CN1042232C - 多元醇组合物 - Google Patents
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Abstract
包含一种具有高官能度的高氧化乙烯含量的多元醇和另一种多元醇的多元醇组合物。从该多元醇制备软泡沫塑料的方法。
Description
本发明涉及用来制造聚酯软泡沫塑料的多元醇组合物以及所述泡沫塑料的制造方法。
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。软泡沫塑料制备中最常用的多元醇是二元醇和三元醇。
业已发现,具有包括极好回弹性的有价值的性能的软泡沫塑料可由包含具有相对较高氧化己烯含量的一定量高官能度多元醇的多元醇组合物来制备。
因此,本发明提供一种多元醇组合物,其平均标称羟基官能度为2.5-6,该组合物包含:
(a)5-30重量%的聚氧化烯多元醇,其平均标称羟基官能度至少为4,平均羟基当量为100-1500,最好为100-1000,且氧化己烯含量至少为50重量%,和
(b)95-70重量%另一种多元醇。
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)。
具有组分(a)所需特性的聚氧化烯多元醇是本领域公知的,并且可按常规方法制得,即,将氧化乙烯,或者氧化乙烯和氧化丙烯同时和/或以任意顺序,与带有至少四个活性氢原子的引发剂(例如:多元醇、多元胺等)反应。
多元醇组分(b)以平均标称羟基官能度是2-6(尤其是2-4)为宜,平均羟基当量以1000-3000为宜,并且可以选自用于聚氨酯制造中公知的任何一类多元醇,例如:聚酯、聚酯酰胺、聚硫醚、聚碳酸酯、聚缩醛、聚烯烃和聚硅氧烷。但是,组分(b)最好是与组分(b)的官能度和/或氧化乙烯含量不同的聚氧化烯多元醇,例如:组分(b)可以是氧化烯含量低于50重量%(一般低于20重量%)的聚氧化烯三元醇。
优选的多元醇组合物含有至少6重量%,较好至少6重量%至低于20重量%,最好至少10重量%至低于20重量%的组分(a)。此外,构成组分(a)的聚氧化烯多元醇最好具有至少下列特性之一:
(ⅰ)平均标称羟基官能度大于4,例如6;
(ⅱ)氧化乙烯含量至少为70重量%,例如90-100重量%。
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原位反应得到的产物。
上述多元醇组合物在制造软聚氨酯泡沫塑料中,特别是回弹性数值(ISO 8307测得)至少为55%,最好至少为58%的泡沫塑料中具有特别价值。
从而,本发明的又一方面是提供制备软聚氨酯泡沫塑料的方法,即,在发泡剂存在下,将聚异氰酸酯与至少两种多元醇反应,这两种多元醇合起来的平均标称羟基官能度为2.5至6,第一种多元醇用量是两种多元醇总重的5-30重量%,且第一种多元醇是聚氧化烯多元醇,其平均标称羟基官能度至少为4,平均羟基当量为100-1500,且氧化乙烯含量至少为50重量%,第二种多元醇是另一种多元醇,其用量是两种多元醇总量的95-70重量%。
可用来制备软泡沫塑料的有机聚异氰酸酯包括脂肪族、环脂族和芳脂族聚异氰酸酯,尤其是芳香族聚异氰酸酯例如二异氰酸甲苯酯(TDI)和二苯基甲烷二异氰酸酯(MDI)通常用于软泡沫塑料的制造。
优选的聚异氰酸酯是二苯基甲烷二异氰酸酯组合物,尤其是正常室温下为液体的组合物。因此,适当的聚异氰酸酯包括MDI异构体的液体混合物,尤其是包含4,4′-异构体以及不超过60%的2,4′-异构体和不超过5%的2,2-异构体的混合物,上述组合含量均以占总组合物重量的百分数表示。
其它可用的二苯基甲烷二异氰酸酯包括由聚亚甲基聚亚苯基聚异氰酸酯构成的或包含它的组合物。从而,可使用这样的混合物:它含至少70重量%纯MDI(4,4′-异构体或异构体混合物)和不超过30重量%的所谓聚合MDI,聚合MDI含有25-65重量%的二异氰酸酯,其余主要是异氰酸酯官能度大于2的聚亚甲基聚亚苯基聚异氰酸酯。也可使用纯MDI与含有较多(直至100%)所述高官能度聚异氰酸酯的聚合MDI组合物的混合物。
其它可用的MDI组合物包括改性形式的MDI,也就是说,以已知方法通过引入例如:氨基甲酸乙酯、脲基甲酸酯、脲、缩二脲、碳化二亚胺、uretonimine或异氰脲酸酯残基将MDI改性。其它可用的MDI的改性形式包括例如EP-A-0103996所述的聚脲在MDI中的分散体。
还有一类可用的二苯基甲烷二异氰酸酯组合物包括上述的MDI异构体、异构体混合物、聚合MDI、改性MDI等和不超过20重量%的另一种聚异氰酸酯或聚异氰酸酯混合物。其它可与MDI混合使用的聚异氰酸酯包括脂肪族、环脂族和芳脂族聚异氰酸酯,特别是二异氰酸酯,例如六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、环己烷-1,4-二异氰酸酯、4,4′-二环已基甲烷二异氰酸酯和间和对四甲基二甲苯二异氰酸酯特别是芳香族聚异氰酸酯,例如甲苯二异氰酸酯和苯二异氰酸酯。
