CN113631607A - 聚氨酯及其制造方法 - Google Patents
聚氨酯及其制造方法 Download PDFInfo
- Publication number
- CN113631607A CN113631607A CN202080024684.2A CN202080024684A CN113631607A CN 113631607 A CN113631607 A CN 113631607A CN 202080024684 A CN202080024684 A CN 202080024684A CN 113631607 A CN113631607 A CN 113631607A
- Authority
- CN
- China
- Prior art keywords
- weight
- prepolymer
- polyurethane polymer
- mannich base
- isocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 238000000034 method Methods 0.000 title claims description 18
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- 150000003077 polyols Chemical class 0.000 claims abstract description 55
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 46
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 21
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 21
- 239000012948 isocyanate Substances 0.000 claims description 35
- 150000002513 isocyanates Chemical class 0.000 claims description 34
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- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
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Abstract
聚氨酯是通过以下制成的,在一个或多个反应步骤中使a)至少一种有机聚异氰酸酯、b‑1)一种或多种羟基当量重量大于250g/mol且标称羟基官能度为2至4的多元醇和b‑2)至少一种烷氧基化曼尼希碱反应,以生产出密度为至少750kg/m3并且硬段含量为20至80重量%的聚氨酯聚合物。
Description
本发明涉及聚氨酯及制造它们的方法。
弹性聚氨酯广泛用于许多涂料、粘合剂、密封剂和弹性体(“CASE”)应用。
聚氨酯在许多情况下是有机聚异氰酸酯、端羟基增链剂和羟基当量重量大于250的聚醚多元醇的反应产物。聚醚多元醇通常具有对异氰酸酯基团反应缓慢的仲羟基。为此,反应通常被催化。最普遍的氨基甲酸酯催化剂是金属催化剂(诸如锡、汞和锌催化剂)以及低分子量胺催化剂(诸如某些叔胺和二氮杂化合物)。一般而言,已发现这些催化剂对于提供经济上可行的固化速率是必要的。
在一些情况下,消除催化剂是有益的,有重要原因。如果不需要催化剂,成本会降低。许多金属催化剂与环境和/或健康和安全问题有关。
若干问题与胺催化剂有关。它们通常是吸湿的并且有时是对湿气敏感的。非反应性低分子量胺催化剂通常具有一定的挥发性,并且可导致气味以及产品中挥发性有机化合物(VOC)的存在。此外,胺催化剂的存在通常减少前体(特别是端异氰酸酯预聚物)的保存期限。
此外,聚氨酯中的催化剂残余物可以催化(特别是在较高温度下)解聚反应。在固化产品的正常使用期间有时遇到这些较高的温度。有时聚氨酯用于高温环境或暴露于短暂的温度偏移。在其他情况下,聚氨酯用于外部和内部摩擦可将聚合物加热至高温的动态应用。暴露于高温可导致解聚,从而降低性能或导致材料失效。
需要一种在基本上不存在金属和/或低分子量的胺氨基甲酸酯催化剂的情况下制造聚氨酯的方法。所述方法应在相当短的固化时间内生产出具有良好性质和良好高温稳定性的聚氨酯。在这个过程中生产的聚氨酯优选具有良好的高温性质。
本发明的一个方面是一种密度为至少750kg/m3的聚氨酯聚合物,其为包括以下的反应物的反应产物:
