CN1229413C - 聚氨酯泡沫塑料的制备方法 - Google Patents
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Abstract
一种制备密度为50至100kg/m3的粘弹性泡沫塑料的方法,它包括将一种异氰酸酯成分和一种多元醇成分反应,其中所述异氰酸酯组分具有2.1至2.7的官能度,如通式(I):其中φ表示苯基并且n为大于或等于1的整数;且其中所述多元醇组分包括80至100重量%的具有1000至4000平均分子量的双官能团多元醇聚醚,0至5重量%的单官能醇,0至20重量%的具有等于或大于3的官能度并具有92至4000的平均分子量的多元醇。
Description
本发明涉及一种制备聚氨酯泡沫塑料的方法。具体地说,本发明涉及一种通过使用基于MDI(二苯基甲烷二异氰酸酯)的异氰酸酯成分制备粘弹性聚氨酯泡沫塑料的方法。
这里使用的术语“粘弹性聚氨酯泡沫塑料”尤其指块状和模制的(热和冷的)实质上具有50至100kg/m3密度的聚氨酯膨胀型材料或泡沫塑料,并且其适当地具有低于30%的回弹值,其根据UNI 6357-68测试方法(软质聚氨酯微孔材料-回弹性(落球回弹)的测定)测量,并且根据ISO 1856-80测试方法测量的在23℃时的50%压缩变定值小于4%,优选小于3%。这些泡沫塑料在被压缩后具有缓慢回复至原始形状的特性。
具有该特性的材料被用于缓冲物品的制造,被用于制造床垫和软垫的家具工业,并且更普遍地被用于能够移动而不弹起或回弹的物体需要支撑的应用中以及被用于保健家具市场,例如,镇痛椅和镇痛床的生产。
粘弹性聚氨酯泡沫塑料可以通过将甲苯二异氰酸酯(TDI)和多元醇化合物以及用于该类型反应的常规添加剂进行反应来制备,这里的多元醇包括多元醇聚醚或聚酯。然而,在泡沫塑料的制备阶段及使用过程中,TDI的使用可能会引起自然卫生环境的问题,原因是未反应单体可能会存在,其可能在其制备后从最终产品中释放出来。
可选的异氰酸酯如MDI的使用,典型地需要使用某种材料,聚醚,聚酯或添加剂以保护所需的粘弹性能。MDI和常规的原材料的使用典型地生产出传统的软质泡沫塑料(回弹性大于30%)或非膨胀型材料(收缩性产品),这是由于MDI是难以加工的。
令人惊讶的是现已发现粘弹性聚酯泡沫塑料可以从基于MDI的异氰酸酯成分和某类传统的聚醚多元醇进行制备并且在本领域中典型的缺点例如高回弹性和收缩性泡沫等可以被降低或避免。
第一方面,本发明提供了一种制备具有50-100kg/m3密度的粘弹性泡沫塑料的方法,它包括将以下组分进行反应:
a)一种具有如下通式(I)的官能度为2.1-2.7的异氰酸酯成分:
其中,φ表示苯基并且n为大于或等于1的整数;
b)一种包括如下物质的多元醇成分:
i)基于总多元醇组分,80至100重量%,优选85至95重量%的具有1000至4000,优选1500至3000平均分子量的双官能多元醇聚醚;
ii)基于总多元醇组分,0至5重量%,优选1至5重量%的单官能醇R-OH,其中R选自C1-C20,优选C1-C12,的烷基和/或异烷基(这里是指(异)烷基)以及通过在C1-C20的烷基和/或异烷基上缩合C2-C6烯属氧化物得到的基团;
iii)基于总多元醇组分,0至20重量%,优选5至15重量%的具有等于或大于3的官能度和92至4000的平均分子量的多元醇;以及
c)水。
存在的水的量的选择要确保能够获得聚氨酯泡沫塑料理想的密度。
具有通式(I)的异氰酸酯组分适合于通过甲醛-苯胺缩合物的光气化获得并且通常被称作粗MDI或聚合MDI。为了获得2.1至2.7的理想的异氰酸酯官能度,如果必要的话,具有通式(I)的异氰酸酯组分可以用4,4’-二苯基甲烷二异氰酸酯稀释,非必要地可与2,4’-二苯基甲烷二异氰酸酯混合。
根据该方法,用于制备粘弹性膨胀型材料的双官能多元醇聚醚(i)适合选自通过在具有两个活泼氢原子的化合物(这里作为“引发剂”),如二甘醇、一缩二丙二醇或水,上缩合C2-C6烯属氧化物获得的多元醇聚醚。环氧乙烷,环氧丙烷或其混合物是优选的烯属氧化物。
单官能醇ii)适合具有200-1500的分子量并且尤其为250-1200。这里醇ii)是一组通过在C1-C20的烷基和/或异烷基上缩合烯属氧化物获得的物质,该烯属氧化物优选包括环氧乙烷和/或环氧丙烷。在一个优选的实施方案中,R为一个通过在C1-C12并且尤其C2-C8的烷基和/或异烷基上缩合环氧乙烷并且非必要的环氧丙烷获得的基团。
