CN102066518A - 基于氢氟烯烃的组合物 - Google Patents

基于氢氟烯烃的组合物 Download PDF

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CN102066518A
CN102066518A CN2009801220025A CN200980122002A CN102066518A CN 102066518 A CN102066518 A CN 102066518A CN 2009801220025 A CN2009801220025 A CN 2009801220025A CN 200980122002 A CN200980122002 A CN 200980122002A CN 102066518 A CN102066518 A CN 102066518A
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维萨姆·拉切德
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    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-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
    • C08J9/14Working-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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    • C09K5/044Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
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Abstract

本发明涉及包含氢氟烯烃的组合物以及它们作为传热流体、发泡剂、溶剂和气溶胶的用途。更具体地,本发明涉及包含10~90重量%的2,3,3,3-四氟丙烯、5~85重量%的HFC-134a和2~20重量%的HFC-152a的(准)共沸组合物。

Description

基于氢氟烯烃的组合物
本发明涉及包含氢氟烯烃的组合物以及它们作为传热流体、发泡剂、溶剂和气溶胶的用途。
在蒙特利尔商议了由损耗大气臭氧层(ODP:臭氧损耗潜势)的物质所引起的问题,在蒙特利尔签署了强制减少氯氟烃(CFC)的制造和使用的议定书。该议定书已经形成这样的修正案的主题,所述修正案要求撤消CFC并且将规章管理扩展至其它产品,包括氢氯氟烃(HCFC)。
制冷工业和制造空调的工业已经在这些制冷剂的替代方面进行了大量投资,因此氢氟烃(HFC)已经上市。
用作发泡剂或溶剂的(氢)氯氟烃也已经被HFC替代。
在机动车工业中,许多国家中出售的车辆的空调系统已经由氯氟烃(CFC-12)制冷剂变为对臭氧层的危害较小的氢氟烃(1,1,1,2-四氟乙烷:HFC-134a)制冷剂。然而,从由京都议定书所设定的目标的观点来看,HFC-134a(GWP=1300)被认为具有高的热值(heating power)。制冷剂对温室效应的贡献通过标准即GWP(全球增温潜势)量化,GWP是热值的集中体现,将二氧化碳作为基准值1。
由于二氧化碳是无毒的和不可燃的并且具有非常低的GWP,因此已经提出将二氧化碳作为HFC-134a的替代品用作空调系统的制冷剂。然而,使用二氧化碳具有若干缺点,所述缺点特别是与在现有设备和技术中使用二氧化碳作为冷却剂时的非常高的压力有关。
文献JP 4110388描述了其中m和n代表1~5的整数(包括端点)且m+n=6的式C3HmFn的氢氟丙烯(特别是四氟丙烯和三氟丙烯)作为传热流体的用途。
文献WO 2004/037913公开了包含至少一种具有3个或4个碳原子的氟烯烃的组合物作为传热流体的用途,所述氟烯烃特别是五氟丙烯和四氟丙烯,优选具有至多150的GWP。
文献WO 2005/105947教导了向四氟丙烯(优选1,3,3,3-四氟丙烯)中添加助发泡剂(coblowing agent),例如二氟甲烷(HFC-32)、五氟乙烷(HFC-125)、四氟乙烷、二氟乙烷、七氟丙烷、六氟丙烷、五氟丙烷、五氟丁烷、水和二氧化碳。
文献WO 2006/094303公开了包含70.4重量%的2,3,3,3-四氟丙烯(1234yf)和29.6重量%的1,1,1,2-四氟乙烷(HFC-134a)的共沸组合物。该文献还公开了包含91重量%的2,3,3,3-四氟丙烯和9重量%的二氟乙烷(HFC-152a)的共沸组合物。
本申请人公司现已开发了包含氢氟丙烯的组合物,其不呈现上述缺点并且既具有零ODP又具有比现有HFC例如R407C(HFC-134a(52重量%)、HFC-125(25重量%)和HFC-32(23重量%)的三元混合物)的GWP低的GWP。
此外,这些组合物是准共沸的(quasiazeotropic)。
根据本发明的组合物的特征在于它们包含10~90重量%的2,3,3,3-四氟丙烯、5~85重量%的HFC-134a和2~20重量%的HFC-152a。
根据本发明的优选形式,所述组合物包含2~15重量%的HFC-152a、15~70重量%的2,3,3,3-四氟丙烯和15~70重量%的HFC-134a。
包含10~11重量%的HFC-152a、82~83重量%的2,3,3,3-四氟丙烯和6~7重量%的HFC-134a的组合物是特别有利的。这些组合物是共沸的并且在1巴绝对压力下具有-29.5℃(±0.5℃)的沸点。
有利地,根据本发明的组合物主要包含作为(饱和的或不饱和的)氢氟烃的2,3,3,3-四氟丙烯、HFC-134a和HFC-152a。
根据本发明的组合物可用作传热流体并且特别适合用于用于空气调节和加热的压缩系统,特别是热泵,其优选作为R407C和HFC-134a的替代品用于上述用途。这些组合物可在新装置中替代R407C,而对于HFC-134a,这些组合物在现有装置和新装置两者中替代HFC-134a都是合适的。
根据本发明的组合物可包含2,3,3,3-四氟丙烯的稳定剂。所述稳定剂占全部组合物的至多5重量%。
作为稳定剂,可特别提及硝基甲烷,抗坏血酸,对苯二甲酸,唑类(azoles)例如甲苯三唑(tolutriazole)或苯并三唑,酚类化合物例如生育酚、对苯二酚、叔丁基对苯二酚或2,6-二(叔丁基)-4-甲基苯酚,环氧化物(烯基环氧化物或芳族环氧化物、或者任选地氟化或全氟化的烷基环氧化物)例如正丁基缩水甘油醚、己二醇二缩水甘油醚、烯丙基缩水甘油醚或丁基苯基缩水甘油醚,亚磷酸酯,磷酸酯,膦酸酯或者硫醇和内酯。
根据本发明的组合物可包含润滑剂例如矿物油、烷基苯、聚亚烷基二醇和聚乙烯基醚。
另外,根据本发明的组合物可用作发泡剂、气溶胶和溶剂。
实验部分
在下表中给出了根据本发明的组合物在空气调节热泵(air conditioning and heat pump)操作条件中的性能。各组分(1234yf、134a和152a)的值以重量百分比给出。
蒸发温度:                        -5℃
冷凝温度:                        70℃
压缩机入口温度:                  5℃
过冷液体(subcooled liquid)的温度:65℃
压缩机的等熵效率:                70%
Evap P:蒸发器中的压力
Cond P:冷凝器中的压力
Ratio:压缩比
T comp outlet:压缩机出口温度
COP:性能系数,当涉及热泵时,其定义为系统所提供的有用的热能量(hot power)与系统所引入或消耗的功率之比。
COP值大于使用R407C时所获得的值,此外,根据本发明的组合物是共沸的或者准共沸的。
对于R407C,蒸发器处的温度偏移(glide)为4℃,而对于根据本发明的组合物,蒸发器处的温度偏移为至多0.2℃。