a)至少一种有机聚异氰酸酯和
b)多元醇,其包括
b-1)一种或多种羟基当量重量大于250g/mol且标称羟基官能度为2至4的多元醇和
b-2)一种或多种羟基当量重量为至多250的多元醇,其中至少50重量%的b-2)是至少一种平均羟基官能度为2至7的烷氧基化曼尼希碱;
其中聚氨酯聚合物的硬段含量为聚氨酯聚合物的20-80重量%。
本发明还是一种用于制造聚氨酯聚合物的方法,其包括在一个或多个步骤中使反应物反应,所述步骤包括异氰酸酯指数为90至150的最终固化步骤,所述反应物包括
a)至少一种有机聚异氰酸酯;和
b)多元醇,其包括b-1)至少一种羟基当量重量大于250g/mol的多元醇,和b-2)一种或多种羟基当量重量为至多250的多元醇,其中至少50重量%的b-2)是至少一种平均羟基官能度为2至7的烷氧基化曼尼希碱;
其中聚氨酯聚合物的硬段含量为聚氨酯聚合物的20-80重量%,并且聚氨酯聚合物的密度为至少750kg/m3。
本发明具有重要的优势。即使在不存在金属和/或胺氨基甲酸酯催化剂的情况下,烷氧基化曼尼希碱对异氰酸酯基团的反应也以商业上有用的速率进行;因此,此类催化剂可以被消除或仅以非常少的量使用。聚氨酯聚合物具有良好的机械和热性质,在一些情况下优于用其他不含胺基团的交联剂或固化剂制成的聚合物。可以生产出空隙体积非常低的聚氨酯。聚合物的热性质意外地好。
有机聚异氰酸酯的平均官能度优选地为约1.9至4,并且更优选地为2.0至3.0、2.0至2.5或2.0至2.3。在一些实施方案中,异氰酸酯平均当量重量可为约80至250,更优选地为80至200,并且仍更优选地为125至175。聚异氰酸酯可为芳香族的、脂肪族的和/或脂环族的。聚异氰酸酯的实例包括例如间苯二异氰酸酯、2,4-和/或2,6-甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)的各种异构体、六亚甲基-1,6-二异氰酸酯、四亚甲基-1,4-二异氰酸酯、环己烷-1,4-二异氰酸酯、六氢甲苯二异氰酸酯、氢化MDI(H12 MDI)、萘-1,5-二异氰酸酯、甲氧基苯基-2,4-二异氰酸酯、4,4'-联苯二异氰酸酯、3,3'-二甲氧基-4,4'-联苯二异氰酸酯、3,3'-二甲基二苯基甲烷-4,4'-二异氰酸酯、4,4',4”-三苯基甲烷三异氰酸酯、聚亚甲基聚苯基异氰酸酯、氢化聚亚甲基聚苯基异氰酸酯、甲苯-2,4,6-三异氰酸酯和4,4'-二甲基二苯基甲烷-2,2',5,5'-四异氰酸酯。优选的聚异氰酸酯包括MDI和MDI的衍生物,诸如缩二脲修饰、脲酮亚胺修饰和/或碳二亚胺修饰的“液体”MDI产物和聚合MDI。“聚合MDI”是MDI(任何异构体或异构体的混合物)与一种或多种具有三个或更多个苯基异氰酸酯基的聚亚甲基聚苯基异氰酸酯的混合物。“聚合MDI”的异氰酸酯当量重量例如为126至150,并且数均异氰酸酯官能度为2.05至3.5,尤其是2.2至3.2或2.2至2.8。“液体”MDI的平均官能度可为2.01至2.2并且异氰酸酯当量重量为126至150,尤其是140至150。
可以使用两种或更多种有机聚异氰酸酯的混合物。
多元醇b)包括b-1)一种或多种羟基当量重量大于250g/mol且标称羟基官能度为2至4的多元醇。
在一些实施方案中,多元醇b-1)的羟基当量重量可为至少400、至少450、至少500、至少700或至少900,并且至多5000、至多4000、至多3000、至多2000、至多1500或至多1200。在一些实施方案中,多元醇b-1)的标称羟基官能度为2至3。
在一些实施方案中,多元醇b-1)为一种或多种聚醚。这种聚醚可以是氧化烯诸如氧化乙烯、1,2-氧化丙烯、1,2-氧化丁烯、2,3-氧化丁烯和四氢呋喃的均聚物或者两种或更多种氧化烯的共聚物。如果是共聚物,则聚醚多元醇b-1)可为嵌段和/或无规共聚物以及封端共聚物。氧化丙烯的均聚物、氧化丙烯与至多20重量%的氧化乙烯的共聚物(基于所有氧化烯的重量)以及氧化丙烯和氧化丁烯的无规和/或嵌段共聚物都是有用的。
其他有用的多元醇b-1)包括聚酯多元醇、端羟基聚(丁二烯)多元醇、聚丙烯酸酯多元醇等,其羟基官能度和羟基当量重量如上文所述。
在一些实施方案中,b-1)多元醇的羟基中至少50%、至少70%或至少80%是伯羟基。
b-2)多元醇的羟基当量重量为至多250。在一些实施方案中,b-2多元醇当量重量为至多200、至多150或至多130。至少50重量%的b-2)为至少一种烷氧基化曼尼希碱,其平均羟基官能度为2至7,优选为3至5。烷氧基化曼尼希碱可以构成所有b-2)多元醇的总重量的至少75%、至少90%、至少95%或至少99%,并且可为唯一的b-2)多元醇。
