CN102203038B - 1,1,1,2,3-五氯丙烷和氟化氢的类共沸组合物 - Google Patents

1,1,1,2,3-五氯丙烷和氟化氢的类共沸组合物 Download PDF

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CN102203038B
CN102203038B CN200980143596.8A CN200980143596A CN102203038B CN 102203038 B CN102203038 B CN 102203038B CN 200980143596 A CN200980143596 A CN 200980143596A CN 102203038 B CN102203038 B CN 102203038B
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H·S·童
H·T·范
R·R·辛赫
D·C·默克尔
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Abstract

本发明提供基本上由1,1,1,2,3-五氯丙烷和氟化氢组成的类共沸组合物,以及涉及该类共沸组合物的方法。

Description

1,1,1,2,3-五氯丙烷和氟化氢的类共沸组合物
相关申请的交叉引用
本申请要求2008年10月31日申请的、美国临时申请号61/110,216的优先权,在此通过引用方式并入本文。
发明背景
1.发明领域:
本发明涉及类共沸组合物。更具体地,本发明涉及包含氢氟烯烃和氟化氢的类共沸组合物。
2.现有技术描述:
许多共沸物具有适合用作溶剂的特性。例如,共沸物沸点恒定,这避免在操作和使用过程中沸腾温度随意变化。除此之外,当共沸物用作溶剂时,由于在沸腾或回流过程中溶剂的组成不变,所以溶剂的特性保持不变。用作溶剂的共沸物也可通过蒸馏很便利地回收。
然而,共沸物的形成不容易预见,这一事实导致可商用的新的、对环境安全的、不分馏的混合物的鉴定复杂化。因此,工业上一直在寻找新的共沸物和类共沸混合物。本发明尤其满足了这些需要。
发明概述
已经发现基本上由1,1,1,2,3-五氯丙烷(HFC-240db)和氟化氢(HF)组成的类非均相共沸组合物。该类共沸组合物可在不同应用,例如清除金属表面氧化中,用作溶剂。并且,该类共沸组合物可在某些氢氟烯烃,例如HFO-1234yf,的合成中用作中间体。
相应地,提供基本上由1,1,1,2,3-五氯丙烷和氟化氢组成的类共沸组合物。
本发明的另一方面中,提供形成共沸或类共沸组合物的方法,包括在大约0℃至大约60℃温度下、大约7psia至大约58psia压力下将氟化氢和1,1,1,2,3-五氯丙烷混合,以制备基本上由大约1至大约95重量百分数的氟化氢和大约5至大约99重量百分数的1,1,1,2,3-五氯丙烷组成的类共沸混合物。
在本发明的另一方面中,提供溶剂,该溶剂包括基本上由1,1,1,2,3-五氯丙烷和氟化氢组成的类共沸组合物。
在本发明的另一方面中,提供可喷涂的组合物,包括基本上由1,1,1,2,3-五氯丙烷和氟化氢组成的类共沸组合物。
在本发明的又一方面中,提供从基材清除表面氧化的方法,包括在对从所述表面清除一定数量的金属氧化物有效的条件下将金属基材被氧化的表面与包括本文所述的新颖的类共沸组合物的溶剂接触。
附图说明
图1显示了实施例2中形成的混合物在0、25和60℃测量的蒸气压。
本发明优选实施方案详述
本发明提供包含在量上有效形成类共沸组合物的氟化氢(HF)和1,1,1,2,3-五氯丙烷(HFC-240db)的组合物,以及涉及该类共沸组合物的方法。在某些优选实施方案中,这些类共沸组合物是基本上由仅氟化氢和HFC-240db的组合形成的二元共沸物。
本文所用术语“类共沸物”涉及严格共沸和/或通常表现类似共沸混合物的组合物。共沸混合物是两种或更多种组分的体系,在该体系中在指定的压力和温度下液相组成和气相组成相同。在实践中,这意味着共沸混合物的组分的沸点恒定或基本上恒定,通常在相变中无法进行热力学分离。共沸混合物通过沸腾或蒸发形成的气相组成与起始液相组成是相同或基本相同的。因此,随着组合物沸腾或以其它方式蒸发,类共沸组合物的液相和气相中的组分浓度仅仅最低程度地改变(如果改变的话)。与之相反,非共沸混合物的沸腾或蒸发很大程度地改变了液相中的组分浓度。
本文所用术语“非均相共沸物”和“非均相的共沸物”表示包含气相和两种液相的类共沸组合物。
本文中对于类共沸组合物的组分,术语“基本上由…组成”表示该组合物含有类共沸比例的所提到的组分,并可能含有额外组分,前提是所述额外组分不形成新的类共沸体系。例如,基本上由两种化合物组成的类共沸混合物是那些形成二元共沸物的混合物,其可任选地包括一种或多种额外组分,前提是所述额外组分不使该混合物成为非共沸的,并不与所述化合物之一或二者形成共沸物(例如,不形成三元共沸物)。
本文所用术语“有效量”指每一组分的量,其与另外一种组分组合时导致本发明类共沸组合物的形成。
本文所用术语“分配形式”指流体铺展、分布和/或扩散在面积上或通过体积时的物理形式。分配形式的例子包括气溶胶和喷雾。
在某些优选的实施方案中,类共沸组合物含有大约1至大约90重量百分数的HF和大约10至大约99重量百分数的HFC-240db,更优选大约5重量百分数至大约88重量百分数的HF和大约12重量百分数至大约95重量百分数的HFC-240db,最优选大约55重量百分数至大约85重量百分数的HF和大约15重量百分数至大约45重量百分数的HFC-240db。
本发明的组合物优选在大约7psia至大约52psia的压力下具有大约0℃-大约60℃的沸点。例如,优选的类共沸组合物基本上由大约85±2重量百分数的HF和大约15±2重量百分数的HFC-240db组成,名义沸点为大约23℃。
本发明的类共沸组合物可通过组合有效量的HFC-240db和HF制备。本领域中已知的组合两种或更多种组分以形成组合物的各种各样的方法的任何均能够适用于本方法中。例如,HFC-240db和HF可以混合、掺和、或利用手动和/或机器以其它方式组合,作为间歇或连续反应和/或方法的一部分,或通过两个或更多个此类步骤的组合。根据本文公开的内容,本领域技术人员不需要过多的实验即可容易地制备本发明的类共沸组合物。
在本发明的另一实施方案中,本文所述类共沸组合物可用作溶剂,尤其是清洁溶剂。在某些实施方案中,该溶剂与金属基材的被氧化表面接触以除去或减少至少一部分的被氧化表面。这类溶剂可通过所属领域已知的任何方法例如浸泡、喷涂、和擦拭等用于目标基材。
在某些优选实施方案中,提供包括本文所述的新颖的类共沸组合物的可喷涂的组合物。在某些实施方案中,该可喷涂的组合物是气溶胶。在某些中,该可喷涂的组合物进一步包括其他组分例如惰性成分、助溶剂、推进剂、和辅助推进剂等。
在某些实施方案中,本文所述的新颖的类共沸组合物是衍生自某些氢氟烯烃例如2,3,3,3-四氟丙烯(HFO-1234yf)的合成的有用的中间体。例如,在HFO-1234yf合成反应过程中将HFC-240db和HF引入反应器的情况下,这些组分的至少一部分形成共沸物,其可随后从相关反应产物物流中回收。
实施例
本发明通过下列实施例进一步举例说明,所述实施例用作说明但并不以任何方式构成限制。
实施例1:
在大约23℃和大约14.4psia下,将大约15g的1,1,1,2,3-五氯丙烷(HFC-240db)混入85g HF中。观察到非均相类共沸组合物的形成。
实施例2:
HFC-240db和HF混合形成不同组成的非均相共沸混合物。测量该混合物在大约0、25、和60℃的蒸气压。测量结果列于表1。
表1:HFC-240db/HF体系的P-T-X
表1中数据证明这些混合物表现类共沸特性,因为在所有标明的混合比例的HFC-240db和HF混合物的蒸气压比单独HFC-240db和HF的蒸气压更高,单独HFC-240db和HF的蒸气压即当HF为0.0wt.%且HFC-240db为100.0wt%时和HFC-240db为0.0wt.%且HF为100.0wt.%时的蒸气压,如第一行和最后一行所示。
表1中的数据在图1中以图形显示。
实施例3:
该实施例通过气-液-液平衡(VLLE)证明HFC-240db/HF混合物的类共沸特性。
大约14.6g的1,1,1,2,3-五氯丙烷(HFC-240db)与16.8g的HF混合,通过目视观察,在23℃形成非均相混合物。该两种混合物的气相组成在室温23℃取样。结果显示在23℃形成具有大约85±2wt.%HF的类共沸组合物。

