CN103974989A - 包括可塑性形变的硬质聚氨酯泡沫、粘合剂和覆盖材料的复合部件 - Google Patents
包括可塑性形变的硬质聚氨酯泡沫、粘合剂和覆盖材料的复合部件 Download PDFInfo
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- CN103974989A CN103974989A CN201280058489.7A CN201280058489A CN103974989A CN 103974989 A CN103974989 A CN 103974989A CN 201280058489 A CN201280058489 A CN 201280058489A CN 103974989 A CN103974989 A CN 103974989A
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- basic metal
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Abstract
本发明涉及一种由可热成型的硬质聚氨酯泡沫和覆盖材料制备复合部件的方法,其中所述可热成型的聚氨酯泡沫提供至并粘附于覆盖材料,其中使用通过与碱金属碱性水溶液接触而固化的湿固化聚氨酯粘合剂作为粘合剂。本发明还涉及可由所述方法得到的复合部件以及所述复合部件在汽车中的用途。
Description
本发明涉及一种制备包括可热成型的硬质聚氨酯泡沫和覆盖材料的复合部件的方法,其中,可热成型的聚氨酯泡沫提供至或粘附于覆盖材料,其中以通过与碱金属碱性水溶液接触而固化的湿固化聚氨酯粘合剂用作粘合剂。本发明还涉及可通过所述方法得到的复合部件,以及所述复合部件在交通工具中的用途。
下文中,可塑性形变的硬质聚氨酯泡沫也指可热成型硬质聚氨酯泡沫,且其作为机动车内的内镶板的用途是已知的且记载于例如"Kunststoffhandbuch,卷7,Polyurethane",Carl Hanser Verlag,第3版,1993,第6.5.4.1章中。在内镶板的制备过程中,可塑性形变的硬质聚氨酯泡沫在模具中发生塑性形变,并且在成型步骤过程中或在成型完成后,用覆盖材料对其层压。可使用的覆盖材料为例如增强材料,如玻璃纤维毡和/或装饰材料例如无纺织物。在塑性形变过程中或在塑性形变完成后,将这些覆盖材料通过粘合剂粘附于所述硬质聚氨酯泡沫上,所述粘合剂通常为聚氨酯基粘合剂。对于用覆盖材料进行层压,特别有利的是在一步中与塑性形变一起进行。这类可塑性形变的硬质聚氨酯泡沫及这些可热成型的硬质聚氨酯泡沫与覆盖材料的层压例如记载于EP 437787和DE 4333795中。
优选使用的聚氨酯基粘合剂具体为湿固化单组分粘合剂。此情况下,将所述粘合剂施用至尚未压制的硬质泡沫上,用水喷洒,用覆盖材料层压并在模具中于升温下压制。
对于湿固化单组分粘合剂,优选使用提供有催化剂的异氰酸酯封端的聚氨酯预聚物。这类含有锡基催化剂或叔胺作为催化剂的湿固化单组分粘合剂记载于例如EP 464483中。这类粘合剂的优点在于,其不仅具有有限的储存稳定性且通常仅具有较短的处理时间。此外,从毒理学的角度来看,有机锡化合物有问题的。
WO 2010/139708记载了一种将可塑性形变的硬质聚氨酯泡沫粘附于覆盖材料的方法,其中,湿固化聚氨酯粘合剂通过加热碱金属硅酸盐水溶液而固化。此方法中,虽然可以不使用催化剂,但这样做的结果是粘合剂的处理时间显著延长。即使周围空气中存在少量的二氧化碳,碱金属硅酸盐溶液也会与其反应,这导致难以移除所用设备上的硅酸盐沉积物。此外,所得复合体的机械性能有待提高。
