CN103270067B - 来自具有非常低游离单体异氰酸酯的预聚物的mdi基衬里和膜 - Google Patents

来自具有非常低游离单体异氰酸酯的预聚物的mdi基衬里和膜 Download PDF

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CN103270067B
CN103270067B CN201180061326.XA CN201180061326A CN103270067B CN 103270067 B CN103270067 B CN 103270067B CN 201180061326 A CN201180061326 A CN 201180061326A CN 103270067 B CN103270067 B CN 103270067B
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mishmash
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CN103270067A (zh
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I·乌尔克姆
A·F·安德鲁斯
M·温特尔
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Akzo Nobel Coatings International BV
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Abstract

本发明涉及用于制备弹性体材料的两部分聚氨酯和/或聚氨酯聚脲混杂物基体系，其包含具有低游离单体的异氰酸酯部分和胺/多元醇部分，其中异氰酸酯部分包含聚氨酯的预聚物，且其中预聚物为具有低游离MDI单体并用来自第二相对较高蒸气压异氰酸酯的异氰酸酯基团封端的基于MDI的预聚物，且预聚物含有小于约0.3%总游离单体且具有约0.1至约10%的NCO%。

Description

来自具有非常低游离单体异氰酸酯的预聚物的MDI基衬里和膜
发明背景
本发明涉及弹性体和/或塑料状膜或衬里。工业中部分这些类型的材料/产品先前通过使用异氰酸酯化学制备。使用异氰酸酯化学的产品的实例包括纯聚氨酯或纯聚脲或者聚氨酯和聚脲的混杂物。这些产品通常由两种组分组成并通过在使用时将产品的部分A与部分B混合而制备。一部分通常称为异氰酸酯部分，其含有异氰酸酯材料，同时另一部分通常称为胺/多元醇部分，其含有多元醇、胺或一组相容性含活性氢材料的组合。工业上常用的异氰酸酯组分为二苯基甲烷二异氰酸酯(MDI)单体或MDI单体与MDI聚合物/低聚物的组合。一般而言，在工业中了解当单体MDI单独或者有时与聚合MDI组合在产品的一部分中连同产品的另一部分中的芳族二胺一起使用时，得到较好的产品(例如具有较好的机械性能和耐化学品性)。这类材料在工业中的用途通常已知为生产具有良好耐透水性和耐化学品性以及良好的耐腐蚀性和机械性能的产品。建议在这类体系中使用单体MDI以帮助降低粘度，调整反应速度，以及得到更好的交联以提供最终产品的良好机械和化学性能。
然而，由于它为单体，单体MDI的使用具有潜在的负面的健康和安全顾虑。这通常是对于几乎所有单体异氰酸酯体系的情况。就这点而言，有利的是制备其中具有非常低(或无)游离单体的产品，同时仍实现所需机械、化学和应用性能目标。从毒物学观点看有利的还有这种产品在其胺/多元醇部分中不含芳族二胺，因为可能产生来自芳族二胺的物种，其被报告为致癌的。
在这种情况下，如果异氰酸酯部分不含(或含有非常低)单体材料以及胺/多元醇部分不含芳族二胺，则通常认为材料的性能(包括反应速度)受到不利影响。因此，需要在类似于通过使用游离单体MDI和芳族二胺制备产品的反应速度下实现所需性能。因此，有利的是不使用如上所述常用材料得到理想的产品性能，如果那些产品也可在类似于常用材料的反应速度和应用条件下工作的话特别如此。
