泡沫的合适的多元醇包括聚醚多元醇、聚酯多元醇、脂族多元醇和聚氧亚烷基二醇(polyoxyalkylene glycol)。可以使用两种或更多种多元醇的混合物。用于形成硬质聚氨酯泡沫的优选多元醇包括聚酯多元醇。
可以使用的聚氧亚烷基二醇包括聚氧亚乙基二醇、聚氧亚丙基二醇，以及混嵌的(block and heteric)聚氧亚乙基-聚氧亚丙基二醇。
脂族多元醇通常每个分子含有至多约18个碳原子。合适的脂族多元醇包括乙二醇、丙二醇、异构丁二醇、二甘醇、1，5-戊二醇、1，6-己二醇、三甘醇、甘油、三羟甲基乙烷、三羟甲基丙烷、1，2，6-己烷三醇、季戊四醇、四甘醇、二季戊四醇、山梨糖醇、蔗糖和α-甲基糖苷。
聚醚多元醇是通过使一种或多种在亚烷基残基中具有2个至约8个碳原子的环氧烷烃与含有两个或更多个羟基的引发剂分子反应制得的。合适的聚醚多元醇包括蔗糖/甘油聚醚多元醇；基于甘油、环氧丙烷和环氧乙烷的蔗糖聚醚多元醇；甘油引发(glycerin-initiated)的聚醚多元醇，例如甘油/环氧丙烷聚醚多元醇；和基于曼尼希的聚醚多元醇。
聚酯多元醇是通过将聚羧酸或其衍生物(例如其酰氨或酸酐)与多元醇聚合而制得的。合适的聚酯多元醇包括芳族聚酯多元醇和二甘醇-邻苯二甲酸酐聚酯多元醇。
为了形成柔性聚氨酯泡沫和硬质聚氨酯泡沫，基于B侧组分(配方)的总重量，多元醇的量通常在约40重量％至约80重量％的范围内，并且常常在约50重量％至约70重量％的范围内。当存在多于一种多元醇时，这些量是指配方中多元醇的总量。
可在本发明中用于形成柔性聚氨酯泡沫和硬质聚氨酯泡沫的发泡剂包括水，挥发性烃，诸如正戊烷、异戊烷、环戊烷的烃；卤代烃(halocarbon)(完全卤化的氯氟烃)，尤其是三氯氟甲烷(CFC-11)；以及卤代烃(含氢的氯氟烃或HCFC)，诸如1，1-二氯-1-氟乙烷(HCFC-141b)、1-氯-1，1-二氟乙烷(HCFC-142b)、氯二氟甲烷(HCFC-22)。可以使用任何两种或更多种发泡剂的混合物。在某些情况下，DBAA允许使用其中水是唯一发泡剂的配方。
当形成柔性聚氨酯泡沫时，在本发明的实践中其它合适的发泡剂包括二氯甲烷(亚甲基氯)和丙酮。用于柔性聚氨酯泡沫的优选的发泡剂包括水。基于B侧组分(配方)的总重量，用于形成柔性泡沫的发泡剂的量可以在约0.5重量％至约20重量％，优选约2.5重量％至约15重量的范围内。
为了形成硬质聚氨酯泡沫，在本发明的实践中可以使用的发泡剂包括部分氟化的烃(HFC)。用于硬质泡沫的合适发泡剂包括反式-1-氯-3，3，3-三氟丙烯(HFO-1233zd(E))、1，1，1，3，3-五氟丙烷(HFC-245fa)、1，1，1，2-四氟乙烷(HFC-134a)、1，1，1，3，3，3-六氟丙烷(HFC-236fa)、1，1，2，3，3，3-六氟丙烷(HFC-236ea)、1，1，1，4，4，4-六氟丁烷(HFC-356mffm)和1，2-双(三氟甲基)乙烯；和烃，诸如正戊烷、异戊烷和环戊烷。可以使用任何两种或更多种发泡剂的混合物。
当形成硬质泡沫时，优选的发泡剂包括水、1，1，1，3，3-五氟丙烷、反式-1-氯-3，3，3-三氟丙烯、1，2-双(三氟甲基)乙烯以及水与1，1，1，3，3-五氟丙烷、反式-1-氯-3，3，3-三氟丙烯或1，2-双(三氟甲基)乙烯的混合物。在一些情况下，2，3-二溴烯丙基醇允许使用其中水是唯一发泡剂的配方。基于B侧组分的总重量，用于形成硬质泡沫的发泡剂的量可以在约0.5重量％至约20重量％，优选约2.5重量％至约15重量％的范围内。
当形成柔性聚氨酯泡沫或硬质聚氨酯泡沫时，在本发明的实践中可以使用各种类型的催化剂，包括叔胺、锡催化剂(通常为有机锡化合物)、铋催化剂、其它有机金属催化剂和有机羧酸的钾盐。在本发明的实践中可以使用相同类型和/或不同类型的催化剂的混合物。
在胺催化剂中，胺上的基团优选是烷基；更优选地，该基团是含氧基团，诸如醚基或饱和醇基。合适的胺催化剂包括二甲基乙基胺、三亚乙基二胺、二甲基乙基胺、二甲基环己基胺、二甲基苄基胺、四甲基二亚丙基三胺、五甲基二亚乙基三胺、三(二甲基氨基丙基)-氢化三嗪、1-甲基-4-(2-二甲基氨基乙基)哌嗪、1，4-二氮杂(2，2，2)双环辛烷、3-甲氧基-N，N-二甲基丙基胺、N-甲基吗啉、N-乙基吗啉、N-椰油基吗啉(N-cocomorpholine)、双(二甲基氨基乙基)醚，和乙醇胺催化剂，诸如二甲基乙醇胺、2-(2-二甲基氨基乙氧基)乙醇和N，N，N′-三甲基氨基乙基-乙醇胺。对于柔性泡沫，优选的催化剂包括2-(2-二甲基氨基乙氧基)乙醇。对于硬质聚氨酯泡沫，胺催化剂优选为叔胺。
可以用作催化剂的锡化合物的类型包括二烷基(二烷基硫基)锡烷、有机羧酸的亚锡(II)盐和羧酸的二烷基锡(IV)盐。在本发明的实践中合适的锡催化剂包括二丁基双(十二烷基硫基)锡烷、辛酸亚锡(II)、乙酸亚锡(II)、二月桂酸二丁基锡和二乙酸二辛基锡。
又一种类型的催化剂是一种或多种有机羧酸钾盐。合适的钾盐包括乙酸钾和辛酸钾。
对于柔性聚氨酯泡沫和硬质聚氨酯泡沫，基于配方(B侧组分)的总重量，催化剂通常以约0.25重量％至约10重量％，优选约1重量％至约8重量％的总量使用。当存在多于一种催化剂时，这些量是指配方中催化剂的总量。
生产聚氨酯泡沫常常需要表面活性剂，当形成柔性聚氨酯泡沫和硬质聚氨酯泡沫时通常使用表面活性剂。
对于柔性聚氨酯泡沫和硬质聚氨酯泡沫，合适的基于硅酮的表面活性剂包括硅酮二醇、硅酮二醇共聚物、聚醚改性的聚硅氧烷、聚醚改性的二甲基聚硅氧烷诸如聚醚聚二甲基硅氧烷共聚物、聚硅氧烷聚氧亚烷基共聚物、聚硅氧烷聚氧亚烷基共聚物、聚硅氧烷共聚物等。基于硅酮的表面活性剂是用于形成柔性聚氨酯泡沫和硬质聚氨酯泡沫的优选类型的表面活性剂。聚醚改性的二甲基聚硅氧烷和聚硅氧烷共聚物是优选的基于硅酮的表面活性剂。
开孔剂(通常为聚亚烷基氧化物)是用于柔性泡沫的优选类型的表面活性剂。在本发明的实践中合适的聚亚烷基氧化物开孔剂包括聚乙二醇单烯丙基醚、聚乙二醇烯丙基甲基二醚、聚乙二醇单烯丙基醚乙酸酯、聚乙二醇单甲基醚、聚乙二醇甘油醚、聚乙二醇-聚丙二醇单烯丙基醚、聚乙二醇-聚丙二醇单烯丙基单甲基二醚和聚乙二醇-聚丙二醇烯丙基醚乙酸酯。
形成硬质聚氨酯泡沫时可使用的其它表面活性剂包括乳化剂，诸如蓖麻油硫酸酯或脂肪酸的钠盐；含胺的脂肪酸盐，例如油酸二乙基胺和硬脂酸二乙醇胺；磺酸的盐，例如十二烷基苯二磺酸和蓖麻油酸的例如碱金属或铵盐；乙氧基化烷基酚、乙氧基化脂肪醇；醚胺季铵化合物；2-羟丙基三甲基甲酸铵；羟基-壬基苯基-N-甲基甘氨酸钠(N-((2-羟基-5-壬基苯基)甲基)-N-甲基-甘氨酸的钠盐)和蓖麻油。
