CN101400769B - 冷冻机油组合物 - Google Patents
冷冻机油组合物 Download PDFInfo
- Publication number
- CN101400769B CN101400769B CN2007800084946A CN200780008494A CN101400769B CN 101400769 B CN101400769 B CN 101400769B CN 2007800084946 A CN2007800084946 A CN 2007800084946A CN 200780008494 A CN200780008494 A CN 200780008494A CN 101400769 B CN101400769 B CN 101400769B
- Authority
- CN
- China
- Prior art keywords
- base oil
- oil composition
- kinematic viscosity
- refrigerated machine
- machine oil
- 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
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- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 239000010721 machine oil Substances 0.000 title claims description 57
- 239000002199 base oil Substances 0.000 claims abstract description 97
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- 239000002480 mineral oil Substances 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005057 refrigeration Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 235000010446 mineral oil Nutrition 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 238000004378 air conditioning Methods 0.000 claims description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical group CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011651 chromium Substances 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
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- 238000010438 heat treatment Methods 0.000 claims description 3
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 3
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- 239000002904 solvent Substances 0.000 description 4
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-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
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials 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
- C09K5/042—Materials 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 compounds containing carbon and hydrogen only
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- C10M171/02—Specified values of viscosity or viscosity index
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- C10M2203/1025—Aliphatic fractions used as base material
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Abstract
