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CN108137778A - 用于纺织品的无卤阻燃水性涂料组合物 - Google Patents

用于纺织品的无卤阻燃水性涂料组合物 Download PDF

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Publication number
CN108137778A
CN108137778A CN201680056595.XA CN201680056595A CN108137778A CN 108137778 A CN108137778 A CN 108137778A CN 201680056595 A CN201680056595 A CN 201680056595A CN 108137778 A CN108137778 A CN 108137778A
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China
Prior art keywords
weight
isocyanate
coating composition
polyurethane
composition according
Prior art date
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Pending
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CN201680056595.XA
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Inventor
约翰·赖施
理查德·柯顿
安妮·汉迪
米恩德勒·巴勒库恩
罗伯特·普恩布洛克
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DSM IP Assets BV
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DSM IP Assets BV
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Publication of CN108137778A publication Critical patent/CN108137778A/zh
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    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
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    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Polyurethanes Or Polyureas (AREA)

Abstract

本发明涉及一种阻燃水性涂料组合物，所述涂料组合物包含：a)水分散型羟基封端的聚氨酯颗粒，和b)异氰酸酯交联剂，其中(i)所述羟基封端的聚氨酯含有相对于其的量为3‑75重量份的膦酸酯低聚物作为结构单元，其中所述膦酸酯低聚物含有根据以下结构式的单元，其中n为1‑20的整数，R是C1‑20烷基、C2‑20烯烃、C2‑20炔烃、C5‑20环烷基或C6‑20芳基，且R2是脂族或芳族基团，(ii)所述羟基封端的聚氨酯的羟值为5‑180mg KOH/g聚氨酯，(iii)所述羟基封端的聚氨酯中存在的羟基与所述交联剂的异氰酸酯基团的摩尔比为0.2‑2.0。

Description

用于纺织品的无卤阻燃水性涂料组合物
本发明涉及阻燃水性(waterborne)聚氨酯涂料组合物，更具体地，本发明涉及用于纺织品上的阻燃水性聚氨酯涂料组合物。具体而言，本发明涉及含有无卤阻燃剂的阻燃聚氨酯涂料组合物，其制备方法以及所述无卤涂料组合物用于涂布纺织物的用途。
聚氨酯(PU)涂料被涂覆到纺织品上以提供耐流体静压性(hydrostaticresistance)、耐久性、透气性和/或阻燃性。历史上主要使用溶剂基PU涂料。但是，由于溶剂基PU可能会释放有毒物质，因此开发了水性PU。溶剂是挥发性有机化合物，会促成空气污染。水性涂料本身对环境更安全。本发明旨在开发一种使用非卤化阻燃剂的环保型阻燃纺织物。本发明为各种纺织物基材提供了一种含水、无卤、有效地阻燃的末道漆(finish)。
纺织品是日常生活中不可或缺的一部分，例如，可以在布料、服装、家具和车辆垫衬物、玩具、包装材料以及许多其它应用中找到纺织品。因此，纺织品的易燃性受到关注。
