CN1051334C - 含三氟乙烷的致冷工质组合物 - Google Patents
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Abstract
公开了致冷工质组合物,它含有1,1,1-三氟乙烷致冷剂和3,5,5-三甲基已酸的新戊二醇酯或65wt%3,5,5-三甲基已酸、22.2wt%正庚酸和12.8wt%甲基已酸的混合物的三羟甲基丙烷酯。这样的酯显示出合适的粘度范围且在宽的组成范围内与致冷剂混溶。
Description
本发明涉及致冷工质组合物。更确切地说,本发明涉及含有唯一致冷剂1,1,1-三氟乙烷(CH3CF3)和具有适当粘度且能与该致冷剂在低温下混溶的某些多醇酯润滑剂构成的混合物的致冷工质组合物。
业已知道包括致冷机、冷冻机、加热泵、空调系统等等的机械汽相压缩型冷却系统。在这类装置中,沸点适当的致冷剂在低压下蒸发,从周围区域吸收热量。然后,所得蒸汽被压缩并通到冷凝器中,在此它冷凝并给第二区放出热量。之后,冷凝液通过膨胀阀送到蒸发器中,于是完成了循环。
已公认,目前使用的含氯致冷剂(如二氯二氟甲烷将被无氯致冷液所替代,因为氯化物质对大气臭氧层有破坏作用。现在认为,四氟乙烷异构体,特别是“Refrigerant134a”--1,1,1,2-四氟乙烷是用于致冷系统较为理想的液体。另一种这样的致冷剂是1,1,1-三氟乙烷。
要求致冷工质具有与致冷剂相容和混溶的润滑剂,以便适当润滑系统的移动部件。迄今这种润滑剂由烃矿物油构成,这类矿物油能与含氯致冷液混溶并提供有效的润滑作用。
使用这类无氯致冷剂产生了对新的润滑剂的需求,因为矿物油与这些物质不相容。这种需求被本技术领域公认,而且近来有许多公开文献和专利介绍了不同类型的合成润滑剂,据说这些类润滑剂能与这类致冷液相容。特别强调多醇的酯适用于无氯致冷剂、特别是Refrigerant 134a。
Zehlrer等人的美国专利5,021,179(1991年6月4日发布)公开多醇的酯,其中酰基具有至少22%的(a)支链酰基或(b)酰基(含不高于6个碳原子)。该专利还指出,该酯的含8个或8个以上碳原子且未支化的酰基百分数与含不高于6个碳原子且支化的酰基百分数之比为一定,该比值不高于1.56。而且,该专利要求支化或未支化的至少具有9个碳原子的酰基百分数不高于81。
PCT申请WO90/12849(申请人:Jolley等人,公开日:1990年11月1日)概括地公开了液体组合物,这类组合物含有主要量的至少含一个氟的C1或C2烃和微量的至少一种可溶的有机润滑剂,后者含有至少一种含至少两个羟基且通式为R〔OC(O)R′〕n的多羟基化合物的羧酸酯,其中R是烃基,各R′独立地为氢、直链低级烃基、支链烃基或含8-约22个碳原子的直链烃基,条件是:至少一个R1基为氢、低级直链烃基或支链烃基、或含羧酸或含羧酸酯的烃基,且n至少为2。
Imperial Chemical Industries的U.K.专利2,216,541(1991年10月23日授权,公开日1989年10月11日)公开了任何分子量250或更高的酯都适用作Refrigerant 134a或某些相关致冷液的相容润滑剂。该专利举例了己二酸酯、1,2,4,5-苯四酸酯和苯甲酸酯。
Kao公司的欧洲专利申请440069(公开日:1991年8月7日)公开了由氟乙烷和酯构成的致冷工质,其中所述酯是通过使脂族多醇和直链或支链醇与C1-20脂族多羧酸反应制得的。
Kao公司的欧洲专利申请415778(公开日:1991年3月6日)公开了含氢化氟乙烷和酯化合物的致冷工质组合物,其中所述酯化合物是由脂族多元醇、饱和的脂族二酸和饱和脂族二羧酸制得。
Kyodo Oil Technidcal Rearch Center Co.Ltd的欧洲专利申请406479(公开日:1991年1月9日)公开了据说能与R134a相容的润滑剂。合适的润滑剂是:新戊二醇和直链或支链C3-18一元脂肪酸的酯;季戊四醇、二季戊四醇和三季戊四醇与直链或支链C2-18一元脂肪酸的酯;式RC(CH2OH)3的三羧基多元醇(其中R是C1-3烷基)与C2-18直链或支链一元脂肪酸和不高于全部脂肪酸25%的至少一种C4-36多元酸的酯。
Nippon Oil Co.Ltd.的欧洲专利申请435253(公开日:1991年7月3日)公开了许多据说能与R134a相容的酯,这类酯被定义为具有特定的结构,是一-、二-和三-季戊四醇和其它多醇(如三羟甲基乙烷,三羟甲基丙烷,三羟甲基丁烷或其二聚体或三聚体)与C2-15一羧酸和C2-10三羧酸构成的酯。这类酯一般被说成具有约200-3000分子量。
