CN1059697C - 电冰箱用的工作流体 - Google Patents
电冰箱用的工作流体 Download PDFInfo
- Publication number
- CN1059697C CN1059697C CN98118659A CN98118659A CN1059697C CN 1059697 C CN1059697 C CN 1059697C CN 98118659 A CN98118659 A CN 98118659A CN 98118659 A CN98118659 A CN 98118659A CN 1059697 C CN1059697 C CN 1059697C
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- China
- Prior art keywords
- lubricating oil
- working fluid
- polyvalent alcohol
- oil
- refrigerator
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- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
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- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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- C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
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Abstract
由部分醚化的多元醇活性成分构成的润滑油添加剂,所述多元醇具有至少两个羟基和通过醚键键合带有至少一个具有至少一个双键的烃基。润滑油添加剂加到润滑基础油中形成润滑油,它赋予了优良的耐磨性、几乎无金属腐蚀、树脂或橡胶溶涨以及因热氧化形成的淤渣。润滑油与致冷剂混合得到了适用于家用电冰箱、汽车空调、工业用致冷机和空调的致冷压缩机的工作流体。
Description
本发明涉及一种提供优良耐磨性的润滑油,以及用于电冰箱的使用这种润滑油的工作流体。具体地讲,本发明涉及一种适用于电冰箱压缩机的使用氢氟烃致冷剂的润滑油,以及电冰箱用的包括润滑油和氢氟烃致冷剂的工作流体。
致冷压缩机用于家用电冰箱、汽车空调、工业用致冷器和室内空调,而已用于这类致冷压缩机的致冷剂包括氯氟烃(其中所有氢原子被氯和氟原子置换了的烃)和氢氯氟烃(其中一些氢原子被氯和氟原子置换了的烃)。但从环保角度看,已决定限制使用这些致冷剂,因此注意力集中到氢氟烃(非氯化的烃,即,不含有任何氯原子,且其中至少一些氢原子被氟原子置换;以下称作“HFC致冷剂”)作为上述致冷剂的代用品。已提出的HFC致冷剂包括R134a,R125,R32,R143a和R152a(它们各由单独氢氟烃构成)和R407C,R407C,R410A和R410B(一种氢氟烃的混合物)。
当使用HFC致冷剂时,很难使用常规矿物润滑基础油。所以,已提出使用聚亚氧烷基乙二醇、多元醇酯、多醚或聚碳酸酯作为润滑基础油。
使用HFC致冷剂导致润滑性较差。此外,使用铜和铝材以及铁材作为构成致冷剂压缩机润滑表面的材料,从而要求压缩机用的润滑油能满意地改善由这种黑色或有色材料制成的摩擦表面的耐磨性。用于满足这种要求的已知添加剂包括C8-14烷二醇(日本专利公开未决号199296/1991)、磷酯、亚磷酯和多元醇与脂肪酸的偏酯(WO91/09097)、具有两个羟基和具有带其它极性基团的C1-C18烷基、芳基、芳烷基或烷芳基的醇衍生物(日本专利公开未决号337391/1992),等等。这些添加剂的问题是摩擦面的耐磨性不能充分改进,在压缩机内出现金属腐蚀,它们很可能将橡胶和树脂硬化造成在压缩机密封件或接头中的泄漏,以及因热降解或氧化形成淤渣降低了热交换效率,尽管这些添加剂也有某些作用。所以,上述添加剂不能被认为是充分适用于实际应用。
