CN107074740B - 阻燃剂多元醇 - Google Patents

阻燃剂多元醇 Download PDF

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Publication number
CN107074740B
CN107074740B CN201480082776.0A CN201480082776A CN107074740B CN 107074740 B CN107074740 B CN 107074740B CN 201480082776 A CN201480082776 A CN 201480082776A CN 107074740 B CN107074740 B CN 107074740B
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component
polyol
cardanol
isocyanate
flame retardant
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CN107074740A (zh
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王蓓蕾
Y·张
H·陈
R·范
M·杨
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Abstract

诸如用于形成硬质聚氨酯泡沫的反应体系包括阻燃剂多元醇，该阻燃剂多元醇是腰果酚组分、溴组分和添加剂组分的溴化反应产物。腰果酚组分包括以该腰果酚总重量计至少80wt％的腰果酚，且该溴组分包括以该溴组分总重量计至少80wt％的溴。

Description

阻燃剂多元醇
技术领域
实施例涉及利用腰果壳液制备的阻燃剂多元醇、其制造方法及由其制备的硬质聚氨酯泡沫。
背景技术
需要使得聚氨酯生产商能够满足严格的市政建筑规范和消防法规的新产品。如在美国专利第4,511,688号中讨论的，已经采取了几种途径来降低硬质聚氨酯泡沫的可燃性。这些途径划分成两个主要类别：(1)使用聚氨酯改性的异氰脲酸酯，其可以使用最小量的阻燃剂；和(2)使用硬质聚氨酯，其可使用量相对较高的阻燃剂材料。然而，这些途径会遭受加工约束和/或泡沫物理性能中的缺点。例如，卤代阻燃剂倾向于成为固体或高粘度液体。聚氨酯制造商对于此类卤代阻燃剂可能没有操纵能力和/或此类材料的操纵可能具有挑战性。因而，需要如下新型阻燃剂产品：该阻燃剂具有相对较低的粘度(例如低粘度液体)，其可以被容易地结合到现有加工设备中和/或相对较易操纵。
此外，已经提出了可以用天然油和/或植物源多元醇如源自腰果壳液的多元醇代替石化源多元醇，例如在美国专利第7,244,772中讨论的。然而，仍然需要兼具阻燃性、低粘度和源自植物来源的多元醇。
发明内容
实施例可以通过提供以下反应体系来实现：该反应体系包括阻燃剂多元醇，该该阻燃剂多元醇是腰果酚组分、溴组分和添加剂组分的溴化反应产物。所述腰果酚组分包括以该腰果酚总重量计至少80wt％的腰果酚，且该溴组分包括以该溴组分总重量计至少80wt％的溴。该反应体系可以用于制备硬质聚氨酯泡沫，例如用于器具的硬质聚氨酯泡沫。
附图说明
图1示出描述如在实例中讨论的结构式1Br-C-M和2Br-C-M的示范性1H-NMR。
具体实施方式
硬质聚氨酯泡沫可以用于器具或结构应用，例如提供优异的绝热性能。在这样的应用中，可能对阻燃性存在严格的要求。之前，已经提出了使用有机阻燃剂添加剂来改善阻燃性。然而，这些添加剂可能使所得泡沫产品的物理性能劣化。已经提出了兼具阻燃剂性能和植物源材料的阻燃剂多元醇。反应性阻燃剂多元醇既可以提供改善的阻燃剂性能同时又维持和/或改善所得泡沫产品的物理性能。
