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CN103703046A - 用聚脲浸渍的纸结构及其制造方法 - Google Patents

用聚脲浸渍的纸结构及其制造方法 Download PDF

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CN103703046A
CN103703046A CN201280037726.1A CN201280037726A CN103703046A CN 103703046 A CN103703046 A CN 103703046A CN 201280037726 A CN201280037726 A CN 201280037726A CN 103703046 A CN103703046 A CN 103703046A
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R.阿尔巴赫
H-D.阿恩茨
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Abstract

本发明涉及抗压和抗弯的用氨基甲酸酯改性的聚脲浸渍的纸结构及其制备方法。

Description

用聚脲浸渍的纸结构及其制造方法
本发明涉及抗压和抗弯的用氨基甲酸酯改性的聚脲浸渍的纸结构及其制备方法。
承重结构的构造中,例如在汽车构造中,使用夹层构件用于减轻重量。所述夹层构件由轻质的芯层和结实的粘附在两侧的面层构成。作为轻质的芯层使用得自聚苯乙烯、聚氨酯的硬质泡沫,塑料织物或纸结构,例如纸蜂窝。作为面层尤其可使用胶合板、玻璃纤维增强塑料或金属箔。
这种复合材料的目的是,在尽可能小的重量的情况下实现最大承载能力。但是,在使用便宜的纸蜂窝时,湿敏性是一个屏障。为了提高纸蜂窝在潮湿条件下的负荷能力,通常将其用合成树脂浸渍并由此使其加强。相应合适的合成树脂可以是甲醛缩合物 (US-A 6372322) 和聚酯树脂。也描述了基于异氰酸酯的合成树脂。醇酸树脂与异氰酸酯的组合也是已知的 (US-A 2744042)。
W. J. McKillip等人描述甲苯二异氰酸酯优于脂族异氰酸酯。根据该作者,亚甲基二苯基二异氰酸酯在其反应性方面又优于甲苯二异氰酸酯。
US-A 5008359中表明,聚合的二苯基甲烷二异氰酸酯 (MDI)是合适的。这里明确无需催化剂。
US-A 5292391和US-A 5332458 同样使用便宜的未改性的聚合二苯基甲烷二异氰酸酯 (MDI)。在US-A 5580243中使用的聚合MDI具有40-60%的单体4,4'-二苯基甲烷二异氰酸酯含量并具有宽的官能度和粘度范围。
US-A 5140086中公开了用有机溶剂,尤其是用丙二醇,稀释聚合二苯基甲烷二异氰酸酯带来反应速度的提高。三乙酸甘油酯和柠檬酸三乙酯 (US-A 5580922)以及磷酸酯 (US-A 5580243)同样被描述为溶剂和阻燃剂,并相应地使用。
描述于DE-A 102006016943、DE-A 102008033559和DE-A 102008051436中的夹层构件由具有改善了抗压强度的用异氰酸酯-改进的纸蜂窝的芯材料制成。
因此,本发明的目的是提供纸结构,其a)不包含溶剂或不使用溶剂制成并因此可用于室内,b) 可以没有困难地并且在短时间内制成支承元件和c) 使用足够亲水的合成树脂用于其湿固化。如此得到的纸结构应具有显著改善的抗弯刚性或抗压刚性。
