CN102448716B - 用于制备泡沫材料复合元件i的方法 - Google Patents

用于制备泡沫材料复合元件i的方法 Download PDF

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CN102448716B
CN102448716B CN201080023928.1A CN201080023928A CN102448716B CN 102448716 B CN102448716 B CN 102448716B CN 201080023928 A CN201080023928 A CN 201080023928A CN 102448716 B CN102448716 B CN 102448716B
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bonding coating
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J·范德布拉克
R·阿贝尔斯
R·罗尔斯
P·哈斯
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Abstract

本发明涉及用于制备泡沫材料复合元件的方法，其包括准备覆盖层的步骤、在该覆盖层上施加增附剂层的步骤(其中增附剂层包含改性异氰酸酯)和在该增附剂层上施加包含聚氨酯和/或聚异氰脲酸酯的泡沫材料层的步骤。在施加时，增附剂层中的改性异氰酸酯具有≥10％至≤29％的游离异氰酸酯基团的含量。此外，本发明涉及具有≥10％至≤29％的游离异氰酸酯基团含量的改性异氰酸酯在泡沫材料复合元件的制备中作为增附剂的用途以及通过根据本发明的方法获得的泡沫材料复合元件。

Description

用于制备泡沫材料复合元件I的方法
本发明涉及用于制备泡沫材料复合元件的方法，其包含准备覆盖层的步骤、在该覆盖层上施加增附剂层的步骤(其中该增附剂层包含改性异氰酸酯)和在该增附剂层上施加包含聚氨酯和/或聚异氰脲酸酯的泡沫材料层的步骤。在施加时，该增附剂层中的改性异氰酸酯具有≥10％至≤25％的游离异氰酸酯基团含量。此外，本发明涉及具有≥10％至≤25％的游离异氰酸酯基团含量的改性异氰酸酯在泡沫材料复合元件的制备中作为增附剂的应用以及通过根据本发明的方法获得的泡沫材料复合元件。
对于基于聚氨酯-硬质泡沫材料(即不仅聚氨酯的而且聚异氰脲酸酯的硬质泡沫材料)的金属夹层元件的连续生产，金属覆盖层至泡沫的粘附强度是重要的，特别是如果泡沫为聚异氰脲酸酯泡沫。在市场中已经确立了二组分-聚氨酯-增附剂体系。通过使用这样的二组分增附剂体系，粘附强度原则上得到显著改善，这对于成品零件的制造者意味着产品改进。特别是极大地降低了粘附失败的长期风险。
然而，在这样的二组分增附剂体系的加工中可能出现增附剂组分的充分均匀化的困难。就金属复合元件的长期结合性而言，不充分的均匀化可能意味着高的风险，更确切地说，在温度交变时可能出现覆盖层至泡沫的粘附失败。此外，二组分增附剂体系的加工会意味着在生产阶段开始的时候相对高的次品率。
为了避免由于两种增附剂组分的不充分均匀化所致的结合性不足的风险，出现了单组分解决方案。例如EP 1 516 720 A1公开了聚氨酯增附剂用于改善复合元件(包含聚异氰脲酸酯泡沫材料和覆盖层)的层之间粘附的应用，以及这样的复合元件本身及其制备方法。
