CN110527130A - 一种混合发泡剂组合物及其发泡体组合物 - Google Patents
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Abstract
本发明提供了该发泡剂组合物包括五氟丙烷,1,1,2,3,3‑六氟丙烷,由选自以下环戊烷、异戊烷,正戊烷组成至少之一形成的组合物。该组合物具有GWP值低,导热系数小,能耗低且易存储的优点。本发明还涉及可由此获得的发泡体组合物,该组合物可用于聚合物泡沫的生产。
Description
技术领域
本发明涉及一种混合发泡剂组合物,也涉及由该混合发泡剂组合物制成的聚合物发泡体。
背景技术
HCFC-141b又是聚合物泡沫行业应用最广泛的发泡剂品种,但是HCFC-141b 属于消耗臭氧层物质(ODS),具有较高的消耗臭氧潜能值(ODP值)和全球变暖潜能值(GWP值),且ODP值是所有HCFCs物质中最高的。根据《蒙特利尔协定》: HCFC-141b在发达国家的使用期限是到2010年为止,目前美国、日本等国已经限用。在发展中国家如中国的使用期限可以到2040年,中国作为《关于消耗臭氧层物质的蒙特利尔议定书》从2012年开始使用蒙特利尔议定书多边基金支持符合资助条件的聚氨酯泡沫企业开展第一阶段HCFC-141b淘汰工作,141b淘汰势在必行。由于氯与“臭氧消耗潜能”(ODP)之间存在不确定联系,与141b 有类似结构特性的HCFC,也将成为停止使用的目标。
在工业上,一直寻找新的基于碳氟化合物上的替代品,该替代品被认为是 HCFC类的环境安全替代品。所述替代化合物是本发明的目的。
如公开号为CN1756793A的专利:氢氟碳化合物组合物,该发明是一种包含 1,1,1,3,3-五氟丁烷(HFC-365mfc)和1,1,1,3,3-五氟丙烷(HFC-245fa)的组合物,其中HFC-365mfc/HFC-245fa重量比为60:40-75:25。
又如公开号为CN103370390A的专利公开了反式-1,1,1,4,4,4-六氟-2-丁烯与水的共沸和类共沸组合物,可用于在生产过程中分离E-1,1,1,4,4,4-六氟-2- 丁烯和杂质,共沸混合物可用于发泡剂、推进剂、制冷剂和稀释剂等。
上述专利中公开混合发泡剂,热传导率的改善效果也只停留在微弱的程度,导热系数依旧很大,而且由于这些原料的售价较高,具有在成本方面不利的缺点。
烷烃类(HC)发泡剂中最具常用的是3种戊烷类发泡剂:环戊烷 (cyclopentan,CP)、正戊烷(n-pentane,NP)及异戊烷(isopentane,IP),它们在室温下皆为液态,ODP值均为零,GWP值很低,对环境影响极小,因此戊烷类发泡剂自从引入到聚氨酯领域,就很快得到了广泛的应用。环戊烷的ODP为0, GWP较小,是目前用量较大的聚氨酯发泡剂,然而烷烃类发泡剂易燃易爆,而且烷烃类发泡剂的导热系数较高。因此戊烷发泡剂在使用时还需要克服其易燃易爆导致的安全问题,并且其由于导热系数较高而导致所制备的聚氨酯硬泡保温性能有待提高。
如中国专利CN101665578A公开的一种用于保温聚氨酯塑料的发泡剂,其中所用的发泡剂组成为HFC-365mfc 1-15重量份、HFC-227ea 0-5重量份、 HFC-245fa1-15重量份、戊烷2-18重量份、水0.3-3重量份,其中戊烷选自戊烷、异戊烷,正戊烷中的一种。该文献虽然给出了一种含环戊烷的发泡剂,以及利用所述发泡剂制备聚氨酯泡沫的方法,但是,所述发泡剂以HFC为主要成分,而且采用所述发泡剂制得的聚氨酯泡沫的导热系数仍然偏高,导致保温性能不够理想,压缩强度和尺寸稳定性方面的性能也不太理想。
因此需要开发具有更好发泡性能和环保性能的并且成本较低的发泡剂组合物。
发明内容
本发明提供了发泡剂组合物,该组合物包括括五氟丙烷,1,1,2,3,3- 六氟丙烷,由选自以下环戊烷、异戊烷,正戊烷组成至少之一形成的组合物。
优选的,1,1,2,3,3-六氟丙烷含量为6~20wt%,五氟丙烷6~20wt%,所述戊烷组合物含量为60~88wt%。