烷氧基化曼尼希碱为酚、甲醛和烷醇胺的烷氧基化反应产物。烷醇胺可为例如:二烷醇胺,诸如二乙醇胺、乙醇异丙醇胺、乙醇-2-羟基丁胺、二异丙醇胺、异丙醇-2-羟基丁胺、二异丁醇胺、异丙醇-2-羟基己胺、乙醇-2-羟基己胺等;N取代的单烷醇胺,诸如N-甲基乙醇胺、N-乙基乙醇胺、N-甲基异丙醇胺、N-乙基异丙醇胺、N-甲基-2-羟基丁胺、N-苯基乙醇胺等;或单烷醇胺,诸如单乙醇胺或单异丙醇胺。
酚为至少一个羟基直接键合至芳环的环碳上的化合物。酚可以是酚本身、取代的酚或也可以被取代的多酚。取代的酚或多酚可以被例如一个或多个具有1至18个碳原子的烃基取代。任何这样的烃基可以是直链的、支链的和/或环状的并且可以是饱和的或不饱和的。特别感兴趣的是烷基和具有一个或多个碳-碳双键的烯基。酚化合物的实例包括苯酚、甲酚、二甲苯酚、儿茶酚、丙基苯酚、丁基苯酚、戊基苯酚、庚基苯酚、辛基苯酚、壬基苯酚、十二烷基苯酚、腰果酚、强心酚、甲基强心酚、对苯基苯酚等。
苯酚、甲醛和烷醇胺参与缩合反应以形成含有羟基(一个酚羟基和一个或多个脂肪族羟基)的曼尼希碱。曼尼希碱的羟基被烷氧基化以产生烷氧基化曼尼希碱。
在一些实施方案中,烷氧基化曼尼希碱由以下结构表示:
其中每个R独立地为氢、具有1至18个碳原子的直链或支链烷基或具有1至18个碳原子的直链或支链烯基,m为0至2的数,每个R1独立地为氢或具有1至6个、优选地1至2个碳原子的直链或支链烷基,每个n为使羟基当量重量为至多250的数字,x为1至3的数字,R2为氢、具有1至6个、优选地1至3个碳原子的烷基、苯甲基或苯基,o为1至4的数字,并且p为0或1。R优选地为C6-16烷基,尤其是C6-12烷基,每个R1独立地优选为氢或甲基,并且每个n优选为1或2。p优选为零。m优选为1。o优选为1至2。x优选为1或2。每个R2,当存在时,优选为C1-3烷基。
在一些实施方案中,烷氧基化曼尼希碱为丙氧基化和/或乙氧基化曼尼希碱,其中曼尼希碱为烷基酚或烯基酚(其中烷基或烯基具有1-18个碳原子)、甲醛和二乙醇胺的缩合产物,并且其中x使得烷氧基化曼尼希碱的平均官能度为3至5或3至4。
其他b-2)多元醇,当存在时,包括每分子具有2至8个,优选地2至4个或2至3个羟基并且当量重量如上文所述的化合物。这些实例包括例如甘油、乙二醇、丙二醇、二丙二醇、二乙二醇、山梨糖醇、庚七醇、苏糖醇、核糖醇、甘露糖醇、麦芽糖醇、艾杜糖醇、岩藻糖醇、半乳糖醇、阿拉伯糖醇、赤藓糖醇、季戊四醇、三羟甲基丙烷、三异丙醇胺、三乙醇胺和双(羟甲基)哌嗪,以及当量重量不大于250的其烷氧基化物。此类其他b-2)多元醇优选不含有任何胺基团。用于本发明目的的胺基团为含有具有孤电子对的碱性氮原子的基团。
组分b-2),并且特别是烷氧基化曼尼希碱,可以构成例如组分a)、b-1)和b-2)的总组合重量的5至60%。在一些实施方案中,烷氧基化曼尼希碱构成组分a)、b-1)和b-2)的组合重量的7.5%至50%、或10%至50%、或20%至50%。
产生本发明的聚氨酯的反应物可包括(除多元醇b-1)和b-2)之外)一种或多种其他异氰酸酯反应性材料,诸如分子量大于350的含有一个或多个伯氨基和/或仲氨基的化合物以及具有两个或多个环氧基的化合物。如果存在的话,此类其他异氰酸酯反应性材料优选构成所有有机聚异氰酸酯和异氰酸酯反应性成分的总组合重量的不多于10重量百分比、更优选不多于5重量百分比或不多于2重量百分比。可以不存在此类其他异氰酸酯反应性材料。
本发明的聚氨酯可以通过使有机聚异氰酸酯与异氰酸酯反应性化合物在一个或多个步骤中反应来生产。
因此,在本发明的一个实施方案中,反应在单个步骤中进行,在所述步骤中将有机异氰酸酯和所有异氰酸酯反应性化合物(包括如上文所述的多元醇b-1)和b-2))全部组合以形成反应混合物,然后固化以形成聚氨酯。在这样的实施方案中,单个步骤为所述过程的“最终”固化步骤,并且异氰酸酯指数为90至150。“异氰酸酯指数”为向反应混合物中提供的异氰酸酯基与异氰酸酯反应性基团之比的100倍。异氰酸酯指数可为至少95或至少98,并且可为至多135、至多110、至多105或至多102。
在替代实施方案中,使一些或全部多元醇b-1)与有机聚异氰酸酯预反应以形成含有异氰酸酯基的预聚物或准预聚物。预聚物或准预聚物的异氰酸酯含量可为例如1至20重量百分比。在一些实施方案中,异氰酸酯含量可为至少2.5%或至少4%,且至多15%、至多12%或至多10%。在最终固化步骤中,使预聚物或准预聚物与多元醇b-2)和多元醇b-1)的任何剩余部分以90至150的异氰酸酯指数反应以生产聚氨酯。如前所述,异氰酸酯指数可为至少95或至少98,并且可为至多135、至多110、至多105或至多102。