具有3或更高官能度的适合的多元醇的例子包括基于环氧乙烷和/或环氧丙烷的多元醇聚醚并且其中引发剂为三元醇,如甘油或三羟甲基丙烷;四元醇,如季戊四醇;烷醇胺,如三乙醇胺,或多官能羟基烷烃,如木糖醇,阿糖醇,山梨糖醇,甘露醇及其类似物。
这些多元醇可以就这样被使用或者,在分散体中或以部分被接合至多元醇链上的方式,它们可以含有固体微粒,优选聚合物,适当地其尺寸低于20微米。适合于该目的的聚合物包括聚丙烯腈,聚苯乙烯,聚氯乙烯,聚脲,它们的混合物,以及它们的共聚物。通过在多元醇中原位聚合的方式可以制备这些固体微粒,或者像所希望的那样他们可以单独被制备,并且随后被加至多元醇中。
该多元醇组合物也可以进一步包括常用于聚氨酯膨胀型产品制备中的添加剂,如,胺类催化剂,例如,三亚乙基二胺,和/或金属催化剂,例如,辛酸亚锡,交联剂,孔径调节剂,热氧化稳定剂,颜料,防燃剂等等。在Interscience(纽约,1964)的“Saunder&Frisch-聚氨酯,化学和技术”中以及在由G.Oertel编辑,Hanser Publishers(慕尼黑,纽约,1993)出版的“聚氨酯手册”中提供了聚氨酯聚合的细节。
根据本发明,在粘弹性聚氨酯泡沫塑料的生产中,发泡剂适当地包括水和一种发泡助剂,例如,液态或气态的CO2,优选包括水。水具有重要的作用,因为它可以促使与二氧化碳的形成有关的脲键的形成,所述二氧化碳可促使聚氨酯聚合物的膨胀工艺,从而获得粘弹性的。对于100份多元醇组分,适合使用的水量为1至3重量份。
在一个优选的实施方案中,该泡沫塑料的回弹率低于30%并且理想地低于10%。合适地,该多元醇组分至少包括一些如通式R-OH的单醇,如这里所规定的,这样有助于提供更低的弹性。
适当地,本发明的方法使用至少70并且优选至少90的异氰酸酯指数。
下面提供了一些说明性的但非限定性的实施例。
实施例1
依据“自由膨胀”技术,将42.7重量份的具有通式(I)并具有2.2的异氰酸酯官能度的异氰酸酯组分(埃尼化学有限公司的TEDIMON4420)与一种多元醇配制剂;1.5重量份的水;0.7重量份的基于硅氧烷的表面活性剂(Goldschmidt的TEGOSTAB B 8002);0.05重量份的叔脂肪胺(Crompton公司的NIAX A-1);0.23重量份的二丁基二月桂酸锡溶液和0.5重量份的二乙醇胺进行反应,其中所述配制剂由95重量份的平均分子量为2000的双官能聚醚多元醇(埃尼化学有限公司的TERCAROL VD 2000);5重量份的平均分子量为300的三官能聚醚(TERCAROL G 310,埃尼化学有限公司)组成。该反应指数为100。
在该反应结束时,可获得粘弹性泡沫塑料,其具有65kg/m3的密度,2.35%的压缩变定值以及24%的回弹率。
实施例2(比较)
采取如实施例1所描述的相同程序,只是使用39.2份的官能度为2的4,4’-二苯基甲烷二异氰酸酯来替换TEDIMON 4420和0.25重量份的胺类催化剂(Witco公司的NIAX A 107)。在该反应结束时,可获得收缩性产品。
实施例3
根据“自由膨胀”技术,将43.3重量份的TEDIMON 4420与一种多元醇配制剂;1.5重量份的水;0.7重量份的基于硅氧烷的表面活性剂(TEGOSTAB B 8002);0.3重量份的二丁基二月桂酸锡溶液,0.05重量份的NIAX A 107和0.01重量份的二甲基乙醇胺(Air Products的DABCO DMEA)进行反应,所述多元醇配制剂由93重量份的平均分子量为2000的双官能多元醇聚醚(TERCAROL VD 2000);7重量份的平均分子量为300的三官能聚醚(TERCAROL G 310)组成。该反应指数为98。
在该反应结束时,可获得粘弹性泡沫塑料,其具有55kg/m3的密度,3.5%的压缩变定值以及29%的回弹率。
实施例4
根据“自由膨胀”技术,将43.75重量份的TEDIMON 4420与一种多元醇配制剂;1重量份的平均分子量为4000并且含有高含量环氧乙烷的三官能多元醇聚醚(埃尼化学有限公司的TERCAROL 241)作为单体断开剂;1.6重量份的水;0.8重量份的硅氧烷表面活性剂(TEGOSTAB B 8002);0.23重量份的二丁基二月桂酸锡溶液和0.5重量份的二甲基乙醇胺进行反应,所述多元醇配制剂由95重量份的平均分子量为2000的双官能多元醇聚醚(TERCAROL VD 2000);5重量份的平均分子量为300的三官能聚醚(TERCAROL G 310)组成。该反应指数为100。