Claims (8)

1.组合物,其包含由23.09至89.94重量百分数的1,1,1,2,3-五氯丙烷和10.06至76.91重量百分数的氟化氢组成的类共沸混合物。
2.如权利要求1所述的组合物,其中类共沸混合物由17.02至54.10重量百分数的所述氟化氢和45.90至82.98重量百分数的所述1,1,1,2,3-五氯丙烷组成。
3.如权利要求1所述的组合物,其中所述组合物由所述类共沸混合物组成。
4.如权利要求1所述的组合物,进一步包含至少一种选自惰性稀释剂、清洁剂、推进剂、辅助推进剂、和助溶剂的组分。
5.如权利要求1所述的组合物,具有至少50重量百分数的所述类共沸混合物。
6.包含权利要求1-5任一项的组合物的可喷射的组合物。
7.氟化有机化合物的方法,包括:
a、提供由23.09至89.94重量百分数的1,1,1,2,3-五氯丙烷和10.06至76.91重量百分数的氟化氢组成的类共沸组合物;以及
b、使处于气相中的至少一部分所述1,1,1,2,3-五氯丙烷与氟化剂反应以制备至少一种氟化的有机化合物。
8.形成共沸或类共沸组合物的方法,包括在0℃至60℃的温度以及7psia至58psia的压力下,混合氟化氢和1,1,1,2,3-五氯丙烷以制备由10.06至76.91重量百分数的氟化氢和23.09至89.94重量百分数的1,1,1,2,3-五氯丙烷组成的类共沸混合物。
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US12/607,851 US8410040B2 (en) 2008-10-31 2009-10-28 Azeotrope-like compositions of 1,1,1,2,3-pentachloropropane and hydrogen fluoride
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EP2344433B1 (en) 2021-10-06
CN102203038A (zh) 2011-09-28
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