CN1181155C - 氢氟碳化合物组合物 - Google Patents

氢氟碳化合物组合物 Download PDF

Info

Publication number
CN1181155C
CN1181155C CNB971995761A CN97199576A CN1181155C CN 1181155 C CN1181155 C CN 1181155C CN B971995761 A CNB971995761 A CN B971995761A CN 97199576 A CN97199576 A CN 97199576A CN 1181155 C CN1181155 C CN 1181155C
Authority
CN
China
Prior art keywords
hfc
weight
lsy
composition
fluorochemical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB971995761A
Other languages
English (en)
Other versions
CN1237197A (zh
Inventor
Vm
V·M·菲利克斯
��˹��ŵ��
B·H·米诺尔
ά
A·C·斯维尔特
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of CN1237197A publication Critical patent/CN1237197A/zh
Application granted granted Critical
Publication of CN1181155C publication Critical patent/CN1181155C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00Acyclic saturated compounds containing halogen atoms
    • C07C19/08Acyclic saturated compounds containing halogen atoms containing fluorine
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J9/143Halogen containing compounds
    • C08J9/144Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J9/149Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/30Materials not provided for elsewhere for aerosols
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/04Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041Materials 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
    • 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
    • C09K5/045Materials 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 containing only fluorine as halogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2207/00Foams characterised by their intended use
    • C08J2207/04Aerosol, e.g. polyurethane foam spray
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/11Ethers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/12Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22All components of a mixture being fluoro compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/32The mixture being azeotropic

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

本发明涉及如下发现,即包含氟乙烷、2-氟丙烷或叔丁基氟化物的组合物。这些组合物可在纯组分时或可以至少和四氟乙烷、二氟乙烷、六氟丙烷、烃或二甲醚中的一种一起是有用途的。这些组合物是用于气溶胶推进剂、致冷剂、清洁剂、聚烯烃和聚氨酯的膨化剂、致冷剂、传热介质、气态电介质、灭火剂、动力循环工作流体、聚合介质、颗粒清除流体、载流体、抛光研磨剂和置换干燥剂等。