迄今为止，将聚氨酯涂料涂覆到各种纺织品已广泛实施，例如涂覆到聚酰胺和聚酯纺织品。但是，那些经涂布的织物极其易燃，因此有必要使其具有阻燃性。因为聚氨酯也具有差的阻燃性并且因此也容易点燃，所以已经进行了许多尝试以获得阻燃聚氨酯涂料组合物。就其本身而言，阻燃水性聚氨酯涂料组合物是已知的。溴化阻燃添加剂和氯化阻燃添加剂被广泛用于为涂层提供阻燃性。氧化锑也常与其他阻燃添加剂一起用作增效剂。环境和健康问题已导致卤化阻燃涂料不合需要，并且它们受到越来越多的监管。例如，美国环境保护局(EPA)最近禁止了十溴二苯醚，其是一种常用的溴化阻燃添加剂。含有氯、溴或重金属的产品在使用寿命结束被处理时需要特别谨慎。
本发明的主要目标是提供一种无卤阻燃水性聚氨酯涂料组合物，其具有优异的阻燃性，当涂覆到纺织品时尤为如此。本发明的另一个目标是提供一种经改进的阻燃剂涂布的织物。
出乎意料地发现：通过一种阻燃水性涂料组合物能够实现该目标，所述涂料组合物包含：
a)水分散型羟基封端的聚氨酯颗粒，和
b)异氰酸酯交联剂，
其中
(i)所述羟基封端的聚氨酯含有相对于其的量为3-75重量份的膦酸酯低聚物作为结构单元，其中所述膦酸酯低聚物含有根据以下结构式的单元，
其中n为1-20的整数，R是C1-20烷基、C2-20烯烃、C2-20炔烃、C5-20环烷基或C6-20芳基，且R2是脂族或芳族基团，
(ii)所述羟基封端的聚氨酯的羟值为5-180mg KOH/g聚氨酯，
(iii)所述羟基封端的聚氨酯中存在的羟基与所述交联剂的异氰酸酯基团的摩尔比为0.2-2.0。
出乎意料地发现：当用根据本发明的涂料组合物涂布纺织品时，可使该纺织品具有优异的阻燃性。还出乎意料地发现：在本发明中，将经涂布的织物浸在水中时，阻燃剂不会被浸出；在水中洗涤经涂布的织物时，阻燃剂也不会被洗掉。
本发明的阻燃聚氨酯涂料源自至少含有根据上文所给式的单元的膦酸酯二醇与异氰酸酯的反应，该反应导致阻燃物质引入聚合物的骨架中。
US-A-20100152374公开了阻燃水性聚氨酯分散体，其中聚磷酸酯被引入聚氨酯骨架中。对比实验B中尝试了与US-A-20100152374中公开的磷酸酯相似的磷酸酯(ExolitOP550)，其阻燃性能劣于本发明的膦酸酯二醇。
本发明中使用的膦酸酯二醇可从FRX Polymers,Inc.商购获得，其组成和制备描述于美国专利US 8,530,044、US 8,563,638和US 8,779,041和US2014/0000751中。
膦酸酯低聚物结构单元含有根据以下结构式的单元，
其中n、R和R2如上所述。优选地，R2是芳族基团；更优选地，-O-R2-O-衍生自间苯二酚、对苯二酚或双酚。最优选地，-O-R2-O-衍生自双酚-A。优选地，n为1-10的整数。优选地，R是甲基。
用于制备羟基封端的聚氨酯的膦酸酯低聚物是膦酸酯二醇，优选地选自无规共-低聚(膦酸酯碳酸酯)、嵌段共-低聚(膦酸酯碳酸酯)、无规共-低聚(膦酸酯)、嵌段共-低聚(膦酸酯)或其任何混合物。
更优选地，膦酸酯低聚物结构单元具有根据下式之一的结构：
其中R1和R2是脂族烃或芳族烃，且n为1-20、优选1-10的整数。
甚至更优选地，用于制备羟基封端的聚氨酯的膦酸酯低聚物是双酚-A和二苯基甲基膦酸酯(diphenyl methyl phosphonate)的共聚物。这样的化合物可以具有的结构例如但不限于以上所示羟值的三种结构。
优选地，用于制备羟基封端的聚氨酯的膦酸酯低聚物的羟值为10-200mg KOH/g膦酸酯低聚物，更优选20-200mg KOH/g膦酸酯低聚物，甚至更优选40-120mg KOH/g膦酸酯低聚物。在本文中使用时，根据ASTM D4272-11确定膦酸酯低聚物的羟值。
优选地，用于制备羟基封端的聚氨酯的膦酸酯低聚物的OH当量重量(equivalentweight)为280-5610，更优选280-2805，甚至更优选450-1400。通过将56100除以OH数来确定OH当量重量。
羟基封端的聚氨酯的羟值为5-180mg KOH/g聚氨酯，优选10-130mg KOH/g聚氨酯，更优选10-50mg KOH/g聚氨酯。在本文中使用时，根据ASTM D4274-11确定羟基封端的聚氨酯的羟值。
本发明中使用的异氰酸酯交联剂是水分散性多异氰酸酯。可以使用任何已知的水分散性多异氰酸酯，但优选使用水分散性脂族或脂环族多异氰酸酯，更优选水分散性脂族或脂环族二官能或三官能多异氰酸酯，其优选由异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)或4,4'-亚甲基-二环己基二异氰酸酯(H12MDI)或这些二异氰酸酯中至少两种的共混物制成。
在本发明中，基于OH官能聚氨酯分散体的重量，异氰酸酯交联剂的量优选为0.5-20％；基于羟基封端的聚氨酯的重量，异氰酸酯交联剂的量更优选2-10％。