EP 1 593 438 A2公开了用于制备夹层复合元件的设备和方法。该设备至少由两个覆盖层供给设备组成，增附剂施加设备、核心层施加设备、传送设备和致偏设备先后与其连接。增附剂施加设备至少由增附剂供给管道、具有至少一个侧面出料口以及用于圆盘给料机的驱动装置的圆盘给料机组成。作为增附剂可以使用单组分体系，例如基于聚氨酯的，例如包含NCO基团的预聚物。其他可能的单组分体系基于聚氯丁二烯、环氧化物或聚醋酸乙烯。增附剂也可以由多组分体系，优选地由二组分体系构成。优选的二组分体系为聚氨酯体系。
本发明的任务是改善泡沫材料复合元件中泡沫和覆盖层之间的粘附。因此存在对用于制备这些复合元件的备选的和改善的方法的需求，该方法特别使在气泡和/或削弱点(Sollbruchstellen)较少出现的同时改善泡沫材料复合元件中泡沫和覆盖层之间的粘附成为可能。在实际使用中，对于覆盖层与泡沫材料层之间足够的粘附强度来说，将0.20N/mm2(依据DIN 53292测量)的下限被视为临界界限。因此，任务是，在使用的增附剂的量尽可能少的同时，覆盖层与泡沫材料层之间的粘附强度达到尽可能高的水平。
令人意外地发现，根据本发明的任务通过用于制备泡沫材料复合元件的方法得到解决，该方法包括以下步骤：
A)准备覆盖层；
B)在该覆盖层上施加增附剂层，其中该增附剂层包含改性异氰酸酯；
C)在该增附剂层上施加包含聚氨酯和/或聚异氰脲酸酯的泡沫材料层，
其特征在于，在施加时，该增附剂层中的改性异氰酸酯具有≥10％至≤29％，优选地≥10％至≤25％的游离异氰酸酯基团的含量。
游离异氰酸酯基团的含量数据在每一情况下基于所使用的异氰酸酯量的重量百分比。
已发现通过使用根据本发明的改性异氰酸酯作为增附剂，相对于已知体系，泡沫在覆盖层的粘附可以得到改善。特别是应用预聚物形式的改性异氰酸酯，即根据习惯命名学的单组分体系，能够避免在使用二组分体系情况下的不充分的混合比。未充分混合的增附剂体系可能导致复合材料中的气泡形成或削弱点。有利地，预聚物形式的改性异氰酸酯的应用也使覆盖层的整面的润湿成为可能。
根据本发明制备的泡沫材料复合元件特别适合作为隔热元件。
根据本发明的方法的步骤A)涉及覆盖层的准备。这可以在连续生产设备中例如从卷材通过展开卷起的覆盖层来进行。不首先详细确定覆盖层的类型，其中优选地可以应用在绝热范围内通常使用的材料用于覆盖层。覆盖层的厚度可以例如为≥200μm 至≤5mm，优选地为≥300μm至≤2mm，和特别优选地，为≥400μm至≤1mm。
在步骤B)中，在准备的覆盖层上施加包含改性异氰酸酯的增附剂层。该施加可以用常规技术例如喷涂或辊涂来进行。优选的改性异氰酸酯包含：脲改性异氰酸酯；缩二脲改性异氰酸酯；氨基甲酸酯改性异氰酸酯；异氰脲酸酯改性异氰酸酯；脲基甲酸酯改性异氰酸酯；碳二亚胺改性异氰酸酯；异氰酸酯二聚体改性异氰酸酯和脲酮亚胺改性异氰酸酯。这样的改性异氰酸酯是购买可得的和通过异氰酸酯与低于化学计量量的异氰酸酯反应性化合物或与自身的反应来制备。例如可以通过二或多异氰酸酯与少量水或二胺或与二醇反应分别制备脲改性和氨基甲酸酯改性的异氰酸酯。通过在合适的催化剂存在下异氰酸酯与自身的交换反应来制备碳二亚胺、脲酮亚胺和异氰脲酸酯改性的异氰酸酯。
作为改性异氰酸酯，特别优选的是碳二亚胺改性的或氨基甲酸酯改性的异氰酸酯。