因此,本发明的目的在于提供一种将可塑性形变的硬质聚氨酯泡沫粘附连接于覆盖材料的方法,其中,聚氨酯粘合剂中可以不使用催化剂,并且避免了难以移除所用设备上的沉积物的问题。本发明的另一个目的在于提供一种包括可热成型聚氨酯泡沫和覆盖材料并表现出优异的机械性能的复合部件。
本发明的目的通过制备包括可热成型聚氨酯泡沫和覆盖材料的复合部件的方法实现,其中将可热成型聚氨酯泡沫提供至并粘附于覆盖材料,其中以通过与碱金属碱性水溶液接触而固化的湿固化聚氨酯粘合剂作为粘合剂。此外,本发明的目的还通过复合部件实现,所述复合部件可由所述方法得到,并包括可热成型硬质聚氨酯泡沫和覆盖材料。
作为覆盖材料,优选使用用于覆盖可热成型硬质聚氨酯泡沫的常规覆盖材料。这些材料包括玻璃纤维毡;柔性泡沫层;纤维,如织物纤维、编织物和无纺布;以及这些常规覆盖材料的结合。
作为硬质聚氨酯泡沫材料,可使用任何常规硬质聚氨酯泡沫。这类硬质聚氨酯泡沫记载于例如EP 437787、DE 4333795和DE102004062540中。这些硬质聚氨酯泡沫材料优选为开孔且优选不释放任何产生异味的物质。在一个优选的实施方案中,本发明提及的此类可热成型硬质聚氨酯泡沫通过将以下物质混合以形成反应混合物并使所述反应混合物反应完全而得到,所述物质为a)有机多异氰酸酯;和b)聚醚多元醇,其含有b1)羟值为150-650且伯羟基比例大于70%的2-4官能的聚氧亚烷基多元醇和b2)羟值为25-40且伯羟基的比例大于70%的双官能至三官能聚氧亚烷基多元醇;任选地c)扩链剂和/或交联剂;d)发泡剂;e)催化剂;和任选地f)助剂和添加剂。
本发明的可热成型的硬质聚氨酯泡沫可为可塑性形变的,优选在80至160℃、特别优选在100至150℃的模具温度(tool temperature)下。本文中,以聚氨酯化学中已知的常规起始材料作为起始材料a)至f)。聚氧亚烷基多元醇b1)优选包含至少30重量%、特别优选包含至少50重量%的环氧乙烷。聚氧亚烷基多元醇b2)优选包含至少50重量%、特别优选包含至少80重量%的环氧丙烷。
除了上述聚氧亚烷基多元醇b1)和聚氧亚烷基多元醇b2)以外,还可以使用其他多羟基化合物,例如其他聚醚多元醇、聚酯多元醇或其他对异氰酸酯呈活性的化合物,如多硫醇或多胺。基于组分b)的总重量计的化合物b1)和b2)的重量比优选为至少50重量%、特别优选为至少70重量%且特别是至少80重量%。聚氧亚烷基多元醇b1)与聚氧亚烷基多元醇b2)之比优选为0.8:1至1.5:1。
作为用于制备可热成型的硬质聚氨酯泡沫的扩链剂和/或交联剂c),优选使用二丙二醇和/或三丙二醇。
为了本发明的目的,湿固化聚氨酯粘合剂为一种包含含有异氰酸酯基团的预聚物的混合物或者是含有异氰酸酯基团的预聚物自身,其中所述混合物包含至少50重量%、优选至少80重量%且特别是至少95重量%的具有异氰酸酯基团的预聚物。此外,本发明的湿固化聚氨酯粘合剂可包含其他添加剂,所述添加剂例如表面活性物质;抑制剂,如二甘醇二氯甲酸酯或正磷酸;增塑剂;无机填料,如砂、高岭土、白垩、硫酸钡、二氧化硅;氧化稳定剂;染料和颜料;稳定剂,如耐水解稳定剂、光稳定剂、热稳定剂或变色稳定剂;无机和/或有机填料;乳化剂;阻燃剂;老化抑制剂;胶粘剂和增强材料;以及聚氨酯化学中的常规催化剂。根据DIN53018,在25℃下测定的本发明的湿固化聚氨酯粘合剂的粘度优选在500至5000mPas的范围内,特别优选在1000至3000mPas的范围内。
为了本发明的目的,含有异氰酸酯基团的预聚物为多异氰酸酯与含有至少两个对异氰酸酯呈活性的基团的聚合化合物、任选地含有一个对异氰酸酯呈活性的化合物以及任选的扩链剂和/或交联剂的反应产物,其中多异氰酸酯过量使用。