Ashai Denka Kogyo Kabushiki的欧洲专利申请430657(公开日:1991年6月5日)公开了与R134a相容的润滑剂,其特征在于是C2-6脂肪酸的新戊多醇酯。该文献指出,如果C2-6酸的用量不是20mol%或更高,从而对每个新戊二醇的羟基来说脂肪酸平均碳原子数为6或以下,那么用具有7个或7个以上碳原子的酸会产生不相容问题。合适的新戊多醇有一-、二-和三-季戊四醇;三羟甲基丙烷和三羟甲基乙烷。这类多醇必须具有至少3个羟基。
涉及R134a润滑剂相容性问题的其它文献是McGraw等人的美国专利4,851,144(1989年7月25日授权),其中公开了作为润滑剂的多醚多醇和酯的混合物,以及Magid等人的美国专利4,755,316(1988年7月5日授权),其中公开了用于三氟乙烷致冷剂的多醚二醇润滑剂。
Kao公司的欧洲专利申请475751(公开日:1992年3月18日)公开了致冷工质,它含有烃和由新戊多醇和饱和的C7-9脂族一元羧酸制得的酯以及含有环氧环己基或环氧环戊基的类似酯。
Hagihara等人的美国专利5,096,606(1992年3月17日授权)公开了致冷油组合物,它含有氢化氟乙烷,和具有1-6个羟基的脂族多醇与直链或支链C2-9一元羧酸和直链或支链C2-10二羧酸的混合物制成的酯,该酯是通过这三种组分一起反应制取的。
Kyodo Oil Technical.Rearch Center Co.,Ltd.的欧洲专利申请480479(公开日:1992年4月15日)公开了以酯为基础的致冷润滑剂,所述酯是通过使一-、二-或三季戊四醇与直链或支链一价C2-G18饱和脂族酸反应形成的。
CPI Engineering Services,Inc.的欧洲专利申请498152(公开日:1992年8月12日)公开了无氯制冷剂用润滑剂组合物,它是通过包括新戊多醇、三羟甲基丙烷、三羟甲基乙烷、一-和二季戊四醇在内的多醇和C4-18支链羧酸制取的。支链酸优选那些支化不是在最远离碳位上的物质。
Kyodo Oil Technical Research Center Co.Ltd.的欧洲专利申请479338(公开日:1992年4月8日)公开了无氯氟烃致冷剂用润滑剂,它是由三羟甲基乙烷、三羟甲基丙烷或三羟甲基丁烷和至少一种直链或支链C2-18一价饱和脂肪酸制成的酯。
Tonen公司的欧洲专利申请449406(公开日:1991年10月2日)叙述了与1,1,1,2-四氟乙烷(R134a)一起使用的润滑剂酯,它一般被看作是于100℃粘度为2-30mm2/s的酯,该酯优选是脂族一元醇和脂肪或芳族二羧酸的二酯,还公开了各种其它类型的酯,包括多醇与C5-12直链或支链羧酸的酯。
以上归纳的现有技术提出了适合无氯致冷剂一起使用的润滑剂冲突情况。本发明人发现,就链烷酸的多醇酯而言,其用作1,1,1-三氟乙烷相容润滑剂的适用性被限制在非常窄的范围内。
本发明基于以下发现,即制备以1,1,1-三氟乙烷为基础的合适的致冷工质组合物,它含有约5-55、优选10-35重量份的合成酯和95-45、优选90-65重量份的1,1,1-三氯乙烷,该合成酯是(d)用3,5,5-三甲基己酸酯化的新戊二醇(NPG)或(b)用含约65wt%3,5,5-三甲基己酸、22.2wt%正庚酸和12.8wt%甲基己酸的酸混合物酯化的三羟甲基丙烷(TMP)。这里所用的术语“甲基己酸”指的是70wt%2-甲基己酸、20wt%2-乙基戊酸、5wt%正庚酸和余量的其它庚酸异构体的异构体混合物。这些工质组合物在其组成范围内,即5-55重量份酯和95-45重量份三氟乙烷,具有-20℃或以下(即温度低于-20℃)的所需混溶值。这些酯用于润滑致冷设备具有合适的润滑粘度。NPG酯的粘度于40℃为13.02cst,于100℃为3.12;TMP酯的粘度于40℃为28.18cst,于100℃为5.10cst。
本发明人评价了实施例中所列的多种其它酯,经实测,这些酯完全不能与1,1,1-三氟乙烷相容,即使这些酯在化学上与上述两种酯类似亦如此。
这里所用的术语“混溶值”指的是在5-55、优选10-55重量份的合成酯润滑剂和95-45、优选90-65重量份1,1,1-三氟乙烷(R143a)的组成范围内发生不混溶的最高温度。
混溶性和不混溶性是以下述方式测定的。特计量的酯润滑剂倒入12mm I.D.的带阀玻璃管。将该管连到致冷剂加料装置,其中空气被抽空,并将一定体积的致冷剂冷凝到玻璃管中直至得到所需的致冷剂气压降。从管子、管子加润滑剂和管子加润滑剂加致冷剂的重量测定计算润滑剂/致冷剂混合物的组成。含润滑剂/致冷剂的管子在高温可见性浴中(恒温控制到高达+60℃或更高)和在低温可见性浴中(恒温控制到低到-80℃)室温目侧混溶性。如果观测不到以下任何一种情况则认为混合物对于给定温度为可混溶;所述情况为混浊,形成絮凝物或沉淀,分成两层液相。如果观测到任何这样一种情况则混合物视为不混溶。