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),反应体系的均异氰酸酯指数可低至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-foameffect)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)聚异氰酸酯组分;
(ⅱ)平均标称羟基官能度为2.5-6的多元醇组合物,它包括:
(a)5-30重量%的聚氧化烯多元醇,其平均标称羟基官能度至少为4;平均羟基当量为100-1500,氧化乙烯含量至少为50重量%
(b)95-70重量%的另一种多元醇;
(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”定义为各组分的一种组合,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。当采用预聚体工艺时,两种多元醇的每一种都可单独或混合使用,与聚异氰酸酯预反应。前述用量的计算是基于预聚体中多元醇和多元醇组合物中多元醇的。
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成分。
术语表
F2805是Daltocel F2805,一种氧化乙烯封端的聚氧化丙烯三元醇,其氧化乙烯含量为15%,分子量为6000,由Imperial ChemicalInduatries PLC购得。Daltocel是ICI的商标。
G2005是AtlasG2005,一种分子量为1800的聚氧化乙烯六元醇,从Imperical Chemical Industries PLC.购得。
A2580是Arcol2580,一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,从Arco购得。
Polyol X是EO含量为15重量%且OHv=160的六官能团多元醇。
Polyol Y是EO含量为15重量%且OHv=91的六官能团多元醇。
Po1yol Z是EO含量为75重量%且OHv=41的六官能团多元醇。
PBA2185是NCO含量为30.7%的聚合MDI,从Imperial ChemicalIndustries PLC购得。
预聚体A的NCO含量为6%,通过将75pbw的OH值=36的三元醇(13%EO-封端)与25pbw MDI(10%2,2′+2,4′)反应获得。
Niax Al:催化剂,可从Union Carbide得到。
Dabco 33LV:催化剂,可从Air Products得到。
Dabco EG:催化剂,可从Air Products得到。
Dabco 80/20:催化剂,可从Air Products得到。
B4113是Tegostab B4113,一种硅酮表面活性剂,可从Goldshmidt AG得到。Tegostab是Goldschmidt的商标。
回弹率按ISO8307测定,CLD 40%和滞后损失按ISO3386-I测定。
CLD 40%是在40%压缩下的压缩载荷挠度。
实施例1
将表Ⅰ给出的配方台式混合,制得软泡沫塑料,数量均为重量份。表1也给出了所得泡沫塑料的性质。
表1
对比实施例:A2580(三元醇)实验 1 2 3 4 5预聚体 A 90 90 90 90 90pBA 2185 10 10 10 10 1033LV 0.8 0.8 0.8 0.8 0.8Niax Al 0.1 0.1 0.1 0.1 0.1A2580 0 2 4 6 10水 1.8 1.8 1.8 1.8 1.8指数 100 99 98 98 96密度 51 56 57 55 58kg/m3CLD 40%, 3.4 4.1 3.5 4.8 3.7kPa滞后损失 29 22 18 19 16%回弹率 49 54 54 52 45%
表1(续)实施例:G2005:六官能团多元醇实验 6 7 8 9 10预聚体 A 90 90 90 90 90pBA 2185 10 10 10 10 1033LV 0.8 0.8 0.8 0.8 0.8Niax Al 0.1 0.1 0.1 0.1 0.1G2005 0 2 4 6 10水 1.8 1.8 1.8 1.8 1.8指数 100 100 100 100 100密度 51 56 60 61 62kg/m3CLD 40%, 3.4 4.5 4.6 4.4 3.5KPa滞后损失, 29 23 19 18 15%回弹率, 49 52 54 59 60%
实施例2
软泡沫塑料是通过将聚异氰酸酯与含有高含量氧化乙烯的聚醚六元醇的反应混合物反应而制得。表2给出配方(重量份)和泡沫塑料性质。表2实验 1 2 3 4F2805 100 95 90 85G2005 0 5 10 15Niax Al 0.1 0.1 0.1 0.1Dabco 33LV 0.5 0.5 0.5 0.5B4113 0.5 0.5 0.5 0.5水 3 3 3 3pBA 2185 46 47 49 50指数 90 89 90 90密度 46 56 57 61kg/m3回弹率 54 61 65 70%CLD 40%, 3.5 6.1 4.7 3.8KPa滞后损失 27 22 17 15,%