作为用于制备本发明的含有异氰酸酯基团的预聚物的多异氰酸酯,可使用现有技术已知的所有脂族、脂环族和芳族双官能或多官能异氰酸酯及其任意混合物。优选使用芳族双官能或多官能异氰酸酯。实例为二苯基甲烷4,4’-二异氰酸酯、二苯基甲烷2,4’-二异氰酸酯和二苯基甲烷2,2’-二异氰酸酯;二苯基甲烷二异氰酸酯单体与含有多于两个环的二苯基甲烷二异氰酸酯同系物(聚MDI)的混合物、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、萘1,5-二异氰酸酯(NDI)、甲苯2,4,6-三异氰酸酯以及甲苯2,4-二异氰酸酯和甲苯2,6-二异氰酸酯(TDI)或其混合物。
特别优选使用如下物质作为多异氰酸酯(a):甲苯2,4-二异氰酸酯、甲苯2,6-二异氰酸酯、二苯基甲烷2,4’-二异氰酸酯和二苯基甲烷4,4’-二异氰酸酯和含有至少两个环的二苯基甲烷二异氰酸酯的同系物(聚MDI)以及这些异氰酸酯的混合物、脲酮亚胺,特别是二苯基甲烷2,4’-二异氰酸酯与二苯基甲烷4,4’-二异氰酸酯的混合物。
作为对异氰酸酯呈活性且含有至少两个对异氰酸酯呈活性的基团的聚合物——其用于制备含有异氰酸酯基团的预聚物,可以使用含有至少两个对异氰酸酯基团呈活性的基团的所有化合物。这些化合物的分子量为至少400g/mol。优选使用聚酯多元醇、聚醚多元醇或聚醚-聚酯多元醇,其可例如通过聚酯的烷氧基化得到。
聚醚多元醇通过已知的方法制备,例如通过如下方法制备:由一种或多种亚烷基中含有2-4个碳原子的环氧烷烃进行阴离子聚合,所述阴离子聚合以碱金属氢氧化物或碱金属氧化物作为催化剂,并加入至少一种起始分子,所述起始分子在含有2-5、优选2-4且特别优选2-3、特别是2个呈键合形式的活性氢原子;或由一种或多种亚烷基中含有2-4个碳原子的环氧烷烃进行阳离子聚合,所述阳离子聚合使用Lewis酸,所述Lewis酸例如五氯化锑或三氟化硼醚合物。此外,还可以使用多金属氰化物作为催化剂,已知为DMC催化剂。合适的环氧烷烃为例如四氢呋喃、1,3-环氧丙烷、1,2-环氧丁烷或2,3-环氧丁烷,且优选环氧乙烷和1,2-环氧丙烷。所述环氧烷烃可单独使用、交替连续使用或以混合物使用。优选使用1,2-环氧丙烷、环氧乙烷或1,2-环氧丙烷与环氧乙烷的混合物。
作为起始分子,优选水或2-元醇和3-元醇,例如乙二醇、1,2-丙二醇或1,3-丙二醇、二乙二醇、二丙二醇、1,4-丁二醇、丙三醇和三羟甲基丙烷。
优选的聚醚多元醇、特别优选的聚环氧丙烷多元醇或聚环氧丙烷-聚环氧乙烷多元醇的官能度为2-5,特别优选为2-3,且分子量为400至9000g/mol,优选为1000至6000g/mol,特别优选为1500至5000g/mol且特别是2000至4000g/mol。特别优选使用重均分子量为1500至2500g/mol的聚丙二醇作为聚醚多元醇。
除了含有至少两个对异氰酸酯基团呈活性的基团的聚合化合物外,还可以使用仅含有一个对异氰酸酯呈活性的基团的化合物。这些化合物优选为聚醚一元醇,其以类似于上述聚醚多元醇的制备方法得自多官能起始分子,例如得自乙二醇单甲醚。所述聚醚一元醇的分子量优选为100至1000g/mol。如使用聚醚一元醇,则该聚醚一元醇与聚醚多元醇的重量比为1:30至4:1。
扩链剂和/或交联剂可任选地用于制备含有异氰酸酯基团的预聚物。扩链剂和/或交联剂可在加入多元醇之前加入、与多元醇一同加入或在多元醇之后加入。对于扩链剂和/或交联剂,使用分子量优选小于400g/mol、特别优选为60至350g/mol的物质,扩链剂含有2个对异氰酸酯呈活性的氢原子,且交联剂含有3个对异氰酸酯呈活性的氢原子。扩链剂和/或交联剂可单独使用或以混合物的形式使用。如使用扩链剂,则特别优选1,3-丙二醇和1,2-丙二醇、二丙二醇、三丙二醇、1,3-丁二醇。