令人惊讶地,所述目的可通过用聚脲-浸渍的纸结构得以实现,其中用含氧化乙烯的长链聚醚化学改性在浸渍中使用的异氰酸酯。由此可提高所述纸结构的硬度,尽管由于用聚醚改性使得在所使用的异氰酸酯中对于所述纸结构和聚脲的交联而言必不可少的每质量单元的异氰酸酯基团的含量明显减少。此外令人惊奇的是,聚脲中柔性链段的引入(得自用含氧化乙烯的聚醚进行的异氰酸酯的改性)导致硬度和抗弯刚性的改善。
本发明的主题是通过用异氰酸酯浸渍和随后与水、水蒸汽和/或空气水分反应制备抗压和抗弯的纸结构的方法,其特征在于,
i) 用至少一种或多种具有氨基甲酸酯基团的NCO-预聚物浸渍所述纸结构,其中,所述NCO-预聚物具有18-27重量%的NCO-含量,其中所述预聚物是下述物质的反应产物:
     A) 二苯基甲烷二异氰酸酯-异构体和任选它们的高级同系物和任选具有至少50重量%,优选60-90重量%单体二苯基甲烷二异氰酸酯的改性的二苯基甲烷二异氰酸酯,与
     B) 聚合的聚环氧烷,其每分子具有1.8-8,优选2-6,特别优选3-6 个异氰酸酯反应性基团(数均官能度)并具有基于聚环氧烷计的至少5-100重量%,优选至少13-90重量%,特别优选至少17-90重量%,非常特别优选至少25-85重量%的氧化乙烯单元,和/或具有分子量为1000-15000的聚合的聚碳酸酯多元醇,
     任选与改性的二苯基甲烷二异氰酸酯混合
     和
ii) 使所述至少一种或多种NCO-预聚物与水、水蒸汽和/或空气水分反应。
所述聚环氧烷优选具有1000-15000,特别优选3000-13000的分子量,并且可以部分或完全被分子量为1000-15000的聚碳酸酯多元醇替代。
优选地,将催化剂以0.05-1重量%的量添加到所述预聚物中,基于组分A)和B)的总和计。使用含金属的催化剂作为优选的催化剂。
在一个优选的工艺方案中,将如在聚氨酯化学中通常使用的催化剂添加到水中。所述催化剂包括例如羧化物、酚盐、氧化胺,且特别优选叔胺催化剂,以基于所使用的用于固化的水计0.05-40重量%的量,其每分子优选包含2-4个羟基。作为优选的胺催化剂例如可提及:每个乙二胺具有3-8分子氧化丙烯的烷氧基化的乙二胺,烷氧基化的三乙醇胺和其它烷氧基化的胺,任选与三亚乙基二胺和/或五甲基二亚乙基三胺、二甲基苄胺或其它现有技术已知的叔胺混合。
4,4'-二苯基甲烷二异氰酸酯与2,4'-二苯基甲烷二异氰酸酯的重量比优选为5:1-1:2。
改性的二苯基甲烷二异氰酸酯,例如脲酮亚胺(uretonimines)、碳二亚胺或异氰脲酸酯,也可用作制备NCO-预聚物的异氰酸酯组分。
为提高该加强纸结构的耐火性,特别有利的是向所述NCO-预聚物中添加由现有技术已知的液体或固体阻燃剂(例如有机和/或无机磷酸盐或亚磷酸盐、可膨胀石墨)。
本发明的另一主题是用至少一种具有氨基甲酸酯基团的聚脲浸渍的抗压和抗弯的纸结构,其中所述具有氨基甲酸酯基团的聚脲可得自
a) 一种或多种具有氨基甲酸酯基团的NCO-预聚物,其具有18-27重量%的NCO-含量,可得自
     A) 二苯基甲烷二异氰酸酯-异构体和任选它们的高级同系物和任选具有至少50重量%,优选60-90重量%单体二苯基甲烷二异氰酸酯的改性的二苯基甲烷二异氰酸酯,与
     B) 聚合的聚环氧烷,其每分子具有1.8-8,优选2-6,特别优选3-6 个异氰酸酯反应性基团(数均官能度)并具有基于聚环氧烷计的至少5-100重量%,优选至少13-90重量%,特别优选至少17-90重量%,非常特别优选至少25-85重量%的氧化乙烯单元,和/或具有分子量为1000-15000的聚合的聚碳酸酯多元醇,
a') 任选与改性的二苯基甲烷二异氰酸酯混合,和
b) 水、水蒸汽和/或空气水分。
本发明另一主题是夹层构件,其特征在于,其具有
i) 由根据本发明的纸结构制成的芯和
ii) 至少一层位于所述芯的两面的至少一面上的纤维增强的聚脲和/或聚氨酯的层。