发明概述
根据本发明，现在发现可制备衬里和膜，同时避免上述与MDI单体和芳族二胺的使用有关的困难。一方面，本发明涉及用于制备衬里材料的两部分体系，其包含具有非常低游离单体作为异氰酸酯的异氰酸酯部分和胺/多元醇部分，而不用芳族二胺，因此消除使用高水平的游离异氰酸酯和芳族二胺的有毒和危险性质。
一方面，异氰酸酯部分包含聚氨酯的预聚物。在一个实施方案中，预聚物为基本不具有或不具有游离MDI单体并用甲苯二异氰酸酯(TDI)基团封端的基于MDI的预聚物。在另一实施方案中，预聚物可用异佛尔酮二异氰酸酯(IPDI)封端。在一个实施方案中，预聚物含有小于0.3重量%总游离异氰酸酯单体，或小于0.2重量%总异氰酸酯单体，或小于约0.1重量%游离单体，或小于约0.05重量%游离单体，即包括游离TDI单体在内的总单体。在一个实施方案中，预聚物含有与低总游离单体组合，小于0.2重量%，或小于0.1重量%，或小于0.05重量%，或小于0.025重量%，或基本不含游离MDI单体。
在另一实施方案中，预聚物具有约0.1至约10%，或约0.5至约5%，或约1至约4%，或约2至约3%的NCO%。
在一个实施方案中，异氰酸酯部分进一步包含其它异氰酸酯。在一个实施方案中，其它异氰酸酯可选自HDI三聚物、IPDI、四甲基亚二甲苯基二异氰酸酯(TMXDI)、脂环族二异氰酸酯如Desmodur W，或其组合。在一个实施方案中，其它异氰酸酯三聚物为六亚甲基二异氰酸酯(HDI)三聚物。在一个实施方案中，基于MDI的预聚物与其它异氰酸酯的比为约0.5至约1.4，或约0.6至约1.2，或0.7至约1.1。
在一个实施方案中，胺/多元醇部分包含选自聚酯/聚醚多元醇混合物的多元醇。多元醇可以为具有伯、仲和/或叔醇基团的二醇、三醇或四醇或其组合。在一个实施方案中，多元醇为具有3.5的官能度的支化聚酯和聚醚基多元醇，其中所有醇官能团由仲羟基构成。
在一个实施方案中，胺/多元醇部分进一步包含仲胺。在一个实施方案中，仲胺可选自Desmophen NH1220、NH1420或NH1520或其组合。
在另一实施方案中，多元醇可以为基于己内酯的多元醇，其中所有羟基为伯醇，同时仲胺仍选自上述Desmophen系列中的一种。在这种实施方案中，多元醇可以为多官能的或不同多官能多元醇的组合。在一个实施方案中，多元醇可选自二官能、三官能、四官能或其组合。也可代替一类多元醇，使用各类多元醇的混合物。
本发明提供的优点是生产不具有与含有游离MDI单体和芳族二胺的两部分聚氨酯(或聚脲)有关的缺点的衬里和膜，同时仍能够在比得上通过使用这类常用材料实现的那些的反应速度的反应速度下实现所需性能特征。
本发明的其它目的、优点和新特征部分地描述于以下说明书和实施例中，且一部分经检查下文而由本领域技术人员获悉，或者可通过本发明的实践学习。本发明的目的和优点可通过所附权利要求书中特别指出的手段和组合实现和获得。
发明详述
在一个实施方案中，基于MDI的预聚物通过首先使MDI单体与多元醇以通过在体系中使用过量多元醇而确保所有或基本所有单体MDI被消耗的方式反应而制备。在一个实施方案中，用于制备预聚物的多元醇为二官能多元醇。
然后可使预聚物与具有相对较高蒸气压的其它异氰酸酯反应以将该附加的异氰酸酯封端在MDI预聚物链的末端或连接在MDI预聚物链的末端。在一个实施方案中，该第二异氰酸酯的蒸气压足够高使得可将未反应的异氰酸酯从反应混合物中汽提出以实现在真空下汽提以后小于0.3或小于0.2重量%的总游离异氰酸酯含量。在一个实施方案中，连接在预聚物链末端的其它异氰酸酯可选自甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、四甲基亚二甲苯基二异氰酸酯(TMXDI)、脂环族二异氰酸酯(t-CHDI)、二甲苯二异氰酸酯(XDI)、亚甲基二环己基二异氰酸酯(H12MDI)或其混合物。在一个实施方案中，其它异氰酸酯为TDI。