实施例3
由表3所示的各组分(重量份)制得了数种其它的软泡沫塑料。示有★符号者为对比试验。
表3
实验 1* 2* 3* 4* 5* 6 7 8 9* 10 11 |
F 2805 50 95 90 95 90 95 90 85 100 95 85 |
G 2005 50 - - - - - - - - - - |
Polyol X - 5 10 - - - - - - - - |
Polyol Y - - - 5 10 - - - - - - |
Polyol Z - - - - - 5 10 15 0 5 15 |
Niax Al - 0.1 0.1 0.1 0.1 0.1 0.1 0.1 - - - |
Dabco 32LV - 0.5 0.5 0.5 0.5 0.5 0.5 0.5 1.5 1.5 2.5 |
Dabco EG 0.4 - - - - - - - - - - |
Dabco 80/20 0.2 - - - - - - - - - - |
水 3 3 3 3 3 3 3 3 10 10 10 |
PBA2185 72.2 48.5 50.5 47.9 50.6 47.3 47.5 47.7 47.5 47.5 47.5 |
指数 100 90 90 90 90 90 90 90 30 30 30 |
自由起发密度- 39.5 38.7 42.5 40.1 43.5 41.7 40.8 31.s 34.9 49.9kg/m3 |
回弹率,% - 49 40 52 48 64 68 69 35 37 50 |
CLD,40%,kPa - 3.7 4.7 3.9 3.8 3.2 2.6 2.5 2.5 2.5 3.2 |
注:实验1中,泡沫塑料瘪泡。
Claims (7)
1.一种多元醇组合物,其平均标称羟基官能度为2.5-6,该组合物包含:
(a)5-30重量%的聚氧化烯多元醇,其平均标称羟基官能度至少为4,平均羟基当量为100-1500,且氧化乙烯含量至少为50重量%,和
(b)95-70重量%的另一种多元醇;其中组分(b)包含聚氧化烯多元醇,其平均标称羟基官能度为2-6,平均羟基当量为1000-3000,氧化乙烯含量在50重量%以下。
2.按权利要求1的组合物,其中聚氧化烯多元醇的平均标称羟基官能度为2-4,氧化乙烯含量在20重量%以下。
3.按权利要求1或2的组合物,它包含至少6重量%至20重量%以下的组分(a)。
4.按权利要求1或2的组合物,其中组分(a)包含平均标称羟基官能度大于4的聚氧化烯多元醇。
5.按权利要求1或2的组合物,其中组分(a)包含氧化乙烯含量至少为70重量%的聚氧化烯多元醇。
6.按权利要求5的组合物,其中聚氧化烯多元醇的氧化乙烯含量为9-100重量%。
7.权利要求1-6任一权利要求的组合物用于制备软聚氨酯泡沫塑料。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9126740.1 | 1991-12-17 | ||
GB919126740A GB9126740D0 (en) | 1991-12-17 | 1991-12-17 | Polyol compositions |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN98114781A Division CN1083462C (zh) | 1991-12-17 | 1998-06-15 | 制备软聚氨酯泡沫塑料的方法 |
Publications (2)
Publication Number | Publication Date |
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CN1073690A CN1073690A (zh) | 1993-06-30 |
CN1042232C true CN1042232C (zh) | 1999-02-24 |
Family
ID=10706387
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN92114553A Expired - Fee Related CN1042232C (zh) | 1991-12-17 | 1992-12-17 | 多元醇组合物 |
