CN111002681B - 一种聚氨酯蜂窝纸板玻毡复合材料及其制备方法 - Google Patents

一种聚氨酯蜂窝纸板玻毡复合材料及其制备方法 Download PDF

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CN111002681B
CN111002681B CN201911293466.4A CN201911293466A CN111002681B CN 111002681 B CN111002681 B CN 111002681B CN 201911293466 A CN201911293466 A CN 201911293466A CN 111002681 B CN111002681 B CN 111002681B
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honeycomb paperboard
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陆伟
李涛
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Huicai Material Science And Technology Suzhou Co ltd
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Abstract

本发明公开了一种聚氨酯蜂窝纸板玻毡复合材料，聚氨酯的原料包括A组分和B组分，按重量份计，A组分包括如下原料：以蔗糖、甘油为起始剂、数均分子量为450～550的聚醚60～70份；以甘油为起始剂、数均分子量为5000～6000的聚醚15～25份；表面活性剂0.5～1.5份；催化剂0.5～1.5份；助剂8～15份；水0.5～1.5份；其中，助剂包括质量比为1:0.6～0.7的交联剂和扩链剂；交联剂为甘油、二乙醇胺、三乙醇胺、乙二胺聚醚中的一种或多种；扩链剂为乙二醇、二乙二醇、丙二醇、二丙二醇、三丙二醇、1，4‑丁二醇中的一种或多种。本发明促进聚氨酯蜂窝纸板玻毡复合材料表面的熟化和成皮，使得聚氨酯蜂窝纸板玻毡复合材料表面光滑和富有光泽，从而使产品的外观得以提高。