在一个实施方案中，将相对高蒸气压异氰酸酯如TDI从所得预聚物反应混合物中真空汽提出以除去过量单体异氰酸酯。在一个实施方案中，如果使用TDI，则最终预聚物产物含有小于约0.3%的其中不具有(或基本不具有)游离单体MDI的单体TDI。在一个实施方案中，所得产物，在聚合物链的末端用第二异氰酸酯如TDI封住的基于MDI的PU具有约0.1至约10%，或约0.5至约5%，或约1.5至约3.5%，或约2约3%，或约2.5%的NCO%。
发现预聚物的该NCO含量产生具有预聚物本身的附加性能特征，而且具有有限网络形成和/或交联能力的最终产物以实现较高水平的机械性能和耐化学品性。然而，发现这样制备的预聚物为非常合适的增韧剂，其具有共价键合能力；因此化学键合于最终产物体系中的其它物种上。
在另一实施方案中，异氰酸酯部分进一步包含一种或多种其它异氰酸酯，例如HDI的三聚物，其能够提供提高的反应性和多官能度以实现较高的交联水平。在一个实施方案中，预聚物材料本身具有非常低单体的游离异氰酸酯(例如小于0.3%)。这样，提供双组分材料的一部分，该部分含有反应性增韧剂(TDI封端的基于MDI的聚氨酯预聚物)和较低粘度但多官能材料(例如三聚物HDI)。发明人发现所需反应速度与所需潜在交联密度可通过在最终产物的异氰酸酯部分中使用这种体系而实现和控制。
认为本发明预聚物的反应性端基能够使它用作反应性材料，这消除了像非反应性增塑剂那样通过迁移至最终产物的表面而相分离的可能性。具有其它异氰酸酯的预聚物的化学稳定性有助于制备具有非常低总游离单体(例如小于约0.3%)的相对稳定部分A。
除化学稳定外，发明人发现其它异氰酸酯(例如HDI三聚物)与本发明预聚物组合使用导致提高的反应速度和对良好机械性能和耐化学品性而言足够稠密的三维网络的形成，同时还通过降低的粘度贡献于良好的应用性能，这是归因于附加异氰酸酯如HDI三聚物的贡献。此外，认为预聚物充当反应性增韧剂，其产生在最终产物的固化和使用条件期间能够分布内应力的最终产物。因此，认为基本不含游离异氰酸酯单体的本发明预聚物与其它材料组合对同时实现多个产物性能特征而言非常有用。
本发明体系的胺/多元醇部分也有助于同时实现所需反应速度和交联密度，但不使用芳族二胺。在一个实施方案中，该结果通过使用基于聚醚-聚酯的支化多元醇得到。在一个实施方案中，多元醇具有2-5或3-4官能度。在实施方案中，多元醇的分子量为800-1800g/摩尔。在实施方案中，该多元醇的粘度在25℃可以为约2800-4000cps。
认为多元醇的聚醚部分贡献于所需耐化学品性，因为它的骨架上缺乏反应性物种，同时认为聚酯部分的主要贡献是改进强度。认为多元醇的聚醚和聚酯组分以及官能度都贡献于体系的机械性能、耐化学品性、结晶度、韧性和反应性。在本发明一个实施方案中，多元醇为支化多元醇。认为多元醇的支化结构以及上述其它特征还贡献于体系的Tg。
在另一实施方案中，胺/多元醇部分进一步包含仲胺。发现与本发明关联使用仲胺实现不太快的固化速率，其(如果太快的话)可防止其它有效活性物种具有反应机会，容许以可接受的速度设置产物并提供在基质上更可控的应用和润湿。
在一个实施方案中，上述所有材料都以提供0.1-2，或0.25-1.5，或0.75-1.25当量的化学计量指数的量用于本发明中，例如含有低单体、基于游离MDI、TDI封端的低异氰酸酯含量聚氨酯预聚物和HDI三聚物的异氰酸酯部分，与含有基于聚醚和聚酯的多元醇基体系和仲胺的胺/多元醇部分组合，产生本身不具有溶剂的混杂聚脲-聚氨酯产物。
当如上所述制备时，获得的最终产物提供至少比得上通过使用含有游离MDI单体和芳族二胺的体系制备的那些的拉伸强度、伸长率%和耐化学品性值。本发明这种两部分体系实现关于商业膜和衬里的所需性能要求而不具有游离单体MDI且不使用任何芳族二胺。