本发明涉及冷冻机油组合物,其特征在于含有在40℃的运动粘度为0.11~8mm2/s的混合基油,该混合基油含有:(A)在40℃的运动粘度为5mm2/s以下的低粘度基油和(B)在40℃的运动粘度为20~400mm2/s的高粘度基油,(A)和(B)均为含有选自矿物油、合成烃化合物、含氧化合物和含硫化合物中的至少一种的基油。上述冷冻机油组合物粘度低,省能源性高,并且密封性良好,且耐载荷性优异,适合用于各种冷冻领域、特别是密闭式冷冻机。
Description
技术领域
本发明涉及冷冻机油组合物,更具体地说,涉及粘度低、可以提高省能源性、密封性良好且耐载荷性优异、适合在各种冷冻领域中、特别是在密闭型冷冻机中使用的冷冻机油组合物。
背景技术
通常,压缩式冷冻机的结构是:至少由压缩机、冷凝器、膨胀机构(膨胀阀等)、蒸发器或者进一步由干燥器构成,致冷剂和润滑油(冷冻机油)的混合液体在该密闭的体系内循环。上述压缩式冷冻机中,根据装置的种类而不同,但通常压缩机内为高温、冷却器内为低温,因此致冷剂和润滑油必须在由低温至高温的宽温度范围内不发生相分离地在该体系内循环。通常,致冷剂和润滑油在高温区和低温区具有相分离的区域,低温区的分离区域的最高温度优选-10℃以下,特别优选-20℃以下。而高温区的分离区域的最低温度优选30℃以上、特别优选40℃以上。如果冷冻机的运转中发生相分离,则对装置的寿命或效率产生显著的不良影响。例如,如果在压缩机部分发生致冷剂与润滑油的相分离,则活动部润滑不良,发生胶着等,使装置的寿命显著缩短,而如果在蒸发器内发生相分离,则存在粘度高的润滑油,导致热交换效率降低。
以往,冷冻机用的致冷剂主要使用氯氟烃(CFC)、氢氯氟烃(HCFC)等,但由于是含有引起环境问题的氯的化合物,因此人们对氢氟烃(HFC)等不含氯的替代致冷剂进行了研究。但是,HFC对于地球暖化也有影响,因此,作为更加适合于环境保护的致冷剂,人们开始关注烃、氨、二氧化碳等所谓的自然致冷剂。
冷冻机用润滑油是为了使冷冻机的活动部分润滑而使用,因此润滑性当然重要。特别是压缩机内为高温,可以保持润滑所必须的油膜的粘度是很重要的。所必须的粘度根据所使用的压缩机的种类、使用条件而不同,通常,与致冷剂混合之前的润滑油的粘度(运动粘度)在40℃下优选为10-200mm2/s,粘度比此低则油膜变薄,容易发生润滑不良,过高则热交换效率降低。
例如公开了一种润滑油组合物,该润滑油组合物是使用二氧化碳作为致冷剂的蒸汽压缩式冷冻装置用润滑油,其以气相色谱蒸馏法的10%馏出点为400℃以上、且80%馏出点为600℃以上、100℃下的运动粘度为2-30mm2/s、粘度指数为100以上的润滑油基油为主要成分(例如参照专利文献1)。
该润滑油组合物中所使用的基油在40℃下的运动粘度在实施例中是17-70mm2/s的范围。
使用上述粘度高的冷冻机油,则不可避免冷冻机的能量消耗增多。因此,为了使冷冻机节省能源,人们对于冷冻机油的低粘度化和润滑中的摩擦特性的改善进行了研究。
以冰箱用冷冻机为例,使粘度降低至VG32、22、15、10,则可以改善省能源性。但是,如果进一步降低粘度,则发生密封性或润滑性降低等问题。
专利文献1:日本特开2001-294886号公报
发明内容
鉴于上述状况,本发明的目的在于提供粘度低、省能源性提高、密封性良好且耐载荷性优异,适合于在各种冷冻领域中、特别是密闭式冷冻机中使用的冷冻机油组合物。
本发明人为了开发具有上述优选性质的冷冻机油组合物而进行了深入的研究,结果发现:使用混合基油可以实现上述目的,其中,所述混合基油含有具有特定的低粘度的基油和具有特定的高粘度的基油作为基油,是将它们混合并调节成特定低粘度而成。本发明基于上述认识完成。
即,本发明提供:
1.冷冻机油组合物,其特征在于含有在40℃的运动粘度为0.11~8mm2/s的混合基油,该混合基油含有:(A)在40℃的运动粘度为5mm2/s以下的低粘度基油和(B)在40℃的运动粘度为20~400mm2/s的高粘度基油,(A)和(B)均为含有选自矿物油、合成烃化合物、含氧化合物和含硫化合物中的至少一种的基油。
2.上述1所述的冷冻机油组合物,其中,低粘度基油(A)在40℃的运动粘度为0.1~2.8mm2/s。
3.上述1所述的冷冻机油组合物,其中,低粘度基油(A)和高粘度基油(B)的含有比例为(A):(B)的质量比是99~5:1~95。
4.上述1所述的冷冻机油组合物,其中,矿物油的低粘度基油的硫分为50质量ppm以下。
5.上述1所述的冷冻机油组合物,其中,合成烃化合物是选自碳原子数为2~20的烯烃均聚物、共聚物以及它们的氢化物、具有环己基的脂环烃化合物、以及直链或支链烷基取代的芳族化合物中的至少一种化合物。
6.上述1所述的冷冻机油组合物,其中,合成烃化合物是碳原子数为6~20的α-烯烃的低聚物或将该α-烯烃的低聚物氢化所得的物质。
7.上述6所述的冷冻机油组合物,其中,碳原子数为6~20的α-烯烃的低聚物是使用金属茂催化剂得到的低聚物。
8.上述1所述的冷冻机油组合物,其中,含氧化合物和含硫化合物是选自醚化合物、硫醚化合物、酮化合物、醇化合物和硫醇化合物中的至少一种化合物。
9.上述8所述的冷冻机油组合物,其中,醚化合物是选自单醚化合物、氧亚烷基二醇衍生物和聚乙烯基醚化合物中的至少一种化合物。
10.上述1所述的冷冻机油组合物,其含有选自极压剂、油性剂、抗氧化剂、酸捕获剂和消泡剂中的至少一种添加剂。
11.上述1所述的冷冻机油组合物,其适用于使用烃系、二氧化碳系、氢氟烃系或氨系制冷剂的冷冻机。
