CN108359121A - 一种共沸和类共沸组合物 - Google Patents
一种共沸和类共沸组合物 Download PDFInfo
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Abstract
本发明提供了由(E)‑1,1,1,4,4,4‑六氟‑2‑丁烯、(E)‑1‑氯‑,3,3,3‑三氟丙烯和1,1,1,2,3,3‑六氟丙烷组成的共沸和类共沸组合物,该共沸和类共沸组合物具有GWP值低,导热系数小,能耗低的优点。
Description
技术领域
本发明涉及共沸和类共沸组合物,尤其涉及一种由(E)-1,1,1,4,4,4-六氟-2-丁烯、(E)-1-氯-,3,3,3-三氟丙烯和1,1,1,2,3,3-六氟丙烷组成的共沸和类共沸组合物。
背景技术
由于蒙特利尔议定书规定逐步停止使用损耗臭氧层的氯氟烃(CFC)和氢氯氟烃(HCFC),现在被广泛用于聚氨酯发泡剂的HCFC-141b就是氢氯氟烃,属于必须加快淘汰的对象,因此从过去十几年,碳氟化合物产业一直致力于寻找合适的替代发泡剂。1,1,1,4,4,4-六氟-2-丁烯(HFO-1336mzz),有反式(HFO-1336mzz(E))和顺式(HFO-1336mzz(Z))两种,沸点分别为8.5℃和32℃,因其分子中含有的双键,排入大气后很快便能与OH自由基加成,通过氧化而降解,大气存在寿命短(20天),温室效应值(GWP≈9)低。发泡、隔热性能优异,成为最佳替代物之一,属于第四代发泡剂,具有广阔的市场前景。
Z-HFO-1336mzz可以直接用于发泡剂,它具有环境可持续性和卓越的隔热保温性能,该发泡剂室温下为稳定液体,通过调整在配方中的含量可以达到满意的发泡性能,与金属材料、塑料、弹性体材料以及与主要类型的聚醚多元醇(如曼尼希基聚醚、蔗糖型聚醚、聚芳酯等)生产聚氨酯泡沫时都表现出了良好的性能。与目前应用的发泡剂相比,该产品环保、隔热保温特性显著,不易燃、不消耗臭氧,可以低转换成本取代其他液体发泡剂,具有广泛的应用前景。E-HFO-1336mzz可以作为制冷剂,也可以混配作为发泡剂。但HFO-1336mzz单组份所形成的泡孔稳定性差、隔热效果差,因此常与其他组分混配使用。
如公开号为CN101743270A和CN101878253A的专利使用包含Z-HFO-1336和相容性较差的具有两个或更多个活性氢的含活性氢化合物的组合物,作为一种发泡剂,和适宜的多异氰酸酯反应可制得聚氨酯或聚异氰脲酸酯聚合物闭孔泡沫。基于多异氰酯的闭孔泡沫被广泛用于绝缘用途,可用于节能电气设备;聚氨酯和聚异氰脲酸酯板材由于其良好的隔热性能和承载能力在建筑工业中广泛用于屋顶材料和覆面材料。
又如公开号为CN102015592A的专利使用Z-HFO-1336和乙醚、2-氯丙烷或全氟2-甲基-3-戊酮组成的共沸或类共沸混合物作为发泡剂来制备热塑性或热固性泡沫。
又如公告号为CN103228757B的专利公开了氯三氟丙烯和六氟丁烯的组合物,优选(E)-1,1,1,4,4,4-六氟-2-丁烯,作为氯三氟丙烯,优选1-氯-,3,3,3-三氟丙烯,存在于该组合物中的1-氯-,3,3,3-三氟丙烯90重量%是反式异构体,其可用作制冷剂、传热流体、发泡剂、溶剂和喷射剂,满足低或零的臭氧消耗潜值。
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。
上述专利中公开的发泡剂组合物存在或GWP值高、或导热系数大、或使用时整机能耗高等缺点,因此,需要开发具有更好发泡性能和环保性能的发泡剂组合物。
发明内容
本发明的目的是克服现有技术的缺点,提供一种GWP值低,导热系数小,能耗低的共沸和类共沸组合物。
为了解决上述技术问题,本发明是通过以下技术方案实现的:一种发泡组合物,由(E)-1,1,1,4,4,4-六氟-2-丁烯(HFO-1336mzz(E))、(E)-1-氯-,3,3,3-三氟丙烯(HCFO-1233zd(E))和1,1,1,2,3,3-六氟丙烷(HFC-236ea)组成。
作为本发明的优选实施方式,所述的共沸和类共沸组合物优选由80-95重量%的(E)-1,1,1,4,4,4-六氟-2-丁烯、1-19重量%的(E)-1-氯-,3,3,3-三氟丙烯和1-10重量%的1,1,1,2,3,3-六氟丙烷组成,所述组合物在14psia±0.5psia的压力下沸点为8.5℃±0.5℃。