采用本领域公知的方法,在能形成充分酯化的产物的温度下,使醇与酸(最好酸摩尔过量)进行反应制备用于本发明的酯。需要的话,可使用诸如有机锡或有机钛催化剂之类的催化剂。制备用于本发明的酯的具体方法对实施本发明并不关键,只要达到实质上完全酯化便可。
本技术领域都知道,本发明合适的酯润滑剂和工质组合物可含有非常微量的多种特殊目的添加剂(累积高达约8%重量),例如金属减活剂、抗氧剂、缓蚀剂、消泡剂、抗磨剂、耐特压添加剂、粘度改进剂,等等。
以下用实施例进一步说明本发明,这些实施例并不意味着限制本发明的范围。
实施例1
本实施例报道了表1中本发明两种酯的实施方案的混溶性数据。“NPG”指的是新戊二醇,“TMP指的是三羧甲基丙烷”,“TFE”指的是1,1,1-三氟乙烷。
表1
酸 多醇 wt% wt% 混溶性值
润滑剂 TFEA. 12.8wt%甲基己酸 TMP 10 90 -50℃
22.2wt%正庚酸 25 75 -20
65wt%3,5,5-三甲 35 65 -20
己酸B. 3,5,5-三甲基己酸 NPG 10 90 -80℃
25 75 -80℃
35 65 -80℃
实施例2(比较)
表2报道了实测与1,1,1-三氯乙烷完全不相溶和不混溶的多醇和酸的多种酯。在该表中,TPE指的是工业级季戊四醇(85-92at%一季戊四醇,7-14wt%二季戊四醇和2wt%以下的三季戊四醇),“none”意指该酯,TFE在-80℃-+60℃检测的比例不能混溶。
表2
酸 | 多醇 | 润滑剂wt.% | wt%TFE | 混溶值 |
A.n-C7,n-C8,n-C10混合物B.3,5,5-三甲基己酸C.2-乙基己酸D.异壬酸E.异癸酸F.2-甲基己酸G.2-乙基己酸H.15%异辛酸,85%3,5,5-三甲基己酸I.异壬酸J.异辛酸K.25%异癸酸,75%3,5,5-三甲基已酸L.异癸酸 | TMPTMPTMPTMPTMPTPETPETPETPETPETPETPE | 102555102535102535102535102535102535102535102535102535102535102535102535 | 907565907565907565907565907565907565907565907565907565907565907565907565 | nonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenonenone |
Claims (4)
1.一种致冷工质,它包括5-55重量份的合成酯润滑剂和95-45重量的1,1,1-三氟乙烷致冷剂,其中所述的酯由用3,5,5-三甲基己酸酯化的新戊二醇组成,且所述致冷工质的混溶值为-20℃或以下。
2.按照权利要求1的致冷工质,其中所述酯的含量为10-35重量份且所述致冷剂的含量为65-90重量份。
3.一种致冷工质,它包括5-55重量份的合成酯润滑剂和95-45重量份的1,1,1-三氟乙烷致冷剂,其中所述酯由用12.8wt.%甲基己酸、22.2wt.%正庚酸和65wt.%3,5,5-三甲基己酸的混合物酯化的三羟甲基丙烷组成,且所述致冷工质的混溶值为-20℃或以下。
4.按照权利要求3的致冷工质,其中所述酯的含量为10-35重量份,且所述致冷剂的含量为65-90重量份。
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ZA928934B (en) * | 1991-12-06 | 1994-05-19 | Exxon Chemical Patents Inc | Refrigeration working fluid compositions |
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FR2734576B1 (fr) * | 1995-05-24 | 1997-07-18 | Elf Antar France | Composition lubrifiante pour compresseurs frigorifiques |
DE69625088T2 (de) * | 1995-09-25 | 2003-07-24 | Kao Corp | Verwendung von esterverbindungen in schmierölzusammensetzungen |