在本发明的一个实施方式中，阻燃水性涂料组合物是单组分(1K)体系。在该实施方式中，异氰酸酯交联剂是封闭型多异氰酸酯。
在本发明中，阻燃水性涂料组合物优选通过在即将应用之前混合包含至少两种包装的多包装体系来获得。一种包装包含如上所述的水分散聚氨酯，另一种包装包含异氰酸酯。优选地，应用双包装体系(双组分(2K)体系)。第二包装异氰酸酯交联剂的非限制性实例有302、303、304、VPLS 2306，所有这些均可从Bayer Material Science(现称为Covestro)获得。
可以使用许多不同的第二包装异氰酸酯交联剂，包括衍生自以下的那些：六亚甲基二异氰酸酯(HDI)三聚体、HDI缩二脲、HDI脲基甲酸酯、异佛尔酮二异氰酸酯三聚体、异氰酸酯与三羟甲基丙烷的加合物以及已被亲水改性(hydrophically)以使其与水相容的异氰酸酯加合物。可以使用的异氰酸酯交联剂的实例包括但不限于以下：Desmodur N3300、Desmodur N3400、Desmodur N100、Desmodur N3200，所有这些均可从Bayer MaterialScience(现称为Covestro)获得；和Tolonate HDT-LV、Tolonate HDT、Tolonate HDB，这些都可以从Vencorex获得。可以使用的经亲水改性的异氰酸酯交联剂的实例包括但不限于：Bayhydur 302、Bayhydur 303、Bayhydur 304、Bayhydur VPLS 2306，所有这些均可从BayerMaterial Science(现称为Covestro)获得；和Easaqua XL 600、Easaqua SC 803、EasaquaXB 401、Easaqua M 502、Easaqua M 501、Easaqua Wat-4和Easaqua WAT-3，所有这些都可以从Vencorex获得。
根据本发明的阻燃水性涂料组合物中羟基封端的聚氨酯的量为10-99重量％，优选20-97重量％，更优选25-75重量％(相对于总涂料组合物)。
羟基封端的聚氨酯中存在的羟基与交联剂的异氰酸酯基团的摩尔比为0.2-2.0，优选0.2-1.0。
优选地，本发明的涂料组合物不含溴，优选不含卤素。
羟基封端的聚氨酯优选地是通过以下方法获得的：使
(a)5-50重量份的至少一种多异氰酸酯，
(b)3-75重量份的至少一种如上所述的膦酸酯二醇低聚物，
(c)0.5-30重量份的至少一种含有非离子型、离子型和/或潜在离子型水分散基团的异氰酸酯反应性多元醇，
(d)0-75重量份的至少一种不包含在(b)或(c)中的异氰酸酯反应性多元醇，
反应，以获得异氰酸酯封端的聚氨酯预聚物，并使所述异氰酸酯封端的聚氨酯预聚物与以下物质反应：
(e)0-20重量份的中和剂，和
(f)1-20重量份的至少一种含活性氢的扩链化合物，其能够形成羟基，
其中(a)、(b)、(c)和(d)的量相对于用于制备所述异氰酸酯封端的聚氨酯预聚物的组分的总量给出，所述异氰酸酯封端的聚氨酯预聚物的结构单元来源于所述异氰酸酯封端的聚氨酯预聚物，其中(e)和(f)的量相对于所述异氰酸酯封端的聚氨酯预聚物的重量给出。
用于制备聚氨酯的方法在本领域中是已知的，描述于例如G.Oertel的Polyurethane Handbook第二版,a Carl Hanser publication,1994中。
组分(a)
组分(a)是至少一种多异氰酸酯，优选至少一种有机双官能异氰酸酯。相对于用于制备‘异氰酸酯封端的聚氨酯预聚物的结构单元所来源于的异氰酸酯封端的聚氨酯预聚物’的组分的总量，组分(a)的量优选为5-50重量％，更优选为10-35重量％。
优选地，多异氰酸酯选自甲苯二异氰酸酯(TDI)、对亚苯基二异氰酸酯(PPDI)、4,4'-二苯基甲烷二异氰酸酯(MDI)、p,p'-二苯基二异氰酸酯(BPDI)、异佛尔酮二异氰酸酯(IPDI)、1,6-六亚甲基二异氰酸酯(HDI)、氢化二苯基甲烷-4,4'-二异氰酸酯(H12MDI)、间-四甲基二甲苯二异氰酸酯(TMXDI)、三甲基六亚甲基二异氰酸酯(TMHDI)及其任何混合物。
组分(b)
组分(b)是至少一种如上所述的膦酸酯二醇低聚物。相对于用于制备‘异氰酸酯封端的聚氨酯预聚物的结构单元所来源于的异氰酸酯封端的聚氨酯预聚物’的组分的总量，组分(b)的量优选为3-75重量％，更优选为5-20重量％。
组分(c)
组分(c)是至少一种含有非离子型、离子型和/或潜在离子型水分散基团的异氰酸酯反应性多元醇。相对于用于制备‘异氰酸酯封端的聚氨酯预聚物的结构单元所来源于的异氰酸酯封端的聚氨酯预聚物’的组分的总量，组分(c)的量为0.5-30重量％，优选为6-21重量％。潜在离子型水分散基团包括随后(中和后)被转化为水分散基团的基团。例如，游离(未离子化的)羧酸基团可被中和为羧化物阴离子水分散基团。
组分(c)优选包含
