CN117264163A - 将co2基多元醇用于聚氨酯泡沫以提高再加工能力的方法 - Google Patents

将co2基多元醇用于聚氨酯泡沫以提高再加工能力的方法 Download PDF

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CN117264163A
CN117264163A CN202310714862.XA CN202310714862A CN117264163A CN 117264163 A CN117264163 A CN 117264163A CN 202310714862 A CN202310714862 A CN 202310714862A CN 117264163 A CN117264163 A CN 117264163A
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polyurethane foam
polyol
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阿尔珀·克孜尔塔斯
黛博拉·弗朗西斯·米耶斯基
刘望成
张锦文
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Ford Motor Co
Washington State University WSU
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Abstract

本公开提供“将CO2基多元醇用于聚氨酯泡沫以提高再加工能力的方法”。一种可回收的聚氨酯泡沫通过使含二氧化碳基多元醇的组合物与异氰酸酯组合物反应来产生。所述聚氨酯泡沫可包含摩尔比为1:0.9的活性氢与异氰酸酯基团。所述聚氨酯泡沫可包含约大于或等于约0.5重量份百分比至小于或等于约1.5重量份百分比的催化剂。

Description

将CO2基多元醇用于聚氨酯泡沫以提高再加工能力的方法
技术领域
本公开涉及可回收的聚氨酯泡沫。
背景技术
本部分中的陈述仅提供与本公开相关的背景信息，并且可能不构成现有技术。
开发聚氨酯泡沫的常规方法通常包括在存在诸如发泡剂、表面活性剂、催化剂和任何其他期望添加剂等添加剂的情况下，通过在氨基甲酸酯聚合发生时形成气体(例如，二氧化碳)，使具有至少一种具有羟基的多元醇(诸如石油基多元醇)的混合物(在本文中也称为含多元醇的组合物)与具有至少一种二异氰酸酯和/或聚异氰酸酯的混合物(在本文中也称为异氰酸酯组合物)反应(多元醇混合物、异氰酸酯混合物和任何添加剂的混合物也称为反应混合物)。多元醇混合物可包含添加剂。气体是由于发泡剂(通常为水)与异氰酸酯反应而形成的，从而形成二氧化碳和聚脲键。其他添加剂会增强所得泡沫的性质，控制上述反应，诸如此类。
聚氨酯泡沫是热固性材料，并且因此，在其使用寿命结束时，重复使用此类聚氨酯泡沫或回收所述聚氨酯泡沫可能具有挑战性。类玻璃高分子(Vitrimer)是最近推出的一种交联聚合物材料，其在高温下具有类似塑料的性质和特征。更具体地，类玻璃高分子在高温下表现出延展性，从而允许大分子网络的重排，并且由此实现了可再加工性。应注意到，聚氨酯的氨基甲酸酯和脲键本质上是可互换的，从而提供了网络结构的一定程度的重排，并且因此提供了一种可再加工性。然而，聚氨酯的再加工通常是缓慢的过程，对于由石油基醚多元醇制备的那些来说尤其如此。尽管高加工温度(如180℃至220℃)可促进网络重排并因此提高可再加工性，但是在>160℃的温度下可能会发生聚氨酯的热降解和分解。
本公开解决了与可回收的聚氨酯泡沫的设计相关的这些问题，特别是在汽车应用中。
发明内容
本部分提供了对本公开的总体概述并且不是对其全部范围或其所有特征的全面公开。