本发明的组分可任选在聚氨酯催化剂的存在下反应。合适的聚氨酯催化剂为常用的并可以以常规量使用。
可使用的各类交联剂包括但不限于异氰酸酯、封端异氰酸酯（blockedisocyanates）和/或对多元醇和/或胺呈反应性的其它交联剂。
本发明涂料组合物还可包含约1至约50重量%的树脂(基料)，例如丙烯酸类树脂、聚酯、醇酸树脂、酚醛树脂、环氧树脂、聚醚、聚氨酯及其混合物。
本文所述涂料组合物可用作底漆、底涂层、顶涂层、中间涂层和透明涂层，但优选作为顶涂层，其中在金属和混凝土基质上使用或不使用底漆。
任选，颜料可存在于本发明涂料组合物中。有用的颜料为本领域中常用的各种类型，包括但不限于二氧化钛、石墨、炭黑、氧化锌、硫化钙、铬氧化物、硫化锌、铬酸锌、铬酸锶、铬酸钡、钛镍黄、钛铬黄、氧化铁红、氧化铁黄、氧化铁黑、萘酚红和棕、蒽醌、二氧杂锌紫、异吲哚黄、芳基化物黄和橙、群青蓝、酞菁配合物、苋菜红、喹吖啶酮、卤代硫靛颜料、体质颜料如硅酸镁、硅酸铝、硅酸钙、碳酸钙、热解法二氧化硅、硫酸钡和磷酸锌。
本发明涂料组合物还可包含其它组分如溶剂、催化剂、稳定剂、填料、流变控制剂、流动添加剂、流平添加剂、分散剂和本领域技术人员已知的其它组分。
本发明涂料组合物可通过使用多组件高压喷雾应用技术施涂于许多熟知基质上。一种优选的基质为金属。另一优选的基质为混凝土物体/结构。涂层的固化可在本领域技术人员已知的多种条件下进行，但上述双组分体系的固化优选在环境温度条件，通常环境温度至约40℃下进行。
该组合物特别适用于保护性涂料工业，特别是金属和采矿业、水和废水市场、工业机械应用和通常用于保护金属和混凝土基质的建筑工业中。
本发明的优选应用技术是多组件机器在常规较高压力下的使用。该技术还使用一套静态混合机且该应用以体积1:1比进行。该技术还使用热控制粘度、稳定喷雾条件和所需固化速度。
前述本发明的一般讨论通过以下具体但非限定性实施例进一步阐述。
以下实施例包括根据本发明制备两部分体系中的异氰酸酯部分和多元醇/胺部分以及该体系在涂料中的用途。还包括根据本发明生产的衬里/膜材料的性能试验。
方法
在下文所述实施例中，张力和拉伸试验根据ASTM D-412进行。耐化学品性试验使用非常类似于ASTM D-543的试验方法进行。附着力试验通过使用ASTM D-4541类型4试验方法进行。磨损试验根据ASTM D4060进行。冲击试验性能通过使用非常类似于ASTM G-14的方法评估。
产物对一些化学品的耐化学品性通过将试样浸入液体化学试剂中而评估。这实际上为所需交联密度的间接测量。
实施例
实施例1：
两部分聚氨酯和/或聚氨酯聚脲混杂物体系的异氰酸酯部分通过将18g的基于MDI的预聚物与25g的HDI三聚物(来自Bayer的XP-2410)组合而制备。所用基于MDI的预聚物为二官能多元醇与MDI的反应产物，其被TDI封端，基本不具有游离MDI单体，具有小于0.1%总游离单体和2-3%的NCO%。将预聚物/三聚物组合在第一小密闭容器中使用环动混合器(gyro mixer)以约1500-2000RPM速度混合2分钟。
实施例2：
两部分聚氨酯和/或聚氨酯聚脲混杂物体系的胺/多元醇部分通过将10g支化聚醚-聚酯基多元醇(Sovermol1080)(11.6%)与33.5g仲胺(BayerNH-1420)(38.7%)组合而制备。将多元醇/胺组合在第二小密闭容器中使用环动混合器以约1500-2000RPM速度混合2分钟。
实施例3：
试验涂料通过将第二容器的内容物倒入第一容器中，然后使用环动混合器以约1500-2000RPM速度混合约1.5-2分钟而制备。将所得混合物倒在水平特氟隆板(约25cm×25cm)上并使其均匀地散布(约3mm厚)而不具有小孔，然后在环境温度下固化。在约1星期以后，从固化涂层上切下试样用于以下实施例5所述试验。
实施例4：
