CN1270608A - 硬质聚氨酯泡沫塑料的制法 - Google Patents
硬质聚氨酯泡沫塑料的制法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
制备硬质聚氨酯泡沫塑料或氨基甲酸酯改性的聚异氰脲酸酯泡沫塑料的方法,其使用包含1~50mol%的1,1,1,3,3-五氟丙烷和50~99mol%的异戊烷和/或正戊烷的混合物作为发泡剂。
Description
本发明涉及硬质的聚氨酯泡沫塑料或氨基甲酸酯改性的聚异氰脲酸酯泡沫塑料的制法,并涉及由其制成的泡沫塑料体,还涉及在该制法中使用的新颖组合物。
一般地,硬质的聚氨酯泡沫塑料和氨基甲酸酯改性的聚异氰脲酸酯泡沫塑料按如下方法制备:在发泡剂存在下,让合适的聚异氰酸酯和异氰酸酯反应性化合物(通常为多元醇)反应。这种泡沫塑料的一个用途例如用作冷藏设备结构中的热绝缘介质。硬质泡沫塑料的热绝缘性能取决于许多因素,包括(对闭孔硬质泡沫塑料而言):孔腔大小和孔腔中内含物的导热性。
在聚氨酯泡沫塑料或氨基甲酸酯改性的聚异氰脲酸酯泡沫塑料的生产中广泛用作发泡剂的一类材料是完全卤化的氯氟烃,特别是三氯氟甲烷(CFC-11)。这些发泡剂特别是CFC-11的极低的导热性能够制备具有绝缘性能良好的硬质泡沫塑料。近来对氯氟烃潜在的引起大气中臭氧的消耗的关注急需开发其中氯氟烃发泡剂被替代材料取代的反应体系,这些替代材料是环保上可以接受的,也能生产出具有许多泡沫塑料应用中必备的性能的泡沫塑料来。
起初,出现的最有希望的替代物是含氢的氯氟烃(HCFC),例如US4076644公开了使用1,1-二氯-2,2,2-三氟乙烷(HCFC-123)和1,1-二氯-1-氟代乙烷(HCFC-141b)作发泡剂的生产聚氨酯泡沫塑料方法。但HCFC也有某些臭氧消耗的潜能。因此有压力去寻求HCFC和CFC的替代物。
目前认为有希望的替代的发泡剂是部分氟化的烃(HFC)和烃(HC),由于它们不含有消耗臭氧的氯。最可行的HFC选择之一是1,1,1,3,3-五氟丙烷〔HFC-245fa〕,如US5496866和EP381989所述,对于HC,特别考虑的是五个碳的烃,如异戊烷和正戊烷,如WO90/12841所述。
目前倍受关注的是发泡剂混合物,除了成本可降低外,还能提供诸如泡沫塑料密度减小和导热系数等附加效益。US5562857描述了使用包含50~70mo1%的HFC-245fa和30~50mo1%的异戊烷的混合物作发泡剂来制备硬质聚氨酯泡沫塑料。
本发明的一个目的是提供一种新颖发泡剂混合物,它不含氯从而不能消耗臭氧,可生产具有良好热绝缘性和物理性能的泡沫塑料。
这一目的可通过下述途径实现:在由聚异氰酸酯和异氰酸酯-反应性组分制备硬质聚氨酯泡沫塑料或氨基甲酸酯改性的聚异氰脲酸酯泡沫塑料的方法中使用含1~50mol%HFC-245fa和50~99mol%异戊烷和/或正戊烷的混合物。
优选HFC-245fa/异-和/或正-戊烷的摩尔比为10/90~40/60。优选在烃的这一方面只使用异戊烷或正戊烷,最优选只用异戊烷。但也可使用异戊烷和正戊烷的混合物,在这些混合物中优选异戊烷/正戊烷摩尔比为80/20至20/80之间。
在本发明方法中使用的适合的异氰酸酯-反应性化合物包括任何本领域制备硬质聚氨酯泡沫塑料或氨基甲酸酯改性的聚异氰脲酸酯泡沫塑料熟知的那些。制备硬质泡沫塑料特别重要的是多元醇和多元醇混合物,其平均羟值为300~1000,特别是300~700mg KOH/g,羟基官能度为2~8,特别是3~8。适合的多元醇在先有技术中已充分描述过,包括环氧烷如环氧乙烷和/或环氧丙烷与每分子含有2~8个活性氢原子的引发剂的反应产物。适合的引发剂包括:多元醇,如甘油,三羟甲基丙烷,三羟乙基胺,季戊四醇,山梨糖醇,蔗糖;多胺,如1,2-乙二胺,甲苯二胺(TDA),二氨基二苯基甲烷(DADPM),和聚亚甲基多亚苯基多胺;氨基醇,如乙醇胺和二乙醇胺;以及这些引发剂的混合物。其它的适合的聚合多元醇包括聚酯,它由适当比例的二元醇和更高官能度的多元醇与二羧酸或聚羧酸缩合而得。其它的适合的聚合多元醇包括羟基封端的聚硫醚,聚酰胺,聚酯酰胺,聚碳酸酯,聚缩醛,聚烯烃和聚硅氧烷。
本发明发泡剂混合物尤其适合用于含聚醚多元醇的异氰酸酯-反应性组合物,特别是由含脂族或芳族胺,尤其是如TDA和DADPM的那些芳族胺的引发剂衍生的那些。优选的异氰酸酯-反应性组合物包含10~75wt%(以异氰酸酯-反应性组分的总量计)的芳族胺引发的聚醚多元醇。