Description

一种聚氨酯蜂窝纸板玻毡复合材料及其制备方法
技术领域
本发明属于化工材料领域，具体涉及一种聚氨酯蜂窝纸板玻毡复合材料及其制备方法。
背景技术
聚氨酯泡沫具有绝热效果好，比强度大，电学性能、耐化学药品以及隔音效果优越等特点，广泛用作绝热保温材料、结构材料以及隔音材料等。今天，聚氨酯泡沫已渗透到建筑、石油化工、冷藏、造船、车辆、航空、机械、仪表等很多部门。聚氨酯泡沫是以异氰酸酯和聚醚为主要原料，在发泡剂、催化剂、阻燃剂等多种助剂的作用下，通过专用设备混合，发泡而成的高分子聚合物。随着汽车行业对于轻量化、低油耗、低成本、低污染、高安全性和高舒适性的要求越来越严格，更多的新型材料被应用于汽车零件的制造中。聚氨酯蜂窝纸板玻纤复合材料具有重量轻、弯曲强度大、尺寸稳定性好、耐腐蚀、生产效率高、设计灵活等优点，可大大节约原料成本和制造成本，符合轻量化的大趋势。在汽车结构中，聚氨酯蜂窝纸板玻纤复合材料可应用于天窗、备胎盖板、行李箱隔板、搁物板等多个部位。聚氨酯蜂窝纸板玻纤复合材料一般采用喷涂布料，模压发泡成型的工艺。操作过程是：由高压发泡机将A组分、B组分混合后均匀喷涂在铺设玻毡的蜂窝纸板上，送入预热的模具，经模压反应约100秒左右成型后取出零件，修边。
聚氨酯蜂窝纸板玻纤复合材料成型快，在快速熟化过程中，如何形成良好的零件表面状态和填充状态是一个需要持续改进的问题。为了妥善协调解决这些技术问题，发泡料配方的调节是关键。目前市场上的产品出现的问题多是光泽度差，零件表面状态不良，不适合用于高端车中使用的不覆面的聚氨酯蜂窝纸板玻纤复合材料零件的生产。
发明内容
本发明的目的是提供一种表面光泽度好的聚氨酯蜂窝纸板玻毡复合材料及其制备方法。
为实现上述目的，本发明采用如下技术方案：
本发明一方面是提供一种聚氨酯蜂窝纸板玻毡复合材料，包括蜂窝纸板、铺设在所述的蜂窝纸板上的玻纤毡、成型在所述的玻纤毡上的聚氨酯，所述的聚氨酯的原料包括A组分和B组分，
按重量份计，所述的A组分包括如下原料：
Figure BDA0002319840680000011
Figure BDA0002319840680000021
其中，所述的助剂包括质量比为1:0.6～0.7的交联剂和扩链剂；所述的交联剂为甘油、二乙醇胺、三乙醇胺、乙二胺聚醚中的一种或多种；所述的扩链剂为乙二醇、二乙二醇、丙二醇、二丙二醇、三丙二醇、1，4-丁二醇中的一种或多种；
所述的B组分包括异氰酸酯。
本发明通过采用特定的交联剂和扩链剂，并与配方中的其他原料复配，促进聚氨酯表面的熟化和成皮，使得聚氨酯蜂窝纸板玻毡复合材料表面光滑、富有光泽，从而使产品的外观得以提高。
优选地，所述的交联剂为三乙醇胺，所述的扩链剂为二丙二醇，从而可以进一步提高产品的外观。
优选地，所述的以蔗糖、甘油为起始剂、数均分子量为450～550的聚醚的聚合单体为环氧丙烷，以环氧丙烷封端。
优选地，所述的以甘油为起始剂、数均分子量为5000～6000的聚醚的聚合单体为质量比为70～100:0～30的环氧丙烷和环氧乙烷，以环氧乙烷封端。
优选地，所述的助剂还包括2～4份的着色剂。
进一步优选地，所述的着色剂为3U-504、5U-506、X41LV、X95AB中的一种或多种。
优选地，所述的表面活性剂为聚氨酯硬泡表面活性剂。
进一步优选地，所述的表面活性剂为L-6900、B 8462、B 8465、B 8474、B 8870中的一种或多种。
优选地，所述的催化剂为胺类催化剂。
进一步优选地，所述的胺类催化剂为三亚乙基二胺、N,N-二甲基环已胺、三乙胺、二甲基苄胺、N，N’,N”-三(二甲氨丙基)-六氢三嗪、N,N,N’,N”-四甲基丁二胺、四甲基已二胺、五甲基二亚乙基三胺、四甲基二氨基乙基醚、二甲基哌嗪、1,2-二甲基咪唑、三乙醇胺、二乙醇胺、三异丙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、二甲基乙醇胺中的一种或多种。
优选地，所述的异氰酸酯为聚合MDI。
优选地，所述的A组分和所述的B组分的投料质量比为1:1.5～2.0。
本发明另一方面是提供一种所述的聚氨酯蜂窝纸板玻毡复合材料的制备方法，将所述的A组分和所述的B组分经高压发泡机混合后，喷涂在铺设有所述的玻纤毡的蜂窝纸板上，经模压成型制得。
本发明第三方面是提供一种所述的聚氨酯蜂窝纸板玻毡复合材料在汽车配件中的应用。
本发明中的汽车配件可以为汽车天窗、备胎盖板、行李箱隔板、搁物板等功能性配件。
本发明中的原料均可市购获得，各原料只需满足本专利所要求的指标，均可解决本发明的技术问题。例如，以蔗糖、甘油为起始剂、数均分子量为350～450的聚醚和以甘油为起始剂、数均分子量为5000～6000的聚醚均可从市场上几家主流的聚醚生产厂家购得；聚合MDI可以使用亨斯迈公司的H5005、巴斯夫的M20S、科思创的44V20L和万华的PM 200等。
由于以上技术方案的实施，本发明与现有技术相比具有如下优点：
本发明在不改变生产设备和工艺的条件下，通过聚氨酯A料配方中交联剂和扩链剂的改进，与聚氨酯其他原料组分的配合，促进聚氨酯蜂窝纸板玻毡复合材料表面的熟化和成皮，使得聚氨酯蜂窝纸板玻毡复合材料表面光滑和富有光泽，从而使产品的外观得以提高。
具体实施方式
下面将对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。本发明以下实施例中未注明的实验手段或测试手段，在没有特别说明时，均为本领域常规手段。本发明以下实施例中未注明的用量及用量比均为质量及质量比。
以下实施例和对比例所涉及的原料：
(1)以蔗糖、甘油为起始剂，1,2-环氧丙烷为聚合单体，1,2-环氧丙烷封端的数均分子量为500的聚环氧丙烷聚醚多元醇；
(2)以甘油为起始剂，1,2-环氧丙烷为聚合单体，环氧乙烷封端的数均分子量为5000的聚环氧丙烷/环氧乙烷聚醚多元醇；
(3)用于硬质聚氨酯泡沫的表面活性剂B 8462；
(4)用于硬质聚氨酯泡沫的催化剂三亚乙基二胺；
(5)交联剂三乙醇胺；
(6)扩链剂二丙二醇；
(7)交联剂三乙醇胺：扩链剂二丙二醇＝1：2；
(8)交联剂三乙醇胺：扩链剂二丙二醇＝2：3；
(9)交联剂三乙醇胺：扩链剂二丙二醇＝1：1；
(10)交联剂三乙醇胺：扩链剂二丙二醇＝3：2；
(11)交联剂三乙醇胺：扩链剂二丙二醇＝2：1；
(12)着色剂5U-506；
(13)水
用以上13种原料按表1的配方比例(重量份)分别配制成A组分，然后取A组分的重量100份，和170份异氰酸酯聚合MDI反应，生成硬质聚氨酯泡沫。硬质聚氨酯泡沫密度的检测方法为ISO 845；各配方在实验室用模具制成10mm厚度平板样件后测试表面光泽度，表面光泽度测试标准依据GB 8807-88；以最好的配方在客户生产线上喷涂并模压成型制作聚氨酯蜂窝纸板玻毡复合材料零件并测试表面光泽度。各实施例和对比例的检测结果见表1。
表1
Figure BDA0002319840680000041
Figure BDA0002319840680000051
从表1可见，由于对比例配方中的交联剂和扩链剂比例没有优化，表面光泽度都不理想。在交联剂较多的情况下造成泡沫在发泡过程中受到的流动阻力偏大，泡沫表面受到较大的剪切力，使表面平整度下降，影响了表面光泽度；而在扩链剂较多的情况下泡沫熟化较慢，表面成皮较薄，平整度不够，影响了表面光泽度。由此可见，实施例1的配方是最佳配方，聚氨酯蜂窝纸板玻毡复合材料零件产品光泽度高，物理性能好。
需要说明的是，以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (9)