12.上述11所述的冷冻机油组合物,其适用于使用烃系制冷剂的冷冻机。
13.上述1所述的冷冻机油组合物,其适用于滑动部分为包含工程塑料、或者具有有机涂布膜或无机涂布膜的滑动部分的冷冻机。
14.上述13所述的冷冻机油组合物,其中,有机涂布膜是聚四氟乙烯涂布膜、聚酰亚胺涂布膜或聚酰胺酰亚胺涂布膜。
15.上述13所述的冷冻机油组合物,其中,无机涂布膜是石墨膜、类金刚石碳膜、锡膜、铬膜、镍膜或钼膜。
16.上述1所述的冷冻机油组合物,其用于汽车空调、气体热泵、空调、冰箱、自动销售机、陈列柜的冷冻系统以及各种热水供应系统、或者制冷/暖气系统。
17.上述16所述的冷冻机油组合物,其中,系统内的水分含量为60质量ppm以下,残留空气量为8kPa以下。根据本发明,可以提供粘度低、省能源性提高、密封性良好且耐载荷性优异、适合在各种冷冻领域中、特别是密闭式冷冻机中应用的冷冻机油组合物。
具体实施方式
本发明的冷冻机油组合物中,使用含有特定基油(化合物)的低粘度基油(A)与高粘度基油(B)的混合基油。低粘度基油(A)在40℃的运动粘度要为5mm2/s以下,优选3.0mm2/s以下,进一步优选2.8mm2/s以下。低粘度基油(A)在40℃的运动粘度超过5mm2/s,则难以将混合基油的运动粘度调节至规定的粘度范围,无法实现本发明的省能源性提高的目的。对低粘度基油(A)在40℃的运动粘度的下限值没有特别限定,从使用性角度考虑,在室温下必须为液体,从确保必要的闪点的角度考虑,优选0.1mm2/s以上,更优选0.2mm2/s以上,进一步优选0.5mm2/s以上。
低粘度基油(A)优选闪点为0℃以上,更优选20℃以上,进一步优选50℃以上。分子量分布(重均分子量/数均分子量)优选1.5以下,更优选1.2以下。如果闪点或分子量分布满足上述条件,则可以抑制密封性的降低。
另一方面,高粘度基油(B)在40℃的运动粘度要为20mm2/s以上,优选30mm2/s以上,特别优选32mm2/s以上。高粘度基油(B)在40℃的运动粘度为20mm2/s以上,则可以提高密封性,同时可以使润滑性提高。要求高粘度基油(B)在40℃的运动粘度的上限为400mm2/s,优选200mm2/s,进一步优选150mm2/s。如果高粘度基油(B)在40℃的运动粘度为400mm2/s以下,则可以使混合基油在40℃的运动粘度保持在规定的低粘度范围,且可以提高密封性、润滑性。
本发明中,在低粘度基油(A)、高粘度基油(B)各自满足上述40℃下的运动粘度范围的前提下,均可以使用含有选自(1)矿物油、(2)合成烃化合物、(3)含氧化合物和(4)含硫化合物中的至少一种的基油。
本发明的低粘度基油(A)优选以下物质。
上述(1)的矿物油例如有:将石蜡系、中间基系、或环烷系原油进行常压蒸馏或者将常压蒸馏的渣油减压蒸馏,将所得润滑油馏分进行溶剂脱沥青、溶剂萃取、氢解、溶剂脱蜡、氢纯化等处理的一种以上而纯化所得的矿物油;或者是将矿物油系蜡或通过费托工艺等制备的蜡(ガストウリキツドワツクス)异构化制备的基油等。
这些矿物油优选硫分含量为400质量ppm以下,更优选100质量ppm以下,特别优选50质量ppm以下,进一步优选30质量ppm以下。另外,矿物油的芳族成分(%CA)优选为5以下,更优选为3以下,进一步优选为1以下。矿物油的硫分含量为400质量ppm以下、芳族成分(%CA)为5以下,则可以获得良好的氧化稳定性。
上述矿物油中,低粘度基油(A)可以适当选择在40℃的运动粘度为5mm2/s以下的使用。特别优选硫分含量为50质量ppm以下的,更优选硫分含量为30质量ppm以下的。
上述(2)的合成烃化合物可以是直链烃化合物、支链烃化合物、脂环式烃化合物、芳族烃化合物中的任一种。其中,作为低粘度基油(A),优选总碳数为5-24的化合物,更优选总碳数为6-20的化合物。
直链烃化合物、支链烃化合物可列举碳原子数为2-20的烯烃均聚物、共聚物或它们的氢化物,具体有:乙烯、丙烯、丁烯、异丁烯等碳原子数为2-4的烯烃的均聚物,或乙烯与碳原子数为3-20的α-烯烃共聚物或它们的氢化物,以及由碳原子数为6-20的α-烯烃得到的α-烯烃低聚物或其氢化物等。
乙烯的均聚物或其氢化物是直链烃化合物的例子。
上述碳原子数为6-20的α-烯烃低聚物或其氢化物是使用通常的BF3催化剂、齐格勒型催化剂等得到的低聚物或其氢化物,更优选为使用以下说明的金属茂催化剂得到的α-烯烃的低聚物或将其氢化所得物质。其中特别优选氢化了的。
这里,碳原子数为6-20的α-烯烃例如有1-己烯、1-辛烯、1-癸烯、1-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯等,优选其中的1-己烯、1-辛烯、1-癸烯和1-十二碳烯。它们可以单独使用一种,也可以将两种以上组合使用。
使用所述金属茂催化剂得到的α-烯烃的低聚物例如如下制备。
首先,使用金属茂催化剂作为催化剂将上述α-烯烃聚合,获得α-烯烃低聚物。金属茂催化剂可优选使用含有元素周期表第4族元素、具有共轭碳五元环的络合物、即金属茂络合物与含氧有机铝化合物的组合。
作为上述金属茂络合物中的元素周期表第4族元素,使用钛、锆和铪,特别优选锆。具有共轭碳五元环的络合物通常使用具有取代或无取代的环戊二烯基配体的络合物。
金属茂络合物可从以往公知的化合物中适当选择使用。