用于本发明方法中的适合的有机聚异氰酸酯包括制备硬质聚氨酯泡沫塑料或氨基甲酸酯改性的聚异氰脲酸酯泡沫塑料技术领域中已知的那些,特别是芳族聚异氰酸酯,如形式为2,4′-,2,2′-,4,4′-异构体的二异氰酸二苯甲酯,及其混合物;二异氰酸二苯甲酯(MDI)与其低聚物的混合物,本领域中该低聚物已知为“粗制品”或异氰酸酯官能度大于2的聚合MDI(多异氰酸多亚甲基多亚苯基酯);形式为2,4-和2,6-异构体的甲苯二异氰酸酯及其混合物;1,5-萘二异氰酸酯;以及1,4-二异氰酸根苯。可以提到的其它有机聚异氰酸酯包括脂族二异氰酸酯如异佛尔酮二异氰酸酯;1,6-二异氰酸根己烷和4,4′-二异氰酸根二环己基甲烷。
待反应的聚异氰酸酯组合物和多官能的异氰酸酯-反应性组合物的量取决于待生产的硬质聚氨酯泡沫塑料或氨基甲酸酯改性的聚异氰脲酸酯泡沫塑料的性能。本领域技术人员很容易确定这个量。
用于生产硬质聚氨酯泡沫塑料的其它已知的物理发泡剂以小剂量(至多为物理发泡剂混合物总量的30wt%)同本发明的发泡剂混合物一起使用。这些实例包括:二烷基醚,环亚烷基醚,酮,(全)氟化的醚,氯氟烃,全氟化烃,氢氯氟烃,其它的氢氟烃,和其它烃类。例如可使用HFC-245fa、异戊烷和环戊烷的混合物。
与本发明类似,可使用HFC-245fa和其它含3~7个碳原子的烃(优选直链烷烃,如环戊烷,异丁烷和正己烷)的混合物作制备硬质聚氨酯泡沫塑料的发泡剂。
通常,与物理发泡剂一起使用水或其它放出二氧化碳的化合物。其中水用作化学发泡剂,典型用量为0.2~5%,优选0.5~3%(重量),以异氰酸酯-反应性化合物为基础计。
在生产泡沫塑料聚合材料的反应体系中所用的发泡剂总量由本领域技术人员方便地确定,不过典型地为2~25%(重量),以总反应体系计。
除了聚异氰酸酯和多官能的异氰酸酯-反应性组合物以及发泡剂,形成泡沫塑料的反应混合物通常包含一种或多种其它的助剂或添加剂,这些都是制备硬质聚氨酯泡沫塑料或氨基甲酸酯改性的聚异氰脲酸酯泡沫塑料的配制物中常用的。这些任选的添加剂包括交联剂,例如三羟乙基胺等低分子量多元醇,泡沫塑料稳定剂或表面活性剂,如硅氧烷-氧化乙烯共聚物;氨基甲酸酯催化剂,例如辛酸亚锡或二月桂酸二丁基锡等锡化合物,或如二甲基环己胺或三亚乙基二胺等叔胺;异氰脲酸酯催化剂,例如季铵盐或钾盐;阻燃剂,例如三(氯丙基)磷酸盐等的如卤代烷基磷酸盐,以及填料如碳黑。
在本发明方法操作中,常使用70~140的异氰酸酯指数,如需要,也可使用较低的指数。较高的指数,如150~500,甚至高达3000,可以与三聚催化剂结合使用,以制备含异氰脲酸酯键的泡沫塑料,这些较高指数的泡沫塑料体通常使用聚酯多元醇作为异氰酸酯-反应性材料而制备。
在按本发明制备硬质泡沫塑料的方法中,可与常规的混炼方法一起使用熟知的一步法,预聚物或半预聚物技术。硬质泡沫塑料可以制成块状泡沫塑料、模制品、模腔充料、喷雾泡沫塑料、发泡泡沫塑料,或与诸如硬纸板、石膏板、塑料、纸张或金属等其他材料的层合物的形式。
许多应用中,便利地是以基于初级多异氰酸酯和异氰酸酯-反应性组分中的每一个的预混配制物为生产聚氨酯提供组分,特别地,许多反应体系使用多异氰酸酯-反应性组合物,该组合物除了一种或多种多异氰酸酯-反应性组分外,还含有主要添加剂、如发泡剂和催化剂。因此本发明可提供含有本发明发泡剂混合物的多异氰酸酯-反应性组合物。
下述实施例说明了但不限制本发明的各个方面。
实施例中下述反应组分表示:
多元醇1:OH值为495mg KOH/g的蔗糖引发的聚醚多元醇。
多元醇2:OH值为310mg KOH/g的芳族胺引发的聚醚多元醇。
多元醇3:OH值为500mg KOH/g的芳族胺引发的聚醚多元醇。
多元醇4:OH值为55mg KOH/g的甘油引发的聚醚多元醇。
Arconate 1000:来自Arco的碳酸丙二酯。
L6900:来自联碳公司的硅酮表面活性剂。
Polycat 8:来自Air Products的胺催化剂。
Desmorapid PV:来自Bayer的胺催化剂。
异戊烷:来自Halterman的99.7%纯异戊烷。
HFC-245fa:来自PCR的1,1,1,3,3-五氟丙烷。
RUBINATE M:来自Imperial Chemical Industries的聚合MDI。RUBINATE是Imperial Chemical Industries的一个商标。
