CN1043235C - 聚氨酯泡沫塑料 - Google Patents

聚氨酯泡沫塑料 Download PDF

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CN1043235C
CN1043235C CN92114545A CN92114545A CN1043235C CN 1043235 C CN1043235 C CN 1043235C CN 92114545 A CN92114545 A CN 92114545A CN 92114545 A CN92114545 A CN 92114545A CN 1043235 C CN1043235 C CN 1043235C
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G·马列蒂
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Abstract

从聚异氰酸酯、作为发泡剂的水以及异氰酸酯反应性组合物制备软泡沫塑料的方法，所述组合物包含一种低氧化乙烯(EO)含量的多元醇、一种高EO含量的多元醇和胺链扩展剂/交联剂。

Description

聚氨酯泡沫塑料
将有机聚异氰酸酯如甲苯二异氰酸酯(TDI)或二苯基甲烷二异氰酸酯(MDI)与聚醚多元醇以及发泡剂一起反应制备聚氨酯软泡沫塑料的方法已相当成熟。聚醚通常是由氧化丙烯得出的聚氧化丙烯多元醇或是由氧化丙烯和氧化乙烯的各种组合得出的聚(氧化丙烯一氧化乙烯)多元醇。氧化乙烯封端的聚氧化丙烯多元醇类中，氧化烯基只占总氧化烯残系物的极小部分，由于它们对异氰酸酯有较高的反应性，从而特别重要。氧化乙烯含量较高的多元醇，例如含50％(重量)或更多氧化己烯的多元醇通常作为微量添加物使用，以确保泡沫塑料具有开孔结构。
现在发现，从二苯基甲烷二异氰酸酯和含一定比例含氧化乙烯多元醇和/或交联剂的多元醇组合物可制备具有有用特性的软泡沫塑料。特别是发现了本发明配方，它能够惊人地容许异氰酸酯指数的改变，所得泡沫塑料的特点是不需压碎便可得到开孔结构、高回弹性、高舒适指数和密度/硬度的极好组合以及极好的压缩变形性能。
从而，本发明提供从下述反应混合物制备软聚氨酯泡沫塑料的方法，该反应混合物包含聚异氰酸酯组分、多元醇组合物和作为发泡剂的水，其中聚异氰酸酯组分包含平均异氰酸酯官能度为2至2.4的二苯基甲烷二异氰酸酯组合物；多元醇组合物包含：(1)第一种多元醇组分，它包含至少一种含有氧化乙烯残基的聚氧
化烯多元醇，所述组分的平均标称羟基官能度至少为3，最好为
3-4；平均羟基当量至少为1500；平均氧化乙烯含量为10-20
重量％；且平均伯羟基含量大于50％；(2)第二种多元醇组分，它包含至少一种含有氧化乙烯残基的聚氧
化烯多元醇，所述组分的平均标称羟基官能度至少为2,2-4较
好，3-4更好；平均羟基当量至少为1000且平均氧化乙烯含量为
50-85重量％，和(3)一种链扩展剂和/或交联剂，它包含至少一种这样的化合物：
它具有至少两个异氰酸酯反应性基团，其中至少一个是伯或仲
氨基且分子量小于500，所述组成中每100重量份(1)含有4-
20重量份(2)和(3),(2)与(3)的重量比在1∶1到20∶1的
范围内。
本发明方法中，可用的二苯基甲烷二异氰酸酯组合物包括最好含至少60重量％的4,4′-异构体的“纯”MDI。因此，适当的聚异氰酸酯包括基本上纯的4,4′-异构体和异构体混合物，该混合的含不超过40％，不超过30％更好，不超过20％(重量)最好的2,4′-异构体和不超过5重量％的2,2′-异构体。其它适当的二苯基甲烷二异氰酸酯组合物包括平均异氰酸酯官能度为2-2.4、由上述二苯基甲烷二异氰酸酯衍生而来的MDI变体。这样的MDI变体是本领域公知的，并且包括通过引入脲烷、脲、缩二脲、碳化二亚胺、uretonimine和/或异氰脲酸酯残基得到的液体产物。
多元醇组合物中存在的每一种多元醇可以是具有所需官能度、当量和氧化乙烯含量的单一的聚氧化烯多元醇，最好是聚(氧化乙烯-氧化亚烯)多元醇。这样的多元醇是本领域公知的并可由下述常规方法得到：将氧化乙烯和氧化丙烯与具有所需量活性氢原子的引发剂反应，所述引发剂的例子有多元醇、羟胺、多元胺等。
或者，每一多元醇组分可包含两种或多种聚氧化烯多元醇混合物[最好是聚(氧化乙烯-氧化丙烯)多元醇]，使得总组成具有所需的平均官能度、当量和氧化乙烯含量(和包含第一种多元醇组分时，伯羟基的含量)。
此处“平均标称羟基官能度”是指在假设聚氧化烯多元醇的平均官能度与制备过程中所用的引发剂的平均官能度(每个分子中活性氢的数目)相同--尽管实际上由于终端不饱和常常较少--的条件下，多元醇组合物的平均官能度(每个分子中羟基的数目)。各多元醇组分的平均标称羟基官能度为3至4为好，最优选的聚氧化烯多元醇是三元醇。
第一种多元醇组分的平均羟基当量最好为1500-3000，第二种多元醇组分的平均羟基当量最好为1000-3000。
必要时，聚氧化烯多元醇(或当使用其混合物时，一种或多种聚氧化烯多元醇)可含有分散的聚合物颗粒。这样的聚合物改性多元醇在先有技术中已有详尽描述，它还包括在聚氧化烯多元醇中，一种或多种乙烯基单体(例如乙腈和苯乙烯)原位聚合得到的产物，或在聚氧化烯多元醇中，聚异氰酸酯与氨基或羟基官能化合物(例如三乙胺)原位反应得到的产物。