Description

氢氟碳化合物组合物
                      相关申请
本申请要求1996年11月4日提交的美国临时申请第60/029,971号的权利。
                      发明领域
本发明涉及如下发现,即包含氟乙烷,2-氟丙烷或叔丁基氟的组合物。这些组合物作为纯组分,或者与四氟乙烷,二氟乙烷,六氟丙烷,烃或二甲基醚中至少一种联合应用是有用途的。
这些组合物可用作气溶胶推进剂,致冷剂,清洁剂,聚烯烃和聚氨酯类的膨化剂,致冷剂,传热介质,气态电介质,灭火剂,动力循环工作流体,聚合介质,颗粒清除流体(particulate removal fluid),载流体,抛光研磨剂,以及置换干燥剂使用。
                      发明背景
氟化烃有许多用途,例如用作气溶胶推进剂,发泡剂和致冷剂,这些化合物包括三氯氟甲烷(CFC-11),二氯二氟甲烷(CFC-12)和氯二氟甲烷(HCFC-22)。
近年来已经有人指出,某些种类的氟化烃释放到大气中,对平流层的臭氧层会有不利的影响。虽然这种提议并没有完全被接受,但是按照一个国际协议,已形成一种控制使用和生产某些氯氟碳(CFC)和氢氯氟碳(HCFC)化合物的运动。
人们对于光化学活性显著地低于烃类的气溶胶推进剂和发泡剂也有需求,烃类是造成环境臭氧和地面上烟雾的原因之一。这些化合物典型地被称作低VOC(volatile organic compound,挥发性有机化合物)或非VOC。
因此,要求有比现有的致冷剂具有更低的臭氧损耗潜能(ozonedepletion potential)而在制冷用途上性能仍然能满足要求的改进的致冷剂。由于HFC不含氯且因此臭氧损耗潜能(ozone depletion potential)为零,所以氢氟碳(HFC)被建议用来代替CFC和HCFC。
在冷藏用途上,致冷剂在运作过程中通过轴封,软管连接处,焊接接点和破损的管线这些漏洞时经常散失。另外,在致冷设备维修过程中致冷剂可能会释放到大气中。如果致冷剂不是纯组分、共沸物或类共沸物,当其从致冷设备中渗漏或散发到大气中时,该致冷剂组成可能发生变化。致冷剂组成的变化会使致冷剂成为易燃物或降低其致冷性能。
因此,希望仅使用氟化烃或含一种或多种氟化烃的共沸或类共沸物作为致冷剂。
被划分为低VOC或非VOC类的氟化烃,由于它们不会造成显著的地面上污染,因此也被用作气溶胶推进剂或发泡剂。
氟化烃也可以用作清洁剂或清洗溶剂,例如清洗电路板的溶剂。因为在蒸气除油操作中清洁剂通常要在最终的漂洗清洗中被再蒸馏和再使用,所以希望该清洗剂是共沸物或类共沸物。
包含氟化烃的共沸物或类共沸物也可作为制造闭孔聚氨酯和酚醛塑料的热塑性泡沫塑料的发泡剂,作为传热介质、气体电介质、灭火剂或例如用于蒸汽泵的动力循环工作流体等。这些组合物也可以用作聚合反应的惰性介质,用作从金属表面去除颗粒的流体,可作为载流体使用,例如,在金属部件上辅置润滑剂的薄膜,或者作为抛光研磨剂,从抛光表面如金属面上去除抛光研磨化合物。它们还可以用作脱水的置换干燥剂,例如从宝石或金属部件中脱水,用作电路制造技术中常用的抗蚀显影剂,包括氯型显影剂,或者当与例如氯烃如1,1,1-三氯乙烷或三氯乙烯一起使用时作为光刻胶剥离剂。
                    发明概述
本发明涉及如下发现,即包含氟乙烷、2-氟丙烷或叔丁基氟化物的组合物。这些组合物臭氧损耗潜能(ozone depletion potential,ODP)为零,使全球变暖的潜能低,是比烃类挥发性更低的VOC,这些组合物作为纯组分,或者与四氟乙烷,二氟乙烷,六氟丙烷,烃或二甲醚中至少一种一起应用是有用途的。这些组合物可作为气溶胶推进剂、致冷剂、清洁剂、聚烯烃和聚氨酯类的膨化剂、传热介质、气态电介质、灭火剂、动力循环工作流体、聚合介质、颗粒清除流体、载流体、抛光研磨剂,以及置换干燥剂使用。
再者,本发明涉及如下发现,即双组分共沸物或类共沸物。该组合物包含:有效量的氟乙烷、2-氟丙烷或叔丁基氟化物;以及作为第二组分的四氟乙烷、二氟乙烷、六氟丙烷、烃或二甲醚,以形成共沸物或类共沸物。对致冷剂来说非常希望它是共沸物,但对气溶胶推进剂则不是必需的。
本发明的化合物包含下列组分:
1.乙烷(HFC-161,或CH3CH2F,沸点=-38℃),
2.1,1,2,2-四氟乙烷(HFC-134,或CHF2CHF2,沸点=-20℃),
3.1,1,2,2-四氟乙烷(HFC-134a,或CF3CH2F,沸点=-26℃),
4.1,1-二氟乙烷(HFC-152a,或CH3CHF2,沸点=-25℃),
5.2-氟丙烷(HFC-281ea,或CH3CHFCH3,沸点=-11℃),
6.叔丁基氟化物(HFC-3-10-lsy,或(CH3)3CF,沸点12℃),
7.1,1,1,2,3,3-六氟丙烷(HFC-236ea,或CF3CHFCHF2,沸点=6℃),
8.1,1,1,3,3,3-六氟丙烷(HFC-236fa,或CF3CH2F3,沸点=-1℃),
9.二甲基醚(DME,或CH3OCH3,沸点=-25℃),
10.丁烷(CH3CH2CH2CH3,沸点=-0.5℃),
11.异丁烷((CH3)3CH,沸点=-12℃),
12.丙烷(CH3CH2CH3,沸点=-42℃),
按照Grosse和Lin在J.Org.Chem.,Vol.3,pp 26-32(1938)中的报导,HFC-161(CAS登记号353-36-6)和HFC-281ea(异丙基氟化物,CASs登记号420-26-8)可由氟化氢分别与乙烯和丙烯反应制备。
2-氟-2-甲基丙烷(叔丁基氟化物,HFC-3-10-ly,CAS登记号[353-61-7])可以按照Milos Hudlicky著“有机氟化物化学”第二版,1976,689页中记载的由叔丁醇与氟化氢水溶液反应制备而成的。
                        附图简述
图1是-14.15℃时混合物HFC-161/HFC-134a的气/液平衡曲线图;
图2是-0.05℃时混合物HFC-161/HFC-152a的气/液平衡曲线图;
图3是-10℃时混合物HFC-161/HFC-281ea的气/液平衡曲线图;
图4是-20℃时混合物HFC-161/HFC-3-10-lsy的气/液平衡曲线图;
图5是-20℃时混合物HFC-161/丁烷的气/液平衡曲线图;
图6是-10℃时混合物HFC-161/异丁烷的气/液平衡曲线图;
图7是0℃时混合物HFC-161/DME的气/液平衡曲线图;
图8是-10℃时混合物HFC-281ea/HFC-134a的气/液平衡曲线图;
图9是-10.01℃时混合物HFC-281ea/HFC-152a的气/液平衡曲线图;
图10是0℃时混合物HFC-281ea/HFC-3-10-lsy的气/液平衡曲线图;
图11是-10℃时混合物HFC-281ea/丙烷的气/液平衡曲线图;
图12是-9.95℃时混合物HFC-281ea/DME的气/液平衡曲线图;
图13是-21.7℃时混合物HFC-3-10-lsy/HFC-134的气/液平衡曲线图;
图14是0℃时混合物HFC-3-10-lsy/HFC-134a的气/液平衡曲线图;
图15是0℃时混合物HFC-3-10-lsy/HFC-152a的气/液平衡曲线图;
图16是-1.7℃时混合物HFC-3-10-lsy/HFC-236ea的气/液平衡曲线图;
图17是-2.5℃时混合物HFC-3-10-lsy/HFC-23fa的气/液平衡曲线图;
图18是0℃时混合物HFC-3-10-lsy/丁烷的气/液平衡曲线图;
图19是0℃时混合物HFC-3-10-lsy/异丁烷的气/液平衡曲线图;
图20是-20℃时混合物HFC-3-10-lsy/丙烷的气/液平衡曲线图;
图21是-10℃时混合物HFC-3-10-lsy/DME的气/液平衡曲线图。
                     发明详述
本发明涉及下列组合物:
(a)氟乙烷(HFC-161);
(b)2-氟丙烷(HFC-281ea);
(c)叔丁基氟化物(HFC-3-10-lsy);
(d)HFC-161和1,1,1,2-四氟乙烷(HFC-134a);HFC-161和1,1-二氟乙烷(HFC-152a);HFC-161和2-氟丙烷(HFC-281ea);HFC-161和叔丁基氟化物(HFC-3-10-lsy);HFC-161和丁烷;HFC-161和异丁烷;或HFC-161和二甲基醚(DME);
(e)HFC-281ea和HFC-134a;HFC-281ea和HFC-152a;HFC-281ea和HFC-3-10-lsy;HFC-281ea和丙烷;或HFC-281ea和DME;或
(f)HFC-3-10-lsy和1,1,2,2-四氟乙烷(HFC-134);HFC-3-10-1sy和HFC-134a;HFC-3-10-lsy和HFC-152a;HFC-3-10-lsy和1,1,1,2,3,3-六氟丙烷(HFC-236ea);HFC-3-10-lsy和1,1,1,3,3,3-六氟丙烷(HFC-236fa);HFC-3-10-lsy和丁烷;HFC-3-10-lsy和异丁烷;HFC-3-10-lsy和丙烷;或HFC-3-10-lsy和DME。
组合物中1-99%(重量)的每一种组分可用作为气溶胶推进剂、致冷剂、清洁剂、聚烯烃和聚氨酯类的膨化剂、致冷剂、传热介质、气体电介质、灭火剂、动力循环工作流体、聚合介质、颗粒清除流体、载流体、抛光研磨剂,以及置换干燥剂等。再者,本发明还涉及如下新的发现,即共沸物或类共沸物,该组合物包含有效量的上述每一种混合物以形成共沸物或类共沸物。
“共沸物”组合物意指两种或多种物质的有恒定沸点的混合物,其行为与单一物质相同。表征共沸物的一种方法是,由部分蒸发或液体蒸馏而产生的蒸气与被蒸发或蒸馏的液体具有相同的组成,也就是说,蒸馏液回流液的混合物没有组成的改变。与那些由相同组分构成的非共沸物相比,恒沸物由于它们显示出或者最高或者最低的沸点,可以被认为是有共沸特点的组合物。
“类共沸物”意指两种或多种物质的有恒定的沸点、或基本上恒定的沸点的混合物,其行为与单一物质相同。表征类共沸物的一种方法是,由液体部分蒸发或蒸馏而产生的蒸气与被蒸发或被蒸馏的液体有基本上相同的组成,也就是说,蒸馏液/回流液的混合物基本上没有组成的改变。表征类共沸物的另一种方法是组合物在特定温度下的泡点蒸气压力与露点蒸气压力基本相同。
本领域技术人员已知,如果一种组合物是类共沸物,用例如蒸发或沸腾的方法除去50%(重量)的该组合物后,用绝对单位测量时,原组合物的蒸气压与已除去50%(重量)的原组合物后剩余的组合物的蒸气压之间的差距小于大约10%。绝对单位意指按照如下单位计算的压力,例如,帕斯卡、大气压、巴、托、达因/平方厘米、毫米汞柱、英寸水柱以及其它本领域技术人员所共知的等价的术语。如果是共沸物,则在原组合物的蒸气压与已除去50%(重量)的原组合物后剩余的组合物的蒸气压之间没有差别。
因此,包括在本发明范围内的组合物是含有效量如下成分的组合物:
(a)HFC-161和1,1,1,2-四氟乙烷(HFC-134a);HFC-161和1,1-二氟乙烷(HFC-152a);HFC-161和2-氟丙烷(HFC-281ea);HFC-161和叔丁基氟化物(HFC-3-10-lsy);HFC-161和丁烷;HFC-161和异丁烷;或HFC-161和二甲醚(DME);
(b)HFC-281ea和HFC-134a;HFC-281ea和HFC-152a;HFC-281ea和HFC-3-10-lsy;HFC-281ea和丙烷;或HFC-281ea和DME;或
(c)HFC-3-10-lsy和1,1,2,2-四氟乙烷(HFC-134);HFC-3-10-lsy和HFC-134a;HFC-3-10-lsy和HFC-152a;HFC-3-10-lsy和1,1,1,2,3,3-六氟丙烷(HFC-236ea);HFC-3-10-lsy和1,1,1,3,3,3-六氟丙烷(HFC-236fa);HFC-3-10-lsy和丁烷;HFC-3-10-lsy和异丁烷;HFC-3-10-lsy和丙烷;或HFC-3-10-lsy和DME;
使得在50%(重量)的原组合物经蒸发或沸腾除去之后形成剩余的组合物,原组合物蒸气压与剩余组合物蒸气压之间的差别是10%或更小。
对共沸物来说,通常在共沸点附近有一定的组成范围,对有最高沸点的共沸物,其在特定压力下的沸点高于该组合物各纯组分在那一压力下的沸点,并且其在特定温度下的蒸气压低于该组合物各纯组分在那一温度下的蒸气压,而对有最低沸点的共沸物,其在特定压力下的沸点低于该组合物各纯组分在那一压力下的沸点,并且其在特定温度下的蒸气压高于该组合物各纯组分在那一温度下的蒸气压。高于或低于纯组分的沸腾温度和蒸气压力是由组合物的分子之间的意料不列作用力引起的,分子间力可以是排斥力与吸引力例如范德华力与氢键的综合效果。
在特定压力下有最高或最低沸点,或者在特定温度下有最大或最小蒸汽压的组成范围与那些蒸发掉50%(重量)的组合物时其蒸气压力的变化小于10%的组成范围可以相同或不同。在特定压力下有最高或最低沸点的或者在特定温度下有最大或最小蒸汽压的情况下的组成范围比蒸发掉50%(重量)的组合物时蒸气压力的变化小于约10%的组成范围要宽,在这种情况下,所不希望的分子间力对于具有这些力的致冷剂组合物耒说相信仍然是重要的,将使它基本上不是恒定沸点的,而是在效能或效率上随致冷剂组成的变化而显出所不希望的增加。本发明的沸点基本上恒定的、共沸的或类共沸的组合物包含如下的组成:
组分   NTS               T℃    重量范围        优选范围
                                 (wt.%/wt/%)    (wt.%/wt.%)
HFC-161/HFC-134a           -20     1-99/1-99       10-90/10-90
HFC-161/HFC-152a           -30     1-99/1-99       10-90/10-90
HFC-161/HFC-281ea          -10     73-99/1-27      73-99/1-27
HFC-161/HFC-3-10-lsy       -20     75-99/1-25      75-99/1-25
HFC-161/丁烷               -20     67-99/1-33      67-99/1-33
HFC-161/异丁烷             -20     52-99/1-48      52-9/1-48
HFC-161/DME                -30     1-99/1-99       10-90/10-90
HFC-281ea/HFC-134a         -10     1-99/1-99       10-90/10/90
HFC-281ea/HFC-152a         -20     1-99/1-99       10-90/10-90
HFC-281ea/HFC-3-10-lsy     0       41-99/1-59      41-99/1-59
HFC-281ea/丙烷             -10     1-41/59-99      1-41/59-99
HFC-281ea/DME              -9.95   1-99/1-99       10-90/10-90
HFC-3-10-lsy/HFC-134       -21.7   1-44/56-99      1-44/56-99
HFC-3-10-lsy/HFC-134a      0       1-32/68-99      1-32/68-99
HFC-3-10-lsy/HFC-152a      0       1-30/70-99      1-30/70-99
HFC-3-10-lsy/HFC-236ea     -1.7    11-60/40-89和   11-60/40-89和
                                   1-3/97-99       1-3/97-99
HFC-3-10-lsy/HFC-236fa     -2.5    1-52/48-99      1-52/48-99
HFC-3-10-lsy/丁烷          0       1-99/1-99       10-90/10-90
HFC-3-10-lsy/异丁烷        0       1-45/55-99和    1-45/55-99和
                                   89-99/1-11      89-99/1-11
HFC-3-10-lsy/丙烷          -20     1-19/81-99      1-19/81-99
HFC-3-10-lsy/DME           -10     1-42/58-99      1-42/58-99
对本发明而言,“有效量”是按照本发明的组合物中每一组分的量来定义的,当本发明的组合物按这些量混合时,会形成共沸物或类共沸物。这一定义包括每一种组分的量,该量可以根据施用于该组合物的压力而改变,只要在不同的压力下共沸物或类共沸物继续存在,但是可能有不同的沸点。
因此,有效量包括本发明的组合物的每一组分的量,例如以重量百分数表示的,使该组合物形成共沸物或类共沸物,其温度和压力不一定与此处所指出的相同。
对此论述而言,共沸或恒沸点的意思也是指基本上共沸或基本上恒沸点。换言之,这些术语中所包含的意义不但是对上面介绍的真正的共沸物,而且包括其他的含有同样的组分但有不同比例的组合物,它在其他温度和压力下是真正的共沸物;以及包括那些属于相同的共沸物体系的一部分且性质上是类共沸物的等价的组合物。本领域所已知的是,有一个和共沸物相同组分的组成范围,它将不仅在制冷和其他用途中表现出基本相同的性质,而且将根据沸点恒定的特点或沸腾时不离析或有不能分馏的倾向而显示出其与真正的共沸物基本上相同的性质。
实际上,可以通过以下几条标准中任何一条鉴别一种依赖于所选择的条件而以多种形式出现的恒沸物。
*之所以某组合物能够被称为A,B,C(和D…)的共沸物,是因为共沸物一词既是明确的同时亦是有限制的,对此独特的组合物,它要求A,B,C(和D…)有这样一个有效量,使它是恒沸点的组合物。
*为本领域技术人员所熟知的是,在不同的压力下,所给定的共沸物的组成将至少在某种程度上有所改变,压力的变化也将在一定程度上改变沸点温度。因此,A,B,C(和D…)的共沸物代表一个独特类型的、取决于温度和/或压力的、可变的组成关系。因此,经常用一定范围的组成而不是用固定的组成来定义共沸物。