在该反应结束时,可获得粘弹性泡沫塑料,其具有77kg/m3的密度,2.70%的压缩变定值以及28%的回弹率。
实施例5(比较)
根据“自由膨胀”技术,将60.5重量份的TEDIMON 4420与一种多元醇配制剂;3.1重量份的水;3.5重量份的二乙醇胺;0.15重量份的叔脂肪胺(DABCO 33 LV);0.6重量份的硅氧烷表面活性剂(TEGOSTAB B 8636);0.15重量份的二丁基二月桂酸锡溶液(AirProducts的DABCO T-12)进行反应,所述多元醇配制剂由90重量份的平均分子量为6000的三官能多元醇聚醚(Enichem S.p.A的TERCAROL 427);10重量份的平均分子量为4000的三官能多元醇聚醚(TERCAROL 241)组成。该反应指数为100。
在该反应结束时,可获得高回弹性泡沫塑料,其具有36kg/m3的密度,11.5%的压缩变定值以及51%的回弹率。
实施例6
将37.6份的TEDIMON 4420与一种多元醇配制剂;1.6重量份的水;0.3重量份的基于硅氧烷的表面活性剂(TEGOSTAB B 8002);0.3重量份的胺类催化剂(NIAX A-1)和0.6重量份的二乙醇胺在预混合后加入一个立方形的模具中,所述多元醇配制剂由90重量份的平均分子量为2000的双官能多元醇聚醚(TERCAROL VD 2000);10重量份的平均分子量为2700的六官能聚醚(埃尼化学有限公司的GLEDIONPS 1504)组成。该反应指数为95。
在该反应结束时,可获得一种粘弹性泡沫塑料,其具有100kg/m3的密度,2.1%的压缩变定值以及18%的回弹率。
Claims (10)
1.一种制备具有50至100kg/m3的密度的粘弹性泡沫塑料的方法,该方法包括将以下成分进行反应:
a)一种具有如下通式(I)的官能度为2.1-2.7的异氰酸酯成分:
其中,φ表示苯基并且n为大于或等于1的整数;
b)一种包括如下物质的多元醇成分:
i)基于总多元醇组分,80至100重量%的具有1000至4000的平均分子量的双官能多元醇聚醚;
ii)基于总多元醇组分,5至15重量%的具有等于或大于3的官能度和92至4000的平均分子量的多元醇;以及
c)水。
2.如权利要求1所述的方法,其中所述多元醇成分进一步含有基于总多元醇组分,1至5重量%的单官能醇R-OH,其中R选自C1-C20烷基和/或异烷基以及通过在C1-C20的烷基和/或异烷基上缩合C2-C6烯属氧化物得到的基团。
3.如权利要求1所述的方法,其中具有通式(I)的异氰酸酯组分通过甲醛-苯胺缩合物的光气化获得。
4.如权利要求3所述的方法,其中具有通式(I)的异氰酸酯组分可通过甲醛-苯胺缩合物和4,4’-二苯基甲烷的光气化获得。
5.如权利要求4所述的方法,其中所述的4,4’-异构体混有它的2,4’-异构体。
6.如权利要求1或2中任意一项所述的方法,其中该双官能多元醇聚醚包括一种在具有两个活泼氢原子的化合物上缩聚C2-C6烯属氧化物得到的多元醇聚醚。
7.如权利要求1所述的方法,其中具有等于或大于3的官能度并且平均分子量为92至4000的多元醇以5-15重量%的量存在。
8.如权利要求1所述的方法,其中具有等于或大于3的官能度的多元醇包括在三元醇、四元醇、链烷醇胺或多官能羟基烷烃上缩合的基于环氧乙烷和/或环氧丙烷的多元醇聚醚。
9.如权利要求1所述的方法,其中对于100份的多元醇成分,水以1至3重量份的量存在。
10.一种可根据权利要求1所述的方法获得的粘弹性聚氨酯泡沫塑料,该泡沫塑料具有50至100kg/m3的密度,具有在23℃由ISO1856-80规则测得的低于4%的50%压缩变定值并且具有根据UNI6357-68规则测得的低于30%的回弹率。
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US20130289150A1 (en) * | 2012-04-26 | 2013-10-31 | Bayer Materialscience Ag | Viscoelastic polyurethane foams |
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