本发明方法中可用的链扩展剂包括带有伯和/或仲氨基的二胺，例如二乙基甲苯二胺(如：DETA和N,N′-二叔丁基二氨基二苯甲烷)。适当的交联剂包括三元胺和羟胺，例如二乙醇胺。
用作发泡剂的水最好在无其它发泡剂的情况下使用，其用量可用已知的方式改变，以达到期望的泡沫塑料密度。水的适当用量通常为每100重量份第一种多元醇组分至少3.5重量份，最好4-8重量份。考虑到多元醇的组成、链扩展剂和交联剂和水，反应体系的异氰酸酯指数可低至10或高达120。
发泡反应混合物可包含一种或多种这样的反应混合物常用的添加剂。所述添加剂包括催化剂，例如叔胺和锡化合物；表面活性剂和泡沫稳定剂，例如硅氧烷一氧化烯共聚物；阻燃剂；有机和无机填料；颜料；抑制所谓沸腾发泡效应(boiling-foam effect)的物质，例如聚二甲基硅氧烷；和内部脱模剂。
因此，另一方面，本发明提供一种反应体系，它包含：(A)平均异氰酸酯官能度为2-2.4的二苯基甲烷二异氰酸酯组合物；(B)一种多元醇组合物，它包含：
(1)第一种多元醇组分，它包含至少一种含氧化乙烯残基的聚
氧化烯多元醇，该组分的平均标称羟基官能度至少为3，平均羟
基当量至少为1500，平均氧化乙烯含量为10-20重量％且平均伯
羟基含量大于50％；
(2)第二种多元醇组分，它包含至少一种含氧化乙烯残基的聚
氧化烯多元醇，该组分的平均标称羟基官能度至少为2，最好至
少为3，均羟基当量至少为1000且平均氧化乙烯含量为50-85重
量％，和
(3)一种链扩展剂和/或交联剂，它至少包含一种至少带有两
个异氰酸酯反应性基团的化合物，其中至少有一种是伯或仲氨基
，且分子量低于500，所述组成中每100重量份(1)含有4-20重
量份(2)和(3),(2)与(3)的重量比为1∶1至20∶1。
(C)作为发泡剂的水，不可包含
(D)一种或多种泡沫塑料配方中常用的添加剂。该反应体系最
好用来制备软泡沫塑料。“反应体系”一词定义为这样一种组分
的结合：其中聚异氰酸酯组合物保持在与体系中异氰酸酯反应性
成分分开的容器中。
在实施本发明方法时，可使用常规的混合设备按一步法或半预聚体工艺进行，泡沫塑料可制成块料或模塑等形式。对于在半预聚体工艺中实施本发明方法来说，可按下述已知的方式制备预聚体：先将全部或部分二苯基甲烷二异氰酸酯组合物与部分多元醇组合物反应；可使用多元醇组合物的任一异氰酸酯反应性成分或异氰酸酯反应性成分的混合物。
本发明还提供一种多元醇组合物，它包括：(1)第一种多元醇组分，它包含至少一种含有氧化乙烯残基的聚氧
化烯多元醇，所述组分的平均标称羟基官能度至少为3，平均羟
基当量至少为1500；平均氧化乙烯含量为10-20重量％；且平均
伯羟基含量大于50％；(2)第二种多元醇组分，它包含至少一种含有氧化乙烯残基的聚氧
化烯多元醇，所述组分的平均标称羟基官能度至少为2，最好至
少为3；平均羟基当量至少为1000且平均氧化乙烯含量为50-85
重量％，和(3)一种链扩展剂和/或交联剂，它包含至少一种这样的化合物：
它具有至少两个异氰酸酯反应性基团，其中至少一个是伯或仲
氨基且分子量小于500，所述组成中每100重量份(1)含有4-
20重量份(2)和(3),(2)与(3)的重量比在1∶1到20∶1。
该多元醇组合物最好用于制备软泡沫塑料的方法和反应体系。
本发明用下述实施例说明，但不限于此。
实施例1
在模具中制备软泡沫塑料，方法如下：将指数为70的SuprasecVM27聚异氰酸酯(可由Imperial Chemical Industries PLC购得，Suprasec是ICI PLC的商标)与一种多元醇组合物反应，该组合物包含50重量份(pbw)Daltocel F2805多元醇，这是一种OHv为28、具有15重量％EO-封端且伯羟基含量大于75重量％的聚氧化丙烯三元醇，可从ICI PLC获得(Datocel是ICI PLC的商标)；50pbw的FA702，FA702是从OHv为38mg KOH/g的季戊四醇制得的聚氧化丙烯氧化乙烯多元醇，其EO含量为11.2重量％，伯羟基含量为70.3％，可从SanyoKasei得到；0.4pbw的Dabco 33 LV，一种可从Air Products获得的叔胺催化剂；0.3pbw的二甲基氨基丙基胺；0.4pbw的SF2962，一种可从Toray-Silicone获得的硅表面活性剂；5.5pbw的水；0.5pbw的二乙基甲苯二胺；8.5pbw的Arcol 2580，一种OHv为42并且含约75重量％无规分布EO的聚氧化丙烯氧化乙烯三元醇，可从Arco获得，和2.7pbwUnilink 4200，它是可从UOP获得的N,N′-二叔丁基二氨基二苯基甲烷。所得泡沫塑料的密度是43.9kg/m3，落球回弹(％)是58(∥)和52(_)。
实施例2
重复实施例1，但高EO多元醇的用量为4.8pbw而不是8.5pbw，所用聚异氰酸酯是可从ICI PLC购得的PBA2189。
反应分别在指数为70,75和80下进行。所得泡沫塑料密度分别为44.0,43.9和43.7kg/m3。落球回弹(％,∥)分别是62,61和59。