*该组合物可以以A,B,C(和D…)的特定重量百分比关系或摩尔百分比关系来定义,同时应认识到这样的特殊值仅指明一个特定的关系,以及在实际上对于一个给定的共沸物,由A,B,C(和D…)所表示的一系列这种关系确实是存在的,并受压力的影响而变化。
*A,B,C(和D…)的共沸物可以被表征,即定义该组合物为一个用在给定压力下的沸点所表征的共沸物。这样给定的鉴别特征并没有用几个特殊的组成数据而过份地限制本发明的范围,这几个特殊的组成是受所用的分析装置的精确度所限制的,并且只能达到所用的分析装置的精确度。
本发明的共沸物或类共沸物可以通过任何一种常用的方法制得,包括按所需量混合或配合的方法。优选的方法是称量所需量的组分后在适当的容器中混合。
下面给出一些具体的实例说明本发明,所有的百分比都是重量百分比,除非在那里有另外的说明。可以理解的是这些实例只是举例说明,而不会构成对本发明范围的限制。
                           实例1
相态研究
相态研究表明以下的组合物是共沸的,都是在指定温度下。
组分                     T℃                重量范围       蒸气压
                                                     psia(kPa)
HFC-3-10-lsy/HFC-134      -21.7       13.9/86.1      14.7  101
HFC-3-10-lsy/HFC-236ea    -1.7        33.6/66.4      14.7  101
HFC-3-10-lsy/HFC-236fa    -2.5        12.7/87.3      14.7  101
                           实例2
蒸气渗漏的影响
在指定温度下将初始组合物装到一容器中,该组合物的初始蒸气压已经测定。在温度保持恒定的情况下使该组合物从此容器中渗漏出,直到除去50%(重量)的该原始组合物,这时测量剩余在该容器中的组合物的蒸气压。结果总结如下。
A的重量%/B的重量%        原始的            50%泄漏后的
                      PSIA       KPA      PSIA      KPA      DELTA%P
HFC-161/HFC-134a(-20℃)
1/99                  19.6        135       19.5       134       0.5
10/90                 22.0        152       21.2       146       3.6
20/80                 24.1        166       22.9       158       5.0
30/70                 25.8        178       24.6       170       4.7
40/60                 27.2        188       26.1       180       4.0
50/50                 28.3        195       27.5       190       2.8
60/40                 29.2        201       28.6       197       2.1
70/30                 29.9        206       29.5       203       1.3
80/20                 30.5        210       30.3       209       0.7
90/10                 30.9        213       30.8       212       0.3
99/1                  31.2        215       31.2       215       0.0
HFC-161/HFC-152a(-30℃)
1/99                  11.7        80.7      11.7       80.7      0.0
10/90                 12.7        87.6      12.3       84.8      3.1
20/80                 13.8        95.1      13.1       90.3      5.1
30/70                 14.9        103       14.0       96.5      6.0
40/60                 15.9        110       14.9       103       6.3
50/50                 16.9        117       15.9       110       5.9
60/40                 17.8        123       16.9       117       5.1
70/30                 18.7        129       18.0       124       3.7
80/20                 19.5        134       19.0       131       2.6
90/10                 20.3        140       20.0       138       1.5
99/1                  20.9        144       20.9       144       0.0
HFC-161/HFC-281ea(-10℃)
99/1                  44.9     310      44.8      309      0.2
90/10                 42.7     294      41.1      283      3.7
80/20                 40.0     276      37.1      256      7.2
73/27                 38.1     263      34.3      236      10.0
HFC-161/HFC-3-10-lsy(-20℃)
99/1                  31.1     214      31.0      214      0.3
90/10                 29.7     205      28.6      197      3.7
80/20                 28.1     194      25.9      179      7.8
75/25                 27.2     188      24.6      170      9.6
74/26                 27.1     187      24.3      168      10.3
HFC-161/丁烷(-20℃)
99/1                  31.1     214      31.0      214      0.3
90/10                 29.8     205      29.1      201      2.3
80/20                 28.4     196      26.9      185      5.3
70/30                 26.9     185      24.6      170      8.6
67/33                 26.5     183      23.9      165      9.8
66/34                 26.3     181      23.6      163      10.3
HFC-161/异丁烷(-20℃)
99/1                  31.2     215      31.2      215      0.0
90/10                 30.5     210      30.3      209      0.7
80/20                 29.6     204      29.0      200      2.0
70/30                 28.6     197      27.5      190      3.8
60/40                 27.4     189      25.6      177      6.6
52/48                 26.4     182      23.9      165      9.5
51/49                 26.3     181      23.6      163      10.3
HFC-161/DME(-30℃)
1/99                  11.6     80.0     11.6      80.0     0.0
10/90                 12.4     85.5     12.1      83.4     2.4
20/80                 13.2     91.0     12.7      87.6     3.8
30/70                 14.1     97.2     13.3      91.7     5.7
40/60                 15.0     103      14.1      97.2     6.0
50/50                 16.0     110      15.0      103      6.3
60/40                 17.0     117      16.0      110      5.9
70/30                 17.9     123      17.1      118      4.5
80/20                 18.9     130      18.3      126      3.2
90/10                 19.9     137      19.6      135      1.5
99/1                  20.8     143      20.8      143      0.0
HFC-281ea/HFC-134a(-10℃)
1/99                 29.1        201      29.0      200      0.3
10/90                26.7        184      25.6      177      4.1
20/80                24.4        168      22.7      157      7.0
30/70                22.4        154      20.4      141      8.9
40/60                20.6        142      18.8      130      8.7
50/50                19.1        132      17.5      121      8.4
60/40                17.8        123      16.5      114      7.3
70/30                16.7        115      15.8      109      5.4
80/20                15.7        108      15.1      104      3.8
90/10                14.9        103      14.6      101      2.0
99/1                 14.2        97.9     14.2      97.9     0.0
HFC-281ea/HFC-152a(-20℃)
1/99                 17.8        123      17.8      123      0.0
10/90                17.0        117      16.6      114      2.4
20/80                16.0        110      15.3      105      4.4
30/70                15.1        104      14.2      97.9     6.0
40/60                14.2        97.9     13.2      91.0     7.0
50/50                13.3        91.7     12.3      84.8     7.5
60/40                12.4        85.5     11.6      80.0     6.5
70/30                11.6        80.0     10.9      75.2     6.0
80/20                10.8        74.5     10.2      70.3     5.6
90/10                10.0        68.9     9.68      66.7     3.2
99/1                 9.28        64.0     9.23      63.6     0.5
HFC-281ea/HFC-3-10-lsy(0℃)
99/1                 21.0        145      20.9      144      0.5
90/10                20.3        140      20.1      139      1.0
80/20                19.6        135      19.1      132      2.6
70/30                18.8        130      18.0      124      4.3
60/40                17.9        123      16.9      117      5.6
50/50                17.0        117      15.7      108      7.6
41/59                16.1        111      14.5      100      9.9
40/60                16.0        110      14.3      98.6     10.6
HFC-281ea/丙烷(-10℃)
1/99                 35.3        344      49.8      343      0.2
10/90                48.6        335      48.1      332      1.0
20/80                47.1        325      45.7      315      3.0
30/70                45.4        313      42.9      296      5.5
40/60                43.4        299      39.3      271      9.4
41/59                43.2        298      38.9      268      10.0
HFC-281ea/DME(-9.95℃)
1/99                     26.7         184        26.7         184        0.0
10/90                    25.8         178        25.4         175        1.6
20/80                    24.8         171        24.1         166        2.8
30/70                    23 7         163        22.7         157        4.2
40/60                    22.5         155        21.3         147        5.3
50/50                    21.3         147        20.0         138        6.1
60/40                    20.0         138        18.7         129        6.5
70/30                    18.7         129        17.5         121        6.4
80/20                    17.3         119        16.3         112        5.8