优选的金属茂络合物的例子有:双(正十八烷基环戊二烯基)二氯化锆、双(三甲基甲硅烷基环戊二烯基)二氯化锆、双(四氢茚基)二氯化锆、双[(叔丁基二甲基甲硅烷基)环戊二烯基]二氯化锆、双(二-叔丁基环戊二烯基)二氯化锆、(亚乙基-双茚基)二氯化锆、双环戊二烯基二氯化锆、亚乙基双(四氢茚基)二氯化锆和双[3,3-(2-甲基-苯并茚基)]二甲基硅烷二基二氯化锆等。它们可以单独使用一种,也可以将两种以上组合使用。
另一方面,含氧的有机铝化合物例如有甲基铝氧烷、乙基铝氧烷、异丁基铝氧烷等,它们可以单独使用一种,也可以将两种以上组合使用。
低聚化中不一定需要溶剂,低聚化可在悬浮液、液体单体或惰性溶剂中实施。在溶剂中低聚化时,例如可使用苯、乙基苯、甲苯等。低聚化优选在液体单体过量存在的状态下实施。
作为低聚化反应的后处理,加入水、醇类,或者是进行不含有卤素的酸处理,按照上述公知的方法进行催化剂的灭活处理,终止低聚化反应。
低聚化阶段产生的副反应产物α-烯烃异构体,可通过汽提在低聚化反应之后除去,也可以不分离低聚化物,在氢化处理之后在低聚物氢化物蒸馏时除去。
上述处理的低聚化物可以使用碱水溶液、醇碱溶液洗涤除去催化剂成分。
上述得到的α-烯烃低聚物有二聚物、三聚物、四聚物等。
利用金属茂催化剂制备的α-烯烃低聚物具有双键,特别是末端的亚乙烯基双键的含量高。本发明的α-烯烃低聚物的氢化物可以将这些双键氢化,变换成饱和结构。
氢化处理中可使用公知的Ni、Co系催化剂或Pd、Pt等贵金属催化剂。例如有:硅藻土担载Ni催化剂、三乙酰乙酸钴/有机铝催化剂、活性碳担载钯催化剂、氧化铝担载铂催化剂等。
对于氢化条件,温度通常为200℃以下,如果是Ni系催化剂,则为150-200℃左右,如果为Pd、Pt等贵金属催化剂,则为50-150℃左右,如果为三乙酰乙酸钴/有机铝等均相还原剂,则为20-100℃左右。另外,氢压为常压-20MPa左右。
这样得到的氢化物进行蒸馏处理,获得具有所需运动粘度的馏分,作为本发明的基油使用。
这些α-烯烃低聚物中,(A)的低粘度基油优选1-己烯、1-辛烯、1-癸烯、1-十二碳烯等二聚物以及它们的混合物,更优选它们的氢化物。其中特别优选使用金属茂催化剂所得的。
上述合成脂环式烃化合物例如有:具有1个以上环己基环的化合物。其中,作为(A)的低粘度基油,可以使用总碳数为6-24的化合物。
上述合成脂环式烃化合物的低粘度基油的具体例子有:环己烷(40℃下的运动粘度为0.7mm2/s)、辛基环己烷(40℃下的运动粘度为1.5mm2/s)、十二烷基环己烷(40℃下的运动粘度为2.7mm2/s)、二丁基环己烷(40℃下的运动粘度为1.6mm2/s)、二己基环己烷(40℃下的运动粘度为2.6mm2/s)等。
上述的合成芳族烃化合物例如有芳环上具有直链或支链烷基的化合物。芳环上所具有的直链烷基可以是一个基团,也可以是相同或不同的两个以上的基团。该化合物中,作为(A)的低粘度基油,可以使用总碳数为7-24的化合物。
上述合成芳族烃化合物的低粘度基油的具体例子有:甲苯(40℃下的运动粘度为0.8mm2/s)、辛基苯(40℃下的运动粘度为1.6mm2/s)、十二烷基苯(40℃下的运动粘度为2.8mm2/s)、二丁基苯(40℃下的运动粘度为1.7mm2/s)、二己基苯(40℃下的运动粘度为2.7mm2/s)等。
上述(3)的含氧和(4)的含硫化合物优选选自醚化合物、硫醚化合物、酮化合物、醇化合物和硫醇化合物中的至少一种化合物。
该醚化合物有单醚化合物、氧亚烷基二醇衍生物和聚乙烯基醚。
上述单醚化合物例如可使用通式(I)所示的化合物:
R1-O-R2 ...(I)
(式中,R1和R2各自独立,表示碳原子数为1-20的一价烃基)。
上述通式(I)中,R1和R2所示的碳原子数为1-20的一价烃基有:碳原子数为1-20的直链、支链、环状烷基或烯基,碳原子数为6-20的芳基或碳原子数为7-20的芳烷基。该R1和R2互相可以相同或不同。
这些化合物中,作为(A)的低粘度基油,优选使用通式(I)所示化合物中的总碳原子数为4-24的化合物。
上述通式(I)所示的单醚化合物的低粘度基油的代表性例子有:二丁基醚(40℃下的运动粘度为0.8mm2/s)、二辛基醚(40℃下的运动粘度为1.3mm2/s)、异辛基十六烷基醚(40℃下的运动粘度为2.7mm2/s)、环己基癸基醚(40℃下的运动粘度为1.9mm2/s)、苯基癸基醚(40℃下的运动粘度为2.1mm2/s)等。
本发明中,也可以使用将上述通式(I)所示的单醚化合物的氧原子置换为硫原子所得的单硫醚化合物,上述单硫醚化合物的低粘度基油的具体例子例如有:二辛基硫醚(40℃下的运动粘度为1.5mm2/s)、二癸基硫醚(40℃下的运动粘度为2.7mm2/s)等。
接着,上述氧亚烷基二醇衍生物例如可列举下述通式(II)所示的化合物:
R3-[(OR4)m-OR5]n ...(II)
(式中,R3表示氢原子、碳原子数为1-10的一价烃基、碳原子数为2-10的酰基或具有2-6个键合部位(结合部)的碳原子数为1-10的脂肪族烃基,R4表示碳原子数为2-10的亚烷基,R5表示氢原子、碳原子数为1-10的烃基或碳原子数为2-10的酰基,n为1-6的整数,m表示平均值为1-20的数)。
上述通式(II)中,R3和R5各自的一价烃基有:碳原子数为1-10的直链、支链、环状烷基或烯基,碳原子数为6-10的芳基,或碳原子数为7-10的芳烷基。该R3和R5互相可以相同或不同。