如使用扩链剂、交联剂或其混合物,则其有利地以1至60重量%、优选以1.5至50重量%且特别是以2至40重量%的量使用,基于多异氰酸酯、对异氰酸酯呈活性的聚合化合物和扩链剂和/或交联剂的重量计。
异氰酸酯预聚物可通过如下方式得到:例如在30至100℃、优选在约80℃的温度下,过量的上文所述的多异氰酸酯与含有至少两个对异氰酸酯呈活性的基团的聚合化合物、任选地含有一个对异氰酸酯呈活性的基团的化合物和任选地扩链剂和/或交联剂反应形成预聚物。本文中,多异氰酸酯、含有至少两个对异氰酸酯呈活性的基团的聚合化合物、任选地含有一个对异氰酸酯呈活性的基团的化合物和任选地扩链剂和/或交联剂优选以如下比例混合:异氰酸酯基团与对异氰酸酯呈活性的基团之比为1.5:1至15:1、优选为1.8:1至8:1。所述预聚物特别优选通过以下方式制备:将多异氰酸酯、含有至少两个对异氰酸酯呈活性的基团的聚合化合物、任选地含有一个对异氰酸酯呈活性的基团的化合物和任选地扩链剂和/或交联剂彼此以得到的预聚物的NCO含量为5至30重量%、特别是10至25重量%的比例进行混合,所述重量%基于制备的异氰酸酯预聚物的总重量计。挥发性异氰酸酯随后优选可分离出去,优选通过薄膜蒸馏分离。本文中,异氰酸酯预聚物在25℃下的粘度优选为100至5000mPas。基于甲苯异氰酸酯的本发明的异氰酸酯预聚物的粘度通常为500至3000mPas,而基于二苯基甲烷二异氰酸酯的本发明的异氰酸酯预聚物的粘度通常为600至3000mPas,各自均为25℃的粘度。异氰酸酯预聚物的平均异氰酸酯官能度优选为2.0至2.9,特别是2.1至2.6。
湿固化聚氨酯粘合剂也可包含催化剂。这些催化剂包括例如脒,如2,3-二甲基-3,4,5,6-四氢嘧啶;叔胺,如三乙胺、三丁胺、二甲基苄胺、N-甲基吗啉、N-乙基吗啉、N-环己基吗啉、N,N,N',N'-四甲基亚乙基二胺、N,N,N',N'-四甲基丁二胺、N,N,N',N'-四甲基己二胺、五甲基二亚乙基三胺、双(二甲基氨基乙基)醚、双(二甲基氨基丙基)脲、二甲基哌嗪、1,2-二甲基咪唑、1-氮杂双环[3.3.0]辛烷且优选1,4-二氮杂双环[2.2.2]辛烷;和烷醇胺化合物,如三乙醇胺、三异丙醇胺、N-甲基二乙醇胺和N-乙基二乙醇胺以及二甲基乙醇胺。同样可用作催化剂的有有机金属化合物,优选有机锡化合物,例如有机羧酸的锡(II)盐,如乙酸锡(II)、辛酸锡(II)、乙基己酸锡(II)和月桂酸锡(II);和有机羧酸的二烷基锡(IV)盐,如二乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡和二乙酸二辛基锡;以及羧酸铋,如新癸酸铋(III)、2-乙基己酸铋和辛酸铋;或其混合物。有机金属化合物可单独使用或与碱性胺结合使用。
优选加入小于2重量%、特别优选小于1重量%的催化剂或催化剂结合物,基于含有异氰酸酯基团的预聚物的重量计;且特别优选不加入催化剂或催化剂结合物,
在本发明的复合部件的制备过程中,每m2可热成型的硬质聚氨酯泡沫优选使用2至300g、特别优选使用50至200g湿固化聚氨酯粘合剂。
湿固化聚氨酯粘合剂的固化通过与碱金属碱性水溶液接触而进行。所述碱金属碱性水溶液优选基本上不包含硅酸盐。本文中,术语硅酸盐包含可溶性硅-氧化合物,特别包含源自SiO4 4-的所有化合物及其缩合物。本文中,“基本上”意指碱金属水溶液仅以不致于产生沉淀的量含有硅酸盐。所述溶液优选含有小于10重量%、特别优选小于1重量%且特别是小于0.1重量%的可溶性硅酸盐。极特别优选在碱金属碱性水溶液中不加入含有可溶性硅酸盐的化合物,例如水玻璃。本文中,不排除可例如通过玻璃的不想要的溶解进入溶液的可溶性硅酸盐,所述玻璃例如常规的玻璃器皿。