90/10                    15.9         110        15.2         105        4.4
99/1                     14.4         99.3       14.3         98.6       0.7
HFC-3-10-lsy/HFC-134(-21.7℃)
13.9/86.1                14.7         101.4      14.7         101.4      0.0
7/93                     14.5         100.0      14.3         98.6       1.4
1/99                     13.7         94.5       13.5         93.1       1.5
0/100                    13.4         92.4       13.4         92.4       0.0
20/80                    14.6         100.7      14.6         100.7      0.0
30/70                    14.5         100.0      14.2         97.9       2.1
40/60                    14.3         98.6       13.5         93.1       5.6
44/56                    14.2         97.9       12.8         88.3       9.9
45/55                    14.2         97.9       12.6         86.9       11.3
100/0                    3.89         26.8       3.89         26.8       0.0
HFC-3-10-lsy/HFC-134a(0℃)
1/99                     42.9         296        42.9         296        0.0
5/95                     42.3         292        42.1         290        0.5
10/90                    41.5         286        40.8         281        1.7
15/85                    40.6         280        39.4         272        3.0
20/80                    39.7         274        38.0         262        4.3
25/75                    38.9         268        36.4         251        6.4
30/70                    38.0         262        34.7         239        8.7
32/68                    37.7         260        34.0         234        9.8
33/67                    37.5         259        33.6         232        10.4
HFC-3-10-lsy/HFC-152a(0℃)
1/99                     38.4         265        38.4         265        0.0
10/90                    36.8         254        36.0         248        2.2
20/80                    35.0         241        33.1         228        5.4
30/70                    33.2         229        30.0         207        9.6
31/69                    33.0         228        29.6         204        10.3
HFC-3-10-lsy/HFC-236ea(-1.7℃)
33.6/66.4                    14.7        101         14.7        101         0.0
20/80                        14.5        100         14.1        97.0        2.9
11/89                        13.8        94.9        12.4        85.5        9.9
50/50                        14.6        100         14.3        98.5        1.9
60/40                        14.4        99.3        13.2        90.7        8.7
61/39                        14.4        99.3        12.9        88.9        10.4
100/0                        8.91        61.4        8.91        61.4        0.0
0/100                        10.4        71.7        10.4        71.7        0.0
1/99                         11.0        75.6        10.5        72.3        4.4
3/97                         11.9        81.8        10.7        73.9        9.7
HFC-3-10-lsy/HFC-236fa(-2.5℃)
12.7/87.3                    14.7        101         14.7        101         0.0
1/99                         14.2        98.0        14.2        97.8        0.2
0/100                        14.1        97.2        14.1        97.2        0.0
40/60                        13.9        95.6        13.2        91.1        4.7
50/50                        13.4        92.1        12.2        84.0        8.8
52/48                        13.2        91.3        12.0        82.5        9.7
53/47                        13.2        90.9        11.8        81.6        10.2
100/0                        8.64        59.6        8.64        59.6        0.0
HFC-3-10-lsy/丁烷(0℃)
1/99                         14.9        103         14.9        103         0.0
10/90                        14.6        101         14.5        99.8        0.7
20/80                        14.2        97.7        14.0        96.4        1.3
30/70                        13.7        94.7        13.5        92.7        2.0
40/60                        13.3        91.4        12.9        88.9        2.7
50/50                        12.8        87.9        12.3        85.1        3.2
60/40                        12.2        84.1        11.8        81.1        3.6
70/30                        11.6        80.0        11.2        77.1        3.7
80/20                        11.0        75.6        10.6        73.1        3.4
90/10                        10.3        70.8        10.0        69.2        2.2
99/1                         9.59        66.1        9.56        65.9        0.3
HFC-3-10-lsy/异丁烷(0℃)
1/99                 22.6        156        22.6        156        0.0
10/90                21.7        150        21.3        147        2.1
20/80                20.7        143        19.8        136        4.3
30/70                19.6        135        18.3        126        6.5
40/60                18.4        127        16.8        116        8.8
45/55                17.8        123        16.0        111        9.9
46/54                17.7        122        15.9        110        10.1
88/12                11.6        80.2       10.5        72.1       10.1
89/11                11.5        79.0       10.4        71.5       9.5
99/1                 9.69        66.8       9.57        66.0       1.2
HFC-3-10-lsy/丙烷(-20℃)
1/99                 35.2        243        35.0        241        0.6
10/90                33.5        231        31.9        220        4.8
19/81                31.6        218        28.6        197        9.5
20/80                31.4        216        28.2        194        10.2
HFC-3-10-lsy/DME(-10℃)
1/99                 26.7        184        26.7        184        0.0
10/90                26.0        179        25.7        177        1.2
20/80                25.1        173        24.4        168        2.8
30/70                24.2        167        22.9        158        5.4
40/60                23.2        160        21.1        145        9.1
42/58                23.0        159        20.7        143        10.0
43/57                22.8        157        20.5        141        10.1
这个实例的结果显示,因为在50%(重量)的原组合物被除去后,在25℃剩余组合物的蒸气压的变化大约在原组合物蒸气压的10%以内,所以这些组合物是共沸物或类共沸物。
                        实例3
-20℃时蒸气渗漏的影响
用HFC-3-10-lsy和HFC-236fa的组合物在-20℃时进行渗漏试验。结果总结如下。“A”代表HFC-3-10-lsy,“B”代表HFC-236fa。
                                起始物           50%   泄漏后
A的重量%/B的重量%        PSIA      KPA     PSIA      KPA     DELTA%P
HFC-3-10-lsy/HFC-236fa
16.3/83.7                   6.86       47.3     6.86       47.3       0.0
10/90                       6.82       47.0     6.80       46.9       0.3
1/99                        6.49       44.7     6.47       44.6       0.3
30/70                       6.75       46.5     6.66       45.9       1.3
40/60                       6.59       45.4     6.34       43.7       3.8
50/50                       6.37       43.9     5.90       40.7       7.4
55/45                       6.25       43.1     5.63       38.8       9.9
56/44                       6.22       42.9     5.58       38.5       10.3
这些结果显示,HFC-3-10-lsy和HFC-236fa的组合物在不同温度下是共沸物或类共沸物,但是这些组分的重量百分比随着温度的变化而改变。
                            实例4
蒸气压和贝壳松脂丁醇值(Kauri-butanol value)
本发明的化合物的蒸气压在下面给出。数据表明这些化合物可以有效的替代如今广泛应用于气溶胶配制剂中的烃类。HFC-281ea和异丁烷以及HFC-161和丙烷有几乎相等的蒸气压。本发明的化合物的贝壳松脂丁醇值也高于每一个相应的烃。这表明这些化合物有更好的溶解能力以及更好的与气溶胶树脂和与其他活性成分的相容性。
                       蒸气压  (Psig)    贝壳松脂丁醇值
                       70°F   130°F
HFC-161           106          264            16.3
HFC-281ea         31           99             20.3
HFC-3-10-lsy      5            38             -
丙烷              108          262            15
异丁烷            31           97             18
丁烷              17           65             20
                           实例5
VOC(挥发性有机化合物)判定
用实验方法(在喷气推进实验室)进行动力学速率测量,或者用R.Atkinson的基团反应性方法来判定本发明的化合物(参考:Kwok,E.S.C.,和R.Atkinson著“用结构-反应性关系测算气相有机化合物的羟基自由基反应速度常数,修订版”,对CMA的最后报告,合同号ARC-8.0-OR,1994)。如果在298k时,以乙烷为标准,一种化合物的动力学速率小于1.0,该化合物可被认为是非VOC。结果显示于下表中。
                                