在又一替代实施方案中,使一些或全部多元醇b-2)与有机聚异氰酸酯预反应以形成含有异氰酸酯基的“硬段”预聚物或准预聚物。硬链段预聚物或准预聚物的异氰酸酯含量可为例如5至30重量百分比。在一些实施方案中,这种硬段预聚物的异氰酸酯含量为至少7.5%或至少10%,且至多25%、至多22%或至多20%。在最终步骤中,使硬段预聚物或准预聚物与多元醇b-1)和多元醇b-2)的任何剩余部分以90至150的异氰酸酯指数反应以生产聚氨酯。最终固化步骤中的异氰酸酯指数如关于先前实施方案所述。
在预聚物过程中,还可以通过使有机异氰酸酯与多元醇b-1)和b-2)的混合物反应来形成预聚物,然后进行最终固化步骤,在所述步骤中使所得预聚物与剩余的多元醇b-1)和/或b-2)反应以形成聚氨酯。最终固化步骤中的异氰酸酯指数如关于先前实施方案所述。
在前述过程中的任一种中,选择反应物的比例使得聚氨酯的硬段含量为20至80重量%。硬段含量计算如下:
其中Wtiso为起始聚异氰酸酯化合物的重量;Wtce为每个异氰酸酯反应性基团的当量重量为250或更低的所有起始异氰酸酯反应性化合物(包括多元醇b-2)的重量,并且Wt反应物为所有起始聚异氰酸酯化合物和所有异氰酸酯反应性化合物的总组合重量。在一些实施方案中,硬段含量为至少30重量%且至多65重量%、至多55重量%或至多50重量%。
在其中唯一的异氰酸酯反应性化合物为多元醇b-1)和b-2)的优选实施方案中,硬段含量等于:
100%×[(Wtiso+Wt多元醇b-2))÷{Wtiso+Wt多元醇b-2)+Wt多元醇b-1)}]。
本发明的优势在于金属和胺氨基甲酸酯催化剂不是必需的并且可以省略。因此,在一些实施方案中,聚氨酯(和预聚物或准预聚物,如果制备的话)是在基本上不存在这种氨基甲酸酯催化剂的情况下制成的。在特定实施方案中,每个反应步骤中的反应混合物以及聚氨酯反应产物含有不多于20重量份/百万重量份反应混合物(ppm)的锌、锡和汞的组合,并且更优选地不多于10ppm或5ppm,并且不多于0.1重量%、不多于0.05重量%或不多于0.025重量%(基于反应混合物的重量)的分子量低于350的含胺基团化合物(除本文所述的烷氧基化曼尼希碱之外)。在此类实施方案中,反应混合物可含有不多于0.1重量百分比、不多于0.05重量百分比或不多于0.025重量百分比(基于反应混合物的重量)的任何除烷氧基化曼尼希之外的含胺基团化合物。在其他特定实施方案中,各种反应步骤中每一个中的反应混合物优选含有不多于20ppm的金属,并且更优选地不多于10ppm或5ppm,并且另外含有不多于0.1重量百分比、不多于0.05重量百分比或不多于0.025重量百分比除烷氧基化曼尼希碱之外的分子量低于350的含胺基团化合物。在此类其他特定实施方案中,反应混合物可含有不多于0.1重量百分比、不多于0.05重量百分比或不多于0.025重量百分比(基于反应混合物的重量)的任何除烷氧基化曼尼希碱之外的含胺基团化合物。本发明的聚氨酯优选含有对应少量的此类金属和此类低分子量非异氰酸酯反应性含胺基团化合物。
聚氨酯的密度为至少750kg/m3,优选地900kg/m3并且更优选地至少1000kg/m3。它优选为非多孔或微孔的,空隙体积为至多25%、至多10%、至多5%、至多2%、至多1%或至多0.5%。在一些实施方案中,最终固化步骤在不存在水和物理发泡剂的情况下进行。在特别优选的实施方案中,最终固化步骤还在不存在夹带气体的情况下进行。例如,可以进行对在最终固化步骤中所用的反应物进行脱气的步骤以在最终固化步骤之前从中除去夹带气体。
如果需要,在最终固化步骤期间可存在少量物理发泡剂和/或夹带气体以降低密度,如当生产微孔聚氨酯时。可以将空气、二氧化碳、氮气或其他气体搅入最终固化步骤的反应混合物中以形成泡沫,将其固化以形成微孔弹性体。
各种反应步骤可在略低于室温(诸如0℃或更高,但优选地至少10℃或至少15℃)至多达120℃的温度范围内进行。如果在最终固化步骤之前进行预聚物形成步骤,在预聚物制造步骤期间使用升高的温度诸如至少50℃并且例如至多90℃、至多80℃或至多70℃通常是有利的。最终固化步骤通常在环境温度或略微升高的温度(诸如10℃至45℃,尤其是15℃至35℃)下进行,特别是在最终聚氨酯产品为固化粘合剂、密封剂或涂料的情况下。最终固化步骤可以在高温下进行,诸如针对预聚物形成步骤所描述;使用这种略微较高的固化温度(尤其是在制造模制或涂覆产品时)以加快固化速度并缩短生产设备的循环时间通常是有利的。