本发明旨在于解决以上问题,其一个目的是提供可赋予耐磨性、不腐蚀金属物质、不硬化由例如橡胶或树脂制成的密封件且几乎不形成因热降解或氧化造成的淤渣的润滑油;和使用该润滑油的电冰箱用工作流体。
本发明人对解决上述问题进行了深入研究,发现通过往里加入一种特定的部分醚化的多元醇可以显著改进润滑油的润滑性(如耐磨性作用)。本发明正是基于这种发现完成的。
也就是说,本发明涉及一种润滑油,它包括有效量的具有至少两个羟基和通过醚键键合具有至少一个带有至少一个双键的脂族烃基的部分醚化的多元醇和润滑基础油;以及电冰箱用的工作流体,它包括致冷剂和上述润滑油。
本发明的润滑油添加剂由具有至少两个羟基并通过醚键键合具有至少一个双键的脂族烃基的部分醚化的多元醇构成。本发明的添加剂必须满足这样的要求,即:它必须具有至少两个羟基且形成醚键的烃基应具有至少一个双键。在此情况下,该添加剂在润滑基础油中的溶解性优良,并能赋予优良的润滑性以显著改进摩擦表面的耐磨性。此外,这种添加剂对与润滑油接触并构成密封件的树脂或橡胶的溶涨性很低。
带有至少具有一个双键的脂族烃基的部分醚化的多元醇的这些性质出人意料,换句话说,非常独特。
这是因为不带有至少具有一个双键而是具有相应数目的碳原子的烷基或芳基并通过醚键键合的脂族烃基的部分醚化的多元醇在润滑基础油中的润滑性很差,不能赋予优良的润滑性。此外,带有较短烷基的部分醚化的多元醇也不能提供优良的润滑性,尽管它在润滑基础油中的润解性优良。
从在润滑基础油中的溶解性和防止树脂或橡胶溶涨的角度看,优选具有至少一个双键并构成本发明润滑油添加剂的脂族烃基为C12-C24烃基、更优选C16-C20烃基。此外,在化学稳定性方面,优选脂族烃基具有一个碳-碳双键,尽管也可具有两个或多个双键。此外,其中双键存在于烃链内的上述部分醚最好容易获取。另外,具有至少一个双键的脂族烃基最好是直链的,因为其润滑性比其中基团是支链的烃基更优异。本发明部分醚化的多元醇可带有两个或多个至少具有一个双键并分别通过醚键键合的脂族烃基。至少具有一个双键的脂族烃基可含有氧原子或羟基。至少具有一个双键的脂族烃基的例子包括:
CH3(CH2)6CH=CH(CH2)2CH2-(4-十二烯基),
CH3(CH2)8CH=CH(CH2)2CH2-(4-十四烯基),
CH3(CH2)8CH=CH(CH2)3CH2-〔植烯基(5-十五烯基)〕,
CH3(CH2)5CH=CH(CH2)7CH2-〔棕榈油烯基(9-十六烯基)〕,
CH3(CH2)7CH=CH(CH2)7CH2-〔油烯基(9-十八烯基)〕,
CH3(CH2)5CH=CH(CH2)9CH2-〔十八碳烯基(11-十八碳烯基)〕,
CH3(CH2)9CH=CH(CH2)7CH2-〔9-二十碳烯基)〕,
CH3(CH2)7CH=CH(CH2)9CH2-〔11-二十碳烯基)〕,
CH3(CH2)9CH=CH(CH2)9CH2-〔11-二十二碳烯基)〕,
CH3(CH2)7CH=CH(CH2)11CH2-〔13-二十三碳烯基)〕,
CH3(CH2)7CH=CH(CH2)13CH2-〔15-二十四碳烯基)〕,
CH3(CH2)3(CH2CH=CH)2(CH2)7CH2-〔亚麻油基(9,12-十八碳二烯基)〕,
CH3(CH2CH=CH)3(CH2)7CH2-〔亚麻油基(9,12,15-十八碳三烯基)〕,
CH3(CH2)3(CH2CH=CH)3(CH2)4CH2-〔6,9,12-亚麻油基(6,9,12-十八碳三烯基)〕,