化合物        k,在298K,cm3/分子-秒   k,相对于乙烷    测定或判断
                相对于OH自由基反应
乙烷                2.4×10-13               1.0             测定
丙烷                1.1×10-12               4.6             测定
丁烷                2.54×10-12              10.5            判定
异丁烷              2.33×10-12              9.7             判定
HFC-161             1.7×10-13               0.7             测定
HFC-281ea           4.6×10-13               1.9             测定
HFC-3-10-lsy        7.7×10-14               0.3             判定
本发明的化合物与如今广泛用于气溶胶的丙烷,丁烷和异丁烷这些烃类相比较,其光化学的(羟基自由基)活性显著降低。在气溶胶中使用本发明的化合物可以显著减少地面上的烟雾。由于HFC-161和HFC-3-10-lsy的活性低于乙烷,所以它们被划归为非VOC。HFC-281ea的活性明显低于它的烃类相似物异丁烷。
                          实例6
55%VOC微量喷雾实验范例
本发明的55%VOC(挥发性有机化合物)微量喷雾配制剂配制如下:
                         
                                            %(重量)
辛基丙烯酰胺/丙烯酸酯/丁基氨基乙基甲基
丙烯酸酯共聚物(National Starch)               5.00
AMP(2-氨基-2-甲基-1-丙醇,Kodak)              0.96
Dimethicone Silylate(Hydrolabs)               0.50
水                                            3.54
向这一混合物中加入乙醇和本发明的推进剂,形成55%VOC配制剂:
                       重量%/重量%    乙醇的重量%
HFC-161                  35.00             55.00
HFC-3-10-lsy             35.00             55.00
HFC-161/HFC-134a         5.00/30.00        55.00
HFC-161/HFC-152a         5.00/30.00        55.00
HFC-161/HFC-281ea        35.00/7.00        48.00
HFC-161/HFC-3-10-lsy     28.00/7.00        55.00
HFC-281ea/HFC-134a       7.00/35.00        48.00
HFC-281ea/HFC-152a       7.00/35.00        48.00
HFC-281ea/HFC-3-10-lsy   7.00/35.00        48.00
HFC-3-10-lsy/HFC-134     5.00/30.00        55.00
HFC-3-10-lsy/HFC-134a    5.00/30.00        55.00
HFC-3-10-lsy/HFC-152a    7.00/28.00        55.00
每一种混合物的蒸气压力可能随配制剂而发生变化。这个实例是描述性的,并非最优化体系。
                       实例7
55%VOC微量喷雾实验范例
两种按照本发明的55%VOC微量喷雾配制剂配制如下:
组分                 A                        B
                     Wt%                    Wt%
PVM/MA共聚物         6.00                     6.00
AMP                  0.35                     0.35
水                   29.05                    38.65
乙醇40-1             34.60                    25.00
按重量计,向这些混合物中加入30%的下列本发明的组合物之一,以形成55%VOC的配制剂:
                             表
                             配方
组分                 A                        B
                     Wt%                    Wt%
HFC-161/DME          9.60/20.40               -
HFC-161/丁烷         9.60/20.40               -
HFC-161/异丁烷       9.60/20.40               -
HFC-161/DME          -                        9.60/20.40
HFC-281ea/丙烷       -                        9.60/20.40
HFC-281ea/DME        9.60/20.40               -
HFC-3-10-lsy/丁烷    9.60/20.40               -
HFC-3-10-lsy/丙烷    9.60/20.40               -
HFC-3-10-lsy/DME     9.60/20.40               -
HFC-3-10-lsy/异丁烷  9.60/20.40               -
每种混合物的蒸气压力可能随配制剂而发生变化。这个实例是描述性的,并不反映最优化体系。由于HFC-281ea有显著低的光化学活性,所以含有HFC-281ea的配制剂将比那些含有烃类的配制剂对地面上烟雾的影响更小。
                       实例8
                   芳香味实验例
按照本发明的一个芳香味实验配制剂如下:
                                    Wt%
香气物                              3.0
乙醇40-1                            70.0
水                                  15.0
按重量计,向该混合物中加入12.0%的下列本发明的混合物之一:
                           Wt%        %VOC
HFC-161                    12.0         70
HFC-281ea                  12.0         82
HFC-3-10-lsy               12.0         70
HFC-161/HFC-134a           3.0/9.0      70
HFC-161/HFC-152a           3.0/9.0      70
HFC-161/HFC-281ea          9.0/3.0      73
HFC-161/HFC-3-10-lsy       9.0/3.0      70
HFC-161/丁烷               9.0/3.0      73
HFC-161/异丁烷             9.0/3.0      73
HFC-161/DME                6.0/6.0      76
HFC-281ea/HFC-134a         3.0/9.0      73
HFC-281ea/HFC-152a         3.0/9.0      73
HFC-281ea/HFC-3-10-lsy     3.0/9.0      73
HFC-281ea/丙烷             3.0/9.0      82
HFC-281ea/DME              3.0/9.0      82
HFC-3-10-lsy/HFC-134       2.0/10.0     70
HFC-3-10-lsy/HFC-134a      3.0/9.0      70
HFC-3-10-lsy/HFC-152a      3.0/9.0      70
HFC-3-10-lsy/丁烷          5.0/4.0      74
HFC-3-10-lsy/异丁烷        4.0/5.0      75
HFC-3-10-lsy/丙烷          2.0/10.0     80
HFC-3-10-lsy/DME           3.0/9.0      79
每种混合物的蒸气压力可能随配制剂而发生变化。这个实例是描述性的,并不反映最优化体系。由于HFC-281ea有显著低的光化学活性,所以含有HFC-281ea的配制剂将比那些含有烃类的配制剂对地面烟雾的影响更小。
                     实例9
气溶胶抗汗渗实验例
按照本发明的一个66%VOC气溶胶抗汗渗实验配制剂如下:
                      