这些一价烃基中,优选烷基,其具体例子有:甲基、乙基、正丙基、异丙基、各种丁基、各种戊基、各种己基、各种庚基、各种辛基、各种壬基、各种癸基、环戊基、环己基等。
如果该一价烃基的碳原子数超过10,则与致冷剂的相容性降低,可能发生相分离。
R3和R5的各自的碳原子数为2-10的酰基的烷基部分可以是直链状、支链、环状的任意形式。
R3和R5均为烷基或酰基时,R3和R5可以相同,也可以互相不同。
n为2以上时,一个分子中的多个R5可以相同或不同。
R3为具有2-6个键合部位的碳原子数为1-10的脂肪族烃基时,该脂肪族烃基可以是链状,也可以是环状。具有2个键合部位的脂肪族烃基例如有:乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、环戊烯基、环己烯基等。具有2-6个键合部位的脂肪族烃基例如有:从三羟甲基丙烷、甘油、季戊四醇、山梨醇;1,2,3-三羟基环己烷、1,3,5-三羟基环己烷等多元醇中除去羟基所得的残基。
如果该脂肪族烃基的碳原子数超过10,则与致冷剂的相容性降低,可能发生层分离。优选的碳原子数为2-6。
本发明中,上述R3和R5优选至少一个为烷基,特别优选碳原子数1-3的烷基,尤其是甲基,这从粘度特性考虑优选。并且,由于与上述同样的理由,优选R3和R5两者为烷基,特别是甲基。
上述通式(II)中的R4是碳原子数为2-10的亚烷基,作为重复单元的氧亚烷基可列举:氧亚乙基、氧亚丙基、氧亚丁基、氧亚己基、氧亚辛基、氧亚癸基。一个分子中的氧亚烷基可以相同,也可以含有两种以上的氧亚烷基。
上述通式(II)中的n为1-6的整数,根据R3的键合部位数目确定。例如,R3为一价烃基或酰基时,n为1;R3为具有2、3、4、5和6个键合部位的脂肪族烃基时,n分别为2、3、4、5和6。m为平均值是1-20的数,如果该平均值超过20,则本发明的目的不能充分实现。
这些氧亚烷基二醇衍生物包括一亚烷基二醇二醚[通式(II)中,n=1、m=1、R3=碳原子数为1-10的一价烃基]、聚亚烷基二醇二醚(m≥2)、一或多亚烷基二醇的酰基化衍生物、聚亚烷基二醇一醚(R3=氢原子)等。
这些氧亚烷基二醇衍生物中,作为(A)的低粘度基油,优选通式(II)所示化合物中总碳原子数为6-20的化合物。其具体例子有:二丙二醇二甲醚(40℃下的运动粘度为1.7mm2/s)、丁二醇二丁醚(40℃下的运动粘度为2.3mm2/s)、聚丙二醇二甲醚(40℃下的运动粘度为2.1mm2/s)、聚亚乙基聚亚丙基二醇二甲醚(ポリエチレンポリプロピレングリコ—ルジメチルエ—テル)(40℃下的运动粘度为2.8mm2/s)。
本发明中,也可以使用将上述通式(II)所示的醚化合物的氧原子的一部分或全部置换为硫原子的硫醚化合物。其中,(A)的低粘度基油的具体例子例如有:丁二醇二甲基硫醚(40℃下的运动粘度为1.8mm2/s)、二甘醇二甲基醚硫(40℃下的运动粘度为2.1mm2/s)等。
上述聚乙烯基醚例如可优选列举具有通式(III)所示的重复单元的聚乙烯基醚:
[化1]
(式中,R6、R7和R8分别表示氢原子或碳原子数为1-8的烃基,它们互相可以相同或不同,R9表示碳原子数为1-10的二价烃基,R10表示碳原子数为1-20的烃基,k表示平均值为0-10的数,R6-R8在各构成单元中可以相同,也可以分别不同,R9O为多个时,多个R9O可以相同或不同)。
上述通式(III)中的R6、R7和R8分别表示氢原子或碳原子数1-8、优选1-4的烃基,它们互相可以相同或不同。
上述聚乙烯基醚可通过将1种或2种以上对应的乙烯基醚单体聚合来制备。
这些聚乙烯基醚的详细内容如日本特开2001-49282号公报中段[0027]-[0045]的记载。
其中,作为(A)的低粘度基油优选采用通式(III)所示的化合物中的总碳原子数为8-20的化合物。
作为上述低粘度基油的聚乙烯基醚的具体例子例如优选列举:聚乙烯基醚(40℃下的运动粘度为2.8mm2/s)、聚乙基乙烯基醚-聚异丁基乙烯基醚共聚物(40℃下的运动粘度为3.5mm2/s)等。
上述酮化合物为具有直链、支链、环状烷基或烯基的二酮化合物。其中,(A)的低粘度基油的酮化合物优选总碳原子数为5-24的二酮化合物,具体可列举例如二丁基酮(40℃下的运动粘度为0.9mm2/s)。
作为上述醇化合物,可列举1-6元醇化合物。其中,作为(A)的低粘度基油,可列举烷基是碳原子数为2-24的直链、支链、环状烷基或烯基的伯或仲醇,总碳原子数为3-24的2-6元多元醇。作为低粘度基油的醇化合物的具体例子例如有1,2-羟基癸烷(40℃下的运动粘度为1.1mm2/s)。
本发明中,可以使用将醇化合物的氧原子的一部分或全部置换为硫原子的硫醇化合物。作为低粘度基油的硫醇化合物的具体例子例如有:辛基硫醇(40℃下的运动粘度为0.9mm2/s)、十二烷基硫醇(40℃下的运动粘度为1.2mm2/s)等。
另一方面,高粘度基油(B)可以从上述低粘度基油(A)中说明的(1)矿物油、(2)合成烃化合物、(3)含氧化合物和(4)含硫化合物中适当选择40℃下的运动粘度为20-300mm2/s的使用。此时,优选总碳原子数为35-400的化合物。
本发明中,可以将符合(A)、(B)分别规定的运动粘度的基油从上述(1)-(4)中选择一种基油使用,也可以将两种以上符合规定运动粘度的基油组合使用。
