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CN1215063A - 聚氨酯泡沫塑料 - Google Patents

聚氨酯泡沫塑料 Download PDF

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CN1215063A
CN1215063A CN98114782A CN98114782A CN1215063A CN 1215063 A CN1215063 A CN 1215063A CN 98114782 A CN98114782 A CN 98114782A CN 98114782 A CN98114782 A CN 98114782A CN 1215063 A CN1215063 A CN 1215063A
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G·布莱斯
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Abstract

在发泡剂存在下,将4,4′－MDI含量较多的聚异氰酸酯与EO含量较高的多元醇反应以制备软泡沫塑料的方法。

Description

聚氨酯泡沫塑料
将有机聚异氰酸酯如甲本二异氰酸酯(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余物的极小部分，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。不能将非常高浓度的上述聚醚与通常的异氰酸酯共同使用，这是因为那样便不产生开孔效应，而导致闭孔泡沫塑料。
现在发现，如果采用基本上纯的4,4′-MDI或其衍生物作为聚异氰酸酯，便可从含高浓度具有高氧化乙烯含量的多元醇的配方成功地制得具有有价值性能的软泡沫塑料。
因而，本发明提供一种制备软聚氨酯泡沫塑料的方法，即，在发泡剂存在下，将聚异氰酸酯与多元醇组合物反应。该聚异氰酸酯含至少85重量％，含至少90重量％较好，含至少95重量％更好的4,4′-二苯基甲烷或其变体。该多元醇组合物包含至少一种聚(氧化乙烯-氧化烯)多元醇，其平均标称羟基官能度为2-6，平均羟基当量为1000-3000，平均氧化乙烯含量为50-85，最好为60-85重量％，任何还可加入的多元醇中氧化乙烯含量最好为500当量或者至少占50重量％。
本发明方法所用的聚异氰酸酯组分可主要包含纯4,4′-二苯基甲烷二异氰酸酯或二异氰酸酯与一种或多种其它有机聚异氰酸酯尤其是其它二苯基甲烷二异氰酸酯异构体(例如2,4′-异构体，还可含2,2′-异构体)的混合物。该聚异氰酸酯组分也可以是由含有至少85重量％，4,4′-二苯基甲烷二异氰酸酯的聚异氰酸酯组合物衍生而来的MDI变体。MDI变体是本领域公知的，就本发明用途而言，尤其包括通过将uretonimine和/或碳化二亚胺基团引入上述聚异氰酸酯组合物和/或将该组合物与一种或多种多元醇反应得到的液体产物。
多元醇组合物可包含具有所需官能度、当量和氧化乙烯含量的单一聚氧化烯多元醇，最好是聚(氧化乙烯-氧化丙烯)多元醇，这样的多元醇是本领域公知的，可用常规方法制得，即，同时和/或以任何顺序将氧化乙烯和氧化丙烯与引发剂反应。所述引发剂的例子有：水、多元醇、多元胺和其它具有2至6个活性氢原子的物质。
或者，多元酯组合物可包含两种或多种聚氧化烯多元醇的混合物，使得总组成具有所需的平均官能度、当量和氧化乙烯含量。该混合物中的聚氧化烯多元醇最好是聚(氧化乙烯-氧化丙烯)多元醇，但还可以有一种或多种聚氧化乙烯多元醇和/或聚氧化丙烯多元醇。
优选的多元醇组合物包括：
(a)85-100重量％的含氧化乙烯残基的聚氧化烯多元醇，所述多元醇组分的平均标称羟基官能度为2-6，平均羟基当量为1000-3000且平均氧化乙烯含量为50-85重量％，和
(b)15-0重量％的一种或多种其它多元醇。
多元醇(b)以平均官能度为2-6，平均当量为1000-3000为宜，例如，可以是聚氧化丙烯多元醇、聚氧化乙烯多元醇或含有50重量％以下或85重量％以上氧化乙烯残基的聚(氧化乙烯-氧化丙烯)多元醇。
具有500或更高当量的各多元醇最好含至少50重量％的氧化乙烯。此混合物中的聚氧化烯最好是聚(氧化乙烯-氧化丙烯)多元醇，但还可以含有一种或多种聚氧化乙烯多元醇。
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)。多元醇组合物的平均标称羟基官能度最好为2-4，最优选的聚氧化烯多元醇是三元醇。
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。
本发明方法优选的发泡剂是水，还可同时使用物理发泡剂，例如低沸点有机氟化合物。发泡剂的用量可按已知的方式变化，以达到预期的泡沫密度，例如：水的适当用量以多元醇组合物重量为基准计是0.25-20重量％，优选0.25-8重量％，最佳是0.25重量％至5重量％以下。最好只用水作发泡剂。考虑到多元醇组合物、水和任何其它异氰酸酯反应性物质(例如：链扩展剂或交联剂)，反应体系的异氨酸酯指数可低至10或高至120。
发泡反应混合物可包含一种或多种该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；链扩展剂，例如低分子量二元醇或二元胺；交联剂，例如三乙醇胺；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。
从而，在又一方面，本发明提供的反应体系包括：
(ⅰ)一种含至少85重量％4,4′-二苯基甲烷或其变体的聚异氰酸酯；
(ⅱ)一种多元醇组合物，它包含至少一种含氧化乙烯残基的聚氧化烯多元醇，该多元醇组合物的平均标称羟基官能度为2-6，平均羟基当量为1000-3000，且平均氧化乙烯含量为50-85重量％，多元醇组合物中，当量为500或更高的各多元醇的氧化乙烯含量最好为至少50重量％；
(ⅲ)一种发泡剂，包括水，和可选的
(ⅳ)一种或多种泡沫塑料配方中常用的添加剂。这样的反应体系最好用于制造软泡沫塑料。术语“反应体系”定义为这样的一种体系，其中聚异氰酸酯组分装在一容器中，与异氰酸酯反应性组分分开。
在实施本发明方法时，可采用公知的一步法、半预聚体工艺或全预聚体工艺，同时采用常用的混合设备，泡沫塑料可制成块料或模塑等形式。由上述聚异氰酸酯(过量)和多元醇的反应产物、NCO值为5-50重量％的预聚体地构成了本发明的一部分。所述预聚体的制备是本领域公知的。
本发明方法制得的泡沫塑料具有有价值的能量吸收性质，从而可用于声音振动阻尼以及用作底座。
本发明用下列实施例说明，但并不局限于此。其中全部份数、百分数和比率均以重量计。
下列术语表用来说明实施例中未说明的反应组分。
术语表
A2580是Arcol 2580，一种具有无规氧化乙烯和氧化丙烯残基且氧化乙烯含量为77％的聚醚三元醇，其分子量为4000，可从Arco购得。Arcol是Arco的商标。
Dabco EG是Dabco在乙二醇中的33％溶液，可从Air Products获得。Dabco是Air Products的商标。
Dabco 33LV是从Air Products获得的催化剂。
D80/20是Dabco和二甲基乙醇胺的20/80混合物。
Daltolac C4多元醇是分子量为170的聚氧化丙烯三元醇，可由Imperial Chemical Industries PLC购得。Daltolac是ICI PLC的商标。
Suprasec VM021聚异氰酸酯是NCO含量为23％的4,4′-MDI低官能度变体，可从Imperial Chemical Industries PLC.购得。Suprasec是ICI PLC的商标。