1.一种聚氨酯蜂窝纸板玻毡复合材料，其特征在于：包括蜂窝纸板、铺设在所述的蜂窝纸板上的玻纤毡、成型在所述的玻纤毡上的聚氨酯，所述的聚氨酯的原料包括A组分和B组分，
按重量份计，所述的A组分包括如下原料：
以蔗糖、甘油为起始剂、数均分子量为450~550的聚醚 60~70份；
以甘油为起始剂、数均分子量为5000~6000的聚醚 15~25份；
表面活性剂 0.5~1.5份；
催化剂 0.5~1.5份；
助剂 8~15份；
水 0.5~1.5份；
其中，所述的助剂包括质量比为1:0.6~0.7的交联剂和扩链剂；所述的交联剂为三乙醇胺；所述的扩链剂为二丙二醇；
所述的B组分包括异氰酸酯。
2.根据权利要求1所述的聚氨酯蜂窝纸板玻毡复合材料，其特征在于：所述的以蔗糖、甘油为起始剂、数均分子量为450~550的聚醚的聚合单体为环氧丙烷，以环氧丙烷封端；所述的以甘油为起始剂、数均分子量为5000~6000的聚醚的聚合单体为质量比为70~100:0~30的环氧丙烷和环氧乙烷，以环氧乙烷封端。
3.根据权利要求1所述的聚氨酯蜂窝纸板玻毡复合材料，其特征在于：所述的助剂还包括2~4份的着色剂。
4.根据权利要求3所述的聚氨酯蜂窝纸板玻毡复合材料，其特征在于：所述的着色剂为3U-504、5U-506、X41LV、X95AB中的一种或多种。
5.根据权利要求1所述的聚氨酯蜂窝纸板玻毡复合材料，其特征在于：所述的表面活性剂为聚氨酯硬泡表面活性剂，所述的催化剂为胺类催化剂。
6. 根据权利要求5所述的聚氨酯蜂窝纸板玻毡复合材料，其特征在于：所述的表面活性剂为L-6900、B 8462、B 8465、B 8474、B 8870中的一种或多种；所述的胺类催化剂为三亚乙基二胺、N,N-二甲基环已胺、三乙胺、二甲基苄胺、N，N’,N”-三(二甲氨丙基)-六氢三嗪、N,N,N’,N”-四甲基丁二胺、四甲基已二胺、五甲基二亚乙基三胺、四甲基二氨基乙基醚、二甲基哌嗪、1,2-二甲基咪唑、三乙醇胺、二乙醇胺、三异丙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、二甲基乙醇胺中的一种或多种。
7.根据权利要求1所述的聚氨酯蜂窝纸板玻毡复合材料，其特征在于：所述的异氰酸酯为聚合MDI，所述的A组分和所述的B组分的投料质量比为1:1.5~2.0。
8.一种如权利要求1至7中任一项所述的聚氨酯蜂窝纸板玻毡复合材料的制备方法，其特征在于：将所述的A组分和所述的B组分经高压发泡机混合后，喷涂在铺设有所述的玻纤毡的蜂窝纸板上，经模压成型制得。
9.一种如权利要求1至7中任一项所述的聚氨酯蜂窝纸板玻毡复合材料在汽车配件中的应用。
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