CN98114781A Expired - Fee Related CN1083462C (zh) | 1991-12-17 | 1998-06-15 | 制备软聚氨酯泡沫塑料的方法 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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CN98114781A Expired - Fee Related CN1083462C (zh) | 1991-12-17 | 1998-06-15 | 制备软聚氨酯泡沫塑料的方法 |
Country Status (11)
Country | Link |
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US (1) | US5521226A (zh) |
EP (1) | EP0547764B1 (zh) |
JP (1) | JP3308612B2 (zh) |
KR (1) | KR100251337B1 (zh) |
CN (2) | CN1042232C (zh) |
AU (1) | AU654593B2 (zh) |
CA (1) | CA2084809A1 (zh) |
DE (1) | DE69221274T2 (zh) |
ES (1) | ES2104852T3 (zh) |
GB (1) | GB9126740D0 (zh) |
ZA (1) | ZA929105B (zh) |
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- 1991-12-17 GB GB919126740A patent/GB9126740D0/en active Pending
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- 1992-11-17 ES ES92310469T patent/ES2104852T3/es not_active Expired - Lifetime
- 1992-11-17 DE DE69221274T patent/DE69221274T2/de not_active Expired - Fee Related
- 1992-11-17 EP EP92310469A patent/EP0547764B1/en not_active Expired - Lifetime
- 1992-11-24 ZA ZA929105A patent/ZA929105B/xx unknown
- 1992-11-24 AU AU28570/92A patent/AU654593B2/en not_active Ceased
- 1992-12-08 CA CA002084809A patent/CA2084809A1/en not_active Abandoned
- 1992-12-15 JP JP33412792A patent/JP3308612B2/ja not_active Ceased
- 1992-12-16 KR KR1019920024446A patent/KR100251337B1/ko not_active IP Right Cessation
- 1992-12-17 CN CN92114553A patent/CN1042232C/zh not_active Expired - Fee Related
-
1995
- 1995-01-27 US US08/378,999 patent/US5521226A/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
KR930012851A (ko) | 1993-07-21 |
AU2857092A (en) | 1993-06-24 |
DE69221274D1 (de) | 1997-09-04 |
CA2084809A1 (en) | 1993-06-18 |
CN1083462C (zh) | 2002-04-24 |
ZA929105B (en) | 1994-05-05 |
US5521226A (en) | 1996-05-28 |
AU654593B2 (en) | 1994-11-10 |
EP0547764B1 (en) | 1997-07-30 |
KR100251337B1 (ko) | 2000-04-15 |
CN1073690A (zh) | 1993-06-30 |
DE69221274T2 (de) | 1997-12-04 |
GB9126740D0 (en) | 1992-02-12 |
JPH05262844A (ja) | 1993-10-12 |
EP0547764A1 (en) | 1993-06-23 |
JP3308612B2 (ja) | 2002-07-29 |
ES2104852T3 (es) | 1997-10-16 |
CN1215066A (zh) | 1999-04-28 |
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