为了形成柔性聚氨酯泡沫和硬质聚氨酯泡沫，基于B侧组分(配方)的总重量，表面活性剂通常以约0.1重量％至约5重量％，优选约0.5重量％至约5重量％的量使用。当存在多于一种表面活性剂时，这些量是指配方中表面活性剂的总量。
当形成柔性聚氨酯泡沫或硬质聚氨酯泡沫时，可包含在本发明配方中的一种或多种任选添加剂包括抗氧化剂、稀释剂、扩链剂或交联剂、增效剂(优选蜜胺)、稳定剂、抑真菌剂、颜料、染料、填充剂、抗静电剂和增塑剂。
配方的组分可以以任意顺序组合；优选地，发泡剂是最后添加的成分。更优选地，将DBAA与一种或多种多元醇组合，然后与表面活性剂、催化剂和任何任选的成分组合，然后与发泡剂组合。
在本发明的实践中，在形成聚氨酯泡沫时使用的异氰酸酯或多异氰酸酯(A-侧组分)可以是适当时可用于生产柔性聚氨酯泡沫或硬质聚氨酯泡沫的任何异氰酸酯或多异氰酸酯。当使用聚合多异氰酸酯时，其优选具有约25重量％至约50重量％，优选约25重量％至约40重量％的异氰酸酯(NCO)含量。
当形成柔性聚氨酯泡沫时，异氰酸酯一般具有至少两个异氰酸酯基团。异氰酸酯可以是脂族或芳族的。当形成硬质聚氨酯泡沫时，使用多异氰酸酯，并且该多异氰酸酯可以是芳族或脂族的。在本发明的实践中，用于柔性聚氨酯泡沫和硬质聚氨酯泡沫的合适的多异氰酸酯包括但不限于：1，4-四亚甲基二异氰酸酯、1，5-五亚甲基二异氰酸酯、2-甲基-1，5-五亚甲基二异氰酸酯、1，6-六亚甲基二异氰酸酯(HMDI)、1，7-七亚甲基二异氰酸酯、1，10-十亚甲基二异氰酸酯、环己亚基二异氰酸酯、异佛尔酮二异氰酸酯(IPDI)、4，4’-亚甲基二环己基二异氰酸酯(H12MDI)、六氢甲苯二异氰酸酯及其异构体、2，2，4-三甲基六亚甲基二异氰酸酯、2，4，4-三甲基六亚甲基二异氰酸酯、4，4’-亚甲基双(环己基异氰酸酯)、亚苯基二异氰酸酯、甲苯二异氰酸酯(TDI)、二甲苯二异氰酸酯、其它烷基化苯二异氰酸酯、甲苯二异氰酸酯、1，5-萘二异氰酸酯、二苯基甲烷二异氰酸酯(MDI，有时称为亚甲基二异氰酸酯)、1-甲氧基苯基-2，4-二异氰酸酯、4，4’-二苯基甲烷二异氰酸酯、2，4′-二苯基甲烷二异氰酸酯、4，4’-二苯基甲烷二异氰酸酯和2，4′-二苯基甲烷二异氰酸酯的混合物、4，4’-联苯亚基二异氰酸酯、3，3’-二甲氧基-4，4’-联苯基二异氰酸酯、3，3’-二甲基-4，4’-联苯基二异氰酸酯、4，4′，4″-三苯基甲烷三异氰酸酯、甲苯2，4，6-三异氰酸酯、4，4’-二甲基二苯基甲烷-2，2′，5，5′-四异氰酸酯、聚合多异氰酸酯诸如聚亚甲基聚亚苯基多异氰酸酯，以及上述任意两种或更多种的混合物。
可用于形成本发明的柔性聚氨酯泡沫和硬质聚氨酯泡沫的多异氰酸酯包括通常被称为聚合亚甲基二苯基二异氰酸酯(MDI)的那些异氰酸酯、基于多异氰酸酯的预聚物，及其混合物。聚合MDI含有不同量的异构二苯甲烷二异氰酸酯以及三环、四环和大于四环的低聚物。一般而言，可以使用具有约25重量％或更高的异氰酸酯含量的任何商业聚合MDI。优选的聚合MDI具有约30重量％或更高的异氰酸酯含量。只要多异氰酸酯混合物整体上保持液态，其它异氰酸酯可以较少的量与聚合MDI一起存在。优选地，多异氰酸酯是聚合MDI。
本发明的聚氨酯泡沫组合物由A侧组分和B侧组分形成，其中A侧是如上所述的一种或多种异氰酸酯或多异氰酸酯，并且B侧包含本发明的配方。聚氨酯形成反应一般在室温下容易发生；通常，A侧和B侧一接触便开始彼此反应，并继续反应(固化)，形成聚氨酯泡沫。通常，将A侧和B侧的混合物喷涂或浇铸以形成聚氨酯泡沫。
在本发明的用于形成聚氨酯泡沫的工艺中，使A)至少一种异氰酸酯和/或多异氰酸酯与B)由2，3-二溴烯丙基醇、至少一种多元醇、至少一种发泡剂、至少一种催化剂和至少一种表面活性剂形成的配方接触，以形成混合物；以及使混合物固化以形成聚氨酯泡沫。
异氰酸酯和/或多异氰酸酯的量可以根据异氰酸酯指数来界定。
Figure BDA0002341235890000091
理论异氰酸酯当量等于B侧的每一当量反应性氢的一当量异氰酸酯。在本发明的工艺中，异氰酸酯指数值通常在80至200或约90至约150的范围内。硬质聚氨酯泡沫通常是通过将多异氰酸酯与具有异氰酸酯反应性氢原子(例如羟基)的化合物混合在一起而形成的，所述化合物的用量应使异氰酸酯指数在约85至约1000，优选约95至约400，更优选约95至约200的范围内。
为了形成聚氨酯泡沫，一般由多元醇或多元醇混合物提供的配方(B侧)的官能度(即每分子的平均羟基数)通常为约2或更高，优选约2至约8；更优选约3或更高，特别是约3至约8，更特别是约3至约7。作为一元醇，DBAA的官能度为1(即分子中有一个羟基)，它将使得链终止，所以配方中至少一部分多元醇每分子具有三个或更多个羟基以形成聚氨酯泡沫。在B侧的平均官能度的计算中纳入了DBAA。
在聚氨酯泡沫中，基于聚氨酯泡沫的总重量，2，3-二溴烯丙基醇一般为约0.5重量％至约12.5重量％，优选约1.5重量％至约10重量％，更优选约1.5重量％至约9重量％。基于聚氨酯泡沫的总重量，多元醇通常在约20重量％至约40重量％的范围内，并且常常在约25重量％至约35重量％的范围内。基于聚氨酯泡沫的总重量，表面活性剂以约0.05重量％至约2.5重量％，优选约0.25重量％至约2.5重量％的量存在。基于聚氨酯泡沫的总重量，催化剂以约0.125重量％至约5重量％，优选约0.5重量％至约4重量％的总量存在。对于每种类型的成分，当存在多于一种这种类型的成分时，这些量是指泡沫中这种类型的成分的总量。
在本发明中形成的硬质聚氨酯泡沫的密度范围随最终应用而变化。对于开孔隔热泡沫，密度范围一般为约0.4lb/ft3至约1.2lb/ft3(6.3kg/m3至18.9kg/m3)。对于闭孔隔热泡沫，密度范围通常为约1.6lb/ft3至约3.5lb/ft3(25.6kg/m3至56.1kg/m3)。对于模制建筑泡沫，密度范围通常为约4.0lb/ft3至约31lb/ft3(64.0kg/m3至497kg/m3)。
在本发明中形成的柔性聚氨酯泡沫的密度范围为约0.5lb/ft3至约1.0lb/ft3(8kg/m3至16kg/m3)。柔性聚氨酯泡沫通常用于形成制品，诸如模制泡沫、块状泡沫，并且可以用作家具和汽车座椅中的缓冲材料、床垫中的缓冲材料、地毯背衬、尿布中的亲水泡沫以及包装泡沫。
给出以下实施例是为了举例说明，而不是要限制本发明的范围。除非另有说明，以下实施例中的所有百分比均为重量百分比。
实施例-一般程序
在实施例中，使用的一些物质是以它们的商品名称来提及的。更具体地：
DBAA：2，3-二溴烯丙基醇
Figure BDA0002341235890000111
RB-79：四溴邻苯二甲酸酐与二甘醇和丙二醇的混合酯(AlbemarleCorporation)。