                                    Wt%
水合氯化铝                          10.0
肉豆蔻酸异丙酯                      6.0
聚硅氧烷流体(Dow Corning)DC-344     6.0
滑石粉                              0.5
Quaternium-18 hectorite             0.5
乙醇40-1                            2.0
将以每种75.0%(重量)的下列本发明的混合物之一加入到这混合物中,以形成60%VOC的配制剂。
    HFC-161/DME     17.0/58.0
    HFC-161/丁烷     17.0/58.0
    HFC-161/异丁烷     17.0/58.0
    HFC-3-10-lsy/丁烷     17.0/58.0
    HFC-3-10-lsy/异丁烷     17.0/58.0
    HFC-3-10-lsy/丙烷     17.0/58.0
    HFC-3-10-lsy/DME     17.0/58.0
使用本发明组合物也可以开发空气清新剂、家用消毒剂、杀虫烟雾剂和喷漆等类似的配制剂。
                    实例10
发用喷雾剂性能
下面的实例通过与广泛使用的氢氟碳推进剂HFC-152a(CH3CHF2)相比较,显示了本发明在发用喷雾剂方面的功效,如下表所列。这些配制剂都是单一相的,表明它们是完全可混溶的。用粘性和干燥时间、卷曲下垂和火焰长度试验(flame extention test)来评价其性能。卷曲下垂测量卷曲物在喷雾5分钟之后的伸长百分比。测量火焰长度是测定每一配制剂的可燃性。结果显示每一配制剂都达到80%或更高的卷曲保留量,良好的粘性和干燥时间;尽管配制剂未经优化,其火焰长度结果仍是可接受的。
                             
                            配制剂
组分(Wt%)     A      B     C     D     E     F      G      H
树脂*          25     25    25    25    25    19.5   19.5   19.5
乙醇           43     43    43    43    43    35.0   35.0   35.0
添加剂         2      2     2     2     2     1.7    1.7    1.7
HFC-161        -      30    -     18    -     -      -      10.0
HFC-281ea      -      -     30    -     12    -      10.0    -
HFC-152a       30     -     -     -     18    10.0   -       -
丁烷           -      -     -     12    -     -      -       -
水             -      -     -     -     -     13.8   13.8    13.8
DME            -     -    -    -    -    20.0  20.0   20.0
总重量%       100    100   100   100   100   100    100     100
蒸气压         60     95    31    79    52    47     40      64
@70°F(psig)
%VOC          43     43    73    55    55    55     65      55
卷曲下垂%     9      21    11    17    16    18     11      17
发粘时间(sec)  10     14    4     7     11    8      14      58
干燥时间(sec)  24     28    17    46    54    21     39      73
火焰长度       4      6     9     4     13    4      12      16
(英寸)
*丙烯酸叔丁酯/丙烯酸乙酯/甲基丙烯酸共聚物树脂
                    实例11
空气清新剂性能
为了试验空气清新剂的可燃性和可混溶性,按照下表中所列出的配方将本发明的组合物配制成空气清新剂。这些配制剂都是单一相的,表明它们是完全可混溶的。测出火焰长度值小于18英寸最大允许值。这些配制剂有良好的喷雾方式和喷出性能。
                表
              配制剂
组分   AWt%   BWt%
香料   1   1
  4   4
乙醇   30   30
HFC-161   65   -
HFC-281ea   -   65
总重量%   100   100
蒸气压@70F(psig)   106   33
火焰长度(英寸)   13   16
                    实例12
芳香性能
为了试验芳香剂的可燃性和可混溶性,按照下表中所列出的配制剂将本发明的组合物配制成芳香剂。这些配制剂都是单一相的,表明它们是完全可混溶的。测出火焰长度值小于18英寸最大允许值。这些配制剂有良好的喷雾方式和效率。
                    表
                  配制剂
    组分     AWt%     BWt%
    香料     3     3
    乙醇     70     70
    水     15     15
    HFC-161     12     -
    HFC-281ea     -     12
    100     100
    蒸气压@70F(psig)     46     14
    火焰长度(英寸)     13     10
                    实例13
贮存稳定性
配制下表所列的组合物并装到镀锡钢皮制的气溶胶罐中。这些罐被放置到120°F的炉中或在室温(21-23℃)下保存好几个月。
                           表
组合物             温度         时间           罐内部
HFC-161/乙醇       120°F       2个月          无锈蚀
(30/70%(重量))                                轻度脱锡
                                6个月          无锈蚀
                                               中度脱锡
FC-161/乙醇        室温         24个月         无锈蚀
(30/70%(重量))                                轻度脱锡
HFC-281ea/乙醇     120°F       1个月          无锈蚀或脱锡
(60-40%(重量))                 3个月          无锈蚀或脱锡
HFC-281/乙醇/      120°F       1个月          无锈蚀或脱锡
水(40/54/6%(重量))
如表中显示,在配制剂溶剂中,甚至没有防锈剂的情况下,该喷雾剂组合物表现出良好的稳定性。
                    实例14
下表列出各种致冷剂的性能。这些数据是基于下列条件得到的。
蒸发器温度                      45.0°F(7.2℃)
冷凝器温度                      130.0°F(54.4℃)
过冷度                          15.0°F(8.3℃)
返回气体                        65.0°F(18.3℃)
压缩机效率是75%
致冷能力根据固定气缸工作容量为每分钟3.5立方尺、容积效率为75%的压缩机的致冷能力。致冷效率是指在蒸发器内循环的每磅致冷剂焓的变化,即每次被蒸发器中的致冷剂所带走的热量。运行系数(COP)是指致冷效率与压缩机所作的功之比,它是衡量致冷剂致冷功效的。
                                                                 致冷效率
制冷剂       蒸发器压力   冷凝器压力   压缩机工作容量            BTU/分钟
组合物      Psia(kPa)   Psia(kPa)   温度  °F(℃)    COP     (kW)
HFC-161/HFC-134a
1/99         55   379     215 1482     171   77          3.43   225   4.0
99/1         80   552     279 1924     201   94          3.49   316   5.6
HFC-161/HFC-152a
1/99             51    352    194    1338    204    96    3.60    224    3.9
99/1             90    552    278    1917    200    93    3.53    318    5.6
HFC-161/HFC-281ea
1/99             27    186    106    731     168    76    3.71    123    2.2
99/1             79    545    278    1917    201    94    3.49    314    5.5
HFC-161/HFC-3-10-lsy
1/99             13    90     55     379     148    64    3.75    63     11
99/1             79    545    277    1910    201    94    3.50    314    5.5
HFC-161/丁烷
1/99             20    138    82     565     155    68    3.68    93     1.6
99/1             79    545    277    1910    201    94    3.49    314    5.5
HFC-161/异丁烷
1/99             30    207    65     448     112    44    3.57    123    2.2
99/1             79    545    279    1924    201    94    3.49    315    5.5
HFC-161/DME
1/99             49    338    183    1262    194    90    3.67    215    3.8
99/1             79    545    279    1924    201    94    3.49    315    5.5
HFC-218ea/HFC-134a
1/99             54    372    212    1462    171    77    3.43    222    3.9
99/1             27    186    105    724     168    76    3.70    121    2.1
HFC-281ea/HFC-152a
1/99             50    345    192    1324    204    95    3.61    222    3.9
99/1             27    186    105    724     168    76    3.70    122    2.1
HFC-281ea/HFC-3-10-lsy
1/99             12    83     54     372     148    64    3.68    59     1.0
99/1             26    179    104    717     168    76    3.70    120    2.1
HFC-281ea/丙烷
1/99             83    572    270    1862    166    74    3.32    282    5.0
99/1             27    186    107    738     168    76    3.71    123    2.2
HFC-281ea/DME
1/99             48    331    181    1248    193    89    3.68    213    3.8
99/1             27    186    106    731    168     76    3.70    122    2.1
HFC-3-10-sy/HFC-134a
1/99              42    290    167   1151    182    83    3.60    187    3.3
99/1              12    83     54    372     148    64    3.69    60     1.1
HFC-3-10-lsy/HFC-134a
1/99              54    372    210   1448    171    77    3.44    221    3.9
99/1              12    83     54    372     148    64    3.69    60     1.1
HFC-3-10-lsy/HFC-152a
1/99              50    345    191   1317    203    95    3.60    221    3.9
99/1              13    90     54    372     148    64    3.70    60     1.1
HFC3-10-lsy/HFC-236ea
1/99              15    103    70    483     143    62    3.50    71     1.3
99/1              12    83     53    365     148    64    3.67    59     1.0
HFC-3-10-lsy/HFC-236fa
1/99              20    138    86    593     141    60    3.42    86     1.5
99/1              12    83     53    365     148    64    3.67    59     1.0
HFC-3-10-lsy/丁烷
1/99              19    131    80    552     155    68    3.65    90     1.6
99/1              12    83     53    365     148    64    3.67    59     1.0
HFC-3-10-lsy/异丁烷
1/99              29    200    110   758     152    67    3.56    120    2.1
99/1              12    83     54    372     148    64    3.68    59     1.0
HFC-3-10-sy/丙烷
1/99              83    572    269   1855    166    74    3.33    281    4.9
99/1              13    90     55    379     147    64    3.74    62     1.1
HFC-3-10-lsy/DME
1/99              48    331    181   1248    193    89    3.67    213    3.7
99/1              13    90     55    379     148    64    3.73    62     1.1
附加化合物
可以向上述这些共沸物或类共沸物中添加其他组分,而基本上不改变组合物的性质,包括不改变它所表现出的恒沸点的行为。这些被添加的其他组分有,例如沸点为-60至+60℃的脂肪烃类,沸点为-60至+60℃的氢氟碳烷烃类,沸点为-60至+60℃之间的氢氟丙烷类,沸点为-60至+60℃之间的烃酯类,沸点为-60至+60℃之间的氢氯氟碳类,沸点为-60至+60℃的氢氟碳类,沸点在-60至+60℃之间的氢氯碳类,含氯烃以及全氟化合物。
添加剂如润滑剂、防锈剂、表面活性剂、稳定剂、染料和其他适宜的物质可以加入到本发明的新型组合物中以达到各种目的,只要它们对组合物在它的预定用途中不会产生不利的影响。优选的润滑剂包括分子量大于250的酯类。