其它试样通过将弹性体涂料喷雾在有底漆和无底漆的金属和混凝土基质上而制备。在喷雾应用期间，喷雾设备使用各自含有12个元件的两个静态混合机。将类似于实施例1的异氰酸酯组分加热至32℃(90℉)并将类似于实施例2的多元醇/胺组分加热至21℃(70℉)。喷雾期间的压力为约2800-3000psi。所用喷枪尖的尺寸为0.021”。应用期间放置金属和混凝土基质处的外部温度为13℃(55℉)。将一些金属和混凝土基质用Interseal1036涂底漆(在应用以前24小时)，而其它基质直接用于金属以及直接用于混凝土应用。金属基质的粗糙度为约1.5mils。
实施例5：
使来自实施例3和4的试样经受各个试验，其结果显示于下表中。＊表示根据实施例3生产的试样，且＊＊＊表示根据实施例4生产的试样。
该试样的初始性能特征显示于下表1中。
表1：初始试验
试样的耐化学品性显示于下表2中。
化学品 重量变化%
浸入水中(ASTM D-543—浸没一个月)＊ ～1.2%
浸入10%HCl中(ASTM D-543—浸没一个月)＊ ～0.4%
吸收至20%NaOH中(ASTM D-543—浸没一个月)＊ ～0.1%
吸收至30%H2SO4中(ASTM D-543—浸没一个月)＊ ～0.3%
吸收至50%H2SO4中(ASTM D-543—浸没一个月)＊ ～24.7%
表2：浸没试验

Claims (10)

1.用于制备弹性体和/或塑料状材料的两部分聚氨酯和/或聚氨酯聚脲混杂物基体系，其包含具有低游离单体的异氰酸酯部分和胺/多元醇部分，其中异氰酸酯部分包含：(i)具有低游离MDI单体并用来自甲苯二异氰酸酯(TDI)的异氰酸酯基团封端的基于MDI的预聚物，其中预聚物具有小于0.3％总游离单体和0.1至10％的NCO％，和(ii)其它异氰酸酯，其选自六亚甲基二异氰酸酯(HDI)三聚物、异佛尔酮二异氰酸酯(IPDI)、四甲基亚二甲苯基二异氰酸酯(TMXDI)、脂环族二异氰酸酯、或其结合；并且其中胺/多元醇部分包含：(i)至少一种选自聚酯和/或聚醚多元醇的多元醇，和(ii)仲胺。
2.根据权利要求1的两部分聚氨酯和/或聚氨酯聚脲混杂物基体系，其中预聚物基本不含游离MDI单体。
3.根据权利要求1的两部分聚氨酯和/或聚氨酯聚脲混杂物基体系，其中预聚物具有0.5至5％的NCO％。
4.根据权利要求3的两部分聚氨酯和/或聚氨酯聚脲混杂物基体系，其中预聚物具有1至4％的NCO％。
5.根据权利要求1的两部分聚氨酯和/或聚氨酯聚脲混杂物基体系，其中至少一种选自聚酯和/或聚醚多元醇的多元醇为支化聚酯和聚醚基多元醇。
6.根据权利要求1的两部分聚氨酯和/或聚氨酯聚脲混杂物基体系，其中其它异氰酸酯为HDI三聚物。
7.根据权利要求1的两部分聚氨酯和/或聚氨酯聚脲混杂物基体系，其中其它异氰酸酯为HDI三聚物，且该至少一种多元醇是官能度为2-5的支化聚酯和聚醚基多元醇。
8.根据权利要求7的两部分聚氨酯和/或聚氨酯聚脲混杂物基体系，其中支化聚酯和聚醚基多元醇具有3-4官能度。
9.包含根据权利要求1-8中任一项的两部分聚氨酯体系的涂料组合物。
10.根据权利要求1-8中任一项的两部分聚氨酯和/或聚氨酯聚脲混杂物基体系在膜和衬里中的用途。
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FR3021659B1 (fr) * 2014-05-28 2017-11-17 Bostik Sa Composition de polyurethane a terminaisons nco a base de 2,4-tdi non thermofusible et a faible teneur en monomere tdi, comprenant au moins un compose isocyanate de volume molaire particulier.
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