优选的,戊烷组合物为异戊烷和正戊烷。戊烷价格便宜,比较容易获取,虽然戊烷是易燃易爆品,但是本发明人发现在戊烷中添加了少量的1,1,2,3,3- 六氟乙烷,五氟丙烷显著的改进了戊烷所发泡沫体的可燃性,如上所述,这些发泡剂组合物特别适用制造有改进阻燃性的泡沫体,如聚苯乙烯,酚醛树脂和聚氨酯泡沫体。
一种含有以上发泡剂组合物的聚氨酯发泡体,所述泡沫体质量组成如下14-20 质量份;异氰酸酯130~160质量份;组合聚醚100质量份。
优选的,异氰酸酯为平均官能度为2.5的苯类异氰酸酯。
优选的,组合聚醚为平均官能度为3.7、羟值为470~480mgKOH/g的聚醚多元醇60质量份;平均官能度为4.9、羟值为400~450mgKOH/g的聚醚多元醇30质量份;交联剂5质量份;泡沫稳定剂2质量份;催化剂1.3质量份;阻燃剂2 质量份。
优选的,阻燃剂为有机磷酸脂。
采用本发明的技术方案的有益效果是:
本发明的发泡剂用于发泡剂体系安全稳定,能够用于制造在宽温度范围内表现出良好性能的泡沫。本发明用五氟丙烷,1,1,2,3,3-六氟丙烷,戊烷的组合物作为发泡剂,他能替换HCFC-141b作为发泡剂实用,所得到的泡沫产品与使用HCFC-141b作为发泡剂所得产品性能相同。由于组分中的环戊烷相对于其他卤代烷烃的价格非常低,并且ODP值为0,gwp接近为0,本发明成本低廉,符合环境标准,因此本发明在未来工业生产中能够有着更广泛的应用。
具体实施方式
下面通过实施例来进一步说明本发明,但不局限于以下实施例。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
首选对实施例中的原料料进行说明。
本发明提供的发泡剂混合物,其制备方法是将1,1,2,3,3-六氟丙烷,五氟乙烷和环戊烷、异戊烷,正戊烷组成至少之一按照其相应的质量配比在液相状态下进行物理混合。
上述组分中的六氟丙烷,分子量为152.04g·mol-1,标准沸点为-1.4℃,临界温度为124.9℃,临界压力为3.2MPa,GWP值为630,ODP值为0;
上述组分中的五氟丙烷,分子量为134.05g·mol-1,标准沸点为-15.14℃,临界温度为154.01℃,临界压力为3.651MPa,GWP值为858,ODP值为0;
上述组分中的环戊烷,分子量为72.15g·mol-1,标准沸点为49.3℃,临界温度为238.6℃,临界压力为4.52MPa,GWP值为11,ODP值为0;
上述组分中的异戊烷,其分子量为72.15·mol-1,标准沸点为24.8℃,临界温度为187.24℃,临界压力为5.34MPa,GWP值为11,ODP值为0;
上述组分中的正戊烷,分子量为72.15g·mol-1,标准沸点为36.5℃,临界温度为196.6℃,临界压力为3.37MPa,GWP值为11,ODP值为0。
多亚甲基多苯基异氰酸酯:Suprasec 9582,购自Hunsman聚氨酯公司。
平均官能度为3.7、羟值为370~400mgKOH/g的聚醚多元醇:苯胺聚醚多元醇,甘油聚醚多元醇;平均官能度为4.9、羟值为400~450mgKOH/g的聚醚多元醇:蔗糖聚醚多元醇,山梨醇聚醚多元醇。
催化剂:发泡型催化剂:五甲基二乙烯三胺(PC-5);
凝胶型催化剂:二甲基环乙胺(PC-8);
三聚型催化剂:三(二甲氨基丙基)六氢化三嗪(PC-41)和(二羟基丙基) 三甲基甲酸铵(TMR-2)复配。
交联剂:聚氧化丙烯二醇,选自南通谦和化工。
泡沫稳定剂:含Si-C结构的硅油,选自迈图L-6863。
阻燃剂:DMMP。
实施例1-3及对比例1配比
按照表中配比交联剂、催化剂、泡沫稳定剂、阻燃剂加入组合多元醇中,混合均匀,再按照表中配比加入发泡剂,混合均匀,配置成组合聚醚。将组合聚醚和异氰酸酯在高压下混合房源,注入模具40-45℃的模具中,制得聚氨酯硬质泡沫用来测定性能系数。
实施例1-3及对比例1性能测试结果