Claims (4)

1.一种共沸的或类共沸组合物,该组合物基本上由下列物质所组成:73-99重量%的氟乙烷和1-27重量%的2-氟丙烷;75-99重量%的氟乙烷和1-25重量%的叔丁基氟化物;67-99重量%的氟乙烷和1-33重量%的丁烷;52-99重量%的氟乙烷和1-48重量%的异丁烷;1-99重量%的氟乙烷和1-99重量%的二甲基醚;1-99重量%的2-氟丙烷和1-99%重量的1,1,1,2-四氟乙烷;1-99重量%的2-氟丙烷和1-99重量%的1,1-二氟乙烷;41-99重量%的2-氟丙烷和1-59%的叔丁基氟化物;1-41重量%的2-氟丙烷和59-99重量%的丙烷;1-99重量%的2-氟丙烷和1-99重量%的二甲基醚;1-44重量%的叔丁基氟化物和56-99重量%的1,1,2,2-四氟乙烷;1-32重量%的叔丁基氟化物和68-99重量%的1,1,1,2-四氟乙烷;1-30重量%的叔丁基氟化物和70-99重量%的1,1-二氟乙烷;11-60重量%的叔丁基氟化物和40-89重量%的1,1,1,2,3,3-六氟丙烷;1-3重量%的叔丁基氟化物和97-99重量%的1,1,1,2,3,3-六氟丙烷;1-52重量%的叔丁基氟化物和48-99重量%的1,1,1,3,3,3-六氟丙烷;1-99重量%的叔丁基氟化物和1-99重量%的丁烷;1-45重量%的叔丁基氟化物和55-99重量%的异丁烷;89-99重量%的叔丁基氟化物和1-11重量%的异丁烷;1-19重量%的叔丁基氟化物和81-99重量%的丙烷;或1-42重量%的叔丁基氟化物和58-99重量%的二甲醚。
2.一种制造气溶胶的方法,包括使用权利要求1的组合物。
3.一种致冷的方法,包括冷凝权利要求1的组合物,然后使所述组合物在需要冷却的物体周围蒸发。
4.一种制造热固性或热塑性泡沫的方法,包括使用权利要求1的组合物作为发泡剂。
CNB971995761A 1996-11-04 1997-11-03 氢氟碳化合物组合物 Expired - Fee Related CN1181155C (zh)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US2997196P 1996-11-04 1996-11-04
US60/029,971 1996-11-04
US60/029971 1996-11-04
US08/943420 1997-10-03
US08/943,420 US6261472B1 (en) 1996-11-04 1997-10-03 Azeotrope-like compositions containing fluoroethane
US08/943,420 1997-10-03

Publications (2)

Publication Number Publication Date
CN1237197A CN1237197A (zh) 1999-12-01
CN1181155C true CN1181155C (zh) 2004-12-22

Family

ID=26705527

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB971995761A Expired - Fee Related CN1181155C (zh) 1996-11-04 1997-11-03 氢氟碳化合物组合物

Country Status (10)

Country Link
US (5) US6261472B1 (zh)
EP (1) EP0938527B1 (zh)
JP (1) JP4130477B2 (zh)
CN (1) CN1181155C (zh)
AU (1) AU5160898A (zh)
BR (1) BR9712859A (zh)
CA (2) CA2271666C (zh)
DE (1) DE69714067T2 (zh)
MY (1) MY139234A (zh)
WO (1) WO1998020089A2 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102994051A (zh) * 2006-05-20 2013-03-27 地球关爱产品有限公司 制冷剂