阻燃剂多元醇可以用于泡沫、涂层、胶粘剂、密封剂、和/或寻求改善阻燃性/火情的弹性体应用。阻燃剂多元醇可以用作聚氨酯系反应体系中的反应性组分，使得阻燃剂多元醇以反应性组分的形式引入阻燃性。反应性阻燃剂多元醇既可以提供改善的阻燃剂性能同时又维持和/或改善所得泡沫产品的物理性能。
例如，阻燃剂多元醇可以用于制备硬质聚氨酯泡沫产品(例如用于器具和建筑材料的硬质聚氨酯泡沫)或涂层。硬质聚氨酯泡沫可以通过使异氰酸酯组分(其包括至少一种异氰酸酯，如聚异氰酸酯或异氰酸酯封端的预聚物)和包括至少该阻燃剂多元醇的异氰酸酯反应性组分发生反应来制备。除了阻燃剂多元醇之外，异氰酸酯反应性组分可以包括一种或多种其它多元醇(如基于环氧丙烷、环氧乙烷、和/或环氧丁烷的多元醇)和/或不同的天然油/植物源多元醇。
阻燃剂多元醇的形成
作为至少腰果酚组分、溴组分和添加剂组分的溴化反应产物来制备阻燃剂多元醇。腰果酚组分包括以该腰果酚总重量计至少80wt％的腰果酚，且该溴组分包括以该溴组分总重量计至少80wt％的溴。添加剂组分可以包含氨基醇、醛和/或酮。例如，除了氨基醇之外，添加剂组分可以包括选自醛和酮(例如甲醛、乙醛、丙酮和/或其共混物)中的至少一种。醛和/或酮可以经由Mannich反应与酚反应。阻燃剂多元醇可以包含在聚氨酯泡沫中可表现出良好/改善阻燃性能的溴、苯基和胺。另外，酚醛骨架中的羟基可以帮助增加泡沫强度和/或表现出更好的耐压强度。
用于形成阻燃剂多元醇的腰果酚组分是天然油/植物源材料。腰果酚组分包括大部分的腰果酚，例如以也被称为CNSL的腰果壳液形式提供的腰果酚。腰果酚可以包括一种或多种CNSL。腰果酚可以指在间位具有长烃链的单羟基酚。腰果酚的一个示范性结构是包含一个羟基和在间位上的脂肪族侧链的苯酚，如下式(1)中示出。
Figure GDA0002155349110000031
其中R1是-C15H25、-C15H27或-C15H29。
腰果酚组分中的CNSL可以是腰果加工的副产物(例如，可以从腰果仁和壳之间的层中提取)。CNSL中腰果酚的浓度可以为以CNSL总重量计至少10wt％、至少50wt％、至少80wt％、至少85wt％和/或至少90wt％。同时，腰果酚的浓度可以为以CNSL总重量计99wt％或更低、97wt％或更低或96wt％或更低。在实施例中，腰果酚组分具有以腰果酚总重量计至少80wt％(例如81wt％至100wt％、85wt％至100wt％、90wt％至100wt％、92wt％至100wt％、92wt％至97wt％和/或94wt％至96wt％等)的腰果酚含量。腰果酚组分和/或CNSL可以进行热处理(例如在从腰果中提取时)、脱羧处理和/或蒸馏处理。
根据实施例，CNSL包括腰果酚作为主要成分，并且还可以包括腰果二酚、甲基腰果二酚和/或漆树酸作为次要组分。该次要组分可以包括单醇和/或多元醇，例如在以下对应结构式中示出的。
Figure GDA0002155349110000041
其中，在上述结构式中的每个结构式中的R独立地为下者中的一个。
Figure GDA0002155349110000042
在示范性实施例中，腰果酚组分中的R基团总数的约35％至50％可以为第一结构式(即具有三个碳-碳双键的结构式)。腰果酚组分中的R基团总数的约15％至30％可以为第二结构式(即具有两个碳-碳双键的结构式)。腰果酚组分中的R基团总数的约25％至45％可以为第三结构式(即具有一个碳-碳双键的结构式)。腰果酚组分中的R基团总数的大约不到5％可以为第四结构式(即没有碳-碳双键的饱和结构式)。
在腰果酚组分中使用的该至少一种CNSL中的腰果二酚浓度可以为以该至少一种CNSL总重量计约0.1wt％或更多、约1wt％或更多、或约5wt％或更多；且同时约90wt％或更少、约50wt％或更少或约10wt％或更少。此外，CNSL可以包括低浓度的其它物质如漆树酸、腰果酚低聚物、腰果二酚低聚物及其混合物。在CNSL中存在的其它物质的总浓度可以少于约10wt％。