TCPP：磷酸三(1-氯-2-丙基)酯。
DE：二乙二醇单乙醚。
Figure BDA0002341235890000112
280：官能度为约7.0，羟基数为约280，平均分子量为约1400的聚醚多元醇；370：官能度为7.0的蔗糖/甘油聚醚多元醇；490：官能度为4.3的蔗糖/甘油聚醚多元醇(所有
Figure BDA0002341235890000115
材料均为Dow Chemical Company的产品)。
Figure BDA0002341235890000116
504为非硅酮有机表面活性剂(Dow Chemical Company)。
Figure BDA0002341235890000117
HT5503：羟基数在225至245范围内，官能度为2，当量为239的芳族聚酯多元醇；
Figure BDA0002341235890000118
HT5349：官能度为约2.45，羟基数为295至315的芳族聚酯多元醇(所有材料均为Invista Corporation的产品)。
Figure BDA00023412358900001110
PS-3152为官能度为2且羟基数为315的二甘醇-邻苯二甲酸酐聚酯多元醇(Stepan Chemical Company)。
Figure BDA00023412358900001111
GP-5171：官能度为约3，羟基数为35，平均分子量为约5000的甘油引发的聚醚多元醇；
Figure BDA0002341235890000121
GP-5015：官能度为3，羟基数为34，平均分子量为约5000的甘油引发的聚醚多元醇；
Figure BDA0002341235890000122
GP-1500：官能度为3，羟基数为112，平均分子量为约1500的甘油引发的聚醚多元醇；
Figure BDA0002341235890000123
GSP-280：官能度为7，羟基值为280，平均分子量为约1400的基于甘油、环氧丙烷和环氧乙烷的蔗糖聚醚多元醇；
Figure BDA0002341235890000124
GSP-355：官能度为4.5，羟基值为355的甘油/蔗糖引发的聚醚多元醇；
Figure BDA0002341235890000125
MX-470：官能度为约4，羟基数为470，平均分子量为480的基于曼尼希的聚醚多元醇；
Figure BDA0002341235890000126
GP-700：官能度为3，羟基数为240，平均分子量为约700的甘油和环氧丙烷聚醚多元醇(所有
Figure BDA0002341235890000127
材料均为Carpenter Company的产品)。
Figure BDA0002341235890000128
250为官能度为2且羟基数在235至255范围内的芳族聚酯多元醇(HuntsmanCorporation)。
Figure BDA0002341235890000129
DC193：硅酮二醇表面活性剂；
Figure BDA00023412358900001210
T：具有羟基的胺；
Figure BDA00023412358900001211
T-120：二丁基双(十二烷基硫基)锡烷；
Figure BDA00023412358900001212
PM-300：2-丁氧基乙醇；
Figure BDA00023412358900001213
DC5598：硅酮二醇共聚物表面活性剂；
Figure BDA00023412358900001214
K-15：辛酸钾；TMR：2-羟丙基三甲基甲酸铵(所有
Figure BDA00023412358900001216
材料均为Air Products and Chemicals，Inc.的产品)。
Figure BDA00023412358900001217
204：胺催化剂(Air Products and Chemicals，Inc)。
Figure BDA00023412358900001218
Q17-2PG为在异丙醇中的醚胺季铵表面活性剂(75％)(AirProducts and Chemicals，Inc.)。
Figure BDA00023412358900001219
B8871：聚硅氧烷共聚物；
Figure BDA00023412358900001220
B8407：聚醚聚二甲基硅氧烷共聚物(两者均为Evonik Industries AG，Essen，Germany的产品)。
ZR-70为2-(2-二甲基氨基乙氧基)乙醇，一种乙醇胺催化剂；
Figure BDA00023412358900001222
Z-110为N，N，N′-三甲基氨基乙基-乙醇胺；
Figure BDA00023412358900001223
ZF-20为双-(2-二甲基氨基乙基)醚(所有材料均为Huntsman Corp.，The Woodlands，TX的产品)。
Pel-cat9506为辛酸钾和乙酸钾的混合物；Pel-cat9858-A为羟基-壬基苯基-N-甲基甘氨酸钠(两者均为Elé Corporation的产品)。
LBA：反式-1-氯-3，3，3-三氟丙烯(Honeywell Inc.)。
Figure BDA0002341235890000132
245fa：1，1，1，3，3-五氟丙烷(Honeywell Inc.)。
OpteonTM1100：1，2-双(三氟甲基)乙烯；也称为
Figure BDA0002341235890000133
1100(The ChemoursCompany)。
Figure BDA0002341235890000134
27：NCO含量为31.4重量％，25℃下粘度为150cps至225cps，异氰酸酯当量为134的聚合二苯基甲烷二异氰酸酯(MDI)(Dow Chemical Company)。
根据ASTME-1354在Fire Testing Technology双锥量热仪上进行锥形量热法测量。对于全部实施例，在锥形量热法测试中使用40kW/m2的入射热通量进行预测烟指数计算，在锥形量热法测试中使用100kW/m2的入射热通量进行预测火焰蔓延指数计算。测量了热释放速率峰值(PHRR)，即锥形量热仪中样品燃烧过程中释放出的热量的最大值。热释放速率峰值的数值优选小于250。根据锥形量热法的结果计算出ASTME-84燃烧曲线，用于预测烟指数计算和用于预测火焰蔓延指数计算。使用先前从锥形量热仪和ASTME-84相关性研究得出的数学方程式，将锥形量热仪的结果转换为在ASTME-84中的预测数。火焰蔓延指数的目标值小于25，优选小于20，烟密度指数的目标值小于450，优选小于200。术语“烟指数”是“产生的烟密度”的简称，也称为“烟产生指数”和“烟密度指数”。