由上表2中的实施例1-3和对比例1高低温尺寸变化率有所下降,实施例1-3 与对比例1压力强度显著提高,说明本发明的发泡剂体系较常用的发泡体系使用效果更好。膨胀率更高,产品中用的发泡料用量就可以降低,降低成本。本发明的发泡剂也非常适用于其他体系的发泡,如聚氯乙烯、环氧树脂、不饱和聚酯、酚醛树脂的发泡。
Claims (6)
1. 发泡剂组合物,其特征在于,所述发泡剂组合物包括五氟丙烷,1 ,1 ,2 ,3 ,3-六氟丙烷和由选自以下环戊烷、异戊烷、正戊烷至少之一组成的戊烷组合物;所述1 ,1 ,2 ,3,3-六氟丙烷含量为6~20wt%,五氟丙烷6~20wt%,所述戊烷组合物含量为60~ 88wt%。
2.根据权利要求2所述的发泡剂组合物,其特征在于,所述戊烷组合物为异戊烷和正戊烷。
3.发泡体组合物,其特征在于,包括使用权利要求1的发泡剂组合物作发泡剂和种可发泡聚合物,所述的可发泡聚合物为聚氨酯泡沫前体;所述发泡体组合物按重量份包括:
如权利要求1-3所述的发泡剂组合物14-20质量份;
异氰酸酯130~160质量份;
组合聚醚100质量份。
4.据权利要求3所述的发泡体组合物,其特征在于所述异氰酸酯包括:
平均官能度为2.5的苯类异氰酸酯。
5.根据权利要求3或4所述的发泡体组合物,其特征在于所述的组合聚醚由以下原料混合制成:
平均官能度为3.7、羟值为470~480mgKOH/g的聚醚多元醇60质量份;
平均官能度为4.9、羟值为400~450mgKOH/g的聚醚多元醇30质量份;
交联剂 5质量份;
泡沫稳定剂 2质量份;
催化剂1.3质量份;
阻燃剂2质量份。
6.根据权利要求5所述的发泡体组合物,其特征在于阻燃剂为有机磷酸脂。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1087650A (zh) * | 1992-07-27 | 1994-06-08 | 武田药品工业株式会社 | 开孔硬质聚氨酯泡沫体的制备及其应用 |
CN104262670A (zh) * | 2014-09-17 | 2015-01-07 | 合肥华凌股份有限公司 | 发泡剂组合物、聚氨酯泡沫及其制造方法 |
CN107501517A (zh) * | 2017-09-11 | 2017-12-22 | 合肥华凌股份有限公司 | 聚氨酯泡沫及其制备方法和用途 |
US20170369630A1 (en) * | 2010-07-27 | 2017-12-28 | Honeywell International Inc. | Foams And Articles Made From Foams Containing 1-Chloro-3,3,3-Trifluoropropene (HFCO-1233zd) |
-
2019
- 2019-08-23 CN CN201910782817.1A patent/CN110527130A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1087650A (zh) * | 1992-07-27 | 1994-06-08 | 武田药品工业株式会社 | 开孔硬质聚氨酯泡沫体的制备及其应用 |
US20170369630A1 (en) * | 2010-07-27 | 2017-12-28 | Honeywell International Inc. | Foams And Articles Made From Foams Containing 1-Chloro-3,3,3-Trifluoropropene (HFCO-1233zd) |
CN104262670A (zh) * | 2014-09-17 | 2015-01-07 | 合肥华凌股份有限公司 | 发泡剂组合物、聚氨酯泡沫及其制造方法 |
CN107501517A (zh) * | 2017-09-11 | 2017-12-22 | 合肥华凌股份有限公司 | 聚氨酯泡沫及其制备方法和用途 |
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