腰果酚组分的示范性CNSL可以以商品名F120系列或F-180系列从化大赛高(北京)科技股份有限公司(HDSG Beijing Technology)或化大赛高(烟台)科技有限公司(HuadaSaigao[Yantai]Science&Technology Company Limited)获得。
溴组分包括至少80wt％的溴。溴可以在冰醋酸(HOAc)中提供。例如，溴与HOAc或用于引入溴的任何等效溶剂的重量比可以为4:1至20:1。所使用的溴可以用水密封以使溴的挥发降低和/或最小化。为了实现这点，痕量的Br2可以与水反应(Br2+H2O＝HBr+HBrO)，并且可以添加冰醋酸来使反应最小化/得到抑制。溴组分可以基本上由溴和HOAc或用于在其中引入溴的任何等效溶剂组成。
添加剂组分氨基醇和/或多聚甲醛。添加剂组分还可以包括至少一种溶剂例如水和/或酸中和剂。氨基醇和多聚甲醛的比例可以为0.8至1.5。
溴组分与腰果酚组分的比例可以为1.5至3.5。溴组分与氨基醇的比例可以为0.8至3.0。溴组分与多聚甲醛的比例可以为0.8至3.0。
用于形成阻燃剂多元醇的反应体系还可以包括任选的酚或酚衍生物组分。任选的酚或酚衍生物组分包括至少一种酚和/或至少一种酚衍生物。反应性混合物可以以反应性混合物中该酚或酚衍生物的摩尔与腰果酚的摩尔之比为0.5:1.5至1.5:0.5(例如，0.8:1.2至1.2:0.8、0.9:1.1至1.1:0.9等)的摩尔比包括任选的酚或酚衍生物组分。例如，所使用的腰果酚的摩尔量可以基于所使用的酚或酚衍生物的摩尔量减少。示范性酚衍生物包括基于萘酚的化合物、基于苯酚的化合物和基于六氯酚的化合物。
关于形成阻燃剂多元醇，工艺可以包括至少两个阶段。在第一阶段，将添加剂组分(例如，包括氨基醇和多聚甲醛的添加剂组分)加热至至少70℃(例如75℃至150℃、75℃至125℃、80℃至120℃、和/或85℃至105℃)的温度。在至少1小时(例如1.5小时至10.0小时和/或1.5小时至4.0小时)之后，将腰果酚组分添加至其中具有添加剂组分的经加热混合物。使所得混合物反应例如至少1.0小时(例如1.5小时至12.0小时、2.0小时至8.0小时、3.0小时至7.0小时和/或5.0小时至7.0小时)。在第二阶段，将溴组分添加至来自第一阶段的经反应的所得混合物。溴组分可以以逐滴的方法添加。可以使所得溴化混合物反应至少1.0小时(例如1.5小时至96小时、12.0小时至84小时、24小时至72小时、35小时至55小时、和/或40小时至50小时)。
例如，形成阻燃剂多元醇具有以下两个阶段：(1)通过使用脱羧CNSL、二乙醇胺(DEA)和甲醛经由Mannich反应制备腰果酚Mannich基础多元醇(CMBP)；和(2)利用最终的FR多元醇以特定比例溴化CMBP以形成FR-CMBP。
阻燃剂多元醇的用途
阻燃剂多元醇可以用作用于形成诸如硬质聚氨酯泡沫的产品的聚氨酯系统的异氰酸酯反应性组分的一部分。聚氨酯系统可以是单组分系统或双组分系统。在单组分系统中，可以使用异氰酸酯反应性组分和一种或多种聚异氰酸酯来制备异氰酸酯封端的预聚物。在双组分系统中，可以使异氰酸酯反应性组分与包括至少一种异氰酸酯的异氰酸酯组分反应。用于双组分系统的异氰酸酯可包括更多的聚异氰酸酯和/或一种或多种异氰酸酯封端的预聚物(其中异氰酸酯封端的预聚物可以在使用阻燃剂多元醇或不使用阻燃剂多元醇的情况下制备)。