实施例
以实验室规模;用下述表1所列成分生产硬质聚氨酯泡沫塑料,使用Heidolph RZR 50型混炼装置,在所得泡沫塑料体上测试下述性质:在杯状泡沫塑料体(Cup foams)上测试的自由起发密度;按标准ISO2581测试的室温或70℃下初始和老化后的导热系数(芯部密度约33kg/m3的样品);和按标准DIN 53421测试的,室温下初始和老化五周后的压缩强度(在10%厚度处的应力表示) (只在最弱方向上,芯部密度约33kg/m3的样品)。结果也示于表1中。
表1
泡沫塑料体 | A | B | C | D | |
多元醇1 | pbw | 50.0 | 50.0 | 50.0 | 50.0 |
多元醇2 | pbw | 26.0 | 26.0 | 26.0 | 26.0 |
多元醇3 | pbw | 19.0 | 19.0 | 19.0 | 19.0 |
多元醇4 | pbw | 1.5 | 1.5 | 1.5 | 1.5 |
Arconate 1000 | pbw | 1.5 | 1.5 | 1.5 | 1.5 |
L6900 | pbw | 2.5 | 2.5 | 2.5 | 2.5 |
Polycat 8 | pbw | 2.5 | 2.5 | 2.5 | 2.5 |
Desmorapid PV | pbw | 0.3 | 0.3 | 0.3 | 0.3 |
水 | pbw | 1.4 | 1.4 | 1.4 | 1.4 |
异戊烷 | pbw | 18.5 | 12.4 | 6.2 | 0.0 |
HFC-245fa | pbw | 0.0 | 11.47 | 22.95 | 34.42 |
RUBINATE M | pbw | 136.0 | 136.0 | 136.0 | 136.0 |
指数 | % | 110 | 110 | 110 | 110 |
自由起发密度 | kg/m3 | 24.5 | 24.0 | 24.3 | 23.9 |
λ值 | |||||
室温下初始值 | mW/mK | 23.2 | 21.3 | 20.5 | 19.8 |
室温下2周后 | mW/mK | 23.7 | 21.9 | 21.3 | 20.5 |
室温下3周后 | mW/mK | 24.3 | 22.4 | 21.8 | 21.3 |
室温下5周后 | mW/mK | 24.7 | 22.9 | 22.4 | 21.8 |
70℃下初始值 | mW/mK | 24.1 | 21.6 | 20.8 | 20.3 |
70℃下2周后 | mW/mK | 26.3 | 23.4 | 22.5 | 21.9 |
70℃下3周后 | mW/mK | 27.4 | 24.8 | 24.1 | 23.4 |
70℃下5周后 | mW/mK | 27.6 | 25.2 | 24.6 | 24.1 |
压缩强度 | |||||
初始值 | kPa | 190.5 | 182.3 | 183.2 | 175.1 |
室温下五周后 | kPa | 174.3 | 174.2 | 165.4 | 152.0 |
图1中初始λ值表示为发泡剂混合物组成的函数,在图2中同样表示老化后的λ值(室温下)
从图1中,很明显看出,发泡剂混合物的导热系数,总是低于两个极值的数学平均值(图1中直线所示),对于按照本发明的发泡剂混合物(泡沫塑料B)而言,对数学平均值的偏离大于US5562857中所述的发泡剂混合物(泡沫塑料C)。
因此按照本发明的发泡剂混合物制备的泡沫塑料体的热绝缘值可与US5562857中所述的泡沫塑料相比,尽管使用了固有的导热系数比HFC-245fa大的更多异戊烷。还由于异戊烷比HFC-245fa低廉,所以以较低成本就可得相同的性能,而且泡沫塑料的其他物理性能如压缩强度也没有受到损害。
Claims (10)
1.制备硬质聚氨酯泡沫塑料或氨基甲酸酯改性的聚异氰脲酸酯泡沫塑料的方法,其包括下述步骤:在水和物理发泡剂混合物存在下,使有机多异氰酸酯和多官能的异氰酸酯-反应性组分反应,该物理发泡剂混合物包含1,1,1,3,3-五氟丙烷和异戊烷和/或正戊烷,其特征在于1,1,1,3,3-五氟丙烷/异-和/或正-戊烷的摩尔比为1/99~50/50。
2.权利要求1的方法,其中1,1,1,3,3-五氟丙烷/异-和/或正-戊烷的摩尔比为10/90~40/60。