本发明的含有低粘度基油(A)和高粘度基油(B)的混合基油在40℃的运动粘度必须为0.11-8mm2/s。该混合基油在40℃的运动粘度为0.11mm2/s以上,则可以良好发挥润滑性,同时密封性也好;如果为8mm2/s以下,则省能源性提高的效果可充分发挥。在40℃的混合基油的运动粘度的优选范围为0.11-6mm2/s,进一步优选为0.15-2mm2/s。
混合基油的平均分子量优选50-660,更优选70-330。为了确保安全,混合基油的闪点优选0℃以上,更优选30℃以上,特别优选50℃以上。
关于低粘度基油(A)与高粘度基油(B)的混合比例,没有特别限定,基油(A)和基油(B)的含有比例按照(A):(B)的质量比优选99-5:1-95的比例,更优选90-10:10-90的比例。
如果是上述混合比例,则可以发挥基油(A)和基油(B)的各自作用,密封性良好,且耐载荷性优异,同时粘度低,省能源性提高。
本发明的冷冻机油组合物中可以含有选自极压剂、油性剂、抗氧化剂、酸捕获剂和消泡剂等中的至少一种添加剂。
上述极压剂可以是磷酸酯、酸性磷酸酯、亚磷酸酯、酸性亚磷酸酯和它们的胺盐等磷系极压剂。
这些磷系极压剂中,从极压性、摩擦特性等角度考虑,特别优选磷酸三(甲苯)酯、磷酸三硫代苯酯、亚磷酸三(壬基苯基)酯、亚磷酸二油醇酯(ジオレイルハイドロゲンホスフアイト)、亚磷酸2-乙基己基二苯酯等。
另外,极压剂可以列举羧酸的金属盐。这里所述羧酸的金属盐,优选碳原子数为3-60的羧酸,进一步优选碳原子数为3-30、特别是12-30的脂肪酸的金属盐。还可以列举上述脂肪酸的二聚酸或三聚酸(トリマ—酸)以及碳原子数为3-30的二羧酸的金属盐。其中,特别优选碳原子数为12-30的脂肪酸和碳原子数为3-30的二羧酸的金属盐。另一方面,作为构成金属盐的金属,优选碱金属或碱土金属,特别优选碱金属。
上述羧酸的金属盐的具体例子例如有棕榈酸或油酸的钾盐、钠盐、锂盐等。
上述以外的极压剂例如有:硫化油酯、硫化脂肪酸、硫化酯、硫化烯烃、二烃基聚硫化物、硫代甲酸酯类、硫代萜类、二烷基硫代二丙酸酯类等硫系极压剂。
从润滑性和稳定性的角度考虑,上述极压剂的配合量相对于组合物总量通常为0.001-5质量%,特别优选0.005-3质量%的范围。
上述极压剂可以单独使用一种,也可以将两种以上组合使用。
上述油性剂的例子有硬脂酸、油酸等脂肪族饱和和不饱和一元羧酸、二聚酸、氢化二聚酸等聚合脂肪酸,蓖麻醇酸、1,2-羟基硬脂酸等羟基脂肪酸;月桂醇、油醇等脂肪族饱和和不饱和一元醇,硬脂胺、油胺等脂肪族饱和和不饱和一元胺,月桂酰胺、油酰胺等脂肪族饱和和不饱和一羧酸酰胺,甘油、山梨醇等多元醇与脂肪族饱和或不饱和一元羧酸的偏酯等。
它们可以单独使用一种,也可以将两种以上组合使用。其配合量相对于组合物总量通常从0.01-10质量%、优选0.1-5质量%的范围选择。
作为上述抗氧化剂,优选配合2,6-二叔丁基-4-甲基苯酚、2,6-二叔丁基-4-乙基苯酚、2,2’-亚甲基双(4-甲基-6-叔丁基苯酚)等酚类,苯基-α-萘基胺、N,N’-二苯基-对苯二胺等胺系的抗氧化剂。从效果和经济性等角度考虑,抗氧化剂在组合物中通常配合0.01-5质量%,优选配合0.05-3质量%。
酸捕获剂例如有苯基缩水甘油基醚、烷基缩水甘油基醚、亚烷基二醇缩水甘油基醚、环己烯化氧、α-烯烃氧化物、环氧化大豆油等环氧化合物。其中从相容性的角度考虑,优选苯基缩水甘油基醚、烷基缩水甘油基醚、亚烷基二醇缩水甘油基醚、环己烯化氧、α-烯烃氧化物。
该烷基缩水甘油基醚的烷基、以及亚烷基二醇缩水甘油基醚的亚烷基可以具有支链,碳原子数通常为3-30,优选4-24,特别优选6-16。α-烯烃氧化物一般使用总碳原子数为4-50的,优选使用总碳原子数为4-24的,特别优选使用总碳原子为6-16的。本发明中,上述酸捕获剂可以使用一种,也可以将两种以上组合使用。从效果和抑制残渣的生成的角度考虑,其配合量相对于组合物通常为0.005-5质量%,特别优选为0.05-3质量%。
本发明中,通过配合该酸捕获剂,可以使冷冻机油组合物的稳定性提高。通过将上述极压剂和抗氧化剂并用,可以发挥使稳定性进一步提高的效果。
上述消泡剂有硅油或氟化硅油等。
在不妨碍本发明目的的范围内,本发明的冷冻机油组合物中可以适当配合其它公知的各种添加剂,例如N-[N,N’-二烷基(碳原子数为3-12的烷基)氨基甲基]甲苯基三唑(トルトリアゾ—ル)等钢钝化剂等。
本发明的冷冻机油组合物适用于使用烃系、二氧化碳系、氢氟烃系或氨系致冷剂的冷冻机,特别优选适用于使用烃系致冷剂的冷冻机。
在使用本发明的冷冻机油组合物的冷冻机的润滑方法中,关于上述各种致冷剂和冷冻机油组合物的使用量,以致冷剂/冷冻机油组合物的质量比计为99/1-10/90,进一步优选95/5-30/70的范围。致冷剂的量比上述范围少时,可见冷冻能力降低,比上述范围多时,润滑性能降低,不优选。本发明的冷冻机组组合物可应用于各种冷冻机,特别优选适用于压缩式冷冻机的压缩式冷冻循环中。
本发明的冷冻机油组合物所适用的冷冻机具有含有压缩机、冷凝器、膨胀机构(膨胀阀等)和蒸发器,或者压缩机、冷凝器、膨胀机构、干燥器和蒸发器作为必须构成的冷冻循环,同时,冷冻机油使用上述本发明的冷冻机油组合物,还可以使用上述各种致冷剂作为致冷剂。
这里,干燥器中优选填充含有微孔径为0.33nm以下的沸石的干燥剂。该沸石可以是天然沸石或合成沸石,更优选该沸石在25℃、CO2气体分压为33kPa的条件下的CO2气体吸收容量为1.0%以下。上述合成沸石例如有ユニオン昭和(株)制的商品名为XH-9、XH-600等。