根据本公开的一种形式，一种聚氨酯泡沫通过使含多元醇的组合物与异氰酸酯组合物反应来产生。所述含多元醇的组合物包含活性氢与异氰酸酯基团的摩尔比为1:0.9的二氧化碳基多元醇。
在可单独地或以任何组合实施的这种聚氨酯泡沫的变型中，所述聚氨酯泡沫还包含开孔剂、表面活性剂、交联剂、催化剂和水发泡剂中的至少一种；所述含多元醇的组合物包含约2重量份百分比的开孔剂、约0.5重量份百分比的表面活性剂、约1.5重量份百分比的交联剂、大于或等于约0.5重量份百分比的催化剂和约3重量份百分比的水发泡剂；所述含多元醇的组合物包含大于或等于约0.5重量份百分比至小于或等于约1.5重量份百分比的催化剂；所述聚氨酯泡沫具有大于或等于约124kPa的断裂强度；所述聚氨酯泡沫具有大于或等于约4kNm/kg的比模量；并且车辆部件由所述聚氨酯泡沫形成。
在本公开的另一形式中，一种聚氨酯泡沫通过使含多元醇的组合物与异氰酸酯组合物反应来产生。所述含多元醇的组合物包含CO2-多元醇，其包含大于或等于约0.5重量份百分比至小于或等于约1.5重量份百分比的催化剂。
在可单独地或以任何组合实施的这种聚氨酯泡沫的变型中，所述聚氨酯泡沫还包含开孔剂、表面活性剂、交联剂、催化剂和水发泡剂中的至少一种；所述含多元醇的组合物包含约2重量份百分比的开孔剂、约0.5重量份百分比的表面活性剂、约1.5重量份百分比的交联剂和约3重量份百分比的水发泡剂；所述含多元醇的组合物具有活性氢与异氰酸酯基团的1:0.9的摩尔比；所述聚氨酯泡沫具有大于或等于约124kPa的断裂强度；所述聚氨酯泡沫具有大于或等于约4kNm/kg的比模量；并且车辆部件由所述聚氨酯泡沫形成。
在又一种形式中，一种聚氨酯泡沫通过使含多元醇的组合物与异氰酸酯组合物反应来产生。所述含多元醇的组合物包含CO2-多元醇，其包含约1.5重量份百分比的催化剂。
在可单独地或以任何组合实施的这种形式的变型中，所述含多元醇的组合物具有活性氢与异氰酸酯基团的1:0.9的摩尔比；所述聚氨酯泡沫还包含开孔剂、表面活性剂、交联剂、催化剂和水发泡剂中的至少一种；所述含多元醇的组合物包含约2重量份百分比的开孔剂、约0.5重量份百分比的表面活性剂、约1.5重量份百分比的交联剂和约3重量份百分比的水发泡剂；所述聚氨酯泡沫具有大于或等于约124kPa的断裂强度；并且所述聚氨酯泡沫具有大于或等于约4kNm/kg的比模量。
根据本文中提供的描述，另外的适用领域将变得显而易见。应当理解，描述和具体示例仅意图用于说明目的，而不意在限制本公开的范围。
具体实施方式
以下描述本质上仅仅是示例性的并且不意图限制本公开、应用或用途。
如本文所用，“异氰酸酯”包括二异氰酸酯，例如芳族二异氰酸酯、甲苯二异氰酸酯(“TDI”)和亚甲基二苯基二异丙烯酸酯(“MDI”)，以及聚异氰酸酯，以及它们的混合物。异氰酸酯的非限制性示例包括亚甲基二苯基二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、异氟尔酮二异氰酸酯(IPDI)、4,4'-二异氰酸根合二环己基甲烷(H12MDI)、1,5-萘二异氰酸酯(NDI)、四甲基二甲苯二异氰酸酯(TMXDI)、对亚苯基二异氰酸酯(PPDI)、1,4-环己烷二异氰酸酯(CDI)、联甲苯胺二异氰酸酯(TODI)以及它们的组合。可设想的是，异氰酸酯可包括聚合物材料。
如本文所用，“石油基多元醇”(以下称为“石油-多元醇”)是可在本公开的实践中使用并且是公知的且可广泛商购的聚醚多元醇。此类多元醇通常是至少约80重量％或更多的直接或间接地从不可再生资源(诸如原油)获得的组合物或组合物的共混物。在其他变型中，多元醇通常是直接或间接地从不可再生资源(诸如原油)获得的组合物或组合物的共混物的至少约85重量％、至少90重量％和/或至少95重量％或更多。聚醚多元醇的非限制性示例包括聚氧乙烯二醇、聚氧丙烯二醇、聚氧丁烯二醇、聚四亚甲基二醇；嵌段共聚物，例如聚氧丙烯二醇和聚氧乙烯二醇、聚-1,2-氧丁烯二醇和聚氧乙烯二醇、聚-1,4-四亚甲基二醇和聚氧乙烯二醇的组合；以及由两种或更多种环氧烷的共混物或顺序添加制备的无规和嵌段共聚物二醇。所得聚氨酯泡沫的机械性质可决定多元醇的稠度。更具体地，较高分子量的多元醇通常形成更柔性的聚氨酯，而较低分子量的多元醇通常形成更刚性的聚氨酯。