Suprasec VM022聚异氰酸酯是NCO含量为23％的4,4′-MDI低官能度变体，可从Imperial Chemical Industries PLC购得。
Suprasec MPR聚异氰酸酯是纯4,4′-MDI，可以Imperial ChemicalIndustries PLC购得。
Suprasec VM20聚异氰酸酯是uretonimine改性的、NCO含量为29.3％的4,4′-MDI，可从Imperial Chemical Industries PLC购得。
D8154是Dabco 8154，一种催化剂，可从Air Products获得。
DETDA是含约80％3,5-二乙基-2,4-二-氨基甲苯和20％3,5-二乙基-2,6-二氨基甲苯的混合物，可从Ethyl Corporation购得。
DBDTL是二月桂酸二丁基锡
DMDEE是二(2-二甲基氨基乙基)醚
DMEA是二甲基乙醇胺。
A1是Niax A1：一种可从Union Carbide获得的催化剂。
实施例1
采用一步法工艺，将表1给出的配方进行台式混合，制得软泡沫塑料。表1也给出了所得泡沫塑料的性能；
表1
实验            1        2        3        4        5        6       7       8
A2580          100      100      100      100      100      100     100      -
PEG 1000        -        -        -        -        -        -       -      100
水              3        3        4        5        3        3       4       3
Dabco EG       0.6      0.2      0.1       -        -       0.4     0.1     0.4
D80/20         0.2      0.9       -       0.13      -        -       -      0.2
Daltolac C4     -       0.7      0.3       -        -        -       -       -
DBTDL           -       -        0.6      0.87     0.35     0.1     0.6      -
DMEA            -       -         -        -       0.3       -       -       -
A1              -       -         -        -        -       0.15     -       -
聚异氰酸酯     VM21    VM22    MPR/VM20,  VM20  MPR/VM20, MPR/VM20,MPR/VM20,VM20(指数)                        1∶1               1∶1      1∶1     1∶1(100)    (100)    (100)     (100)  (100)      (100)    (100) (100)
起发时间       137      94       42        71     66        35        44     -(sec)
自由起发密度    39      39       32        26     35        36        31     -(kg/m3)
压缩载荷挠度1  4.1      2.8      4.6       6.6    4.4       4.2       4.5    -40％(kPa)
滞后损失   ％) 26       24       29        39     21        20        28     -
回弹率 (％)    33       29       24        35     21        42        22     -
压缩变形        3        4        4        11      6         6         5     -干燥-50％,(％)
*对比实施例采用分子量为1000的聚乙二醇，不能得到泡沫塑料，所得产物是“口胶糖状”。
实施例2
采用一步法工艺，将表2给出配方机械混合。表2给出了所得泡沫塑料的性能。
表2
实验              1         2         3         4         5
A2580            100       100       100       100       100
水                4         4         4         4         5
D8154             -        0.1       0.1       0.1        -
DETDA             -        0.4       0.4       0.4        -
DBTDL            0.15      0.1       0.1       0.1       0.6
DMCEE            0.35      0.3       0.3       0.3       0.13
异氰酸酯         VM20      VM20      VM20      VM20      VM20
指数             100        90        95       100       100
起发时间(sec)     67        68        70        60        38
自由起发密度      37        33        32        34        23(kg/m2)
芯部密度，(kg/m3)36        34        34        39        25
撕裂强度t,(N/m)  249       266       304       323       279
回弹率t,(％)      29        18        21        26        21
压缩载荷挠度 40％,(kPa)  2.9       1.9       1.9       2.6       6.0
滞后损失(％)      20        27        27        26        34
压缩形变干燥 ％,(％)      -         36        31        30         7
实施例3
将60重量份A2580与40重量份MPR反应，制得预聚体，将预聚体与含有2.47pbw水，1.80pbw Daltolac C4和0.4pbw Dabco 33LV的组合物反应制得软泡沫塑料。自由起发密度为32Kg/m3；压缩载荷挠度(40％)为2KPa；滞后损失为17％；回弹率为45％，未观察到凹入部分。
在上述实施例中，密度、撕裂强度、回弹率、压缩载荷挠度和滞后损失分别按ISO1855 ISO8067、ISO8307、ISO3386和ISO3386测定。