(c.1)0.5-10重量％、优选1-6重量％的含有离子型和/或潜在离子型水分散基团且分子量为100-500g/mol的异氰酸酯反应性多元醇，
(c.2)0-20重量％、优选5-15重量％的至少一种含有非离子型水分散基团的异氰酸酯反应性多元醇，其中(c.1)和(c.2)的量相对于用于制备‘异氰酸酯封端的聚氨酯预聚物的结构单元所来源于的异氰酸酯封端的聚氨酯预聚物’的组分的总量给出。
组分(c.1)是至少一种含有离子型或潜在离子型水分散基团且分子量为100-500g/mol的异氰酸酯反应性多元醇(优选二醇)。
优选的阴离子水分散基团是羧酸基团、磷酸基团和/或磺酸基团。这种化合物的实例包括含羧基的二醇，例如二羟基烷酸例如2,2-二羟甲基丙酸(DMPA)或2,2-二羟甲基丁酸(DMBA)。或者，磺酸基团可被用作潜在的阴离子水分散基团。阴离子水分散基团优选全部或部分呈盐形式。任选地，通过用碱中和聚氨酯预聚物来实现向盐形式的转化，优选在制备聚氨酯预聚物期间和/或在制备本发明的含水组合物期间进行。如果阴离子水分散基团被中和，则用于中和该基团的碱优选为氨、胺或无机碱。合适的胺包括叔胺，例如三乙胺或N,N-二甲基乙醇胺。合适的无机碱包括碱金属氢氧化物和碳酸盐，例如氢氧化锂、氢氧化钠或氢氧化钾。也可以使用氢氧化季铵，例如N+(CH3)4(OH)。通常使用碱，所述碱提供组合物可能期望的反离子。例如，优选的反离子包括Li+,Na+,K+,NH4 +和经取代的铵盐。也可使用阳离子水分散性基团，但其是次优选的。实例包括可被中和或永久离子化(例如用硫酸二甲酯)的吡啶基团、咪唑基团和/或季铵基团。非常合适的组分(c.1.)是二羟甲基丙酸(DMPA)和/或二羟甲基丁酸(DMBA)。
中和剂优选以这样的量使用，使得离子型和潜在离子型水分散基团与中和剂的中和基团的摩尔比为0.7-5.0，更优选0.8-3.0，甚至更优选0.85-1.2。
组分(c.2)是至少一种含有非离子型水分散基团的异氰酸酯反应性多元醇(优选二醇)。非离子型分散基团通常是悬垂的(pendant)聚氧化烯基团，特别是聚氧化乙烯(PEO)基团。例如可以通过在预聚物形成中使用具有悬垂的PEO链的二醇(例如现有技术诸如US3905929中描述的那些)作为反应物来提供这类基团。悬垂链PEO基团也可以通过使用某些胺和羟基官能化合物或二醇来引入，如EP 0317258中所公开。如果期望，除了氧化乙烯单元之外，PEO链还可含有其它氧化烯的单元。因此，可以使用这样的PEO链，其中多达60％的氧化烯单元是氧化丙烯单元，其余为氧化乙烯单元。
组分(d)
组分(d)是至少一种不包含在(b)或(c)中的异氰酸酯反应性多元醇。相对于用于制备‘异氰酸酯封端的聚氨酯预聚物的结构单元所来源于的异氰酸酯封端的聚氨酯预聚物’的组分的总量，组分(d)的量优选为0-60重量％，更优选为10-50重量％。这种多元醇可以选自可用于聚氨酯合成的多元醇的任何化学类别。特别地，多元醇可以是聚酯多元醇、聚酯酰胺多元醇、聚醚多元醇、聚硫醚多元醇、聚碳酸酯多元醇、聚缩醛多元醇、聚乙烯基多元醇和/或聚硅氧烷多元醇。多元醇(d)优选包含聚酯多元醇、聚醚多元醇和/或聚碳酸酯多元醇；更优选地，多元醇(d)是聚酯多元醇，甚至更优选地由乙二醇和己二酸制成和/或由二乙二醇和己二酸制成。
组分(f)
组分(f)是至少一种含活性氢的扩链化合物，其能够形成羟基。
相对于‘异氰酸酯封端的聚氨酯预聚物的结构单元所来源于的异氰酸酯封端的聚氨酯预聚物’的重量，组分(f)的量为1-20重量％，更优选2-10重量％。
组分(f)是至少一种官能度为至少2的活性氢扩链化合物。
含水组合物可以通过以下方法来制备：将异氰酸酯封端的聚氨酯预聚物分散在含水介质中，并在水相中用至少一种官能度为至少2的含活性氢的扩链化合物对预聚物进行扩链。可以与异氰酸酯封端的聚氨酯预聚物反应的含活性氢的扩链剂(组分(f))优选包括含有OH官能团的二胺或多胺，优选使用含有OH官能团的二胺。
优选地，活性氢扩链化合物选自氨基醇，例如N-(2-羟乙基)乙二胺。
可以将扩链剂加入异氰酸酯封端的聚氨酯预聚物的含水分散体中，或者，当将异氰酸酯封端的聚氨酯预聚物分散在含水介质中时，扩链剂可以已经存在于含水介质中。扩链可以在约5℃-95℃或更优选约10℃-60℃的适宜温度下进行。
根据本发明的阻燃水性涂料组合物可进一步包含添加剂，例如流变添加剂。
本发明还涉及如上所述的阻燃水性涂料组合物用于涂布纺织物的用途。本发明还进一步涉及通过将如上所述的涂料组合物涂覆到纺织品而获得的经涂布的织物。优选地，纺织品包含纤维，优选聚酯纤维、聚丙烯纤维和/或聚酰胺纤维。
本发明还涉及包含如本文所述的经涂布的织物的制品。所述制品优选选自家具、布料、服装、亚麻布、床垫、地毯、帐篷、睡袋、玩具、装饰性织物、垫衬物、墙壁织物、窗帘、遮篷、服装服饰、车辆垫衬物、遮篷、航空座椅、气囊盖及其组合。
现在参照以下实施例来阐释本发明。除非另有说明，否则所有份、百分比和比值均以重量计。