碱金属碱性水溶液的碱金属浓度优选为0.1至10mol,且pH为至少10、优选为至少11、特别优选为至少12、更优选为至少13且特别是至少13.5。不对pH值的最大值作任何限制。鉴于加工工艺的原因,OH-浓度优选不超过10mol/l,特别优选不超过5mol/l,更特别优选不超过3mol/l且特别是不超过2mol/l。具体而言,溶液中的碱金属离子为锂离子、钠离子或钾离子或含有选自锂离子、钠离子和钾离子中的至少两种的混合离子,优选为含有钠离子和钾离子的混合离子。碱金属碱性水溶液可例如通过如下方式得到:溶解具有弱酸的碱金属化合物和/或碱金属氢氧化物,以及使碱金属与水直接反应。为了本发明的目的,弱酸为最后一个氢离子去质子化得到的pKa至少为8、优选至少为9且特别是至少为10的化合物。可用的具有弱酸的碱金属化合物的实例为碱金属的异氰酸盐、碱金属硫化物、碱金属磷酸盐和碱金属碳酸盐,优选碱金属碳酸盐。具体而言,使用碱金属氢氧化物和/或碱金属碳酸盐。
碱金属碱性水溶液与湿固化聚氨酯粘合剂的重量比通常为2:1至1:10,优选为1:1至1:5。这对应于每m2可热成型硬质聚氨酯泡沫施用1至150g。
在本发明的复合部件的制备过程中,通常首先提供可热成型硬质聚氨酯泡沫。湿固化聚氨酯粘合剂随后施用至所述可热成型硬质聚氨酯泡沫的一侧或优选两侧,并用喷洒碱金属碱性水溶液。接着施用覆盖材料,并且使复合体在模具中于升温、优选在60至180℃、特别优选在100至150℃下成型,并使湿固化聚氨酯粘合剂固化。如采用优选的质量比,则在此方法中实现湿固化聚氨酯粘合剂的发泡,通过这种方式,不会损害可热成型的硬质聚氨酯泡沫的开孔性。
本发明还提供一种复合部件,其可通过本发明的方法得到。
本发明的复合部件优选用作陆地、水上和航空交通工具的内镶板,特别是用作汽车的内镶板,特别是用作汽车的覆层部件,特别是用作内顶。
本发明的方法可在现有的生产车间施用。这些用作粘合剂的湿固化聚氨酯预聚物长期稳定,并且,由于所述湿固化聚氨酯粘合剂不含或含有相对少量的催化剂,因而可以在室温或在略微升温下长时间处理。
现已出人意料地发现,本发明的方法使可热成型的硬质聚氨酯泡沫有利地硬化。此外,本发明方法的脱模时间更短,因而对于生产加工车间而言更加经济实用。
通过以下实施例阐释本发明。
起始材料
多元醇1:由丙二醇起始制备的聚醚多元醇(OHN30mgKOH/g),其主要含有伯羟基(组成为环氧丙烷80%,环氧乙烷20%)
多元醇2:甲基聚乙二醇(OHN113mg KOH/g)
异氰酸酯:聚二苯基甲烷二异氰酸酯(PMDI)
催化剂1:有机锡酯
催化剂2:硅酸钠的水溶液M2O:SiO2之比:SiO2:Na2O为3.3:1(固含量为16%)
催化剂3:碳酸钠水溶液(0.5mol/l)
催化剂4:氢氧化钠水溶液(0.5mol/l)
催化剂5:碳酸钾水溶液(0.2mol/l)
催化剂6:氢氧化钾水溶液(0.5mol/l)
引发剂1:二乙二醇二氯甲酸酯(DIBIS)
引发剂2:正磷酸85%
实施例:
-制备聚氨酯粘合剂(对比实施例2,实施例1-4)
将70重量份PMDI和0.01重量份引发剂1置于搅拌容器中并在搅拌下加热至80℃。29.6重量份的多元醇1和多元醇2的混合物(重量比为1:2)缓慢加入其中。完全加入后,将混合物再搅拌120分钟,冷却至25℃并包装。得到的聚氨酯预聚物的NCO含量和粘度分别为21%和500mPas。随后加入0.02重量份引发剂1和0.03重量份引发剂2。