3.权利要求1或2的方法,其中物理发泡剂混合物由1,1,1,3,3-五氟丙烷和异戊烷组成。
4.上述权利要求之任一项的方法,其中多官能异氰酸酯-反应性组合物包含聚醚多元醇。
5.权利要求4的方法,其中多官能异氰酸酯-反应性组合物包含10~75wt%(基于总异氰酸酯-反应性组分)的芳族胺引发的聚醚多元醇。
6.权利要求5的方法,其中芳族胺选自甲苯二胺,二氨基二苯基甲烷和聚亚甲基多亚苯基多胺。
7.上述权利要求之任一项的方法,其中,基于总异氰酸酯-反应性组分,水的量为0.2~5%(重量)。
8.通过上述任一权利要求定义的方法制得的硬质聚氨酯泡沫塑料或氨基甲酸酯改性的聚异氰脲酸酯泡沫塑料。
9.包含水和物理发泡剂混合物的多官能异氰酸酯-反应性组合物,所述物理发泡剂混合物包含1~50mol%的1,1,1,3,3-五氟丙烷和50~99mol%的异戊烷和/或正戊烷。
10.权利要求9的多官能异氰酸酯-反应性组合物,其中,1,1,1,3,3-五氟丙烷/异-和/或正-戊烷的摩尔比为10/90~40/60。
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US5565497A (en) * | 1995-12-07 | 1996-10-15 | The Celotex Corporation | Dispersant for filled, rigid cellular polymers |
US5562857A (en) * | 1995-12-22 | 1996-10-08 | Bayer Corporation | Azeotrope-like compositions of 1,1,1,3,3-pentafluoropropane and 2-methyl butane |
US5672294A (en) * | 1996-04-10 | 1997-09-30 | Alliedsignal Inc. | Azeotrope-like compositions of 1,1,1,3,3-pentaflurorpropane and hydrocarbons |
US5788886A (en) * | 1997-05-05 | 1998-08-04 | E. I. Du Pont De Nemours And Company | Pentafluoropropane compositions |
-
1998
- 1998-08-27 TR TR2000/00754T patent/TR200000754T2/xx unknown
- 1998-08-27 BR BR9812508-7A patent/BR9812508A/pt not_active IP Right Cessation
- 1998-08-27 SK SK429-2000A patent/SK4292000A3/sk unknown
- 1998-08-27 ID IDW20000574A patent/ID24457A/id unknown
- 1998-08-27 CA CA002300890A patent/CA2300890A1/en not_active Abandoned
- 1998-08-27 WO PCT/EP1998/005437 patent/WO1999015581A1/en not_active Application Discontinuation
- 1998-08-27 ES ES98946435T patent/ES2165194T3/es not_active Expired - Lifetime
- 1998-08-27 NZ NZ503024A patent/NZ503024A/en unknown
- 1998-08-27 CN CN98809259A patent/CN1097071C/zh not_active Expired - Fee Related
- 1998-08-27 HU HU0003816A patent/HUP0003816A2/hu unknown
- 1998-08-27 KR KR1020007003157A patent/KR20010024270A/ko not_active Application Discontinuation