如本文所用，二氧化碳基多元醇是聚(醚碳酸酯)多元醇(以下称为“CO2-多元醇”)。CO2-多元醇的非限制性示例包括可从Covestro Deutschland AG获得的LC-05。
如上所述，聚氨酯泡沫通常通过在存在添加剂的情况下使异氰酸酯与多元醇反应来制备。以此方式，可设想的是，根据本公开的多元醇溶液包含至少石油基多元醇、CO2基多元醇和任何期望的添加剂。一些可能是任选的此类添加剂包括开孔剂、表面活性剂、交联剂、催化剂和水发泡剂中的至少一种。还设想的是，多元醇溶液可包含石油基多元醇、二氧化碳基多元醇、增强物和任何期望的添加剂。
发泡剂有助于制备泡沫，并且水是非常理想的发泡剂。根据本公开合适的其他发泡剂包括碳氟化合物、氢氯烃、氯氟烃、氢氟烃、碳氢化合物。还设想的是，可将气体直接添加到多元醇异氰酸酯反应混合物中以形成泡沫。
表面活性剂可用于泡沫应用中的泡孔成核和泡孔开口，并且提供泡沫稳定化。一种期望的表面活性剂是可从Evonik Degussa获得的B 4690，但是设想的是，其他非离子表面活性剂可适合于制备本文所公开的聚氨酯泡沫。
交联剂可用于改进交联网络，控制泡沫的抗折性质和其他性质。合适的交联剂包括二乙醇胺(DEA)和三乙醇胺，当用于泡沫应用时，它们建立坚固性并增加催化活性。
催化剂通过促进多元醇与异氰酸酯之间的基本化学反应、水与异氰酸酯之间的反应以及三聚化异氰酸酯的反应来增强聚氨酯泡沫的加工特性和物理性质。可根据特定应用的需要来选择催化剂，例如，以改进各种泡沫(包括高密度未填充泡沫、填充泡沫、高承载柔性泡沫、低密度泡沫和高回弹成型泡沫)的聚醚发泡过程。可选择其他催化剂来延迟泡沫形成反应过程，这可能导致更开放的泡沫结构。根据本公开的合适的催化剂是二丁基二月桂酸锡(DBTDL)和稀释的胺醚(诸如A1)和液体、水溶性叔胺(诸如/>A-300)，它们各自可从Momentive Performance Materials获得。当水存在于多元醇异氰酸酯反应混合物中时，可能期望使用叔胺作为催化剂，因为它会催化异氰酸酯与水反应以与氨基甲酸酯形成脲键。根据一种形式，所述催化剂可包括由稀释的胺醚组成的第一催化剂和由水溶性叔胺组成的第二催化剂。
开孔剂可用于制备主要具有开孔的泡沫结构，这赋予其更大的透气性值，并且包括可从Vantage Specialty Chemicals公司获得的水溶性乳化剂，诸如POE(26)GLYC。
其他任选的添加剂包括缓冲剂、树枝状大分子、无机微粒、本文未列出的其他类型的多元醇、聚异氰酸酯、阻燃剂、除臭剂、着色剂、填料、它们的组合以及本领域技术人员已知的其他添加剂。
基于二氧化碳的聚氨酯泡沫
根据本公开的教导，制备并测试如下表1所示的具有不同组成的基于CO2-多元醇的泡沫。还制备基于石油-多元醇的泡沫作为参考物(对照物)。在以下组合物中，CO2-多元醇是CARDYON LC-05，石油-多元醇是VORANOL 4701，开孔剂是LUMULSE POE(26)，表面活性剂是非反应性的并且是TEGOSTAB B4690，交联剂是DEA，催化剂是DBTDL，发泡剂是水，并且异氰酸酯是RUBINATE 7304。在制备泡沫制剂期间，活性氢M(H)与异氰酸酯(M(NCO))的摩尔比相应地对于样品1-3和对照物为1:0.9，并且对于样品4为1:1。如本文所用，活性氢包括多元醇的羟基、交联剂(例如，DEA)的羟基和胺基以及水的2个氢中的那些。
表1.石油(对照物)和CO2基(样品-1至4)聚氨酯泡沫以重量份百分比计的示例/测试组成