作为本发明的优选实施方式,所述的共沸和类共沸组合物优选由85-95重量%的(E)-1,1,1,4,4,4-六氟-2-丁烯、1-10重量%的(E)-1-氯-,3,3,3-三氟丙烯和1-5重量%的1,1,1,2,3,3-六氟丙烷组成,所述组合物在14psia±0.5psia的压力下沸点为8.5℃±1℃。
作为本发明的优选实施方式,所述的共沸和类共沸组合物优选由90-95重量%的(E)-1,1,1,4,4,4-六氟-2-丁烯、4-9重量%的(E)-1-氯-,3,3,3-三氟丙烯和1-2重量%的1,1,1,2,3,3-六氟丙烷组成,所述组合物在14psia±0.5psia的压力下沸点为8℃±0.5℃。
共沸(Azeotrope)是指处于平衡状态下,气相和液相组成完全相同时的混合溶液,对应的温度称为共沸温度或共沸点。共沸物,是指两组分或多组分的液体混合物,在恒定压力下沸腾时,其组分与沸点均保持不变。并非所有的二元液体混合物都可形成共沸物。这类混合物的温度-组分相图有着显著的特征,即,其气相线(气液混合物和气态的交界)与液相线(液态和气液混合物的交界)有着共同的最高点或最低点。如此点为最高点,则称为正共沸物;如此点为最低点,则称为负共沸物。大多数共沸物都是负共沸物,即有最低沸点。任一共沸物都是针对某一特定外压而言。对于不同压力,其共沸组分和沸点都将有所不同。在共沸物达到其共沸点时,由于其沸腾所产生的气体部分之成分比例与液体部分完全相同,因此无法以蒸馏方法将溶液成份进行分离。也就是说,共沸物的两组分或多组分,无法用单纯的蒸馏或分馏的方式分离。
类共沸组合物是在沸腾或蒸发时具有恒沸特性或不分馏的趋向,因而在沸腾或蒸发过程中形成的蒸汽的组成与初始的液体组成相同或基本上相同,液体组成就算有变化,也是可忽略程度的变化。
共沸混合物或类共沸混合物的本质特征是在给定压力下,液体组合物的沸点固定,并且在沸腾组合物之上的蒸汽的组成基本上为沸腾的液体组合物的组成。
共沸或类共沸取决于压力和组成的变化,本发明的共沸和类共沸组合物基本上由有效的共沸或类共沸量的(E)-1,1,1,4,4,4-六氟-2-丁烯、(E)-1-氯-,3,3,3-三氟丙烯和1,1,1,2,3,3-六氟丙烷组成。本发明的共沸和类共沸组合物可用于许多应用,如所述的共沸和类共沸组合物可用作选自制冷剂组合物、发泡剂组合物、可喷雾组合物、热泵组合物和溶剂组合物的系统组合物的工作组合物。
本发明的一个优选实施方案涉及包含本发明的共沸和类共沸组合物的制冷剂组合物。
本发明的另一个优选实施方案涉及包含本发明的共沸和类共沸组合物的发泡组合物。
与HCFC-141b和单工质HFC-245fa相比,本发明的组合物具有良好的化学稳定性,在通常的条件下,不会发生分解现象,与聚氨酯发泡过程中所使用的金属材料均不会发生反应或表面腐蚀现象,对塑料和弹性体的影响要比HCFC-141b小,泡沫料的流动性、粘合性、泡沫制品的压缩强度和拉伸强度等性能得到提高,泡沫的尺寸稳定性好,泡沫用料也可适当减少,导热系数接近HCFC-141b。
导热系数是衡量聚氨酯硬质泡沫塑料绝热保温性能的重要指标。本发明的混合物气相导热系数与HCFC-141b略高,但泡沫塑料的导热系数不仅取决于发泡剂的热导率还与泡孔的大小、密度及密度是否均匀等因素有关。通过改进发泡配方,能生产出导热系数较低的泡沫。本发明的混合物发泡的聚氨酯泡沫泡孔比较细密,绝热性能与HCFC-141b发泡的泡沫相当,能耗高约1%,而环戊烷的能耗要高出HCFC-141b10%,HFC-365mfc高7%,HFC-134a高13%。
本发明的另一个优选实施方案涉及包含本发明的共沸和类共沸组合物的可喷雾组合物。
本发明的组合物包括氯三氟丙烯、六氟丁二烯和六氟丙烷,优选为由(E)-1,1,1,4,4,4-六氟-2-丁烯、(E)-1-氯-,3,3,3-三氟丙烯和1,1,1,2,3,3-六氟丙烷组成的共沸和类共沸组合物,该共沸和类共沸组合物具有GWP值低,导热系数小,能耗低的优点,为CFC、HFC和HCFC的最佳替代品。
具体实施方式
以下结合具体实施例对本发明进行进一步的说明,但本发明并不局限于所述的实施例。
实施例1
将以下组分按其重量份数在液相状态下进行物理混合,得到共沸和类共沸组合物,物料按质量配比为:(E)-1,1,1,4,4,4-六氟-2-丁烯80%、(E)-1-氯-,3,3,3-三氟丙烯19%,1,1,1,2,3,3-六氟丙烷1%,混合后测定其性能,见表1。
实施例2