对于某些样品，确定了尺寸稳定性，尺寸稳定性的优选体积变化为±15％。对一些样品进行热导率测试，并从热导率计算出R值。R值(或R-值)是隔热效率或耐热性(材料减缓其内部热传递的能力)的量度，常常在建筑业中使用。R-值越高，材料越能阻止热传递。聚氨酯泡沫的R-值优选为约6.5或更高。
实施例1-22
实施例1-16中报告的结果是三个批次的平均值，每批5个样品(每次测试总共15个样品)。除非另有说明，否则每次运行中A侧与B侧的体积比为1∶1。实施例1-16的聚氨酯泡沫按照下面的程序1制备。实施例17-19的聚氨酯泡沫按照下面的程序2制备。实施例20-22的聚氨酯泡沫按照下面的程序1制备；在实施例1-22的所有运行中，A侧均为
Figure BDA0002341235890000141
27。
程序1：为了形成B侧，将DBAA、多元醇、表面活性剂、阻燃剂、发泡剂和催化剂称重到0.5加仑(1.9L)的可重新密封的容器中，并用蝶形领结式搅拌器以2000rpm混合60秒，或直至获得没有可见相分离的均匀混合物。以450克的规模(A侧和B侧的总量)称量所需量的B侧混合物，并将其加入到一升纸杯中。
通过将聚合MDI的所需量的约10％称量到250mL纸杯中，在3秒内倒出聚合MDI，将250mL湿杯再次量皮重，并加入全部量的聚合MDI来对聚合MDI湿法量皮重。然后在三秒的时间跨度内将聚合MDI倒入到含有B侧混合物的一升杯子中，并将一升纸杯中的内容物立即以2000rpm混合5秒。通过此过程，MDI的使用量在所需量的±1％以内。
当泡沫起发时，但在泡沫到达一升纸杯的顶部之前，将纸杯倒置并固定在纸片上。在泡沫继续起发的同时，将杯子向上引导而不妨碍泡沫起发。一旦泡沫具有足以支撑其自身和杯子的强度，就不再引导杯子。在让泡沫静置至少24小时后，将其切割以产生用于锥形量热仪测试的样品。对每个样品称重以确定泡沫密度。
程序2：为了制备每种聚氨酯泡沫，制备了除一种或多种催化剂外的B-例组分(DBAA、多元醇、表面活性剂、阻燃剂和发泡剂)的共混物。将多异氰酸酯和B-例配方称重至16盎司(473mL)纸杯中，然后用蝶形领结式搅拌器以2000rpm混合15秒，此时将一种或多种催化剂注入到混合物中，同时继续搅拌。在20秒标记处，停止搅拌，并将反应混合物立即倒入到10英寸x10英寸x10英寸(25Acm x 25.4cm x 25.4cm)的预先衬有聚乙烯袋的木盒模具中，并将盒子关闭。15分钟后，将聚乙烯袋中包裹的立方体形泡沫从模具中取出。在让泡沫静置至少24小时后，将其切割以产生用于锥形量热仪测试的样品。对每个样品称重以确定泡沫密度。催化剂是在使A侧和B侧接触后添加的，这与实验室规模的操作和时间安排有关。在较大规模上，催化剂被包含在B侧配方中。
在实施例1-4中，制备了开孔喷涂聚氨酯泡沫。实施例2和3供比较用。表1中列出了组分的量和工艺信息；测试结果总结在表2中。在实施例1-4中，水是唯一的发泡剂。
在实施例5-10中，制备了闭孔喷涂聚氨酯泡沫。实施例5、6、8和9供比较用。在实施例9中，
Figure BDA0002341235890000151
RB-79阻燃剂以在2-丁氧基乙醇中的溶液形式加入。表3中列出了组分的量和工艺信息；测试结果总结在表4中。
在实施例11-16中，制备了闭孔喷涂聚氨酯泡沫。实施例12-16供比较用。表5中列出了组分的量和工艺信息；测试结果总结在表6中。
在实施例17-19中，制备了面板聚氨酯泡沫。实施例17和18供比较用。表7中列出了组分的量和工艺信息。测试结果总结在表8中。
在实施例20-22中，制备了闭孔喷涂聚氨酯泡沫。实施例21的运行1与实施例22的运行1和运行2供比较用。表9A-B、11A-B和13A-C中列出了实施例20-22的组分的量和工艺信息；实施例20-22的测试结果总结在表10A-B、12A-B和14A-C中。
表1
Figure BDA0002341235890000161
表2
实施例 1 2 3 4
泡沫性能
密度，lb/ft<sup>3</sup> 0.81 0.70 0.60 0.62
密度，kg/m<sup>3</sup> 13.0 11.2 9.6 9.9
尺寸稳定性<sup>*</sup>(体积变化％) 0.5 -0.5 -5.1 0.5
预测火焰蔓延指数 24 24 23 24
预测烟密度指数 18 11 45 17
预测防火等级 1级 1级 1级 1级
*在70℃、95％相对湿度下测量尺寸稳定性持续14天。
表1和表2表明，可在开孔泡沫中用来使泡沫达到1级阻燃等级的DBAA的量相对于TCPP和RB-79要少得多。含有DBAA的聚氨酯泡沫比含有TCPP或
Figure BDA0002341235890000171
RB-79阻燃剂的泡沫具有更好的尺寸稳定性。
表3
表4
Figure BDA0002341235890000173
表3和表4表明，可在闭孔泡沫中用来使泡沫达到1级阻燃等级的DBAA的量相对于单独的RB-79或TCPP和RB-79的组合要少得多。与含有TCPP和/或
Figure BDA0002341235890000181
RB-79阻燃剂的泡沫相比，含有DBAA的聚氨酯泡沫的R-值得到了改善。
表5
Figure BDA0002341235890000182
表6
Figure BDA0002341235890000183
Figure BDA0002341235890000191
表7
Figure BDA0002341235890000192
表8
实施例 17 18 19
泡沫性能
密度(lb/ft<sup>3</sup>) 1.90 2.0 1.95
密度(kg/m<sup>3</sup>) 30.4 32.0 31.2
压缩强度(kPa) 187 314 214
R-值(/英寸) 6.2 6.8 5.25
R-值(m<sup>2</sup>K/W) 1.092 1.198 0.925
预测火焰蔓延指数 21 22 22.5
预测烟密度指数 25 48 439
预测防火等级 1级 1级 1级
表7和表8表明，在面板泡沫中使用DBAA可使泡沫达到1级阻燃等级。
表9A
Figure BDA0002341235890000201
表9B
Figure BDA0002341235890000211
表10A
Figure BDA0002341235890000212
Figure BDA0002341235890000221
1在70℃、95％相对湿度下测量尺寸稳定性持续14天。
表10B
Figure BDA0002341235890000222