根据以下程序来产生工作示例。首先，通过用手持式混合器将以下项以1500rpm一起混合约5分钟来形成多元醇混合物：约100重量份百分比的石油-多元醇(例如，4701，可从Dow Che mical公司获得)或约100重量份百分比的CO2-多元醇(例如，/> LC-05，可从Covestro Deutschland AG获得)、约2重量份百分比的开孔剂(例如，/>POE(26)GLYC，可从Lambent公司获得)、约0.5重量份百分比的表面活性剂(例如，/>B4690，可从Evonik Nutrition&Care GmbH获得)、约1.5重量份百分比的交联剂(例如，DEA)、约0.925重量份百分比至约1.5重量份百分比的催化剂(例如，DBTDL)和约3重量份百分比的发泡剂(例如，去离子水)。向多元醇混合物添加异氰酸酯(例如，/>7304，可从Huntsman International LLC获得)并且用混合器混合12秒。将反应混合物倒入已涂覆有Chem-Trend PU-11331脱模剂的封闭模具系统中，并且在85℃的预热烘箱中加热10分钟，之后在85℃下固化2小时。泡沫没有表现出溢流或不充分的成型，并且表现出良好的孔分散和分布。
表1所示的工作示例的所得泡沫具有根据ASTM测试来测试的模量、断裂强度、断裂伸长率、密度、比强度和比模量。下表2示出了相应测试的结果。(括号表示标准偏差)。
表2.根据表1形成的组合物的机械性质
如表2所示，基于石油-多元醇的泡沫表现出更大的柔韧性，但是比基于CO2-多元醇的泡沫更薄弱。基于CO2-多元醇的泡沫在室温下也比基于石油-多元醇的泡沫更具刚性，但是它们的多元醇链段仍处于橡胶状态。由于较高的异氰酸酯含量，样品-4比其他三种基于CO2-多元醇的泡沫相对更硬。样品-2和样品-3含有比样品-1更高的催化剂含量，并且因此造成固化反应更好的完成，从而表现出更高的机械性质。
基于石油-多元醇的泡沫表现出比基于CO2-多元醇的泡沫更好的热稳定性特性。虽然不希望受理论束缚，但是这可归因于在基于石油-多元醇的泡沫中形成的醚键的热稳定性优于在基于CO2-多元醇的泡沫中形成的碳酸酯键。
然后对根据表1制备的泡沫进行热再加工以生产致密的片材产品。更具体地，将泡沫在10MPa压力和140℃温度下热压60分钟。随后根据ASTM测试来测试所得片材的模量、断裂强度、断裂伸长率、密度、比强度和比模量。下表3示出了相应测试的结果。(括号表示标准偏差)。
表3.根据表1形成的片材在第一轮热再加工之后的机械性质
将根据表1制备的泡沫各自切成八块，然后通过热压工艺在10MPa压力和140℃温度下热再加工60分钟。随后，将再加工的片材冷却到室温，并且根据ASTM测试来测试模量、断裂强度、断裂伸长率、密度、比强度和比模量。下表4示出了相应测试的结果。(括号表示标准偏差)。
表4.根据表1形成的片材在第一轮热再加工之后的机械性质
将再加工的片材进一步切成十六块，然后通过热压工艺在10MPa压力和140℃温度下热再加工60分钟。这个过程被视为第二轮再加工。随后，根据ASTM测试来测试片材的模量、断裂强度、断裂伸长率、密度、比强度和比模量。下表5示出了相应测试的结果。(括号表示标准偏差)。
表5.根据表1形成的片材在第二轮热再加工之后的机械性质
如表3、表4和表5所示，再加工的基于CO2-多元醇的片材(样品-1至4)在连续的热处理和应力处理之后保留了其大部分的机械性质，而再加工的基于石油-多元醇的片材(对照物)迅速失去了其机械性质。不希望受理论束缚，这个结果表明，基于CO2-多元醇的泡沫在40℃至160℃的温度下表现出类似热塑性的延展性，而基于石油-多元醇的片材保留了其热固性性质并且对于热再加工显示出了较差的延展性。因此，认为基于CO2-多元醇的泡沫可容易地通过热塑性加工技术来回收，并且再加工的基于CO2-多元醇的片材(例如，样品-2和样品-3)可回收多次，而这对于基于石油-多元醇的泡沫来说并不切实可行。此外，在催化剂含量较高的情况下(例如，在样品-2和样品-3中)，应力松弛率似乎更快，这为基于CO2-多元醇的泡沫提供了更好的分子流动性，并且因此提供了更好的可回收和可重复使用的性质。