当进行预聚物形成步骤时,反应通常持续直到达到恒定的异氰酸酯含量,指示所有异氰酸酯反应性化合物被消耗。最终固化步骤通常持续直到聚氨酯达到恒定的机械性质。最终固化步骤可以持续例如至少5分钟、或至少30分钟并且至多7天或甚至更长时间,但从实现商业上合理的反应速率和增加设备利用的角度来看,较短的固化时间诸如至多3小时或至多2.5小时通常是优选的,尤其是在制造模制零件或涂层时。最终固化步骤可以在超大气压力诸如至少2000psi(13.8MPa)或更大压力下进行,以防止单元形成并形成致密的产品。模制聚氨酯可以在模具中固化,直到它具有足以脱模而不损坏或永久变形的生坯强度;在这种情况下,聚氨酯可以在环境温度和/或高温下进行后固化,如刚才所述,以进一步完成固化并发展机械和其他性质。
最终固化步骤中的反应混合物可含有各种任选的成分。这些包括例如增塑剂(反应性和非反应性)、稀释剂、分散剂、阻燃剂、着色剂诸如颜料和染料;微粒增强剂和填料诸如各种粘土、碳酸钙、二氧化硅、石英、氧化铝、滑石、硅灰石、云母、炭黑、石墨和其他微粒含碳材料、二氧化钛、氧化铁、氧化铬、磨碎的热固性聚合物等(应注意,这些增强剂中的某些也将起到着色剂的作用);短增强纤维(长度为例如约2至约150mm)消泡剂;脱模剂;抗微生物剂和其他防腐剂;粘合增进剂诸如反应性硅烷;抗氧化剂等。
当制造模制或成型浇注弹性体产品时,固化可以在可以是开放的或封闭的模具或其他形式中进行。它可以在皮带或其他设备上进行。可将反应混合物在基材上形成为层并在其上固化以形成复合材料。反应混合物可用于浸渍纤维材料,然后在适当的位置固化以形成纤维增强复合材料。
如果需要,可以将最终固化步骤中的反应混合物施加到基材以形成多层结构。在最终固化步骤中用反应混合物浸渍纤维基材诸如增强纤维垫,然后固化反应混合物以形成纤维增强复合材料也在本发明的范围内。
在某些实施方案中,根据本发明制造的聚氨酯被表征为如根据ASTM D1708所测量的断裂伸长率(干燥时)为至少40%的的柔性材料。伸长率可为至少100%、至少150%或至少200%。其拉伸强度可为至少5KPa、至少10KPa或至少20KPa。在一些实施方案中,如通过使用tanδ曲线的峰作为Tg的动态力学分析所测量的,聚氨酯的玻璃化转变温度(Tg)为至多0℃。
本发明的聚氨酯通常表现出优异的热性质。这些通过比较聚氨酯在150℃和200℃下的储能模量来证明,如以下文实施例中所述的方式通过动态力学分析所测量。本发明的优势在于储能模量的绝对值在150℃下趋于高(在给定%硬段下),并且当将聚氨酯进一步加热至200℃时,储能模量损失7little。
在具体实施方案中,150℃下的储能模量为至少5×107Pa、至少为7.5×107Pa或至少9.0×107Pa,并且200℃下的储能模量与150℃下的储能模量之比为至少0.75或至少0.85。在一些实施方案中,此比率为至少0.90。
本发明的浇注弹性体产品可以是静态或动态类型的,静态弹性体是在使用期间不经受频繁变形的产品(诸如衬垫材料和某些类型的辊),而动态弹性体是在使用时经受频繁变形的产品。本发明的弹性体可用作例如垫圈和密封件、管材、用于许多应用的辊,如涂布辊、轧辊、传动带、挤压辊、商用机辊、滑轮、输送机轮、叉车轮、三轮车轮、脚轮、工业轮胎、刮水器、扫雪机叶片、滑槽和旋风衬套、搅拌器叶片等等。
本发明可用作例如密封剂或粘合剂。为了用作密封剂或粘合剂,反应物优选被配制成双组分体系,一种组分含有聚异氰酸酯(更优选端异氰酸酯预聚物或准预聚物),并且另一种组分含有多元醇b-1)和b-2)中的至少一种。优选的密封剂或粘合剂制剂例如包括A)异氰酸酯组分,其包含异氰酸酯含量为至少1重量%、至少2.5重量%或至少4重量%至20重量%、15重量%、12重量%或10重量%的端异氰酸酯预聚物或准预聚物,它是多元醇b-1)与起始有机聚异氰酸酯的反应产物;B)包含多元醇b-2)或完全由其构成的固化剂组分。通过将A)和B)组分混合来形成反应混合物,优选地比率为使得异氰酸酯指数为至少90、至少95或至少98至至多150、至多115、至多110、至多105或至多102。将所得反应混合物施加到两个基材之间(或单个基材的部分内)的粘结层、接缝、裂缝或其他开口并在适当的位置固化,使得其粘附至一个或多个基材并且至少部分地密封开口和/或将基材粘结在一起。这样的粘合剂或密封剂可以配制成具有一种或多种用于例如赋予期望的流变和/或美学特征的填料和着色剂。固化通常在环境条件下进行,但是可以使用高温。
本发明的固化粘合剂和密封剂的特征通常为当根据ASTM 1002-01测量时具有意外的高搭接剪切强度。
通过将反应混合物施加到基材表面以形成膜并在基材上使膜固化以形成粘合剂涂层来形成涂层,粘合剂涂层通常是涂覆基材的暴露外表面。反应混合物可含有所有组分a)、b-1)和b-2),它们在一个步骤中反应以形成涂层。或者,反应混合物可含有如前所述的预聚物或准预聚物,以及组分b-1)和b-2)中的一种或两种。施加步骤通过诸如喷涂、刷涂或辊涂的方法方便地进行。固化可以在环境温度或高温下进行。本发明对于生产厚的保护涂层和/或生产柔软的表面特别有用。涂料组合物可以配制成包括颜料、染料和其他着色剂以及填料颗粒(也可以起着色剂的作用)、各种类型的流变改性剂等。