使用的材料
OL 1001，获自FRX Polymer
OL 3001，获自FRX Polymer
302，一种异氰酸酯交联剂，获自Bayer
OP 550，获自Clariant
6，获自Supresta
W，一种脂族二异氰酸酯，获自Bayer
Bayhydur 302，一种脂族异氰酸酯交联剂，获自Bayer
K-Stay 730增稠剂，获自King Industries
实施例和对比实验
实施例1
合成含有 OL 1001膦酸酯二醇的OH官能水性聚氨酯分散体
将以下物质装入树脂釜中并用氮气覆盖：由己二酸、二乙二醇和三羟甲基丙烷(353.96g，1150当量重量，0.3078当量)组成的聚酯多元醇，OL 1001(25.53g，710.1当量重量，0.0360当量)，二羟甲基丙酸(12.99g，67.07当量重量，0.1937当量)，二环己基甲烷-4,4'-二异氰酸酯(109.44g，131.1当量重量，0.8348当量)，新癸酸铋催化剂(0.15g)，甲基乙基酮(142.88g)。将混合物加热至78℃，持续3小时。通过二丁胺滴定测定NCO值，发现为1.98％(理论值为1.93％)。加入三乙胺(10.19g，101.19当量重量，0.1085当量)，并搅拌混合物10分钟。在迅速混合条件下加入水(786.8g)以形成水性聚氨酯分散体。将N(2-羟乙基)乙二胺(13.84g，52.075胺当量重量，0.2658当量)的混合物与水(30g)混合并缓慢加入分散体中。将混合物搅拌1小时，然后真空汽提以除去甲基乙基酮。产生了含有40％固体的无溶剂水性聚氨酯分散体。聚氨酯的羟值为14.4。
将142.5g这种水性聚氨酯分散体与Bayhydur 302(7.5g)和K-Stay730缔合增稠剂(1.6g)化合，以提供粘度为60000cps的涂料。羟基封端的聚氨酯中存在的羟基与交联剂的异氰酸酯基团的摩尔比为0.47。用辊式刮刀涂布机将化合的涂料涂布在200旦尼尔尼龙牛津织物上，然后在163℃下热固化90秒。织物上的涂层重量为40.7g/m2(1.2盎司/平方码)。
利用垂直阻燃测试CPAI-84“用于露营帐篷的阻燃材料的规格(A Specificationfor Flame-Resistant Materials Used in Camping Tentage)”和NFPA 701“用于阻燃纺织品和膜的着火测试(Fire Tests for Flame-Resistant Textiles and Films)”来检测涂有这些水性聚氨酯阻燃涂料的织物。
要通过CPAI-84测试，最大单独炭化长度(maximum individual char length)为25.5cm(10.04英寸)且最大平均炭化长度(maximum average char length)为21.6cm(8.5英寸)。最大单独残焰(maximum individual after flame)为4秒，最大平均值为2秒。
要通过NFPA 701测试，最大单独炭化长度为16.8cm(6.60英寸)且最大平均炭化长度为14cm(5.50英寸)。最大单独残焰为2秒。
结果如下所示。
PU骨架中具有OL 1001的实施例1的经涂布织物通过了垂直阻燃CPAI-84和NFPA 701测试，平均炭化长度为8.9cm(3.5英寸)并且没有残焰。
将实施例1的经涂布织物在水中浸析72小时，每24小时更换一次水。在阻燃测试中再次检测经浸析的织物。
结果如下所示。
浸析后的阻燃结果非常好，平均炭化长度为9.1cm(3.6英寸)并且没有残焰，因此通过了CPAI-84和NFPA 701测试二者。
因此，阻燃剂OL 1001未从涂料中浸出。
对比实验A
制备与实施例1所述相同的水性聚氨酯分散体，不同之处在于：略去OL1001。聚氨酯的羟值为14.5。
将用于对比实验A的水性聚氨酯分散体以与实施例1中相同的方式化合，并且也涂布在200旦尼尔尼龙织物上。羟基封端的聚氨酯中存在的羟基与交联剂的异氰酸酯基团的摩尔比为0.47。织物上的涂层重量为40.7g/m2(1.2盎司/平方码)。
使用垂直阻燃CPAI-84测试和NFPA 701测试检测固化的经涂布织物的阻燃性能。结果如下所示。
PU骨架中具有OL 1001的实施例1通过了垂直阻燃CPAI-84和NFPA 701测试，平均炭化长度为8.9cm(3.5英寸)并且没有残焰。聚合物骨架中没有膦酸酯二醇的对比实验A没有通过垂直阻燃CPAI-84测试，因为平均残焰为3秒且单独值为15秒。其也没有通过NFPA 701测试，因为有2个单独残焰值超过2秒。
对比实验A的经涂布织物没有经受浸析，因为其在于水中浸析之前甚至没有通过CPAI-84和NFPA-701阻燃测试。
实施例2