除了阻燃剂多元醇之外，异氰酸酯反应性组分可以包括额外的(多种)多元醇和/或(多种)添加剂。以异氰酸酯反应性组分的总重量计，异氰酸酯反应性组分可以包括5wt％至30wt％的阻燃剂多元醇、至少50wt％的多元醇组分，任意的可选剩余物可以为一种或多种添加剂。异氰酸酯反应性组分的多元醇组分包括与阻燃剂多元醇不同的至少一种多元醇。例如，以异氰酸酯反应性组分的总重量计，多元醇组分可以包括30wt％至70wt％的具有至少为5的标称平均羟基官能度的至少一种高官能性聚醚多元醇。多元醇组分可以包括10wt％至35wt％的具有为2至4的标称平均羟基官能度的至少一种低官能性聚醚多元醇。
示范性添加剂包括固化剂、催化剂、表面活性剂、增塑剂、填料、溶剂、硬化剂、增链剂、交联剂、和/或所属领域已知用于聚氨酯产品(例如硬质聚氨酯泡沫)的添加剂。基于聚氨酯系统的期望粘度，可以包括溶剂(例如甲苯)作为添加剂。溶剂可以是在固化过程中会挥发和/或基本上不会影响或可以改善最终固化组合物的力学性能的低蒸气压溶剂。示范性催化剂包括：包括叔胺、由仲胺形成的Mannich碱、含氮碱、碱金属氢氧化物、碱的酚盐、碱金属醇盐、六氢三嗪和有机金属化合物的催化剂。可以以聚氨酯系统总重量计0.001wt％至10wt％的量添加催化剂。催化剂可以加速异氰酸酯部分(可以在异氰酸酯组分中或在预聚物中)和反应性氢(可以是多元醇和/或增链剂)的固化时间以提供力学性能。可以在添加剂组分中包括燃料和/或色素(例如二氧化钛和/或炭黑)以赋予聚氨酯产品颜色性能。色素可以为固体或树脂载体中的分散体的形式。可以使用增强物(例如薄片状或磨碎的玻璃和/或烟雾硅胶)来赋予某些性能。其它添加剂包括例如紫外稳定剂、抗氧化剂、脱泡剂和促粘剂，它们可以根据期望的聚氨酯涂层特性单独使用。
在示范性实施例中，添加剂组分(或整个聚氨酯系统)可以不包括反应任何固体阻燃剂、液体阻燃剂和阻燃剂共混物。例如，聚氨酯系统中的唯一阻燃剂可以被包括作为反应性阻燃剂多元醇的一部分。在示范性实施例中，聚氨酯硬质泡沫可以在不使用有机阻燃剂添加剂如三(2-氯丙烯)(也称为TCPP)和磷酸三乙酯(也称为TEP)的情况下满足有关针对器具的阻燃性的严格要求。
关于单组分聚氨酯系统和双组分聚氨酯系统，异氰酸酯是指聚异氰酸酯(例如至少一种聚异氰酸酯)和/或得自至少一种聚异氰酸酯的异氰酸酯封端预聚物(例如基于至少一种异氰酸酯封端聚氨酯的预聚物)。示范性聚异氰酸酯包括二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)、间苯二异氰酸酯、对苯二异氰酸酯(PPDI)、萘二异氰酸酯(NDI)、异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、及其各种异构体和/或衍生物。使用其2,4'-、2,2'-、和4,4'-异构体中的至少一种，MDI可以具有聚合物、共聚物、混合物或改性聚合物的形式。示范性MDI产品可以以商品名ISONATE、PAPI和VORANATE由陶氏化学公司(Dow Chemical Company)获得。使用其2,4和2,6-异构体中的至少一种，TDI可以具有聚合物、共聚物、混合物或改性聚合物的形式。示范性TDI产品可以以商品名VORANATE由陶氏化学公司获得。
用了形成聚氨酯产品(例如使用双组分系统)，异氰酸酯指数可以为0.9至3.5。异氰酸酯指数是存在的异氰酸酯基团(即NCO部分)的等价物除以存在的包含异氰酸酯反应性氢的基团(即OH部分)的总等价物。换言之，异氰酸酯指数是式中存在的异氰酸酯基团与异氰酸酯反应性氢原子之比。因而，异氰酸酯指数表示式中实际使用的异氰酸酯与理论上用于与式中使用的异氰酸酯反应性氢的量反应的异氰酸酯的量之比。
根据示范性实施例，在异氰酸酯反应性组分中可以使用基于环氧丙烷-丙三醇的多元醇、基于聚(四亚甲基醚)乙二醇的多元醇、基于聚丙二醇的多元醇、和/或基于聚丁二烯的多元醇。另一示范性多元醇具有至少50wt％的聚氧化亚丁基含量(例如环氧丁烷-环氧丙烷多元醇)。例如，在异氰酸酯反应性组分中和/或异氰酸酯组分中可以使用基于环氧丙烷的聚醚(例如可以以商品名VORANOLTM从陶氏化学公司获得的一种)、天然油源多元醇(例如蓖麻油)和/或疏水性多元醇(例如可以以VORANOLTM从陶氏化学公司获得的一种)以形成预聚物。