作为改性异氰酸酯，最特别优选的是氨基甲酸酯改性异氰酸酯。氨基甲酸酯改性异氰酸酯也可以称作聚氨酯预聚物。术语“预聚物”在此理解为其通常含义。术语“聚氨酯预聚物”特别指在从异氰酸酯至聚氨酯聚合物的反应中的反应性中间体。它们通过多元醇组分与过量的异氰酸酯组分反应来制备。
优选地，该异氰酸酯组分选自：二异氰酸四亚甲酯、二异氰酸甲基五亚甲酯、1，6-二异氰酸六亚甲酯、二异氰酸十二亚甲酯、1，4-二异氰酸根合-环己烷、1-异氰酸根合-3，3，5-三甲基-5-异氰酸根合甲基-环己烷、4，4′-二异氰酸根合-二环己基甲烷、4，4′-二异氰酸根合-二环己基丙烷-(2，2)、1，4-二异氰酸根合苯、2，4-二异氰酸根合甲苯、2，6-二异氰酸根合甲苯、4，4′-二异氰酸根合二苯基甲烷、2，2′-和2，4′-二异氰酸根合二苯基甲烷、对二甲苯二异氰酸酯、1，3-和1，4-二异氰酸根合甲基苯以及由这些化合物组成的混合物。特别优选地，该异氰酸酯组分是二苯基甲烷二异氰酸酯。
增附剂层的厚度可以为例如≥200μm至≤5mm，优选地为≥300μm至≤2mm和特别优选地为≥400μm至≤1mm。
改性异氰酸酯作为增附剂的使用允许泡沫材料复合元件的生产中断，而没有因此产生较高量的次品。基于2组分体系的传统增附剂在短时间以后停止反应，而改性增附剂是潜反应性的。因此有利地，如果在生产过程中出现问题，可以停止泡沫材料复合元件的生产，而不必弃去大量的材料。
在步骤C)中，在增附剂层上施加包含聚氨酯和/或聚异氰脲酸酯的泡沫材料层。这也可以在连续生产设备中实现。该层可以例如有≥2cm至≤25cm，从≥5cm至≤23cm和优选≥12cm至≤20cm的厚度。可以在临近施加前才在混料头中使反应组分混合并立即在增附剂层上施加导致泡沫的反应混合物。备选地，可以施加已完成的泡沫材料层，例如铺上。特别地，使用包含聚异氰脲酸酯或主要包含聚异氰脲酸酯的泡沫是有利的，因为它在阻燃剂含量减少时也具有良好的防火特性。
为了制备泡沫材料层，使用普通的脂族、脂环族和特别是芳族多异氰酸酯。优选地，使用甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)和特别是二苯基甲烷二异氰酸酯与聚亚苯基聚亚甲基多异氰酸酯(Roh-MDI)的混合物。作为具有至少两个对异氰酸酯基团有反应性的氢原子的化合物，通常考虑这样的化合物，其在分子中携带两个或更多个选自OH-基团、SH-基团、NH--基团、NH2-基团和CH-酸性基团如β-二酮基团的反应性基团。优选地，使用聚醚醇和/或聚酯醇，其中优选的是聚醚多元醇。所使用的聚醚醇和/或聚酯醇的羟值优选25-800mg KOH/g，其摩尔质量通常大于400g/mol。
根据本发明，在施加时，增附剂层的改性异氰酸酯具有≥10％至≤29％，优选地≥10％至≤25％的游离异氰酸酯基团含量。在此异氰酸酯基团的含量需理解为增附剂层还没与泡沫材料层接触时。特别优选地，游离异氰酸酯基团的含量为≥12％至≤20％的范围。它能够按照DIN 53185标准测定。游离异氰酸酯基团含量的数据说明了在施加到覆盖层上时刻的含量。
在一个优选的实施方案中，该泡沫材料层(其中通常也应当理解为泡沫材料层的泡沫)具有≥85％至≤100％，优选地≥90％至≤100％的闭孔度(Geschlossenzelligkeit)，其中闭孔度根据DIN ISO 4590来测定。优选地，按照ASTM 3576-77，该泡沫材料层具有≥10μm至≤600μm，优选≥50μm至≤400μm的平均孔直径。