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6261472B1 (en) * 1996-11-04 2001-07-17 E. I. Du Pont De Nemours And Company Azeotrope-like compositions containing fluoroethane
KR100398093B1 (ko) * 2000-12-20 2003-09-19 주식회사 제이오 냉장고/에어컨용 혼합냉매
EP1372608B1 (de) * 2001-03-30 2007-10-10 Jagotec Ag Medizinische aerosolformulierungen
AU2002349758A1 (en) * 2002-12-03 2004-06-23 Nihon Freezer Co., Ltd. Refrigerator system using non-azeotropic refrigerant, and non-azeotropic refrigerant for very low temperature used for the system
CN100400615C (zh) * 2003-01-20 2008-07-09 天津大学 一种含有HFC-152a的中高温热泵混合工质
WO2006038766A1 (en) * 2004-08-25 2006-04-13 Yoon-Sik Ham R502, r12 or r22 substitute mixed refrigerant and refrigeration system using thereof
US7379446B2 (en) * 2004-10-14 2008-05-27 Qualcomm Incorporated Enhanced beacon signaling method and apparatus
US8192723B2 (en) * 2006-03-31 2012-06-05 Reckitt Benckiser (Uk) Limited Aerosol composition
CN100457850C (zh) * 2006-06-26 2009-02-04 浙江蓝天环保高科技股份有限公司 一种替代cfc-12的环保型制冷剂
JP2011513538A (ja) 2008-02-29 2011-04-28 アーケマ・インコーポレイテッド ブロックコポリマー油リターン剤
US8436218B2 (en) * 2010-05-27 2013-05-07 Honeywell International Inc. Azeotrope-like composition of hexafluoropropane, hexafluoropropene and hydrogen fluoride
JP5941056B2 (ja) 2011-10-26 2016-06-29 Jxエネルギー株式会社 冷凍機用作動流体組成物及び冷凍機油
KR101909545B1 (ko) 2012-03-27 2018-10-19 제이엑스티지 에네루기 가부시키가이샤 냉동기용 작동 유체 조성물
JP5871688B2 (ja) * 2012-03-29 2016-03-01 Jx日鉱日石エネルギー株式会社 冷凍機用作動流体組成物
CN104540888A (zh) * 2012-08-15 2015-04-22 纳幕尔杜邦公司 2,3,3,4,4,4-六氟-1-丁烯和1,1,1,2,3,3-六氟丙烷的共沸和类共沸组合物及其用途
CN103965836B (zh) * 2014-04-02 2017-04-19 浙江大学 一种用于汽车空调的环保型制冷剂及其制备方法
DE102014112294A1 (de) * 2014-08-27 2016-03-03 Technische Universität Dresden Arbeitsstoffgemisch für Vorrichtungen zum Wärmetransport
CN104974718B (zh) * 2015-06-30 2018-10-23 太原理工大学 一种制冷剂及其应用
KR101866686B1 (ko) * 2017-03-02 2018-06-11 박정배 마이크로 캡슐 기반의 자동 소화 기능을 구비한 배전반 시스템, 그리고 이를 위한 자동 소화 기능을 구비한 마이크로 캡슐 모듈

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2411442A1 (de) * 1974-03-11 1975-10-02 Basf Ag Verfahren zur herstellung von aliphatischen isocyanaten
US4226976A (en) * 1976-09-20 1980-10-07 Tenneco Chemicals, Inc. Process for the removal of vinyl chloride from polyvinyl chloride latexes and slurries with hydrocarbon compounds
JPS5362789A (en) 1976-11-17 1978-06-05 Daikin Ind Ltd Aerosol propellant
JPH0730311B2 (ja) * 1987-09-21 1995-04-05 ダイキン工業株式会社 冷 媒
JPH075880B2 (ja) * 1987-09-21 1995-01-25 ダイキン工業株式会社 冷 媒
US4937398A (en) * 1988-12-27 1990-06-26 Allied-Signal Inc. Process for the preparation of fluorinated alkanes from alkenes
US5370811A (en) * 1989-11-30 1994-12-06 Matsushita Electric Industrial Co., Ltd. Working fluid containing tetrafluoroethane
US5304319A (en) * 1989-11-30 1994-04-19 Matsushita Electric Industrial Co., Ltd. Working fluid
EP0568115B1 (en) 1990-07-26 1996-03-20 E.I. Du Pont De Nemours & Company Incorporated Near-azeotropic blends for use as refrigerants
CN1029625C (zh) 1990-12-17 1995-08-30 纳幕尔杜邦公司 氟化烃的恒沸组合物
DE4113397A1 (de) * 1991-04-24 1992-10-29 Rathor Ag Verfahren zur wiederaufbereitung und rueckgewinnung von polyurethanpraepolymer aus rueckstaenden
US5814674A (en) * 1992-04-23 1998-09-29 Rathor Ag Method for processing residue-containing packages
US5248433A (en) 1992-04-30 1993-09-28 E. I. Du Pont De Nemours And Company Binary azeotropic mixtures of octafluoropropane and fluoroethane
US5605882A (en) * 1992-05-28 1997-02-25 E. I. Du Pont De Nemours And Company Azeotrope(like) compositions of pentafluorodimethyl ether and difluoromethane
US5733472A (en) * 1992-07-15 1998-03-31 E. I. Du Pont De Nemours And Company Compositions which include 1,1,2,2-tetrafluoroethane and fluoropropane
US5441659A (en) 1993-11-12 1995-08-15 E. I. Du Pont De Nemours And Company Compositions including a fluoroamine and a second component
US5417871A (en) 1994-03-11 1995-05-23 E. I. Du Pont De Nemours And Company Hydrofluorocarbon compositions
GB9504955D0 (en) 1995-03-11 1995-04-26 Star Refrigeration High efficiency refrigerant
FR2733241B1 (fr) * 1995-04-20 1997-05-30 Atochem Elf Sa Melanges pseudo-azeotropiques a base de difluoromethane et de pentafluorodimethylether , et leurs applications comme fluides frigorigenes
WO1997015637A1 (fr) * 1995-10-20 1997-05-01 Tsinghua University Refrigerant
US6261472B1 (en) * 1996-11-04 2001-07-17 E. I. Du Pont De Nemours And Company Azeotrope-like compositions containing fluoroethane

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102994051A (zh) * 2006-05-20 2013-03-27 地球关爱产品有限公司 制冷剂

Also Published As

Publication number Publication date
EP0938527B1 (en) 2002-07-17
EP0938527A2 (en) 1999-09-01
US20030199408A1 (en) 2003-10-23
US7384572B2 (en) 2008-06-10
US20050178998A1 (en) 2005-08-18
US6261472B1 (en) 2001-07-17
WO1998020089A2 (en) 1998-05-14
JP2002500684A (ja) 2002-01-08
US7195718B2 (en) 2007-03-27
CA2509506A1 (en) 1998-05-14
WO1998020089A3 (en) 1998-09-17
AU5160898A (en) 1998-05-29
US20010054705A1 (en) 2001-12-27
CN1237197A (zh) 1999-12-01
DE69714067T2 (de) 2003-02-27
CA2271666C (en) 2007-02-13
CA2271666A1 (en) 1998-05-14
US20070034824A1 (en) 2007-02-15
MY139234A (en) 2009-09-30
DE69714067D1 (de) 2002-08-22
US6932918B2 (en) 2005-08-23
CA2509506C (en) 2009-09-15
US6641752B2 (en) 2003-11-04
JP4130477B2 (ja) 2008-08-06
BR9712859A (pt) 1999-12-07

Similar Documents

Publication Publication Date Title
CN1181155C (zh) 氢氟碳化合物组合物
CN1082088A (zh) 氟代醚和氟代烃组合物
CN1083474C (zh) 在热力循环中使用的改进的非共沸工作介质
CN1344305A (zh) 1,1,1,3,3-五氟丁烷的类共沸物组合物
CN1076951A (zh) 三元共沸组合物
CN1071854A (zh) 二氟甲烷和四氟乙烷组合物
CN1291958C (zh) 萘衍生物和含有它的液晶组合物
CN1106838A (zh) 适用于异氰酸酯基聚合物泡沫塑料的含脂环烃的无卤发泡剂
CN1091782A (zh) 混合溶剂组合物及利用该溶剂的洗涤方法和洗涤装置
CN1161441C (zh) 静电气雾剂组合物
CN1298795C (zh) 通过在卡宾基金属催化剂存在下氢化硅烷化可交联成弹性体的硅氧烷组合物及此类催化剂
CN1136176C (zh) α-氟代醚的生产
CN1038342C (zh) 一种润滑油
CN86101036A (zh) 含类萜烯化合物衍生物的液晶材料及该材料的装置
CN1084720C (zh) 从hfc-125中去除cfc-115和氢氟酸的蒸馏方法
CN1042173A (zh) 超扭曲液晶显示器
CN1071187A (zh) 二氟甲烷与三氟乙烷或全氟乙烷的基本上恒沸点的组合物
CN1377397A (zh) R22替代物致冷剂
CN1046357A (zh) 1,1-二氯-2,2,2-三氟乙烷与1,1-二氯-1-氟乙烷的类共沸混合物
CN1069049A (zh) 五氟乙烷和丙烷或异丁烷的共沸组合物或类共沸组合物
CN1910256A (zh) 包含氟代醚的1,1,1,3,3-五氟丁烷制冷剂组合物及其应用
CN1183072C (zh) 提纯全氟环丁烷的方法
CN1071186A (zh) 在热力循环中使用的改进的非共沸工作介质
CN1162503C (zh) 在热力循环中使用的改进的非共沸工作介质
CN1723256A (zh) 适用于宽温度范围的传热流体

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20041222

Termination date: 20091203