所有的百分比都是以重量计，除非另有相反的说明。所有的分子量值都是基于数均分子量，除非另有相反的说明。
实例
以下材料是在实例中主要使用的材料：
CNSL馏出物腰果壳液，其包括大于95wt％的腰果酚(可以作为HD-9603由化大赛高(烟台)科技有限公司获得)。
PFA多聚甲醛具有95％的纯度(可由国药集团化学试剂有限公司(SinopharmChemical Reagent Co.,Ltd)获得)。
DEA二乙醇胺，具有98％的纯度(可由国药集团化学试剂有限公司获得)。
溴溴，具有99％的纯度(可由国药集团化学试剂有限公司获得)。溴以1摩尔溴(160克)比20mL(21克，密度为1.05g/mL)HOAc的比例在冰醋酸(HOAc)中提供。
CCl4四氯甲烷，具有99％的纯度(可由国药集团化学试剂有限公司获得)。
多元醇A山梨糖醇引发的丙氧基化多元醇，其具有为6的标称平均羟基官能度和480mg KOH/g的大致羟基数(可以作为VORANOLTM RN482由陶氏化学公司获得)。
多元醇B丙氧基化乙二胺多元醇，其具有为4的标称平均羟基官能度和640mg KOH/g的大致羟基数(可以作为VORANOLTM RA640由陶氏化学公司获得)。
多元醇C丙三醇引发的丙氧基化多元醇，其具有为3的标称平均羟基官能度和160mg KOH/g的大致羟基数(可以作为VORANOLTM CP1055由陶氏化学公司获得)。
FR共混物阻燃剂多元醇共混物，其包括阻燃剂、多元醇和液体磷酸酯，使得存在四溴酞酸酐和磷酸酯的二酯/醚二醇(可以作为共混合物以商品名
Figure GDA0002155349110000091
RB-79由Albemarle获得)。
CAT1基于N,N,N,N,N-五甲基二亚乙基三胺的催化剂(可以作为
Figure GDA0002155349110000092
5由空气产品公司(Air Products)获得)。
CAT2基于N,N-二甲基环己胺的催化剂(可以作为
Figure GDA0002155349110000093
8由空气产品公司获得)。
CAT3基于三-2,4,6-二甲基氨基-甲基-苯酚的催化剂(可以作为
Figure GDA0002155349110000101
TMR-30由空气产品公司获得)。
表面活性剂硅酮表面活性剂(可以以编号AK8852由Dymatic[Dearmate]获得)。
BA1基于氢氯氟烃的起泡剂(可以作为HCFC-141b由杜邦公司(DuPont)获得)。
BA2水
异氰酸酯聚合亚甲基二苯基二异氰酸酯，即PMDI(可以作为PAPITM 27由陶氏化学公司获得)。
阻燃剂腰果酚改性的溴化多元醇的合成
示范性的阻燃剂腰果酚改性溴化多元醇(FR-CMBP)结构以1Br-C-M和2Br-C-M示意性表示(该结构可以通过1H-NMR证实，其中R是C15H31–n，其中n＝0、2、4、或6，如基于腰果酚和腰果壳液的说明理解的)。具体而言，FR-CMBP可以在两阶段工艺中获得。
Figure GDA0002155349110000102
例如，利用下表1中的各大致配方制备了FR-CMBP 1、FR-CMBP 2和FR-CMBP 3的工作实例。
表1
Figure GDA0002155349110000103
Figure GDA0002155349110000111
关于两阶段工艺，首先，在圆形烧瓶中将PFA-多聚甲醛(也称为x当量)和DEA-二乙醇胺(也称为y当量)的混合物加热至90℃。在2小时之后，将CNSL馏出物添加至经加热的混合物中。在6小时之后，终止反应并且将烧瓶中的反应混合物冷却至室温。其次，将CCl4作为溶剂添加至冷却的烧瓶，并且在室温下将溴在HOAc(醋酸)中的溶液(也被称为z当量)逐滴添加到反应体系中。在逐滴添加完成之后，将混合物加热回流48小时。在减压下浓缩粗混合物，用水洗涤，用乙酸乙酯萃取，然后用饱和碳酸氢钠(NaHCO3)急冷。之后，在无水硫酸钠上干燥所得材料并且在减压下浓缩以获得溴化腰果酚。