1在70℃、95％相对湿度下测量尺寸稳定性持续14天。
Figure BDA0002341235890000231
Figure BDA0002341235890000241
Figure BDA0002341235890000251
Figure BDA0002341235890000261
Figure BDA0002341235890000281
Figure BDA0002341235890000291
表13C
Figure BDA0002341235890000311
Figure BDA0002341235890000321
Figure BDA0002341235890000331
在说明书或权利要求书中任何地方用化学名称或化学式所提及的组分，无论是单数还是复数，都被鉴定为在与另一种用化学名称或化学类型所提及的物质(例如另一种组分、溶剂等)接触之前已经存在。在所得混合物或溶液中发生什么化学变化、转化和/或反应(如果有的话)并不重要，因为这些变化、转化和/或反应是在根据本公开要求的条件下将特定组分放在一起的自然结果。因此，将这些组分鉴定为与进行所需操作或形成所需组合物相关的待放在一起的成分。此外，即使下文的权利要求可能以现在时态(“包含”、“是”等)提及物质、组分和/或成分，也指的是所述物质、组分或成分在第一次与一种或多种根据本公开的其它物质、组分和/或成分接触、共混或混合之前已经存在。因此，物质、组分或成分可能会在接触、共混或混合操作(如果根据本公开和化学家的普通技术进行)的过程中通过化学反应或转化而失去其原始特性，这一事实没有实际意义。
本文描述和要求保护的本发明的范围不受本文公开的具体实施例和实施方案的限制，因为这些实施例和实施方案旨在作为本发明的几个方面的说明。任何等同的实施方案都意图在本发明的范围内。实际上，除了本文中示出和描述的那些修改之外，根据前面的描述，本发明的各种修改对于本领域技术人员将变得显而易见。这样的修改也意图落入所附权利要求书的范围内。

Claims (19)

1.一种由包含2,3-二溴烯丙基醇的成分形成的聚氨酯泡沫。
2.如权利要求1所述的聚氨酯泡沫，其为柔性聚氨酯泡沫。
3.如权利要求1所述的聚氨酯泡沫，其为硬质聚氨酯泡沫。
4.如权利要求1所述的聚氨酯泡沫，其还包含四溴邻苯二甲酸酐与二甘醇和丙二醇的混合酯和/或磷酸三(1-氯-2-丙基)酯。
5.一种配方，其包含2,3-二溴烯丙基醇、至少一种多元醇、至少一种发泡剂、至少一种催化剂和至少一种表面活性剂。
6.如权利要求5所述的配方，其中所述多元醇是聚醚多元醇和/或聚酯多元醇。
7.如权利要求5所述的配方，其中所述发泡剂包含水。
8.如权利要求5所述的配方，其中，基于所述配方的总重量，2,3-二溴烯丙基醇的量为约1重量％至约25重量％，多元醇的量为约40重量％至约80重量％，表面活性剂的量为约0.1重量％至约5重量％，发泡剂的量为0.5重量％至约20重量％，和/或催化剂的量为约0.25重量％至约10重量％。
9.如权利要求5所述的配方，其中所述多元醇具有约3至约7的官能度。
10.如权利要求5-9中任一项所述的配方，其中水是唯一的发泡剂。
11.一种聚氨酯泡沫，其由包含至少一种多异氰酸酯的组分和如权利要求5-10中任一项所述的配方形成。
12.一种用于形成聚氨酯泡沫的工艺，所述工艺包括
使A)至少一种异氰酸酯和/或多异氰酸酯与B)由2,3-二溴烯丙基醇、至少一种多元醇、至少一种发泡剂、至少一种催化剂和至少一种表面活性剂形成的配方接触，以形成混合物；以及
使所述混合物固化以形成聚氨酯泡沫。
13.如权利要求12所述的工艺，其中A)和B)的量使得异氰酸酯指数为约80至约200，并且其中形成柔性聚氨酯泡沫。
14.如权利要求12所述的工艺，其中A)和B)的量使得异氰酸酯指数为约85至约1000，并且其中形成硬质聚氨酯泡沫。
15.一种如权利要求12-14中任一项所述的那样形成的聚氨酯泡沫。
16.一种聚氨酯泡沫，其由包含以下的成分形成：2,3-二溴烯丙基醇、至少一种多元醇、至少一种发泡剂、至少一种催化剂、至少一种表面活性剂和至少一种多异氰酸酯。
17.如权利要求16所述的聚氨酯泡沫，其中所述多元醇是芳族聚酯多元醇以及聚醚多元醇或至少一种蔗糖/甘油多元醇；其中所述发泡剂是水、反式-1-氯-3,3,3-三氟丙烯、1,2-双(三氟甲基)乙烯或这些中的任何两种或更多种的混合物；其中所述催化剂是辛酸钾和/或二丁基双(十二烷基硫基)锡烷；其中所述表面活性剂是硅酮二醇；和/或其中所述多异氰酸酯是二苯基甲烷二异氰酸酯。
18.如权利要求16或17所述的聚氨酯泡沫，其中，基于所述聚氨酯泡沫的总重量，2,3-二溴烯丙基醇的量为约1.5重量％至约10重量％；其中多元醇的量为约25重量％至约35重量％；其中催化剂的量为约0.5重量％至约4重量％；和/或其中表面活性剂的量为约0.25重量％至约2.5重量％。
19.如权利要求17所述的聚氨酯泡沫，其中所述芳族聚酯多元醇具有约1.75至约2.75的官能度和在约200至约350范围内的羟基数。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113227188A (zh) * 2018-12-27 2021-08-06 雅宝公司 溴化阻燃剂和含有该溴化阻燃剂的聚氨酯

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11897993B2 (en) 2017-06-27 2024-02-13 Albemarle Corporation Flame retarded polyurethane foam
US11613621B2 (en) * 2019-05-17 2023-03-28 L&P Property Management Company Expandable graphite flame retardant coating for polyurethane and latex foam
NO346554B1 (en) 2019-08-09 2022-10-03 Klingelberg Products As Flame retardant, method for its manufacture and article comprising such flame retardant

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2344254A1 (de) * 1972-09-07 1974-03-14 Gaf Corp Verfahren zur herstellung bromierter alkenole