- 1998-08-27 PL PL98339565A patent/PL339565A1/xx unknown
- 1998-08-27 DE DE69801835T patent/DE69801835T2/de not_active Expired - Lifetime
- 1998-08-27 EP EP98946435A patent/EP1019449B1/en not_active Expired - Lifetime
- 1998-08-27 JP JP2000512883A patent/JP2002505345A/ja not_active Withdrawn
- 1998-08-27 AU AU93473/98A patent/AU740991B2/en not_active Ceased
- 1998-09-22 EG EG116098A patent/EG21433A/xx active
- 1998-09-23 US US09/159,480 patent/US6121338A/en not_active Expired - Lifetime
- 1998-09-24 AR ARP980104773A patent/AR017144A1/es not_active Application Discontinuation
-
2000
- 2000-02-09 US US09/500,469 patent/US6335378B1/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1326920C (zh) * | 2002-04-17 | 2007-07-18 | 拜尔材料科学有限责任公司 | 用氢氟烃和二氧化碳发泡的聚氨酯或者聚异氰脲酸酯泡沫 |
CN101177474B (zh) * | 2007-10-31 | 2010-06-16 | 无锡双象化学工业有限公司 | 建筑用聚氨酯硬泡树脂 |
CN102875833A (zh) * | 2012-09-19 | 2013-01-16 | 合肥美的荣事达电冰箱有限公司 | 发泡剂组合物、聚氨酯硬质泡沫以及制备方法、制冷设备、保温组件 |
CN108250404A (zh) * | 2017-12-28 | 2018-07-06 | 青岛海尔股份有限公司 | 聚氨酯硬质泡沫塑料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
AR017144A1 (es) | 2001-08-22 |
CN1097071C (zh) | 2002-12-25 |
AU740991B2 (en) | 2001-11-22 |
US6335378B1 (en) | 2002-01-01 |
BR9812508A (pt) | 2000-07-25 |
TR200000754T2 (tr) | 2000-11-21 |
KR20010024270A (ko) | 2001-03-26 |
EG21433A (en) | 2001-10-31 |
JP2002505345A (ja) | 2002-02-19 |
US6121338A (en) | 2000-09-19 |
HUP0003816A2 (en) | 2001-03-28 |
AU9347398A (en) | 1999-04-12 |
ID24457A (id) | 2000-07-20 |
DE69801835T2 (de) | 2002-04-11 |
DE69801835D1 (de) | 2001-10-31 |
CA2300890A1 (en) | 1999-04-01 |
ES2165194T3 (es) | 2002-03-01 |
NZ503024A (en) | 2002-03-01 |
WO1999015581A1 (en) | 1999-04-01 |
PL339565A1 (en) | 2000-12-18 |
EP1019449A1 (en) | 2000-07-19 |
EP1019449B1 (en) | 2001-09-26 |
SK4292000A3 (en) | 2000-08-14 |
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