Claims (11)

1．一种NCO值为5-30重量％的预聚物，它是由一种含至少85重量％的4,4′-二苯基甲烷二异氰酸酯的过量的聚异酸酯或其变体与一种多元醇组合物反应得到的反应产物，该多元醇组合物包含至少一种聚(氧化乙烯-氧化烯)多元醇，其平均标称羟基官能度为2-6，平均羟基当量为1000-3000，平均氧化乙烯含量为50-85重量％。
2．权利要求1的预聚物，其中所述的多元醇组合物包含：
(a)85-100重量％的含氧化乙烯残基的聚氧化烯多元醇，所述多元醇组分的平均标称羟基官能度为2-6，平均羟基当量为1000-3000且平均氧化乙烯含量为50-85重量％；
(b)15-0重量％的一种或多种其它多元醇。
3．权利要求1或2的预聚物，其中所述的聚(氧化乙烯-氧化烯)多元醇是聚(氧化乙烯-氧化丙烯)多元醇。
4．权利要求1-3的预聚物，其中所述多元醇组合物的平均标称羟基官能度为2-4。
5．权利要求1-4的预聚物，其中所述聚异氰酸酯含有至少90重量％的4,4′-二苯基甲烷二异氰酸酯。
6．权利要求1-5的预聚物，其中所述聚异氰酸酯含有至少95重量％的4,4′-二苯基甲烷二异氰酸酯。
7．权利要求1-6的预聚物，其中所述的聚(氧化乙烯-氧化烯)多元醇的平均标称羟基官能度为3，并且其中所述氧化乙烯部分是任意分布的。
8．权利要求1-7的预聚物，其中当量为500或更高的每一种多元醇的氧化乙烯含量为至少50重量％。
9．权利要求1-8的预聚物，其中所述的具有50-85％氧化乙烯含量的多元醇具有60-85重量％的氧化乙烯含量。
10．制备软聚氨酯泡沫塑料的方法，其特征在于使权利要求1-9的预聚物与一种包括水的发泡剂反应，发泡剂中可任选含有一种物理发泡剂。
11．权利要求10的方法，其中所述发泡剂是水。
CNB981147828A 1991-12-17 1998-06-15 聚氨酯泡沫塑料 Expired - Lifetime CN1146607C (zh)

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CN100344333C (zh) * 2002-10-29 2007-10-24 株式会社Biopol 用于伤口填充物的聚氨酯泡沫敷料及其制造方法
CN100497427C (zh) * 2003-06-26 2009-06-10 巴斯福公司 粘弹性聚氨酯泡沫

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