在根据本发明的方法中，根据步骤C)，可以在该泡沫材料层上如在步骤B)中所述施加另一个增附剂层，然后在其上如在步骤A中所描述的那样施加另一层覆盖层。于是获得双面配有覆盖层的泡沫材料复合元件。该方法可以例如在传统的双带输送机中进行。
在根据本发明的方法的一个实施方案中，所述覆盖层材料包括铝、钢、沥青、纸、矿物-无纺布、包含有机纤维的无纺布、塑料板、塑料膜和/或木板。特别优选的是，覆盖层是铝金属或钢。这里，铝或钢可以被涂覆。根据本发明所使用的改性异氰酸酯，特别是氨基甲酸酯改性的异氰酸酯，导致特别是在聚异氰脲酸酯泡沫材料与铝覆盖层或钢覆盖层之间特别好的粘附。
在根据本发明的方法的一个优选的实施方案中，增附剂层中的氨基甲酸酯改性异氰酸酯能由单体和/或聚合的二苯基甲烷二异氰酸酯与聚醚多元醇反应获得，该聚醚多元醇具有≥2至≤8，优选≥3至≤8，特别优选≥3至≤6的平均官能度。优选地，聚醚多元醇具有≥50摩尔％至≤100摩尔％的仲羟基基团含量。例如可以使用具有用量比为≥5重量％至≤15重量％的2，4′-异构体、≥75重量％至≤85重量％的4，4′-异构体以及≥5重量％至≤15重量％的在25℃时粘度为≥100mPas至≤300mPas的、聚合MDI的单体二苯基甲烷二异氰酸酯和聚合二苯基甲烷二异氰酸酯的混合物。在此，重量百分比份额的数据相加≤100重量％。聚醚多元醇组分可以例如通过向作为起始分子的甘油加入环氧丙烷和环氧乙烷来制备。环氧丙烷的份额可以有利地为≥80至≤95重量％，而环氧乙烷的份额可以有利地为≥5至≤20重量％。聚醚多元醇中的仲羟基基团的份额也可以特别优选地为≥60摩尔％至≤80摩尔％。
根据本发明的方法，优选在覆盖层上施加≥20g/m2至≤50g/m2的量的增附剂层。与已知方法相比，这表示减少了增附剂层的需要量。此外令人意外地发现，在根据本发明的方法中，当在覆盖层上施加的增附剂层的量在≥30g/m2至≤40g/m2的范围时，达到最佳粘附(比较表2中所表示的结果)。
在根据本发明的方法的一个优选的实施方案中，在施加增附剂层和用于制备泡沫材料层的反应混合物后，将覆盖层加热至≥30℃至≤70℃，特别优选≥40℃至≤60℃，最优选地≥45℃至≤55℃的温度。通过覆盖层的加热，增附剂层的反应被加速并且获得整体更牢固的结合。
在根据本发明的方法的另一个优选的实施方案中，泡沫材料层能由包含多异氰酸酯与至少一种选自聚酯多元醇和聚醚多元醇的化合物的反应混合物反应获得，其中在反应开始的时候在反应混合物中，异氰酸酯基团与羟基基团的摩尔比为≥1∶1至≤5∶1。换言之，该反应混合物的指数为100至500。该指数也可以为≥150至≤350或≥200至≤300。在这样的参数下，主要获得聚异氰脲酸酯泡沫，其可以如已经阐述的用少量阻燃剂就足够并且通过根据本发明的方法仍然可以牢固地与覆盖层，特别是铝覆盖层相粘结。聚异氰脲酸酯泡沫材料优选地是硬质泡沫材料，根据其在10％压缩比时(Stauchung)的压应力界定，或者更准确而言为≥100kPa至≤300kPa。该压应力或抗压强度可以根据DIN 53421/DIN ENISO 604测定。它也可以为≥150kPa至≤250kPa或≥180kPa至≤280kPa的范围。