CH3(CH2)3(CH=CH)3(CH2)7CH2-〔桐烯基(9,11,13-十八碳三烯基)〕
CH3(CH2)6(CH2CH=CH)2(CH2)6CH2-(8,11-二十碳二烯基)和
CH3(CH2)6(CH2CH=CH)3(CH2)3CH2-(5,8,11-二十碳三烯基)。
按照本发明,构成部分醚化的多元醇的多元醇是C3-C10、优选C3-C6醇,其优选的例子包括甘油、季戊四醇、二季戊四醇、1,4-山梨糖和1,5-山梨糖。
本发明润滑油添加剂由部分醚化的多元醇构成,其中具有至少一个双键的脂肪烃基通过醚键键合到羟基上,这种添加剂的优选例子下面进行说明。
这种例子包括由式(1)表示的甘油衍生物,由式(2)表示的三羟甲基丙烷衍生物,由式(3)和(4)表示的1,4-山梨糖衍生物,以及由式(5)和(6)表示的1,5-山梨糖衍生物。本发明部分醚化的多元醇可具有三个或多个羟基(如式(3)表示)。1,4-山梨糖衍生物(a)1,4-山梨糖衍生物(b)1,5-山梨糖衍生物(a)1,5-山梨糖衍生物(b)
在式(1)-(6)中,R代表C12-C24链烯基。
在这些化合物中,优选甘油衍生物和1,4-山梨糖衍生物,尤以甘油衍生物为最佳。优选本发明多元醇衍生物满足以下一或二个要求,即:醚键键合到相邻于键合了羟基的碳原子的碳原子上;至少两个羟基分别键合到三个顺序碳原子之中的两个上。
这种部分醚化的多元醇的具体例子包括甘油一油基醚,1,4-山梨糖一油基醚,1,4一山梨糖一亚油烯基(linolenyl)醚和1,5-山梨糖一油基醚。这些醚可具有其它官能团。
上述部分醚化的多元醇可通过(i)使多元醇的相应的偏氯化物(如甘油α-氯醇或甘油β-氯醇)与R-OH或R-ONa反应的方法,(ii)使三元醇或高级醇与R-Cl反应的方法,(iii)使表氯醇与R-OH反应生成甘油一醚或类似物的方法而制备。
部分醚化的多元醇必须以足以防止要润滑的表面磨损的量使用。具体来说,以润滑油计,该量为0.01-10%(重量)、优选0.1-5%(重量)、更优选0.2-2%(重量)。一般来说,部分醚化的多元醇以在润滑基础油中溶解的量使用,并选择在润滑基础油中易溶解的醇。
用于本发明的润滑基础油包括在石油精炼中制得的矿物油、烷基苯、碳酸酯等等。但当润滑基础油用于致冷压缩机时,从在HFC中溶解性的角度看,优选润滑基础油主要由多醚或多元醇酯构成。多醚是在一个分子中有多个醚键的化合物,包括在其主链中有多个醚键的化合物(如聚亚氧烷基乙二醇),在其侧链中有多个醚键的化合物(如聚乙烯基醚),具有成环醚键的环醚(如冠醚)。在用于本发明的多醚中,碳原子/氧原子之比最好为2-8,更优选2-4。
为了有效地改进磨擦面的耐磨性,优选聚亚氧烷基乙二醇化合物选自下式(7)表示的聚氧丙二醇的一-和二-烷基醚以及下式(8)表示的聚氧亚丙基氧乙二醇的一-和二烷基醚(以下它们一般称作“PAG衍生物”):
R1-O-(PO)m-R2 (7)
R1-O-(PO)m(EO)n-R2 (8)
其中R1代表C1-4烷基,R2代表C1-4烷基或氢原子,R1和R2彼此可相同或不同;m和n各代表平均聚合度;且(PO)m(EO)n代表无规或嵌段共聚物基团。当RAG衍生物以与HFC致冷剂混合态使用时,该衍生物最好具有这样的平均聚合度,以显示出于100℃时5-20cSt粘度且m/n比优选为9∶1-7∶3。PAG衍生物的端羟基可以被酯化。可以使用两种或多种上述PAG衍生物的混合物。
另一方面,按照本发明,由具有2-6个羟基的多元醇和脂肪酸制成的多元醇酯也可有利地用作润滑基础油。具体来说,优选多元醇酯是由具有五个碳原子的新一型骨架的多元醇与一元饱和脂肪酸和/或二元饱和脂肪酸反应制得的中性多元醇酯。这样的多元醇包括新戊二醇、三羟甲基丙烷、季戊四醇和二季戊四醇。一元饱和脂肪酸可以是C5-9非一新型支链酸或其与C5-8直链一元饱和脂肪酸的混合物。优选以上支链一元饱和脂肪酸在α-或β-位碳原子上有甲基或乙基。注意到由C1-4脂肪酸制得的多元醇酯在润滑性、抗水解性和抗金属腐蚀方面是有问题的。