所述纸结构的浸渍例如通过将该纸结构浸在预聚物中或通过将预聚物施加在纸结构上或通过用预聚物喷涂该纸结构来进行。
纸的重量水平、纸的品质(按照纤维结构定义)和蜂窝尺寸对蜂窝的(抗压)-强度具有相互作用。
在将涂层材料(NCO-预聚物) 施加到纸结构(优选纸蜂窝)上之后,其应优选渗透直至进到该纸结构的纤维中。因此,优选使用一方面具有好的吸收能力而另一方面在浸渍时不会太过溶胀并由此失去结构和强度的纸的品质。
为优化材料的使用(NCO-预聚物),在浸渍纸结构之后,优选从纸结构上除去过量的涂层材料(NCO-预聚物),例如通过敲除、擦除或借助干燥的压缩空气或其它干燥的压缩气体。
通过随后添加水,例如通过喷雾、通过浸渍或浇灌,该NCO-预聚物反应,解离出二氧化碳并形成泡沫,该泡沫也可填塞该纸结构(例如纸蜂窝)的内部。
通过根据本发明的纸结构的浸渍,可使其防水、耐化学品以及比未经处理的纸结构显著更加抗弯。因此,它们也适用于室外领域。
所述加强纸结构可用作制造夹层构件的间隔材料。
可借助下面的实施例进一步说明本发明。
实施例:
起始化合物:
异氰酸酯 A是基于二苯基甲烷二异氰酸酯的NCO-预聚物,其具有NCO-含量为23重量%和在25℃下的粘度为405 mPa·s。其包含25重量%基于丙三醇的聚合的聚环氧烷,所述聚环氧烷具有4500的重均分子量和73重量%的氧化乙烯含量。所使用的MDI有83重量%的单体MDI和6重量%的脲酮亚胺,所述单体MDI具有2.9:1的4,4'-MDI与2,4'-MDI的重量比。
异氰酸酯 B是基于二苯基甲烷二异氰酸酯的NCO-预聚物,其具有NCO-含量为21.3重量%和在25℃下的粘度为680 mPa·s。其包含31重量%基于丙二醇和丙三醇的聚合的聚环氧烷,所述聚环氧烷具有3830的重均分子量和61重量%的氧化乙烯含量。所使用的MDI有72重量%的单体MDI,所述单体MDI具有2.2:1的4,4'-MDI与2,4'-MDI的重量比。
异氰酸酯C是基于二苯基甲烷二异氰酸酯的NCO-预聚物,其具有NCO-含量为22重量%和在25℃下的粘度为750 mPa·s。其包含24.7重量%基于丙二醇和丙三醇的聚合的聚环氧烷,所述聚环氧烷具有4840的重均分子量和17重量%的氧化乙烯含量。所使用的MDI有60重量%的单体MDI,所述单体MDI具有2.9:1的4,4'-MDI与2,4'-MDI的重量比。
异氰酸酯D是基于二苯基甲烷二异氰酸酯的NCO-预聚物,其具有NCO-含量为23.5重量%和在25℃下的粘度为534 mPa·s。其包含24.7重量%基于丙三醇的聚合的聚环氧烷,所述聚环氧烷具有6000的重均分子量和17重量%的氧化乙烯含量。所使用的MDI有53重量%的单体MDI和大约2重量%的脲酮亚胺,所述单体MDI具有2.4:1的4,4'-MDI与2,4'-MDI的重量比。
异氰酸酯 E是用异丙二醇碳酸酯稀释的未改性的聚合的二苯基甲烷二异氰酸酯,其具有在25℃下的粘度为63 mPa·s和大约24重量%的NCO-含量。
所使用的纸蜂窝具有5 mm 的蜂窝直径,6.5 mm的高度和430 g/m2的定量。
实验的施行:
在室温下将所述纸浸入相应的异氰酸酯中,并在借助纸浆除去过量的异氰酸酯后,用没有添加催化剂的水在80℃经24小时的时间使异氰酸酯固化。
在经如此浸渍的纸蜂窝上根据DIN EN ISO 826测得抗压强度和根据DIN EN ISO 178测得抗弯强度。结果在下表中给出:
表:
Figure 363659DEST_PATH_IMAGE001
*根据DIN ISO 845
抗弯强度以恒定的80mm的跨距测定。
由该表可知,相较于使用聚合MDI (异氰酸酯 E),使用NCO-预聚物 A、B、C和D赋予纸结构改善的抗弯强度和/或抗压强度。