优选地，在根据本发明的方法中，泡沫材料层的表观密度≥25g/l至≤48g/l，特别优选地≥35g/l至≤45g/l。泡沫材料层的表观密度按照ISO 845标准进行测定。在最优选的实施方案中，泡沫材料层的表观密度为≥37g/l至≤42g/l，进一步优选地≥39g/l至≤40g/l。此外，不依赖于此，也可能的是，泡沫材料层(其中通常也应当理解为泡沫材料层的泡沫)具有≥85％至≤100％，优选≥90％至≤100％的闭孔度，其中闭孔度根据DIN ISO 4590进行测定。此外，根据ASTM 3576-77，泡沫材料层优选地具有≥10μm至≤600μm，特别优选≥50μm至≤400μm的平均孔直径。
此外，本发明涉及具有≥10％至≤29％，优选地≥10％至≤25％，特别优选地≥12％至≤20％的游离多异氰酸酯基团含量的改性异氰酸酯在制备泡沫材料复合元件中作为增附剂的应用。改性异氰酸酯的细节已经在上面作了描述，因此在此可以将其全部内容引入作为参考。
在根据本发明的应用的一个实施方案中，氨基甲酸酯改性异氰酸酯能由单体和/或聚合的二苯基甲烷二异氰酸酯与聚醚多元醇的反应获得，其具有≥2至≤8，优选≥2至≤6，特别优选≥2至≤3的平均官能度。为此，关于细节内容，也将前文描述引入作为参考。
实施例
本发明将借助于后面的实施例进行详细描述。
实施例1：改性异氰酸酯的制备
在搅拌下，在95℃，让527.0g由10.0重量％的2，4′-二苯基甲烷二异氰酸酯、80.0重量％的4，4′-二苯基甲烷二异氰酸酯和10.0重量％聚合MDI组成的、在25℃粘度为200mPas的异氰酸酯和472.0g通过向作为起始分子的甘油加入90重量％的环氧丙烷和10重量％的环氧乙烷而制备的、主要具有仲羟基基团的、OH值为46mg KOH/g的聚醚多元醇的混合物反应两小时。测得的游离异氰酸酯基团的含量为15.3％。在25℃的粘度为1600mPas。
实施例2：
改性异氰酸酯的制备根据实施例1进行。使483.0g实施例1的异氰酸酯混合物与347.0g通过向作为起始物的山梨醇添加81重量％的环氧丙烷和19重量％的环氧乙烷而制备的、主要具有伯羟基基团的、OH值为28mg KOH/g的聚醚多元醇发生反应。测得的游离异氰酸酯基团的含量为18.0％。在25℃的粘度为1100mPas。
实施例3：
改性异氰酸酯的制备根据实施例1进行。450.0g实施例1的异氰酸酯混合物与550.0g实施例1的聚醚多元醇发生反应。测得的游离异氰酸酯基团的含量为12.1％。在25℃的粘度为3856mPas。
实施例4：
改性异氰酸酯的制备根据实施例1进行。700.0g实施例1的异氰酸酯混合物与300.0g实施例1的聚醚多元醇发生反应。测得的游离异氰酸酯基团的含量为21.1％。在25℃的粘度为425mPas。
实施例4A：
改性异氰酸酯的制备根据实施例1进行。700.0g NCO-含量为29.5％以及碳二亚胺含量为23％的碳二亚胺化的4，4′-二异氰酸根合二苯基甲烷与300g通过向作为起始剂的甘油添加90重量％的环氧丙烷和10重量％的环氧乙烷而制备的、主要具有仲羟基基团的、OH值为46的聚醚多元醇发生反应。测得的游离异氰酸酯基团的含量为19.5％。在25℃的粘度为635mPas。
实施例5(对比)：
向1547.0通过向作为起始物的乙二醇添加100重量％的环氧丙烷而制备的、OH值为56mg KOH/g的聚醚多元醇滴加100g实施例1的异氰酸酯并且将反应混合物在95℃加热2小时。不再能检测到游离NCO基团。在25℃的粘度为5497mPas。
实施例6：改性异氰酸酯的制备
在搅拌下，在95℃，让2640.0g实施例1的异氰酸酯混合物、360.0g实施例1的聚醚多元醇的混合物反应两小时。测得的游离异氰酸酯基团的含量为27.8％。在25℃的粘度为96mPas。