提供以下实施例以说明本发明,但不旨在限制本发明的范围。除非另外指示,否则所有份数和百分比都按重量计。
端异氰酸酯预聚物的制备
各种端异氰酸酯预聚物是通过将143当量重量的“液体”MDI产品与聚醚多元醇反应来制成的。在每种情况下,将聚异氰酸酯和多元醇在没有催化剂的情况下在密封干燥容器中混合,并在70℃下储存,偶尔搅拌,直到获得恒定的异氰酸酯浓度。聚醚多元醇和所得预聚物的特征如表1所示。
表1
1羟基当量重量。2异氰酸酯当量重量。
实施例1-4和比较样品A-D
通过在室温下将表1中所示的预聚物与羟基当量重量为119且羟基官能度为3.5的烷氧基化曼尼希碱混合制成实施例1-4,向其中添加了0.65%苯甲酰氯。烷氧基化曼尼希碱是通过将壬基酚、甲醛和二乙醇胺的曼尼希反应产物与氧化丙烯和氧化乙烯进行烷氧基化来制成的。反应混合物中不存在催化剂(除烷氧基化曼尼希碱产物之外)。除烷氧基化曼尼希碱产物之外,反应混合物含有少于20ppm的金属且不含胺化合物。异氰酸酯指数为约101。在充分混合之后,将反应混合物倒入6英寸×6英寸×0.015英寸(15.24cm×15.24cm×0.38mm)槽中,所述槽位于涂覆有脱模剂的0.38mm铝板上。第二块铝板位于填充的槽上方。使组件在60℃下于模压机中在压力下固化2小时。在物理性质测试之前,使固化的样品在环境条件(23±3℃)下静置一周。
比较样品A-D以相同的方式制成,用450数均分子量的聚(氧化丙烯)三醇代替烷氧基化曼尼希碱并添加0.05重量份(基于预聚物和增链剂的总重量)的有机锡催化剂。
根据ASTM D-1708进行拉伸测试。将预先称重的样品在室温下浸入去离子水中7天,去除表面水并重新称重样品之后,以相同的方式进行水老化拉伸测试。干燥样品的结果如表2所示,并且水老化样品的结果如表3所示。
通过动态力学分析,使用在1Hz和3℃/分钟的加热速率下以扭转模式操作的TAInstruments ARES G2流变仪来评估实施例1-3和比较样品A-D的热性质。将玻璃化转变温度视为tanδ曲线的峰值,并且报告于表2中。
表2-干燥样品性质
1在本表和后续表中,“曼尼希”是指烷氧基化曼尼希碱。
表3-水老化样品性质
如表2和表3中的数据所示,用烷氧基化曼尼希碱代替三醇增链剂导致水吸收减少以及在等效或更高的伸长率下拉伸强度和模量增加。尽管在本发明的实施例中不存在单独的氨基甲酸酯催化剂,但仍实现了这些结果。
通过DMA在150℃、175℃和200℃下测量实施例1-3和比较样品A-C中每一个的储能模量(G')。结果在表4中示出。
表4
所有比较样品都显示出储能模量在高于150℃的温度下的大幅降低。当从150℃加热至200℃时,比较样品A损失其多于85%的储能模量。比较样品B和C在相同的温度范围内损失其约75%和约60%的储能模量。
相比之下,实施例1-3不仅在相同温度下具有更高的储能模量(分别与对比样品A-C相比),而且在175℃和200℃下表现出更少的储能模量损失。当加热至200℃时,实施例1仅损失其约17%的150℃的储能模量;实施例2和3显示出甚至更小的损失。
当在高温应用中使用本发明的弹性体制成制品时,这些结果意味着性能和稳定性改良。
搭接剪切测试是使用实施例1和比较样品A进行的。1"x 6"x 0.2"(2.54×15.24×0.51cm)玻璃取样片用丙酮清洗并风干。玻璃取样片在距离末端2.0英寸(5.08cm)处做标记。标记区域涂覆有新鲜混合的反应混合物(实施例1或比较样品A),以及10密耳(0.254mm)玻璃间隔珠。将第二块玻璃取样片施加在反应混合物上并用金属夹固定。将边缘清洁。使样品在室温下固化一小时。去除夹子,将样品平放在60℃烘箱中2小时,然后在环境室温条件下保持7天。根据ASTM 1002-01测试样品。实施例1的搭接剪切强度为101psi(696kPa),而比较样品A的搭接剪切强度仅为64.5psi(445kPa)
实施例5-7和比较样品E和F
实施例5-7和比较样品E和F分别以与实施例1-4和A-D相同的一般方式制成。在实施例5-7中每一个中,除烷氧基化曼尼希碱产物之外,反应混合物含有小于20ppm的金属并且不含胺化合物。物理性质测试如关于较早实施例所述进行。结果在表5和6中示出。
表5-干燥样品性质
表6-水老化样品性质
如前所述,通过在相同指数下用烷氧基化曼尼希碱替代聚醚三醇增链剂,拉伸强度增加并且水分吸收减少。
实施例8-12