US3932181A (en) * 1971-08-04 1976-01-13 National Starch And Chemical Corporation Electrophotographic coating compositions having bromine-containing polymer binders
US4002580A (en) * 1974-09-12 1977-01-11 Gaf Corporation Fire-retardant polyurethane
US4022718A (en) * 1974-03-06 1977-05-10 Gaf Corporation High resilience fire retardant urethane foam
CN1179440A (zh) * 1996-08-29 1998-04-22 巴斯福股份公司 储存稳定、含阻燃剂的多元醇成分
US20060135636A1 (en) * 2004-11-15 2006-06-22 Honeywell International Inc. Isocyanate-based polymer foams with nano-scale materials
CN1946757A (zh) * 2004-04-05 2007-04-11 巴斯福股份公司 生产聚氨酯泡沫材料的方法
CN1957041A (zh) * 2004-05-28 2007-05-02 雅宝公司 阻燃性聚氨酯及其添加剂
CN101484548A (zh) * 2006-05-15 2009-07-15 溴化合物有限公司 阻燃组合物
CN103497322A (zh) * 2013-09-09 2014-01-08 江苏雅克科技股份有限公司 一种反应型含卤阻燃聚醚多元醇的制备方法和用途
CN103724589A (zh) * 2013-11-27 2014-04-16 余姚市吴兴铜业有限公司 一种汽车坐垫用软质聚氨酯泡沫的制备方法
US20140220333A1 (en) * 2011-07-28 2014-08-07 Honeywell International Inc. Foams and flame resistant articles made from foams containing 1-chloro-3,3,3-trifluoropropene (1233zd)

Family Cites Families (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3283013A (en) 1962-06-28 1966-11-01 Du Pont Process for the preparation of 2, 3-dibromo-1-propanol
GB1015028A (en) 1963-09-23 1965-12-31 Berk F W & Co Ltd Halogenated diphenylsulphides and polymer compositions containing them
US3334032A (en) 1964-05-08 1967-08-01 Hanson Van Winkle Munning Co Electrodeposition of nickel
GB1063605A (en) 1965-02-03 1967-03-30 Dow Chemical Co Fire-retardant polyurethanes
US3467607A (en) 1967-01-10 1969-09-16 Union Carbide Corp Polyurethane foams based on a halogenated quasi-prepolymer
US3637813A (en) 1968-12-19 1972-01-25 Gaetano F D Alelio Unsaturated ester of halogenated alkenes
US3950392A (en) 1968-12-19 1976-04-13 Alelio Gaetano F D Unsaturated ester-amides of halogenated alkenes
US3993690A (en) 1969-03-25 1976-11-23 Boris Viktorovich Suvorov Method of obtaining aromatic tri-or-tetracarboxylic acids
US3933690A (en) 1971-03-10 1976-01-20 Ici United States Inc. Dihalobutenediol containing urethane foam compositions
US3780144A (en) 1971-09-10 1973-12-18 Alelio G D Halogenated ethylenically unsaturated phosphates
US3950457A (en) 1973-07-30 1976-04-13 Alelio Gaetano F D Polymers of halogenated esters of phosphorus-containing acids
US3954684A (en) 1974-07-09 1976-05-04 The Upjohn Company Foam process using tertiary amine/quaternary ammonium salt catalyst
US4209609A (en) 1977-11-07 1980-06-24 Mobay Chemical Corporation Toluene diamine initiated polyether polyols
CA1139050A (en) 1978-04-19 1983-01-04 Pennwalt Corporation Smoke suppressed rigid polyurethane foam
US4559366A (en) 1984-03-29 1985-12-17 Jaquelyn P. Pirri Preparation of microcellular polyurethane elastomers