本文公开的聚氨酯泡沫可用于期望有具有本文公开的性质的泡沫的各种应用中，例如像将泡沫用于家具业。此外，本文公开的聚氨酯泡沫可用于各种汽车应用和车辆部件，包括但不限于座椅靠背、扶手、座垫、车顶内衬应用、头枕、NVH(噪声、振动和粗糙性)泡沫、发动机盖、油泵盖、空调压缩机盖、燃油盖和用于机罩盖下方。
除非本文另有明确指示，否则指示机械/热性质、组成百分比、尺寸和/或公差或其他特性的所有数值在描述本公开的范围时应理解为由词“约”或“大约”修饰。出于各种原因期望进行这种修饰，所述原因包括：工业实践；材料、制造和组装公差；以及测试能力。
如本文所用，短语A、B和C中的至少一者应被解释为使用非排他性逻辑“或”表示逻辑(A或B或C)，并且不应被解释为表示“A中的至少一者、B中的至少一者以及C中的至少一者”。
本公开的描述本质上仅仅是示例性的，并且因此，不脱离本公开的实质的变型意图在本公开的范围内。不应将此类变型视为脱离本公开的精神和范围。
根据本发明，提供了一种通过使含多元醇的组合物与异氰酸酯组合物反应来产生的聚氨酯泡沫，所述聚氨酯泡沫具有CO2-多元醇，其包含大于或等于约0.5重量份百分比至小于或等于约1.5重量份百分比的催化剂。
根据本发明，提供了一种通过使含多元醇的组合物与异氰酸酯组合物反应来产生的聚氨酯泡沫，所述聚氨酯泡沫具有CO2-多元醇，其包含约1.5重量份百分比的催化剂。

Claims (15)

1.一种聚氨酯泡沫，所述聚氨酯泡沫通过使含多元醇的组合物与异氰酸酯组合物反应来产生，其中所述含多元醇的组合物包含活性氢与异氰酸酯基团的摩尔比为1:0.9的二氧化碳基多元醇(CO2-多元醇)。
2.根据权利要求1所述的聚氨酯泡沫，其中所述聚氨酯泡沫还包含开孔剂、表面活性剂、交联剂、催化剂和水发泡剂中的至少一种。
3.根据权利要求1所述的聚氨酯泡沫，其中所述含多元醇的组合物还包含：
约2重量份百分比的开孔剂；
约0.5重量份百分比的表面活性剂；
约1.5重量份百分比的交联剂；
大于或等于约0.5重量份百分比的催化剂；以及
约3重量份百分比的水发泡剂。
4.根据权利要求1-3中任一项所述的聚氨酯泡沫，所述聚氨酯泡沫还包含缓冲剂、树枝状大分子、无机微粒、阻燃剂、除臭剂、着色剂和填料中的至少一种。
5.根据权利要求1所述的聚氨酯泡沫，其中所述含多元醇的组合物包含大于或等于约0.5重量份百分比至小于或等于约1.5重量份百分比的催化剂。
6.根据权利要求4所述的聚氨酯泡沫，其中所述含多元醇的组合物包含约1.5重量份百分比的催化剂。
7.根据权利要求1所述的聚氨酯泡沫，其中所述聚氨酯泡沫具有大于或等于约124kPa的断裂强度。
8.根据权利要求1所述的聚氨酯泡沫，其中所述聚氨酯泡沫具有大于或等于约4kNm/kg的比模量。
9.根据权利要求1所述的聚氨酯泡沫，其中所述聚氨酯泡沫具有大于或等于约2kNm/kg的比强度。
10.根据权利要求1所述的聚氨酯泡沫，其中所述聚氨酯泡沫在约40℃与约160℃之间的温度下表现出类似热塑性的延展性。
11.根据权利要求1所述的聚氨酯泡沫，其中所述聚氨酯泡沫可通过热塑性加工技术回收至少一次。
12.根据权利要求1所述的聚氨酯泡沫，其中所述异氰酸酯组合物包含至少二异氰酸酯、聚异氰酸酯以及它们的混合物。
13.根据权利要求1所述的聚氨酯泡沫，其中所述异氰酸酯组合物包含聚合物材料。
14.一种车辆部件，所述车辆部件由权利要求1所述的聚氨酯泡沫组成。
15.一种家具部件，所述家具部件由权利要求1所述的聚氨酯泡沫组成。
CN202310714862.XA 2022-06-21 2023-06-16 将co2基多元醇用于聚氨酯泡沫以提高再加工能力的方法 Pending CN117264163A (zh)

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