实施例8-12以与实施例1-4相同的一般方式制成。在每种情况下,除烷氧基化曼尼希碱产物之外,反应混合物含有小于20ppm的金属且不含胺化合物。物理性质测试如关于较早实施例所述进行。结果如表7和8中所示。
表7-干燥样品性质
表8-水老化样品性质
比较样品G和H
根据前述实施例中所述的一般程序,比较样品G和H通过使PP-1与700分子量的三官能脂肪族聚(氧化丙烯)(化合物G)和195当量重量的3.3-官能性环氧酚醛引发的聚醚多元醇(化合物H)在存在指数为101的有机锡催化剂的情况下反应来制备。
比较样品H具有稍高于比较样品G的拉伸强度(2.9MPa对1.95MPa)、伸长率(143%对112)和拉伸模量(3.3MPa对2.8MPa),显示了用基于芳香族的固化剂替代脂肪族固化剂的作用。然而,与本发明的实施例不同,当从约120℃加热至150℃时,比较样品H表现出其至少80%的储能模量的损失。比较样品H的储能模量在150℃下仅为约1×106Pa。这些结果指示,本发明的优异热性质不仅仅是由于烷氧基化曼尼希碱中存在芳香族基团。
Claims (15)
1.一种密度至少为750kg/m3的聚氨酯聚合物,其为包括以下的反应物的反应产物:
a)至少一种有机聚异氰酸酯和
b)多元醇,其包括
b-1)一种或多种羟基当量重量大于250g/mol且标称羟基官能度为2至4的多元醇和
b-2)一种或多种羟基当量重量为至多250的多元醇,其中至少50重量%的b-2)是至少一种平均羟基官能度为3至7的烷氧基化曼尼希碱;
其中所述聚氨酯聚合物的硬段含量为所述聚氨酯聚合物的20-80重量%。
3.根据权利要求1或2所述的聚氨酯聚合物,其含有不多于10ppm的锌、锡和汞的组合以及除所述烷氧基化曼尼希碱之外,基于所述反应混合物的重量,不多于0.05重量百分比的分子量低于350的含胺基团化合物。
4.根据前述权利要求中任一项所述的聚氨酯聚合物,其含有不多于20ppm的金属并且除所述烷氧基化曼尼希碱之外,另外含有不多于0.05重量百分比的分子量低于350的含胺基团化合物。
5.根据前述权利要求中任一项所述的聚氨酯聚合物,其中多元醇b-1)的羟基当量重量为至少400。
6.一种用于制造聚氨酯聚合物的方法,其包括在一个或多个步骤中使反应物反应,所述步骤包括异氰酸酯指数为90至150的最终固化步骤,所述反应物包括
a)至少一种有机聚异氰酸酯;和
b)多元醇,其包括b-1)至少一种羟基当量重量大于250g/mol的多元醇,和b-2)一种或多种羟基当量重量为至多250的多元醇,其中至少50重量%的b-2)是至少一种平均羟基官能度为3至7的烷氧基化曼尼希碱;
其中所述聚氨酯聚合物的硬段含量为所述聚氨酯聚合物的20-80重量%,并且所述聚氨酯聚合物的密度为至少750kg/m3。
8.根据权利要求6或7中任一项所述的方法,其中所述最终固化步骤在存在以下的情况下进行:不多于10ppm的锌、锡和汞的组合以及除所述烷氧基化曼尼希碱之外,不多于0.05重量份的分子量低于350的含胺基团化合物。
9.根据权利要求6-8中任一项所述的方法,其中所述最终固化步骤在存在以下的情况下进行:不多于20ppm的金属以及除所述烷氧基化曼尼希碱之外,不多于0.05重量%的分子量低于350的含胺基团化合物。
10.根据权利要求6-9中任一项所述的方法,其中将组分a)与组分b-1)的至少一部分反应以形成异氰酸酯含量为1至20重量百分比的预聚物或准预聚物,并且在所述最终固化中步骤中,将所述预聚物或准预聚物与多元醇b-2)和多元醇b-1)的任何剩余部分以90至150的异氰酸酯指数反应以生产所述聚氨酯。
11.根据权利要求10所述的方法,其中使组分a)与组分b-1)的至少一部分反应以形成预聚物或准预聚物的所述步骤在存在以下的情况下进行:不多于20ppm的金属以及除所述烷氧基化曼尼希碱至外,不多于0.05重量百分比的分子量低于350的含胺基团化合物。
12.根据权利要求6-11中任一项所述的方法,其中组分b-1)的羟基当量重量为至少400。
13.一种涂料、粘合剂、密封剂或弹性体,其包含如权利要求1-5中任一项所述的聚氨酯聚合物。
14.一种双组分密封剂或粘合剂组合物,其包含
I.包含异氰酸酯含量为1至20重量百分比的端异氰酸酯预聚物或准预聚物的预聚物组分,所述预聚物或准预聚物为以下的反应产物
a)至少一种异氰酸酯当量重量为80至250的有机聚异氰酸酯和
b-1)一种或多种羟基当量重量大于250g/mol且标称羟基官能度为2至4的多元醇;和
II.单独包装的固化剂组分,其包含b-2)一种或多种羟基当量重量为至多250的多元醇,其中至少50重量%的b-2)是至少一种平均羟基官能度为3至7的烷氧基化曼尼希碱。