FR2576311B1 (fr) 1985-01-24 1987-02-06 Solvay Polyetherpolyols phosphobromes, procedes pour leur obtention et utilisation de ces polyetherpolyols dans la fabrication de mousses souples de polyurethane ignifuges
GB2177405B (en) 1985-06-28 1989-08-23 Basf Corp Flame retardant polyurethane foams
ZA883499B (zh) 1987-05-26 1988-11-28
US4898981A (en) 1988-06-20 1990-02-06 Ciba-Geigy Corporation Heteroatom containing perfluoroalkyl terminated neopentyl glycols and compositions therefrom
CA2144490A1 (en) 1994-03-28 1995-09-29 Michael J. Skowronski Catalyst for polyisocyanurate foams made with alternative blowing agents
JPH0939104A (ja) 1995-08-01 1997-02-10 Inoac Corp Ｆｒｐ製品用成形型およびｆｒｐ製品の製造方法
DE19528537A1 (de) * 1995-08-03 1997-02-06 Basf Ag Flammgeschützte Hartschaumstoffe auf Isocyanatbasis
DE19529080A1 (de) 1995-08-08 1997-02-13 Voss Armaturen Steckverbindung für Druckmittelleitungen
CN1097071C (zh) 1997-09-25 2002-12-25 亨茨曼Ici化学品有限公司 硬质聚氨酯泡沫塑料的制法
US6518324B1 (en) 2000-11-28 2003-02-11 Atofina Chemicals, Inc. Polymer foam containing nanoclay
EP1231197A1 (en) 2001-02-07 2002-08-14 Sumitomo Chemical Company, Limited Process for producing allyl halide compound
TWI296630B (en) 2001-10-31 2008-05-11 Tosoh Corp Process for the production of flexible polyurethane foams
DE10156247A1 (de) 2001-11-15 2003-06-12 Bayer Ag Prepolymere für flammwidrig ausgerüstete Polyurethane
US20030153656A1 (en) 2002-01-11 2003-08-14 Rinus Sjerps Flame retardant polyurethanes and polyisocyanurates, and additives therefor
US20040171722A1 (en) 2003-02-28 2004-09-02 Brown William R. Flame retardant polyurethanes and additive compositions for use in producing them
PL198605B1 (pl) 2003-10-23 2008-07-31 Tsi Ochrony Pracy Pa & Nacute Ekologiczna sztywna pianka poliuretanowa o zmniejszonej palności
CN101501092B (zh) 2006-08-11 2011-09-28 东曹株式会社 用于制备聚氨酯树脂的催化剂组合物以及聚氨酯树脂的制备方法
US7671105B2 (en) 2006-08-22 2010-03-02 Basf Corporation Resin composition and an article formed therefrom
CN101092535B (zh) 2007-07-24 2010-08-18 海洋化工研究院 喷涂阻燃柔性聚脲组合物及其应用
CN101896542A (zh) 2007-12-11 2010-11-24 陶氏环球技术公司 含有作为阻燃添加剂的溴化2-氧代-1,3,2-二氧杂磷杂环己烷化合物的挤出聚合物泡沫体
TWI400121B (zh) 2009-11-25 2013-07-01 Eternal Chemical Co Ltd 微膠囊化阻燃物及其應用
WO2012058538A1 (en) 2010-10-29 2012-05-03 Lubrizol Advanced Materials, Inc. Flame-retarding oligomeric brominated urethane compositions
US9556303B2 (en) 2011-02-21 2017-01-31 Honeywell International Inc. Catalysts for polyurethane foam polyol premixes containing halogenated olefin blowing agents
US20140171525A1 (en) 2011-02-21 2014-06-19 Honeywell International Inc. Polyurethane foam premixes containing halogenated olefin blowing agents and foams made from same
CA2829486C (en) 2011-03-11 2019-03-26 Arkema Inc. Improved stability of polyurethane polyol blends containing halogenated olefin blowing agent
CN102391766B (zh) 2011-07-29 2013-07-24 北京立高防水工程有限公司 一种阻燃型喷涂聚脲弹性体涂料及其制备方法
JP2014525485A (ja) 2011-09-02 2014-09-29 ダウ グローバル テクノロジーズ エルエルシー ポリウレタン硬質フォーム