由聚氨酯粘合剂制备泡沫
对比实施例2,实施例1至4:
20.0重量份聚氨酯粘合剂和1.2重量份催化剂2、3、4、5或6彼此混合,并使所述反应混合反应,生成聚氨酯泡沫。由此得到开孔和粗孔(coarse-cell)泡沫。乳白时间、熟化时间(fiber time)、起发时间(rise time)示于表1中。
对比1:
制备聚氨酯粘合剂:
重复实施例1-4的制备过程,另外加入0.06重量份的催化剂1。
由聚氨酯粘合剂制备泡沫(对比1):
将20.0重量份聚氨酯粘合剂和1.2重量份水彼此混合,并使反应混合物反应,生成聚氨酯泡沫。由此得到开孔和粗孔泡沫。
在55℃下在水浴中搅拌2小时后,各个实施例和对比实施例的用于制备聚氨酯泡沫的反应混合物的活性以及各个实施例和对比实施例的聚氨酯粘合剂的粘度和粘度上升情况示于表1中:
表1:
表中显示,实施例1-4的泡沫不仅呈现出所需的开孔和粗孔结构,还表现出更快的反应速率。由于熟化时间和起发时间更短而实现更短的循环时间。此外,由于本发明的聚氨酯粘合剂,与对比实施例2的粘合剂类似,不包含任何催化剂,因而其在施用前的条件下表现出显著改善的稳定性,称作辊稳定性(roller stability),该条件通过在55℃下于水浴中搅拌2小时模拟。
通过使用本发明的催化(实施例1和2)和对比实施例1和2的催化的湿固化粘合剂制备内顶。依次使用以下层:
1.无纺布190g/m2购自Fytisa(1.1mm)
2.玻璃纤维毡100+/-10g/m2Owens Corning Vetrotex
3.水25g/m2
4.粘合剂100g/m2
5.泡沫RG20Elastoflex E3943/11210.6mm(22kg/m3)
6.粘合剂100g/m2
7.水25g/m2
8.玻璃纤维毡100+/-10g/m2Owens Corning Vetrotex
9.在不可见的一侧具有LDPE的PET无纺布(45g/m2PET纤维+15g/m2LDPE),购自Fytisa(0.25mm)
将材料在模具中于130℃下压制25秒钟,压成11mm的厚度,并根据基于DIN53423的方法测定制得的内顶的挠曲强度。本文中,试样的宽度为50mm,厚度为11mm。测试速度为50mm/分钟。所有试样在约5mm的偏转下均达到力的最大值。试样随后并未断裂,但力的最大值在更大的偏转下再次下降。力的最大值、E模量、20mm偏转时的力、力的最大值和刚性(通过力-偏转曲线在线性区域的初始梯度得到)示于下表中。本文中,测量三个单独试样的平均值。通过下式计算E模量:
表2:
C1 | C2 | E1 | E2 | |
力的最大值(N) | 13.46 | 17.79 | 24.68 | 24.40 |
20mm偏转时的力(N) | 8.56 | 10.71 | 15.40 | 18.06 |
刚性(N/mm) | 6.34 | 9.18 | 9.80 | 10.84 |
E模量(MPa) | 24.30 | 34.16 | 38.78 | 41.99 |
本发明的内顶,与对比实施例的内顶相比,具有明显更高的E模量和刚性。
Claims (13)
1.一种制备复合部件的方法,所述复合部件包括可热成型的硬质聚氨酯泡沫和覆盖材料,其中可热成型的聚氨酯泡沫提供至且粘附于覆盖材料,其中以通过与碱金属碱性水溶液接触而固化的湿固化聚氨酯粘合剂用作粘合剂。
2.权利要求1的方法,其中所述碱金属碱性水溶液基本不包含硅酸盐。
3.权利要求1或2的方法,其中所述碱金属碱性水溶液的浓度为0.1至10摩尔,基于碱金属计。
4.权利要求1-3中任一项的方法,其中所述碱金属碱性水溶液的pH值至少为10。