15.一种密封剂或粘合剂,其是通过以下形成的:将如权利要求14所述的双组分密封剂或粘合剂组合物的组分I和II以产生90至150的异氰酸酯指数的比率组合以形成反应混合物,以及固化所述反应混合物以形成包括对应于组分I和II的反应产物的聚氨酯聚合物的密封剂或粘合剂,所述聚氨酯聚合物的硬段含量为20至80重量%。
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US5059670A (en) * | 1990-04-27 | 1991-10-22 | Arco Chemical Technology, Inc. | Thermosettable compositions containing alkoxylated aromatic compounds |
CN105637041B (zh) * | 2013-10-11 | 2018-07-17 | 亨茨曼国际有限公司 | 基于多异氰酸酯的膨胀型涂料 |
-
2020
- 2020-03-23 WO PCT/US2020/024198 patent/WO2020210012A1/en unknown
- 2020-03-23 CN CN202080024684.2A patent/CN113631607B/zh active Active
- 2020-03-23 EP EP20720960.2A patent/EP3953406B1/en active Active
- 2020-03-23 US US17/438,456 patent/US20220153994A1/en active Pending
- 2020-03-23 ES ES20720960T patent/ES2976662T3/es active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3655619A (en) * | 1969-01-24 | 1972-04-11 | Diamond Alkali Co | Alkoxylated mannich base urethane prepolymer composition and method of preparation |
US4487852A (en) * | 1983-10-25 | 1984-12-11 | Texaco Inc. | Modified Mannich condensates and manufacture of rigid polyurethane foam with alkoxylation products thereof |
US4489178A (en) * | 1983-10-25 | 1984-12-18 | Texaco Inc. | Mannich condensates having fire retardancy properties and manufacture of rigid polyurethane foam therewith |
US4883826A (en) * | 1988-07-27 | 1989-11-28 | The Dow Chemical Company | Tertiary amine-containing polyols prepared in a mannich condensation reaction using a mixture of alkanolamines |
US20030225174A1 (en) * | 2002-03-15 | 2003-12-04 | Rolf Albach | Flame resistant rigid foams and formulations for the production thereof |
Also Published As
Publication number | Publication date |
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ES2976662T3 (es) | 2024-08-06 |
CN113631607B (zh) | 2023-10-27 |
EP3953406A1 (en) | 2022-02-16 |
WO2020210012A1 (en) | 2020-10-15 |
US20220153994A1 (en) | 2022-05-19 |
EP3953406B1 (en) | 2024-02-21 |
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