CN103102844A (zh) 2011-11-11 2013-05-15 沈阳创达技术交易市场有限公司 一种电子胶及生产工艺
CN102964562B (zh) 2012-11-20 2014-07-30 山东一诺威聚氨酯股份有限公司 用于军舰地面铺设的聚氨酯弹性体组合料及其制备方法
PL405383A1 (pl) 2013-09-18 2015-03-30 Wrocławskie Centrum Badań Eit + Spółka Z Ograniczoną Odpowiedzialnością Jednoskładnikowa kompozycja do wytwarzania pianki poliuretanowej w tym o zmniejszonej zawartości MDI i o obniżonej gęstości oraz jej zastosowanie
CN103665915A (zh) 2013-11-30 2014-03-26 青岛科创塑料机械有限公司 一种热固性阻燃塑料
TW201542682A (zh) 2014-02-27 2015-11-16 Sekisui Chemical Co Ltd 用以現場形成難燃性聚胺酯發泡體之現場發泡系統
JP6683696B2 (ja) 2014-11-05 2020-04-22 ダウ グローバル テクノロジーズ エルエルシー 難燃性ポリオール
CN105837781A (zh) 2016-04-19 2016-08-10 滁州环球聚氨酯科技有限公司 一种高强度聚氨酯复合材料
CN105860505A (zh) 2016-04-19 2016-08-17 滁州环球聚氨酯科技有限公司 一种高阻燃改性聚氨酯复合材料的制备方法
WO2017210593A1 (en) 2016-06-02 2017-12-07 Albemarle Corporation Flame-retardant electrolyte composition for lithium-ion batteries
US10131758B2 (en) * 2016-07-25 2018-11-20 Accella Polyurethane Systems, Llc Polyurethane foam-forming compositions, methods of making low density foams using such compositions, and foams formed therefrom
CN106280451A (zh) 2016-09-14 2017-01-04 郑州峰泰纳米材料有限公司 硬质聚酰亚胺泡沫的制备方法
CN106380600A (zh) 2016-09-14 2017-02-08 郑州峰泰纳米材料有限公司 柔性聚酰亚胺泡沫的制备方法
CN106317873A (zh) 2016-09-14 2017-01-11 郑州峰泰纳米材料有限公司 高强度聚酰亚胺泡沫的制备方法
US11897993B2 (en) 2017-06-27 2024-02-13 Albemarle Corporation Flame retarded polyurethane foam

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3932181A (en) * 1971-08-04 1976-01-13 National Starch And Chemical Corporation Electrophotographic coating compositions having bromine-containing polymer binders
DE2344254A1 (de) * 1972-09-07 1974-03-14 Gaf Corp Verfahren zur herstellung bromierter alkenole
US4022718A (en) * 1974-03-06 1977-05-10 Gaf Corporation High resilience fire retardant urethane foam
US4002580A (en) * 1974-09-12 1977-01-11 Gaf Corporation Fire-retardant polyurethane
CN1179440A (zh) * 1996-08-29 1998-04-22 巴斯福股份公司 储存稳定、含阻燃剂的多元醇成分
CN1946757A (zh) * 2004-04-05 2007-04-11 巴斯福股份公司 生产聚氨酯泡沫材料的方法
CN1957041A (zh) * 2004-05-28 2007-05-02 雅宝公司 阻燃性聚氨酯及其添加剂
US20060135636A1 (en) * 2004-11-15 2006-06-22 Honeywell International Inc. Isocyanate-based polymer foams with nano-scale materials
CN101484548A (zh) * 2006-05-15 2009-07-15 溴化合物有限公司 阻燃组合物
US20140220333A1 (en) * 2011-07-28 2014-08-07 Honeywell International Inc. Foams and flame resistant articles made from foams containing 1-chloro-3,3,3-trifluoropropene (1233zd)
CN103497322A (zh) * 2013-09-09 2014-01-08 江苏雅克科技股份有限公司 一种反应型含卤阻燃聚醚多元醇的制备方法和用途
CN103724589A (zh) * 2013-11-27 2014-04-16 余姚市吴兴铜业有限公司 一种汽车坐垫用软质聚氨酯泡沫的制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113227188A (zh) * 2018-12-27 2021-08-06 雅宝公司 溴化阻燃剂和含有该溴化阻燃剂的聚氨酯
CN113227188B (zh) * 2018-12-27 2023-01-06 雅宝公司 溴化阻燃剂和含有该溴化阻燃剂的聚氨酯

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