GB9521920D0 (en) * | 1995-10-26 | 1996-01-03 | Ici Plc | Working fluid compositions |
TW349119B (en) * | 1996-04-09 | 1999-01-01 | Mitsubishi Gas Chemical Co | Polyol ester based-lubricant |
US6278006B1 (en) * | 1999-01-19 | 2001-08-21 | Cargill, Incorporated | Transesterified oils |
US6374629B1 (en) * | 1999-01-25 | 2002-04-23 | The Lubrizol Corporation | Lubricant refrigerant composition for hydrofluorocarbon (HFC) refrigerants |
US6526764B1 (en) * | 2000-09-27 | 2003-03-04 | Honeywell International Inc. | Hydrofluorocarbon refrigerant compositions soluble in lubricating oil |
KR100426229B1 (ko) * | 2001-01-05 | 2004-04-08 | 주식회사 엘지화학 | 폴리염화비닐 수지용 트리메틸올프로판 에스테르 가소제조성물 |
US6742345B2 (en) * | 2002-03-27 | 2004-06-01 | The Penray Companies, Inc. | Temperature control system using aqueous 1,3-propanediol solution |
US6774093B2 (en) * | 2002-07-12 | 2004-08-10 | Hatco Corporation | High viscosity synthetic ester lubricant base stock |
JP2009074018A (ja) * | 2007-02-27 | 2009-04-09 | Nippon Oil Corp | 冷凍機油および冷凍機用作動流体組成物 |
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JP5193485B2 (ja) * | 2007-03-27 | 2013-05-08 | Jx日鉱日石エネルギー株式会社 | 冷凍機油及び冷凍機用作動流体組成物 |
EP2158896A3 (de) | 2009-11-02 | 2010-09-29 | Symrise GmbH & Co. KG | Riechstoffhaltige Zusammensetzungen umfassend Neopentylglycoldiisononanoat |
CN107735484B (zh) * | 2015-06-12 | 2021-05-07 | 诺瓦蒙特股份公司 | 低倾点的三羟甲基丙烷酯 |
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US4755316A (en) * | 1987-10-23 | 1988-07-05 | Allied-Signal Inc. | Refrigeration lubricants |
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BR9006748A (pt) * | 1989-04-25 | 1991-08-06 | Lubrizol Corp | Composicao liquida de refrigeracao |
KR950005694B1 (ko) * | 1989-07-05 | 1995-05-29 | 가부시끼가이샤 교오세끼 세이힝기주쓰 겡뀨쇼 | 냉각윤활제 |
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ZA938322B (en) | 1994-06-07 |
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