聚氨酯硬质泡沫的形成
根据下表2中的各大致配方，制备工作实例1、2和3和对比例A的聚氨酯泡沫样品。
表2
Figure GDA0002155349110000121
为了测量膏化时间和凝胶时间，制备自由发泡面包来测量系统反应性。膏化时间是异氰酸酯组分和异氰酸酯反应性组分的混合开始和发泡开始之间的时间。凝胶时间是其中被引入混合物中和从混合物中拔出时泡沫形成反应性混合物会粘附至探针的时间。作为成型泡沫的内密度测量芯密度，通过水置换法测量自由发泡密度(FRD)。根据ISO-844测量耐压强度。根据EN 12667测量热导率(k-因子)。根据GB/T 2406以百分比测量极限氧指数(LOI)。LOI是以百分比表示的、支持(维持垂直安装样品测试条燃烧所需的)材料燃烧的最低氧浓度。它是通过以下方式测量的：使氧和氮的混合物穿过燃烧样品上方，并且降低氧水平，直至达到临界水平。相应地，LOI是材料可燃性的测试方法。较高的LOI值对应于较高的阻燃剂性能。为了测试硬质聚氨酯泡沫，将样品切割成1cm x 1cm x 15cm的片，该片被固定在样品架上。然后，用顶部带孔的玻璃罩覆盖样品，并且从顶部点着样品。

Claims (8)

1.一种反应体系，其包含：
阻燃剂多元醇，所述阻燃剂多元醇是腰果酚组分、溴组分和添加剂组分的溴化反应产物，所述腰果酚组分包括以所述腰果酚组分总重量计至少80wt％的腰果酚，且所述溴组分包括以所述溴组分总重量计至少80wt％的溴，其中所述添加剂组分包括氨基醇和选自醛和酮中的至少一种，其中所述阻燃剂多元醇通过两个阶段形成：
(1)通过使用脱羧CNSL、二乙醇胺和甲醛经由Mannich反应制备腰果酚Mannich基础多元醇；
(2)利用最终的FR多元醇以特定比例溴化所述腰果酚Mannich基础多元醇以形成阻燃剂腰果酚改性的溴化多元醇结构；
所述溴组分与所述腰果酚组分之比为1.5至3.5，和
所述溴组分与所述氨基醇之比为0.8至3.0，
其中所述阻燃剂腰果酚改性的溴化多元醇结构选自单溴-腰果酚-Mannich基础多元醇和二溴-腰果酚-Mannich基础多元醇。
2.根据权利要求1所述的反应体系，其还包含异氰酸酯组分和异氰酸酯反应性组分，其中：
所述异氰酸酯组分包含至少一种异氰酸酯，其异氰酸酯指数为0.9至3.5，和
所述异氰酸酯反应性组分包括以所述异氰酸酯反应性组分总重量计5wt％至30wt％的所述阻燃剂多元醇和至少50wt％的多元醇组分，所述多元醇组分包括与所述阻燃剂多元醇不同的至少一种多元醇。
3.根据权利要求2所述的反应体系，其中所述多元醇组分包括以所述异氰酸酯反应性组分总重量计30wt％至70wt％的至少一种高官能性聚醚多元醇，所述至少一种高官能性聚醚多元醇具有至少为5的标称平均羟基官能度。
4.根据权利要求2所述的反应体系，其中所述多元醇组分包括以所述异氰酸酯反应性组分总重量计10wt％至35wt％的至少一种低官能性聚醚多元醇，所述至少一种低官能性聚醚多元醇具有2至4的标称平均羟基官能度。
5.根据权利要求1所述的反应体系，其中反应不包括任何固体阻燃剂、液体阻燃剂和阻燃剂共混物。
6.一种使用根据权利要求1至5中任一权利要求所述的反应体系来制备硬质聚氨酯泡沫的方法。
7.一种利用根据权利要求1至5中任一权利要求所述的反应体系制备的硬质聚氨酯泡沫。
8.一种包括利用根据权利要求1至5中任一权利要求所述的反应体系制备的硬质聚氨酯泡沫的器具。
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