Claims (6)

1.制备抗压和抗弯的纸结构的方法,所述方法通过用异氰酸酯浸渍和随后与水、水蒸汽和/或空气水分反应进行,其特征在于,
i) 用至少一种或多种具有氨基甲酸酯基团的NCO-预聚物浸渍所述纸结构,其中,所述NCO-预聚物具有18-27重量%的NCO-含量,其中所述预聚物是下述物质的反应产物:
     A) 二苯基甲烷二异氰酸酯-异构体和任选它们的高级同系物和任选具有至少50重量%的单体二苯基甲烷二异氰酸酯的改性的二苯基甲烷二异氰酸酯,与
     B) 聚合的聚环氧烷,其每分子具有1.8-8个异氰酸酯反应性基团并具有基于聚环氧烷计的至少5-100重量%的氧化乙烯单元,和/或具有分子量为1000-15000的聚合的聚碳酸酯多元醇,
     任选与改性的二苯基甲烷二异氰酸酯混合
ii) 使所述至少一种或多种NCO-预聚物与水、水蒸汽和/或空气水分反应。
2.根据权利要求1的方法,其特征在于,将催化剂以0.05-1重量%的量添加到所述NCO-预聚物中,基于所述NCO-预聚物计。
3.根据权利要求1的方法,其特征在于,将每分子含2-4个羟基的叔胺催化剂以0.05-40重量%的量添加到水中,基于所使用的水计。
4.根据权利要求1的方法,其特征在于,4,4'-二苯基甲烷二异氰酸酯与2,4'-二苯基甲烷二异氰酸酯的重量比为5:1-1:2。
5.用至少一种具有氨基甲酸酯基团的聚脲浸渍的抗压和抗弯纸结构,其中所述具有氨基甲酸酯基团的聚脲可得自
a) 一种或多种具有氨基甲酸酯基团的NCO-预聚物,其具有18-27重量%的NCO-含量,可得自
     A) 二苯基甲烷二异氰酸酯-异构体和任选它们的高级同系物和任选具有至少50重量%的单体二苯基甲烷二异氰酸酯的改性的二苯基甲烷二异氰酸酯,与
     B) 聚合的聚环氧烷,其每分子具有1.8-8个异氰酸酯反应性基团并具有基于聚环氧烷计的至少5-100重量%的氧化乙烯单元,和/或具有分子量为1000-15000的聚合的聚碳酸酯多元醇,
a') 任选与改性的二苯基甲烷二异氰酸酯混合,和
b) 水、水蒸汽和/或空气水分。
6.夹层构件, 其特征在于,所述夹层结构具有
i)由根据权利要求5的纸结构制成的芯和
ii)至少一层位于所述芯的两面的至少一面上的纤维增强的聚脲和/或聚氨酯的层。
CN201280037726.1A 2011-07-29 2012-07-25 用聚脲浸渍的纸结构及其制造方法 Pending CN103703046A (zh)

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SE357222B (zh) * 1968-08-27 1973-06-18 Takeda Chemical Industries Ltd
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US5140086A (en) 1988-11-25 1992-08-18 Weyerhaeuser Company Isocyanate modified cellulose products and method for their manufacture
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