实施例7：改性异氰酸酯的制备
在搅拌下，在95℃，让969.0g实施例1的异氰酸酯混合物、2031.0g实施例1的聚醚多元醇的混合物反应两小时。测得的游离异氰酸酯基团的含量为7.8％。在25℃的粘度为13491mPas。
实施例8至16：
用例如在EP 1 593 438 A2中所描述的装置在预加热至40℃的铝片上施加各个增附剂组合物。在每一情况下所使用的增附剂量说明于表1中。
然后，施加具有以下组成的聚异氰脲酸酯泡沫：
A-组分：
39份官能度为2、羟值为310mg KOH/g的得自邻苯二甲酸酐、二乙二醇和乙二醇的聚醚酯醇1。15.7份具有官能度为2和羟值为28mg KOH/g的自丙二醇、环氧丙烷和环氧乙烷的聚醚醇1；
12份官能度为3和羟值为380mg KOH/g的得自糖、乙二醇和环氧丙烷的聚醚醇2；
25份阻燃剂1(磷酸三氯异丙酯，TCPP)；
5份稳定剂1(含硅酮稳定剂)；
3.5份催化剂1(PIR-催化剂，羧酸的盐)；
2.5份聚酯醇1(由邻苯二甲酸酐和二乙二醇组成)；
2.5份催化剂2(含胺的聚氨酯催化剂)；
发泡剂1(正戊烷)，发泡剂2(水)；
B-组分：
Desmodur 44V70L(聚合的MDI，得自Bayer Material Science AG)。
依据DIN 53292标准检测粘附强度。这里，在实施时与根据DIN 53292-82的垂直于覆盖层平面拉伸试验的区别在于不同的试样厚度和覆盖层数目。在根据DIN 53292-82的试验中，以覆盖层的总厚度为基础。这里，整个试样的最弱区域确定为断裂处。与此不同，本文所描述的变化形式(Abwandlung)中的粘附试验可以评价与面有关的粘附。
因此，为了取样，垂直于覆盖层切割复合元件。在测量中，使用正方形试样，其边长为50mm并且其试样高度为15mm(包括覆盖层在内)。
同样，检测在105℃退火1小时后的气泡形成。
表1：所使用的增附剂的变体
1)由于出现气泡未测量。
2)由于太高的粘度，未施加预聚物。
3)作为增附剂，使用Desmodur 44V70L(聚合的MDI，从Bayer Material ScienceAG获得，所测得的游离异氰酸酯基团的含量为31.0％)。
4)测不到任何粘附，不仅在刚发泡后而且在发泡后24小时覆盖层脱落而没有可测量的聚异氰脲酸酯泡沫的粘附。
Vgl＝对比实施例
此外观察到，在根据本发明的体系中，在将泡沫材料复合元件在105℃热存放1小时后，在下覆盖层范围中的泡沫与覆盖层之间的边界是无气泡的。如果不使用增附剂或者在不充分混合2组分增附剂的情况下，在下覆盖层范围中的热存放期间，形成不希望的气泡。
实施例17至22：
将根据实施例1的改性异氰酸酯作为增附剂使用并且改变所使用的增附剂的量。用例如在EP 1 593 438 A2中所描述的装置在预加热至40℃的铝片上施加增附剂组合物。所使用的增附剂的量如表2中所示。
然后，施加具有下述组成的聚氨酯泡沫：
A-组分：
31份官能度为5、羟值为435mg KOH/g的得自邻苯二甲酸酐、二乙二醇、山梨醇和环氧丙烷的聚醚酯多元醇1。
10份官能度为6.2和羟值为370mg KOH/g的得自邻苯二甲酸酐、己二酸、油酸和三羟甲基丙烷的聚酯多元醇1；
7份官能度为3和羟值为380mg KOH/g的得自三羟甲基丙烷和环氧丙烷的聚醚多元醇1；
3份官能度为4和羟值为420mg KOH/g的得自甲苯二胺和环氧乙烷和环氧丙烷的聚醚多元醇2；