本发明中,如果使用这样的干燥剂,则不会吸收冷冻循环中的致冷剂,可以有效除去水分,同时可以抑制干燥剂本身的劣化导致的粉末化。因此,由粉末化产生的管路的堵塞或进入压缩机滑动部导致的异常磨损等减少,可以长时间稳定运转冷冻机。
采用本发明的冷冻机油组合物的冷冻机中,压缩机内有各种滑动部分(例如轴承等)。本发明中,从密封性的角度考虑,该滑动部分特别优选含有工程塑料,或者具有有机涂布膜或者无机涂布膜。
从密封性、滑动性、耐磨损性等角度考虑,上述工程塑料优选例如聚酰胺树脂、聚苯硫树脂、聚缩醛树脂等。
从密封性、滑动性、耐磨损性等角度考虑,有机涂布膜例如可列举:含氟树脂涂布膜(聚四氟乙烯涂布膜等)、聚酰亚胺涂布膜、聚酰胺酰亚胺涂布膜等。
另一方面,从密封性、滑动性、耐磨损性等角度考虑,无机涂布膜可列举石墨膜、类金刚石碳膜、镍膜、钼膜、锡膜、铬膜等。该无机涂布膜可以通过镀敷处理形成,也可以通过PVD法(物理气相蒸镀法)形成。
该滑动部分可以使用含有以往的合金系例如Fe基合金、Al基合金、Cu基合金等的材料。
本发明的冷冻机油组合物例如可以在汽车空调、气体热泵、空调、冰箱、自动销售机、陈列柜等的各种热水供应系统或者制冷/暖气系统中使用。
本发明中,上述系统内的水分含量优选60质量ppm以下,更优选50质量ppm以下。该系统内的残留空气量优选8kPa以下,更优选7kPa以下。
本发明的冷冻机油组合物含有具有特定粘度的混合基油作为基油,该混合基油含有选自矿物油、合成烃化合物、含氧化合物、含硫化合物中的一种以上,基油的粘度低,省能源性提高,并且密封性、耐载荷性优异。
实施例
下面,通过实施例进一步详细说明本发明,但本发明并不受这些例子的任何限定。
基油的性状和冷冻机油组合物的各特性可如下求出。
<基油的性状>
(1)40℃的运动粘度
按照JIS K2283-1983,使用玻璃制毛细管式粘度计测定。
(2)闪点
按照JIS K2265,通过COC法和PM法测定。
<冷冻机油组合物的各特性>
(3)磨损载荷(焼付荷重)
使用密闭Falex磨损实验机,按照ASTM D3233测定。测定条件是转速290rpm、针的材质AISIC1137、磨块材质SAE3135,致冷剂(异丁烷)吹入量5L/小时。
(4)密封管实验
在玻璃管中加入催化剂Fe/Cu/Al,按照试样的油/致冷剂(异丁烷)=4mL/lg的比例填充并密封,在175℃保持30小时。求出油外观、催化剂外观、是否有残渣以及求出酸值。
(5)油附着量实验
将SPCC板(80×60mm)浸泡在试验油中,涂布油,将该SPCC板在室温下垂直保持24小时,然后测定残留的油附着量(g)。油附着量越多则显示油膜保持性良好。
(6)密封性比较实验
活塞使用各种滑动材料,比较活塞/汽缸之间的间隙的漏气量。漏气量是以参考例1作为10,以指数表示。
实施例1-16和比较例1、2
制备表1所示组成的冷冻机油组合物,测定其磨损载荷,同时进行密封管实验。结果如表1所示。
[表1]
[表2]
表1-2
[注]
A1:环烷系矿物油,40℃运动粘度=0.98mm2/s,S分=25质量ppm,闪点=45℃,平均分子量=120,分子量分布=1.1
A2:石蜡系矿物油,40℃运动粘度=2.24mm2/s,S分=1质量ppm以下,闪点=78℃,平均分子量=170,分子量分布=1.1
A3:C4烯烃(主要成分异丁烯)的低聚物,40℃运动粘度=1.25mm2/s,闪点=49℃,平均分子量=142,分子量分布=1.2
A4:C4烯烃(主要成分异丁烯)的低聚物,40℃运动粘度=2.56mm2/s,闪点=87℃,平均分子量=180,分子量分布=1.3
A5:1-辛烯二聚物的氢化物(使用金属茂催化剂制备的),40℃运动粘度=2.78mm2/s,闪点=132℃,分子量=226,分子量分布=1
A6:癸基苯,40℃运动粘度=2.54mm2/s,闪点=110℃,分子量=218,分子量分布=1
A7:聚丙二醇二甲醚,40℃运动粘度=2.1mm2/s,闪点=65℃,分子量=160,分子量分布=1.3
A8:聚乙基乙烯基醚,40℃运动粘度=2.5mm2/s,闪点=95℃,分子量=180,分子量分布=1.2
A9:乙基十二烷基醚,40℃运动粘度=2.35mm2/s,闪点=138℃,分子量=242,分子量分布=1
B1:环烷系矿物油,40℃运动粘度=32.7mm2/s,S分=300质量ppm
B2:石蜡系矿物油,40℃运动粘度=100.2mm2/s,S分=5质量ppm
B3:1-癸烯的低聚物,40℃运动粘度=63.1mm2/s
B4:烷基苯,40℃运动粘度=56.3mm2/s
B5:聚丙二醇二甲醚,40℃运动粘度=42.1mm2/s
B6:聚乙基乙烯基醚,40℃运动粘度=68.3mm2/s
C1:硅油,40℃运动粘度=2.55mm2/s
C2:硅油,40℃运动粘度=56.5mm2/s
D1:磷酸三(甲苯)酯
D2:C14α-烯烃氧化物
D3:2,6-二叔丁基-4-甲基苯酚
D4:硅氧烷系消泡剂
由表1可知,本发明的冷冻机油组合物(实施例1-16)与比较例1、2相比,磨损载荷高,且密封管实验结果也良好。
实施例17、18和比较例3、4
测定表2所示的供试油的磨损载荷,同时进行油附着量的测定。结果如表2所示。
[表3]
表2
[注]
C3:环烷系矿物油,40℃运动粘度=4.2mm2/s,S分=20质量ppm,闪点=145℃,平均分子量=310,分子量分布=1.2