支链一元饱和脂肪酸的具体例子包括2-甲基戊酸、2-乙基戊酸、2-甲基己酸、2-乙基己酸、2-甲基庚酸、2-乙基庚酸和3,5,5-三甲基庚酸,而直链一元饱和脂肪酸的例子包括正戊酸、正己酸、正庚酸和正辛酸。二元脂肪酸,如琥珀酸、戊二酸、己二酸、庚二酸等等,可与上述一元饱和脂肪酸一起使用,以制备由具有较高粘度的复合酯制成的润滑基础油。在上述多元醇酯中,含新戊二醇酯和季戊四醇酯的混合物因其在HFC致冷剂中的高溶解性而特别优选,虽然热溶解性、抗水解性和抗金属腐蚀性优良的组合物可从上述多元醇酯中适当选择。优选酯的酸值为0.1mg KOH/g或以下,更优选0.02mg KOH/g或以下。
本发明的润滑油可进一步含有各种添加剂,其例子有其它防磨剂、抗氧化剂、稳定剂、消包剂和金属减活剂。具体地说,优选加至少一种磷酸酯,因为它可进一步改进铁-铁材料的耐磨性。作为这样的磷酸酯,可以提到的有磷酸芳基酯和磷酸烷基酯,包括优选C18-70磷酸酯、更优选C18-50磷酸酯。其中,优选加入磷酸芳基酯,特别是磷酸三芳基酯。作为磷酸三芳基更优选加入磷酸三苯酯和磷酯三(烷基苯基)酯。这些磷酸三芳基酯以总共0.1-5.0%(重量)、优选0.3-4.0(重量)的量加入。当总量低于0.1%(重量)时,不能满意地改进对摩擦面的抗磨作用,而当总量超过5.0%(重量),不仅不能另外改进耐磨性,而且因磷酸酯降解造成不希望的生成高含量淤渣。
磷酸三(烷基苯基)酯的具体例子包括磷酸三甲苯酯、磷酸三(3,5-二甲基苯基)酯、磷酸三(2,4-二甲基苯基)酯、磷酸三(一丁基苯基)酯和磷酸三(异丙基苯基)酯。在这些磷酸酯中,磷酸三甲苯酯适用于实用,在抗水解方面,磷酸三(对叔丁基苯基)酯为最佳。以上磷酸酯既可单独使用,也可以作为两种或多种的混合物形式使用。
根据需要,本发明的润滑油可进一步含有其它传统添加剂,这些添加剂的例子有金属减活剂,如苯并三唑衍生物和琥珀酸链烯基酯;抗氧化剂,如DBPC(2,6-二叔丁基对甲苯酚)和p,p′-二辛基二苯胺;以及用于HFC致冷剂的环氧稳定剂,如2-乙基己基缩水甘油基醚、仲丁基苯基缩水甘油基醚和具有5-10个碳原子的酰基的一缩水甘油醚。
本发明的润滑油与致冷剂混合得到适用于家用电冰箱、汽车空调、工业用致冷机和室内空调的致冷压缩机的工作流体。润滑油与致冷剂的重量比一般为10∶90-90∶10,特别优选20∶80-80∶20。优选准备使用的致冷剂是由氟原子置换C1或C2烃的氢原子制得的氢氟烃,例如,1,1,1,2-四氟乙烷(R134a),五氟乙烷(R125),二氟甲烷(R32),1,1,1-三氟乙烷(R143a)或1,1-二氟乙烷(R152a)。另外,也可以使用两种或多种这些烃致冷剂的混合物如,(R407C,R410A,R410B,等等)。润滑油的粘性可以适当控制,按照于40℃测定,一般为5-500cSt。具体地说,于40℃具有8-32cSt粘性的润滑油适用于家用电冰箱;于40℃粘性为25-100cSt的润滑油适用于室内空调和工业用致冷机;于100℃粘性为8-30cSt的润滑油适用于汽车空调。
以下参照实施例进一步说明本发明,尽管本发明不限于这些实施例。
实施例
对于实施例和比较例,制备和评价试验油。
基础油1是多元醇的混合脂肪酸酯,具体地说,是由包括2-乙基己酸和3,5,5-三甲基己酸的支链饱和脂肪酸混合物与季戊四醇反应制得的并于40℃显示64cSt粘性的中性酯。
基础油2是两种多元醇酯的混合物,具体地说,是一种包括80wt.%由新戊二醇与2-乙基己酸反应制得的中性酯和20wt.%由季戊四醇与2-乙基己酸反应制得的中性酯的混合物,其于40℃粘性为10cSt。
基础油3是具有下式(9)表示的结构的聚亚氧烷基乙二醇二甲醚,其于100℃粘性为19cSt:
CH3-O-〔(PO)m(EO)n〕(EO)o-CH3 (9)