将以下组分按其重量份数在液相状态下进行物理混合,得到共沸和类共沸组合物,物料按质量配比为:(E)-1,1,1,4,4,4-六氟-2-丁烯80%、(E)-1-氯-,3,3,3-三氟丙烯10%,1,1,1,2,3,3-六氟丙烷10%,混合后测定其性能,见表1。
实施例3
将以下组分按其重量份数在液相状态下进行物理混合,得到共沸和类共沸组合物,物料按质量配比为:(E)-1,1,1,4,4,4-六氟-2-丁烯95%、(E)-1-氯-,3,3,3-三氟丙烯4%,1,1,1,2,3,3-六氟丙烷1%,混合后测定其性能,见表1。
实施例4
将以下组分按其重量份数在液相状态下进行物理混合,得到共沸和类共沸组合物,物料按质量配比为:(E)-1,1,1,4,4,4-六氟-2-丁烯95%、(E)-1-氯-,3,3,3-三氟丙烯1%,1,1,1,2,3,3-六氟丙烷4%,混合后测定其性能,见表1。
实施例5
将以下组分按其重量份数在液相状态下进行物理混合,得到共沸和类共沸组合物,物料按质量配比为:(E)-1,1,1,4,4,4-六氟-2-丁烯90%、(E)-1-氯-,3,3,3-三氟丙烯9%,1,1,1,2,3,3-六氟丙烷1%,混合后测定其性能,见表1。
实施例6
将以下组分按其重量份数在液相状态下进行物理混合,得到共沸和类共沸组合物,物料按质量配比为:(E)-1,1,1,4,4,4-六氟-2-丁烯90%、(E)-1-氯-,3,3,3-三氟丙烯1%,1,1,1,2,3,3-六氟丙烷9%,混合后测定其性能,见表1。
实施例7
将以下组分按其重量份数在液相状态下进行物理混合,得到共沸和类共沸组合物,物料按质量配比为:(E)-1,1,1,4,4,4-六氟-2-丁烯90%、(E)-1-氯-,3,3,3-三氟丙烯5%,1,1,1,2,3,3-六氟丙烷5%,混合后测定其性能,见表1。
表1实施例1-7混合后的性能
Claims (8)
1.一种共沸和类共沸组合物,其特征在于,由(E)-1,1,1,4,4,4-六氟-2-丁烯、(E)-1-氯-,3,3,3-三氟丙烯和1,1,1,2,3,3-六氟丙烷组成。
2.根据权利要求1所述的共沸和类共沸组合物,其特征在于,由80-95重量%的(E)-1,1,1,4,4,4-六氟-2-丁烯、1-19重量%的(E)-1-氯-,3,3,3-三氟丙烯和1-10重量%的1,1,1,2,3,3-六氟丙烷组成,所述组合物在14psia±0.5psia的压力下沸点为8.5℃±0.5℃。
3.根据权利要求1所述的共沸和类共沸组合物,其特征在于,由85-95重量%的(E)-1,1,1,4,4,4-六氟-2-丁烯、1-10重量%的(E)-1-氯-,3,3,3-三氟丙烯和1-5重量%的1,1,1,2,3,3-六氟丙烷组成,所述组合物在14psia±0.5psia的压力下沸点为8.5℃±1℃。
4.根据权利要求1所述的共沸和类共沸组合物,其特征在于,由90-95重量%的(E)-1,1,1,4,4,4-六氟-2-丁烯、4-9重量%的(E)-1-氯-,3,3,3-三氟丙烯和1-2重量%的1,1,1,2,3,3-六氟丙烷组成,所述组合物在14psia±0.5psia的压力下沸点为8℃±0.5℃。
5.根据权利要求1所述的共沸和类共沸组合物,其特征在于,所述的共沸和类共沸组合物可用作选自制冷剂组合物、发泡剂组合物、可喷雾组合物、热泵组合物和溶剂组合物的系统组合物的工作组合物。
6.一种制冷剂组合物,其特征在于,所述制冷剂组合物包含权利要求1的共沸和类共沸组合物。
7.一种发泡剂组合物,其特征在于,所述发泡组合物包含权利要求1的共沸和类共沸组合物。
8.一种可喷雾组合物,其特征在于,所述可喷雾组合物包含权利要求1的共沸和类共沸组合物。
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PCT/CN2018/000231 WO2019114050A1 (zh) | 2017-12-14 | 2018-06-25 | 一种共沸和类共沸组合物 |
JP2018565725A JP6872565B2 (ja) | 2017-12-14 | 2018-06-25 | 共沸及び共沸様組成物 |
US16/335,680 US10889740B2 (en) | 2017-12-14 | 2018-06-25 | Azeotropic and azeotrope-like composition |
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