C4:1-癸烯的二聚物,40℃运动粘度=4.9mm2/s,闪点=172℃,平均分子量=282,分子量分布=1
其它与表1相同。
由表2可知,本发明的含有混合基油的实施例17、18的冷冻机油组合物与含有单独基油的比较例3、4相比,磨损载荷高,油附着量多。
实施例19-22和参考例1
关于表3所示的供试油,使用表3所示的滑动部材料进行密封性比较实验。结果如表3所示。
[表4]
表3
实施例19 | 实施例20 | 实施例21 | 实施例22 | 参考例1 | |
供试油No. | 供试油12 | 供试油13 | 供试油13 | 供试油13 | 供试油13 |
滑动材料 | E1 | E2 | E3 | E4 | E5 |
漏气量(相对比较) | 3> | 3> | 3> | 8 | 10 |
[注]
E1:聚苯硫
E2:含氟聚合物涂布膜
E3:含聚酰亚胺的涂布膜
E4:镀锡膜
E5:铝合金
由表3可知,滑动材料为工程塑料、有机或无机涂布膜的实施例19-22与不使用它们的参考例1相比,其漏气量少,密封性良好。
产业实用性
本发明的冷冻机油组合物粘度低,省能源性提高,并且密封性良好,且耐载荷性优异,适合在各种冷冻领域中、特别是密闭式冷冻机中使用。
Claims (14)
1.适用于使用烃系制冷剂的冷冻机的冷冻机油组合物,其特征在于仅由在40℃的运动粘度为0.11~4.2mm2/s的混合基油和添加剂构成,所述添加剂选自极压剂、油性剂、抗氧化剂、酸捕获剂和消泡剂中的至少一种,该混合基油含有:(A)在40℃的运动粘度为0.1~2.8mm2/s的低粘度基油和(B)在40℃的运动粘度为20~400mm2/s的高粘度基油,(A)和(B)均为含有矿物油的基油,
所述混合基油中的低粘度基油(A)和高粘度基油(B)的质量比以混合基油总量为基准为((47.5/97.5)×100)~10:((50/97.5)×100)~90。
2.权利要求1所述的冷冻机油组合物,其中,低粘度基油(A)在40℃的运动粘度为0.5~2.8mm2/s。
3.权利要求1所述的冷冻机油组合物,其中,低粘度基油(A)在40℃的运动粘度为0.98~2.24mm2/s。
4.权利要求1所述的冷冻机油组合物,其中,高粘度基油(B)在40℃的运动粘度为30~200mm2/s。
5.权利要求1所述的冷冻机油组合物,其中,高粘度基油(B)在40℃的运动粘度为32.7~100.2mm2/s。
6.权利要求1所述的冷冻机油组合物,其中,矿物油的低粘度基油的硫分为50质量ppm以下。
7.权利要求1所述的冷冻机油组合物,其中,酸捕获剂是必须成分。
8.权利要求1所述的冷冻机油组合物,其中,上述烃系制冷剂是异丁烷。
9.权利要求1所述的冷冻机油组合物,其适用于滑动部分为包含工程塑料、或者具有有机涂布膜或无机涂布膜的滑动部分的冷冻机。
10.权利要求9所述的冷冻机油组合物,其中,有机涂布膜是聚四氟乙烯涂布膜、聚酰亚胺涂布膜或聚酰胺酰亚胺涂布膜。
11.权利要求9所述的冷冻机油组合物,其中,无机涂布膜是石墨膜、类金刚石碳膜、锡膜、铬膜、镍膜或钼膜。
12.权利要求1所述的冷冻机油组合物,其用于汽车空调、气体热泵、空调、冰箱、自动销售机、陈列柜的冷冻系统以及各种热水供应系统、或者制冷/暖气系统。
13.权利要求12所述的冷冻机油组合物,其中,系统内的水分含量为60质量ppm以下,残留空气量为8kPa以下。
14.冷冻机的润滑方法,其使用权利要求1~13中任一项所述的冷冻机油组合物进行润滑。
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PCT/JP2007/053317 WO2007105452A1 (ja) | 2006-03-10 | 2007-02-22 | 冷凍機油組成物 |
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EP (1) | EP1995299B1 (zh) |
JP (1) | JP5330824B2 (zh) |
KR (1) | KR101420447B1 (zh) |
CN (1) | CN101400769B (zh) |
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JP5330824B2 (ja) | 2013-10-30 |
CN101400769A (zh) | 2009-04-01 |
EP1995299B1 (en) | 2018-01-31 |
US20090062167A1 (en) | 2009-03-05 |
TW200801173A (en) | 2008-01-01 |
US7914697B2 (en) | 2011-03-29 |
EP1995299A1 (en) | 2008-11-26 |
KR20080103990A (ko) | 2008-11-28 |
WO2007105452A1 (ja) | 2007-09-20 |
EP1995299A4 (en) | 2011-04-06 |
JPWO2007105452A1 (ja) | 2009-07-30 |
TWI424052B (zh) | 2014-01-21 |
KR101420447B1 (ko) | 2014-07-16 |
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