Claims (9)

1.组合物,其包含10~90重量%的2,3,3,3-四氟丙烯、5~85重量%的HFC-134a和2~20重量%的HFC-152a。
2.根据权利要求1的组合物,其特征在于其包含2~15重量%的HFC-152a、15~70重量%的2,3,3,3-四氟丙烯和15~70重量%的HFC-134a。
3.根据权利要求1或2的组合物,其特征在于其包含10~11重量%的HFC-152a、82~83重量%的2,3,3,3-四氟丙烯和6~7重量%的HFC-134a。
4.根据权利要求1~3中任一项的组合物,其特征在于其是(准)共沸的。
5.包含根据前述权利要求中任一项的组合物的传热流体。
6.根据权利要求5的传热流体,其特征在于其作为R407C和HFC-134a的替代品用在空气调节和加热中。
7.包含根据权利要求1~4中任一项的组合物的发泡剂。
8.包含根据权利要求1~4中任一项的组合物的气溶胶。
9.包含根据权利要求1~4中任一项的组合物的溶剂。
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FR0853861A FR2932494B1 (fr) 2008-06-11 2008-06-11 Compositions a base d'hydrofluoroolefines
PCT/FR2009/050891 WO2010000995A2 (fr) 2008-06-11 2009-05-14 Compositions a base d'hydrofluoroolefines

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FR2932494B1 (fr) 2011-02-25
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US8486294B2 (en) 2013-07-16
KR20110037950A (ko) 2011-04-13
ES2528417T3 (es) 2015-02-09
PL2283103T3 (pl) 2015-04-30
KR20160054607A (ko) 2016-05-16
WO2010000995A2 (fr) 2010-01-07
FR2932494A1 (fr) 2009-12-18
EP2283103A2 (fr) 2011-02-16
EP2283103B1 (fr) 2014-11-26
US20110089366A1 (en) 2011-04-21
TWI460149B (zh) 2014-11-11
KR101618061B1 (ko) 2016-05-04
CN102066518B (zh) 2013-12-25
JP5525518B2 (ja) 2014-06-18
WO2010000995A3 (fr) 2010-03-04

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