5.权利要求1-4中任一项的方法,其中所述碱金属为钠或钾或二者的混合物。
6.权利要求1-5中任一项的方法,其中所述碱金属碱性水溶液以每m2可热成型硬质聚氨酯泡沫10-150g的量施用。
7.权利要求1-6中任一项的方法,其中所述湿固化聚氨酯粘合剂包含基于湿固化聚氨酯粘合剂的总重量计的至少80重量%的异氰酸酯封端的预聚物,所述预聚物通过将如下物质混合得到:化学计量过量的芳族异氰酸酯与含有至少两个对异氰酸酯呈活性的基团的聚合化合物和任选地仅含有一个对异氰酸酯呈活性的基团的化合物和任选地扩链剂和/或交联剂。
8.权利要求7的方法,其中所述异氰酸酯封端的预聚物的NCO含量为5-30重量%。
9.权利要求1-8中任一项的方法,其中除了碱金属碱性水溶液以外,无其他催化剂用于固化所述粘合剂。
10.权利要求1-9中任一项的方法,其中所述粘合剂以每m2可热成型硬质聚氨酯泡沫20-300g的量施用。
11.权利要求1-10中任一项的方法,其中所述可热成型的聚氨酯泡沫、所述覆盖材料和所述湿固化聚氨酯粘合剂粘附结合于模具中,所述模具的模具温度为60至180℃。
12.一种复合部件,其通过权利要求1-11中任一项的方法得到。
13.权利要求12所述的复合部件在交通工具中的用途。
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PCT/EP2012/073048 WO2013079353A1 (de) | 2011-11-28 | 2012-11-20 | Verbundteile enthaltend plastisch verformbaren polyurethanhartschaumstoff, klebstoff und abdeckmaterial |
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CN107001571A (zh) * | 2014-11-14 | 2017-08-01 | 3M创新有限公司 | 两组分聚氨酯粘合剂组合物 |
CN110382581A (zh) * | 2017-03-07 | 2019-10-25 | 科思创德国股份有限公司 | 聚氨酯泡沫及其制备方法 |
CN111565921A (zh) * | 2017-12-21 | 2020-08-21 | 巴斯夫欧洲公司 | 制备聚氨酯夹层模制部件的方法 |
CN112469756A (zh) * | 2018-07-27 | 2021-03-09 | 巴斯夫欧洲公司 | 板件结构、其制备方法及其作为汽车部件的用途 |
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US4769446A (en) * | 1983-04-18 | 1988-09-06 | Hoechst Celanese Corporation | Fiber-reactive red azo dyestuff |
FR2654385B1 (fr) * | 1989-11-10 | 1992-05-29 | Nat Starch Chem Sa | Procede de production d'articles isolants rigides a l'aide d'un adhesif de polyurethanne. |
DE4001249A1 (de) | 1990-01-18 | 1991-07-25 | Bayer Ag | Verfahren zur herstellung von offenzelligen, kaltverformbaren polyurethan-hartschaumstoffen und deren verwendung zur herstellung von autohimmeln |