使用与实施例1相同的组成合成含有OL 3001膦酸酯二醇的OH官能水性聚氨酯分散体，不同之处在于：使用OL 3001代替OL 1001。OL 3001是由双酚-A和二苯基甲基膦酸酯制成的共聚物。OL 3001的OH值为50，OH当量重量为1122。将这种含有OL 3001膦酸酯二醇的OH官能(聚氨酯的羟值为14.2)水性聚氨酯分散体与Bayhydur 302化合，并利用K-Stay 730缔合增稠剂增稠至60000cps。羟基封端的聚氨酯中存在的羟基与交联剂的异氰酸酯基团的摩尔比为0.47。用辊式刮刀涂布机将化合的涂料涂布在200旦尼尔尼龙牛津织物上，然后在163℃下热固化90秒。织物上的涂层重量为40.7g/m2(1.2盎司/平方码)；对于在水中浸析72小时后检测的经涂布织物，为37.3g/m2(1.1盎司/平方码)。使用垂直阻燃CPAI-84测试和NFPA 701测试检测固化的经涂布织物的阻燃性能。
阻燃结果非常好，浸析前的平均炭化长度为9.4cm(3.7英寸)，浸析后的平均炭化长度为8.6cm(3.4英寸)，并且在两种情况下都没有残焰。这些结果通过了CPAI-84和NFPA701测试二者。因此，阻燃剂OL 3001未从涂料中浸出。
实施例3
如下所述合成具有由乙二醇和己二酸组成的聚酯多元醇的OH官能水性聚氨酯分散体：
将以下物质装入树脂釜中并用氮气覆盖：由己二酸和乙二醇组成的聚酯多元醇(320g，1000当量重量，0.320当量)，三羟甲基丙烷(2.46g，44.73当量重量，0.550当量)，OL 1001(29g，710.1当量重量，0.0408当量)，二羟甲基丙酸(25g，67.07当量重量，0.3727当量)，二环己基甲烷-4,4'-二异氰酸酯(149g，131.1当量重量，1.1365当量)，新癸酸铋催化剂(0.10g)，甲基乙基酮(149g)。将混合物加热至78℃，持续3小时。通过二丁胺滴定测定NCO值，发现为2.50％(理论值为2.42％)。加入三乙胺(19.61g，101.19当量重量，0.1938当量)，并搅拌混合物10分钟。在迅速混合条件下加入水(995g)以形成水性聚氨酯分散体。将N(2-羟乙基)乙二胺(18.22g，52.075胺当量重量，0.3498当量)的混合物与水(49g)混合并缓慢加入分散体中。将混合物搅拌1小时，然后真空汽提以除去甲基乙基酮。产生了含有35％固体的无溶剂水性聚氨酯分散体。聚氨酯的羟值为18.0。
将这种OH官能水性聚氨酯分散体(142.5g)与Bayhydur 302(7.5g)和K-Stay 730缔合增稠剂(1.7g)化合，以提供粘度为60000cps的涂料。羟基封端的聚氨酯中存在的羟基与交联剂的异氰酸酯基团的摩尔比为0.59。用辊式刮刀涂布机将化合的涂料涂布在200旦尼尔尼龙牛津织物上，然后在163℃下热固化90秒。织物上的涂层重量为40.7g/m2(1.2盎司/平方码)。检测垂直阻燃结果：
阻燃结果非常好，浸析前的平均炭化长度为9.1cm(3.6英寸)，浸析后的平均炭化长度为9.4cm(3.7英寸)，并且在两种情况下都没有残焰。这些结果通过了CPAI-84和NFPA701测试二者
实施例4以及对比实验B和C
制备分别含有OL 1001磷酸酯二醇(实施例1)、Fyrol 6(对比实验B)或Exolit OP 550(对比实验C)的OH官能水性聚氨酯分散体，并调节三种阻燃添加剂的量以保持所有情况下磷的重量百分比相同。
Exolit OP 550是一种基于低聚有机磷酸酯的非卤化磷多元醇。其羟值为170，OH当量重量为330，其含有17重量％的磷。
Fyrol 6是二乙基-N,N-双(2-羟乙基)氨基甲基膦酸酯。其羟值为460，OH当量重量为122，其含有12.4重量％的磷。
OL 1001是一种由双酚-A和二苯基甲基膦酸酯制成的共聚物。OL1001的OH值为90，OH当量重量为623，其含有8.5重量％的磷。
使用W(H12MDI)、乙二醇己二酸酯聚酯多元醇和DMPA制备聚合物骨架中含有这3种不同的无卤磷基阻燃剂的聚氨酯分散体。使用N-(2-羟乙基)乙二胺(HEEDA)对聚合物进行扩链以使其具有OH功能团。调节三种阻燃添加剂的量以使所有三种情况下磷的重量％保持相同。聚氨酯的羟值分别为18.0(含有OL 1001)、28.8(含有Fyrol 6)和18.5(含有Exolit OP 550)。
合成含有Nofia OL 1001的聚氨酯分散体：将乙二醇己二酸酯聚酯多元醇(320g，1000当量重量，0.320当量)，三羟甲基丙烷(2.46g，44.73当量重量，0.0550当量)，二羟甲基丙酸(25g，67.07当量重量，0.3727当量)，Nofia OL 1001(29.0g，623.3当量重量，0.0465当量)，Desmodur W(149.0g，131.1当量重量，1.1365当量)和甲基乙基酮(150g)在氮气下装入树脂釜中，然后混合并加热至78℃，持续2小时。通过二丁胺滴定测定NCO值，发现为2.50％(理论值为2.42％)。加入三乙胺(19.61g，101.19当量重量，0.1938当量)，并搅拌混合物10分钟。在迅速混合条件下加入水(995g)，然后缓慢加入HEEDA(18.22g，52.075胺当量重量，0.3499当量)和水(49g)的混合物。搅拌混合物1小时，然后通过真空汽提除去甲基乙基酮，从而留下了无溶剂水性聚氨酯分散体。