12份官能度为3和羟值为235mg KOH/g的得自二溴丁烯二醇和表氯醇的具有卤素部分的聚醚多元醇；
31份阻燃剂1(磷酸三氯异丙酯，TCPP)；
3.5份甘油；
2份OS 340(含硅酮的稳定剂，能由Bayer Material Science AG获得)；
2.5份Desmorapid 1792(PIR-催化剂，羧酸的盐，能由Bayer MaterialScience AG获得)；
3.5份Desmorapid VP 1221 VN(含胺的聚氨酯催化剂，能由Bayer MaterialScience AG获得)；
发泡剂1(正戊烷)，
发泡剂2(水)；
B-组分：
Desmodur 44V70L(聚合的MDI，能由Bayer Material Science AG获得)。
如上面所描述地检验粘附强度。
表2：增附剂量的变化(根据实施例1的预聚物)

Claims (11)

1.用于制备泡沫材料复合元件的方法，其包括以下步骤： 
A)准备覆盖层； 
B)在该覆盖层上施加增附剂层，其中该增附剂层包含改性异氰酸酯； 
C)在该增附剂层上施加包含聚氨酯和/或聚异氰脲酸酯的泡沫材料层，其中在施加时，增附剂层中的所述改性异氰酸酯具有≥10％至≤29％的游离异氰酸酯基团含量，其中所述改性异氰酸酯是碳二亚胺改性异氰酸酯或氨基甲酸酯改性异氰酸酯。 
2.根据权利要求1的方法，其中在施加时，增附剂层中的所述改性异氰酸酯具有≥10％至≤25％的游离异氰酸酯基团含量。 
3.根据权利要求1的方法，其中所述覆盖层的材料包括铝、钢、沥青、纸、矿物-无纺布、包含有机纤维的无纺布、塑料板、塑料膜和/或木板。 
4.根据权利要求1的方法，其中所述增附剂层中的氨基甲酸酯改性异氰酸酯能由单体和/或聚合的二苯基甲烷二异氰酸酯与聚醚多元醇的反应获得，其中该聚醚多元醇具有≥2至≤8的平均官能度。 
5.根据权利要求1的方法，其中在所述覆盖层上以≥20g/m2至≤50g/m2的量施加增附剂层。 
6.根据权利要求1的方法，其中在所述覆盖层上以≥30g/m2至≤40g/m2的量施加增附剂层。 
7.根据权利要求1的方法，其中所述泡沫材料层能由包含多异氰酸酯与至少一种选自聚酯多元醇和聚醚多元醇中的化合物的反应混合物反应获得，其中在反应开始的时候，在反应混合物中，异氰酸酯基团与羟基基团的摩尔比为≥1∶1至≤5∶1。 
8.根据权利要求1的方法，其中泡沫材料层的表观密度为≥25g/l至≤48g/l。 
9.根据权利要求1的方法，其中在步骤A)中，所述覆盖层的材料包括铝、钢、纸、塑料板、塑料膜和/或木板，在步骤B)中，增附剂层是氨基甲酸酯改性异氰酸酯，其能由单体和/或聚合的二苯基甲烷二异氰酸酯与聚醚多元醇反应获得，并且其中在该覆盖层上以≥20g/m2至≤50g/m2的量施加增附剂层。 
10.具有≥10％至≤29％的游离异氰酸酯基团含量的改性异氰酸酯在制备泡沫材料复合元件中作为覆盖层与包含聚氨酯和/或聚异氰脲酸酯的泡沫层之间的增附剂层的应用，其中所述改性异氰酸酯是碳二亚胺改性的或氨基甲酸酯改性的异氰酸酯。 
11.根据权利要求10的应用，其中所述氨基甲酸酯改性异氰酸酯能由单体和/或聚合的二苯基甲烷二异氰酸酯与聚醚多元醇反应获得，该聚醚多元醇具有从≥2至≤8的平均官能度。 
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