其中〔(PO)m(EO)n〕表示无规共聚物基团;(n+o)/m是0.2;且n/m是0.1。
甘油一油基醚(以下简写“GMOE”)和1,4-山梨糖一油基醚(以下简写为“SMOE”)用作部分醚化的多元醇添加剂。所用的甘油-油基醚按照元素分析和基于3425cm-1,2926cm-1,1465cm-1和1124cm-1的吸收峰(红外光谱分析发现)验明。所用的1,4-山梨糖一油基醚也以上述同样方式验明。
此外,磷酸三甲苯酯(以下简写为“TCP”)和磷酸三苯酯(以下简写为“TPP”)用作磷酸酯添加剂,而甘油一油酸酯(以下简写为“GMO”)和山梨糖一油酸酯(以下简写为“SMO”)用作比较添加剂。
表1-3的实施例1-12和比较例1-9给出了使用基础油1,2和3制得的试验油组分。各试验油含有0.1wt.%DBPC抗氧化剂。
试验油各与HFC致冷剂混合生成工作流体。这些工作流体进行(1)耐磨试验,(2)稳定性试验和(3)实际机器磨损试验。磨损试验(1)是使用Falex摩擦机在以下条件下进行,表1-3给出了由此测定的磨损情况。
块材:AISI-1137
销材:SAE-3135
载荷:300磅
转数:290rpm
油温:60℃
致冷剂:注入R134a(70ml/min)
表1
基础油1:混合脂肪酸的多元醇酯
粘性:64cSt(40℃)添加剂 实施例 比较例(wt%) 1 2 3 4 1 2 3GMOE 0.2 2.0 - - - - -SMOE - - 0.2 2.0 - - -GMO - - - - - 2.0 -SMO - - - - - - 2.0磨耗[mg] 2.9 1.2 3.9 1.4 8.3 5.6 6.1
表2
基础例2:多元醇酯的混合物
粘性:10cSt(40℃)添加剂 实施例 比较例(wt%) 5 6 7 8 4 5 6GMOE 0.2 2.0 0.5 0.5 - - -TCP - - 1.0 1.0 - 1.0 1.0TPP - - - 0.2 - - 0.2GMO - - - - - 0.5 -SMO - - - - - - 0.5磨耗[mg] 3.0 1.8 1.2 0.8 14.6 4.5 5.2
表3
基础油3:聚亚氧烷基乙二醇二甲醚
粘性:19cSt(100℃)添加剂 实施例 比较例(wt%) 5 6 7 8 4 5 6GMOE 0.2 2.0 0.5 0.5 - - -TCP - - 1.0 1.0 - 1.0 1.0TPP - - - 0.2 - - -GMO - - - - - 0.5 -SMO - - - - - - 0.5磨耗[mg] 2.8 1.5 1.1 0.6 13.5 4.4 5.2
采用密封管法进行稳定性试验(2)。含各试验油和HFC致冷剂(R134a)(体积比为7∶3)的混合物与铁-铜-铝催化剂(基于JISK2211)一起放入玻璃管内。密封所得玻璃管并于175℃保持336小时以确定是否变化。在所有实施例和比较例中,既没有发现外观变化,也没有形成淤渣。
实际机器磨损试验(3)是通过将包括400ml各试验油和590g HFC致冷剂(R407c)的工作流体装入家用电冰箱的压缩机(旋转型致冷压缩机)中进行的。在以下条件下对压缩机进行抗磨试验,之后拆开测定辊和叶轮的磨耗情况。此外,测定所得润滑油的金属含量。结果列于表4。HFC致冷剂R407C是以23∶25∶52的重量比含R32,R125和R134a的混合物。
排放侧压:27kg/cm2G
吸入侧压:5kg/cm2G
排放气温:110℃
工作时间:600小时(连续工作)
频率:60Hz
表4
磨耗(μm) 润滑油中的金属含量