合成含有Fyrol FR6的聚氨酯分散体：将乙二醇己二酸酯聚酯多元醇(320g，1000当量重量，0.320当量)，三羟甲基丙烷(2.46g，44.73当量重量，0.0550当量)，二羟甲基丙酸(25g，67.07当量重量，0.3727当量)，Fyrol FR6(19.88g，121.96当量重量，0.1630当量)，Desmodur W(185.0g，131.1当量重量，1.411当量)和甲基乙基酮(220g)在氮气下装入树脂釜中，然后混合并加热至78℃，持续2小时。通过二丁胺滴定测定NCO值，发现为2.77％(理论值为2.72％)。加入三乙胺(19.61g，101.19当量重量，0.1938当量)，并搅拌混合物10分钟。在迅速混合条件下加入水(1087g)，然后缓慢加入HEEDA(31.09g，52.075胺当量重量，0.5970当量)和水(49g)的混合物。搅拌混合物1小时，然后通过真空汽提除去甲基乙基酮，从而留下了无溶剂水性聚氨酯分散体。
合成含有Exolit O,P 550的聚氨酯分散体：将乙二醇己二酸酯聚酯多元醇(320g，1000当量重量，0.320当量)，三羟甲基丙烷(2.46g，44.73当量重量，0.0550当量)，二羟甲基丙酸(25g，67.07当量重量，0.3727当量)，Exolit O,P 550(14.50g，330当量重量，0.0439当量)，Desmodur W(149.0g，131.1当量重量，1.1365当量)和甲基乙基酮(150g)在氮气下装入树脂釜中，然后混合并加热至78℃，持续2小时。通过二丁胺滴定测定NCO值，发现为2.30％(理论值为2.19％)。加入三乙胺(19.61g，101.19当量重量，0.1938当量)，并搅拌混合物10分钟。在迅速混合条件下加入水(972g)，然后缓慢加入HEEDA(18.22g，52.075胺当量重量，0.3499当量)和水(49g)的混合物。搅拌混合物1小时，然后通过真空汽提除去甲基乙基酮，从而留下了无溶剂水性聚氨酯分散体。
然后将水性聚氨酯分散体与Bayhydur 302异氰酸酯交联剂复合并增稠，然后涂布在200旦尼尔尼龙织物上。羟基封端的聚氨酯中存在的羟基与交联剂的异氰酸酯基团的摩尔比在所有情况下均为0.33。织物上的涂层重量为40.7g/m2(1.2盎司/平方码)(实施例4)、49.2g/m2(1.45盎司/平方码)(对比实验C)和45.8g/m2(1.35盎司/平方码)(对比实验B)。利用CPAI-84测试检测阻燃性能：
BEL*＝烧掉全长
含有OL 1001聚合物的聚合物通过了CPAI-84测试和NFPA-701阻燃测试，平均炭化长度为8.4cm(3.3英寸)并且没有残焰。含有Fyrol 6的聚合物没有通过测试，平均炭化长度为27.4cm(10.8英寸)，平均残焰为72秒。含有Exolit OP 550的聚合物也没有通过测试，平均炭化长度为19.3cm(7.6英寸)，平均残焰为42秒。这些数据显示：在这些OH官能水性聚氨酯分散体中，OL 1001具有优于Exolit OP 550和Fyrol 6的阻燃性能。
使利用含有1001聚合物并与Bayhydur 302交联的聚合物涂布的织物(实施例4)在洗涤机中经受3个洗涤循环，然后再次检测阻燃性能：
即使在3个洗涤循环之后，根据本发明的经涂布织物也通过了CPAI-84和NFPA-701阻燃测试，平均炭化长度为9.1cm(3.6英寸)并且没有残焰。因此，阻燃剂OL 1001未从涂料中洗掉。
对比实验B和C的经涂布织物没有经受洗涤，因为这些经涂布织物在被洗涤之前甚至没有通过CPAI-84和NFPA-701阻燃测试。
对比实验D
将含有1001聚合物(140g)的聚合物用K-stay 730(1.9g)增稠至60000cps，并涂布在不含异氰酸酯交联剂的200旦尼尔尼龙织物上，然后在163℃下热固化90秒。固化织物上的涂层重量为40.7g/m2(1.2盎司/平方码)。使固化织物在洗涤机中经受3个洗涤循环。涂层与织物严重分层。因此，未交联的涂层不耐洗涤循环。
如上所述检测这种经涂布织物的阻燃性能，获得了以下结果：
未交联的涂层没有通过CPAI-84和NFPA-701阻燃测试，平均残焰值为12秒。这表明：未交联的阻燃涂层不如异氰酸酯交联的聚氨酯涂层(如例如实施例1中的那样)耐用。

Claims (17)

1.一种阻燃水性涂料组合物，所述涂料组合物包含：
a)水分散型羟基封端的聚氨酯颗粒，和
b)异氰酸酯交联剂，