DE4021113A1 (de) | 1990-07-03 | 1992-01-09 | Bayer Ag | Klebstoffe auf basis von polyolen und polyisocyanaten |
DE4333795C2 (de) | 1993-10-04 | 2003-04-10 | Basf Ag | Verfahren zur Herstellung von thermoplastisch verformbaren Polyurethan-Hartschaumstoffen und hierfür verwendbare Mischungen aus Polyhydroxylverbindungen |
CN100355852C (zh) * | 2003-05-15 | 2007-12-19 | 亨茨曼国际有限公司 | 用于夹心板的多异氰酸酯基粘合剂配料 |
JP2006070181A (ja) | 2004-09-02 | 2006-03-16 | Inoac Corp | 水分硬化型接着剤及びそれを用いた積層体 |
DE102004062540A1 (de) | 2004-12-24 | 2006-07-06 | Bayer Materialscience Ag | Polyurethan-Hartschaumstoffe, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung |
CN102822221B (zh) * | 2009-06-05 | 2014-10-29 | 巴斯夫欧洲公司 | 含有可塑性形变硬质聚氨酯泡沫、粘合剂和覆盖材料的复合部件 |
JP2012528743A (ja) | 2009-06-05 | 2012-11-15 | ビーエーエスエフ ソシエタス・ヨーロピア | 塑性変形可能な硬質ポリウレタンフォームと接着剤と被覆材料とからなる複合部品 |
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CN107001571A (zh) * | 2014-11-14 | 2017-08-01 | 3M创新有限公司 | 两组分聚氨酯粘合剂组合物 |
CN110382581A (zh) * | 2017-03-07 | 2019-10-25 | 科思创德国股份有限公司 | 聚氨酯泡沫及其制备方法 |
CN111565921A (zh) * | 2017-12-21 | 2020-08-21 | 巴斯夫欧洲公司 | 制备聚氨酯夹层模制部件的方法 |
CN112469756A (zh) * | 2018-07-27 | 2021-03-09 | 巴斯夫欧洲公司 | 板件结构、其制备方法及其作为汽车部件的用途 |
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CN103974989B (zh) | 2016-02-03 |
KR102030863B1 (ko) | 2019-10-10 |
EP2597107A1 (de) | 2013-05-29 |
ES2694159T3 (es) | 2018-12-18 |
EP2785756A1 (de) | 2014-10-08 |
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