辊 叶轮 (铁ppm)实施例1 1.33 1.56 <1实施例2 0.31 0.25 <1实施例3 1.35 1.58 <1实施例4 0.38 0.28 <1比较例1 4.77 4.29 5比较例2 2.74 2.71 3比较例3 3.05 3.00 4实施例9 1.55 1.65 <1实施例10 0.40 0.31 <1实施例11 0.59 0.53 <1实施例12 0.48 0.29 <1比较例7 6.89 5.80 7比较例8 2.70 2.65 3比较例9 2.90 2.88 3
Claims (9)
1.一种电冰箱用的工作流体,它包括一种致冷剂和一种润滑油,后者包括,以润滑油总重计,0.01-10%重量的润滑油添加剂和基础油,润滑油添加剂包括一种部分醚化的多元醇作为活性成分,后者具有至少两个羟基并通过醚键键合带有至少一个具有至少一个双键的脂肪烃基。
2.按照权利要求1的电冰箱用工作流体,其中脂肪烃基是C12-24链烯基。
3.按照权利要求1的电冰箱用工作流体,其中脂肪烃基是C16-20链烯基。
4.按照权利要求3的电冰箱用工作流体,其中构成部分醚化的多元醇的多元醇是C3-6多元醇。
5.按照权利要求4的电冰箱用工作流体,其中构成部分醚化的多元醇的多元醇是甘油。
6.按照权利要求1的电冰箱用工作流体,其中润滑基础油由多元醇酯或多醚构成。
7.按照权利要求1的电冰箱用工作流体,其中以润滑油的总重计,部分醚化的多元醇含量为0.1-5%(重量)。
8.按照权利要求1的电冰箱用工作流体,其中润滑油包括,以润滑油总重计,0.1-5.0重量的至少一种磷酸酯。
9.一种电冰箱用的工作流体,它包括按照权利要求1的润滑油,其中致冷剂主要由一种或多种氢氟烃构成。
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1998
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1047525A (zh) * | 1989-05-23 | 1990-12-05 | 纳幕尔杜邦公司 | 用于制冷的组合物和方法 |
WO1991009097A1 (en) * | 1989-12-14 | 1991-06-27 | Idemitsu Kosan Co., Ltd. | Refrigerator oil composition for hydrofluorocarbon refrigerant |
CN1073473A (zh) * | 1991-12-06 | 1993-06-23 | 埃克森化学专利公司 | 制冷工作液组合物 |
Also Published As
Publication number | Publication date |
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KR960037808A (ko) | 1996-11-19 |
MY115732A (en) | 2003-08-30 |
CN1221783A (zh) | 1999-07-07 |
EP0736591A3 (en) | 1997-04-02 |
TW340870B (en) | 1998-09-21 |
KR100266957B1 (ko) | 2000-12-01 |
SG50653A1 (en) | 1998-07-20 |
CN1047194C (zh) | 1999-12-08 |
CN1134974A (zh) | 1996-11-06 |
DE69617784T2 (de) | 2002-08-08 |
DE69617784D1 (de) | 2002-01-24 |
ES2165956T3 (es) | 2002-04-01 |
EP0736591A2 (en) | 1996-10-09 |
EP0736591B1 (en) | 2001-12-12 |
US5744053A (en) | 1998-04-28 |
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