其中
(i)所述羟基封端的聚氨酯含有相对于其的量为3-75重量份的膦酸酯低聚物作为结构单元，其中所述膦酸酯低聚物含有根据以下结构式的单元，
其中n为1-20的整数，R是C1-20烷基、C2-20烯烃、C2-20炔烃、C5-20环烷基或C6-20芳基，且R2是脂族或芳族基团，
(ii)所述羟基封端的聚氨酯的羟值为5-180mg KOH/g聚氨酯，
(iii)所述羟基封端的聚氨酯中存在的羟基与所述交联剂的异氰酸酯基团的摩尔比为0.2-2.0。
2.根据权利要求1所述的阻燃水性涂料组合物，其中n为1-10，R2为芳族基团且优选地衍生自双酚-A。
3.根据权利要求1或2所述的阻燃水性组合物，其中R是甲基。
4.根据前述权利要求中任一项所述的阻燃水性涂料组合物，其中用于制备所述羟基封端的聚氨酯的所述膦酸酯低聚物为选自无规共-低聚(膦酸酯碳酸酯)、嵌段共-低聚(膦酸酯碳酸酯)、无规共-低聚(膦酸酯)、嵌段共-低聚(膦酸酯)或其任何混合物的膦酸酯二醇。
5.根据权利要求1-3中任一项所述的阻燃水性涂料组合物，其中所述膦酸酯低聚物结构单元具有根据下式之一的结构：
其中R1和R2是脂族烃或芳族烃，且n为1-20、优选1-10的整数。
6.根据前述权利要求中任一项所述的阻燃水性涂料组合物，其中用于制备所述羟基封端的聚氨酯的所述膦酸酯低聚物的羟值为10-200mg KOH/g膦酸酯低聚物，优选40-120mgKOH/g膦酸酯低聚物。
7.根据前述权利要求中任一项所述的阻燃水性涂料组合物，其中用于制备所述羟基封端的聚氨酯的所述膦酸酯低聚物的OH当量重量为280-5610、优选450-1400。
8.根据前述权利要求中任一项所述的阻燃水性涂料组合物，其中用于制备所述羟基封端的聚氨酯的所述膦酸酯低聚物是双酚-A和二苯基甲基膦酸酯的共聚物。
9.根据前述权利要求中任一项所述的阻燃水性涂料组合物，其中所述羟基封端的聚氨酯的量为10-99重量％、优选20-97重量％、更优选25-75重量％(相对于总涂料组合物)。
10.根据前述权利要求中任一项所述的阻燃水性涂料组合物，其中所述组合物不含溴，优选不含卤素。
11.根据前述权利要求中任一项所述的阻燃水性涂料组合物，其中所述羟基封端的聚氨酯是通过以下方法获得的：使
(a)5-50重量份的至少一种多异氰酸酯，
(b)3-75重量份的至少一种如前述权利要求中任一项中所定义的膦酸酯二醇低聚物，
(c)0.5-30重量份的至少一种含有非离子型、离子型和/或潜在离子型水分散基团的异氰酸酯反应性多元醇，
(d)0-75重量份的至少一种不包含在(b)或(c)中的异氰酸酯反应性多元醇，
反应，以获得异氰酸酯封端的聚氨酯预聚物，并使所述异氰酸酯封端的聚氨酯预聚物与以下物质反应：
(e)0-20重量份的中和剂，和
(f)1-20重量份的至少一种含活性氢的扩链化合物，其能够形成羟基，
其中(a)、(b)、(c)和(d)的量相对于用于制备所述异氰酸酯封端的聚氨酯预聚物的组分的总量给出，所述异氰酸酯封端的聚氨酯预聚物的结构单元来源于所述异氰酸酯封端的聚氨酯预聚物，其中(e)和(f)的量相对于所述异氰酸酯封端的聚氨酯预聚物的重量给出。
12.根据权利要求11所述的阻燃水性涂料组合物，其中所述多元醇(d)包含聚酯多元醇、聚醚多元醇和/或聚碳酸酯多元醇；优选地，所述多元醇(d)包含优选由乙二醇和己二酸制成的聚酯多元醇和/或由二乙二醇和己二酸制成的聚酯多元醇。
13.根据权利要求11-12中任一项所述的阻燃水性涂料组合物，其中所述多元醇(c)包含
(c.1)0.5-10重量％、优选1-6重量％的含有离子型和/或潜在离子型水分散基团且分子量为100-500g/mol的异氰酸酯反应性多元醇，
(c.2)0-20重量％、优选5-15重量％的至少一种含有非离子型水分散基团的异氰酸酯反应性多元醇，
其中(c.1)和(c.2)的量相对于用于制备所述异氰酸酯封端的聚氨酯预聚物的组分的总量给出，所述异氰酸酯封端的聚氨酯预聚物的结构单元来源于所述异氰酸酯封端的聚氨酯预聚物。
14.一种经涂布的织物，其是通过将根据前述权利要求中任一项所述的涂料组合物涂覆到织物上而获得的。
15.根据权利要求14所述的经涂布的织物，其中所述织物含有纤维，优选聚酯纤维、聚丙烯纤维和/或聚酰胺纤维。
16.一种制品，其包含根据权利要求14或15所述的经涂布的织物。
17.权利要求16所述的制品，其中所述制品选自家具、布料、服装、亚麻布、床垫、地毯、帐篷、睡袋、玩具、装饰性织物、垫衬物、墙壁织物、窗帘、遮篷、服装服饰、车辆垫衬物、遮篷、航空座椅、气囊盖及其组合。
CN201680056595.XA 2015-10-01 2016-09-28 用于纺织品的无卤阻燃水性涂料组合物 Pending CN108137778A (zh)

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