Claims (4)

1．一种多元醇组合物，它包含：
(1)第一种多元醇组分，它包含至少一种含有氧化乙烯残基的聚氧化烯多元醇，所述组分的平均标称羟基官能度至少为3，平均羟基当量至少为1500；平均氧化乙烯含量为10-20重量％；且平均伯羟基含量大于50％；
(2)第二种多元醇组分，它包含至少一种含有氧化乙烯残基的聚氧化烯多元醇，所述组分的平均标称羟基官能度至少为2，平均羟基当量至少为1000且平均氧化乙烯含量为50-85重量％，和
(3)一种链扩展剂和/或交联剂，它包含至少一种这样的化合物：
它具有至少两个异氰酸酯反应性基团，其中至少一个是伯或仲氨基且分子量小于500；
所述组成中每100重量份(1)含有4-20重量份(2)和(3)，(2)与(3)的重量比在1∶1到20∶1。
2．权利要求1的多元醇组合物，其中第一种多元醇组分的平均标称羟基官能度为3-4，第二种多元醇组分的平均标称羟基官能度为2-4。
3．权利要求1或2的多元醇组合物，其中多元醇组合物中存在的各多元醇组分的平均标称羟基官能度为3-4。
4．权利要求1的多元醇组合物在制备软聚氨酯泡沫塑料中的用途。
CN92114545A 1991-12-17 1992-12-17 聚氨酯泡沫塑料 Expired - Fee Related CN1043235C (zh)

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