CN1108360C - 尤其适于与氟化制冷剂一起应用的多元醇和复合酯 - Google Patents

尤其适于与氟化制冷剂一起应用的多元醇和复合酯 Download PDF

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CN1108360C
CN1108360C CN98805978A CN98805978A CN1108360C CN 1108360 C CN1108360 C CN 1108360C CN 98805978 A CN98805978 A CN 98805978A CN 98805978 A CN98805978 A CN 98805978A CN 1108360 C CN1108360 C CN 1108360C
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acid
ester
carboxylic acid
refrigerant composition
anhydride
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CN1259986A (zh
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K·安克纳
H·拉克拉
J·科伊斯蒂南
E·格拉德
V·萨兰佩尔
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Fortum oil & Gas Co
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Abstract

本发明涉及一种制冷剂组合物，它含有无氯的氟代烃基制冷剂和其中混有含多元醇酯的润滑剂。按照本发明，多元醇酯含有2-丁基-2-乙基-1，3-丙二醇的酯，其羧酸残基得自线型或分支的C4～C18羧酸或它们的酐，或得自线型或分支的C4～C18羧酸或它们的酐的混合物。本发明也关系到新型的2-丁基-2-乙基-1，3-丙二醇的复合酯，它含有一元(价)或二价(元)羧酸的残基。该新型酯表现出在氟代烃中的良好溶解性和优良的润滑性能。

Description

尤其适于与氟化制冷剂一起应用的多元醇和复合酯
本发明涉及按照权利要求1的开头所述的一种制冷剂组合物。这类组合物一般含有非氯化氟代烃基制冷剂组合物，其中同时混有多元醇酯基润滑剂。
本发明还涉及按照权利要求12的复合酯和含有这些酯的润滑剂。
最近，由于许多应用领域的发展，多元醇酯类润滑剂迅速演变。这些产品(或与另外的原(基)油、如烃类，混合)可用作汽车发动机油，飞机和燃气轮机油，如生物降解液压油，金属加工油和压缩机油。这些产品由于其优良的溶解性、良好的技术稳定性和良好的低温特性，尤其与氟化制冷剂一起用作制冷压缩机中的可溶润滑剂组分。
有人建议将新戊二醇和季戊四醇酯与制冷剂一起应用。尽管这些已知的酯原则上显示出优良的润滑性，但它们的在非氯化氟代烃中的溶解度通常仅为中等。由于这一理由，它们不足以在含有氟化烃的制冷剂组合物中起到良好的作用。
本发明的一个目的是消除先前技术中存在的问题并提供一类新型的多元醇和复合酯，它们可以特别与氟化制冷剂液体一起用作润滑剂。本发明的另一个目的是提供一般适于用作润滑剂原(基)油的新型酯类。
本发明是基于发现2-丁基-2-乙基-1，3-丙二醇酯具有优良的润滑性能，尤其是由于它们的化学形式。这些酯显示出润滑剂的典型新戊基结构；可是在2位上的碳的取代是不对称的，即取代基是不同的，和由于这些酯所具有的性质不同于通常的性质。BEPD的酯在水解方面是很稳定的。它们具有良好的润滑性，它们也容易或非常容易溶解在氟化制冷剂中，因而适合于用作利用这种制冷剂的装置中的润滑剂。所用的润滑剂特别含有多元醇或复合酯，它是由像BEPD(2-丁基-2-乙基-1，3-丙二醇)或BEPD和另外的多元醇与一元羧酸或其酐(多元醇酯)的混合物或与一元或二元羧酸的混合物(复合酯)一起制备的。
更准确地说，按照本发明的制冷剂组合物的主要特征是在权利要求1的表征部分所陈述的那样。
BEPD的复合酯作为润滑油的原油是新型的和有益的。这种新型酯的特征是在权利要求12的表征部分说明那样。
本发明提供很多的有利条件。BEPD的酯具有优良的润滑性和在用作制冷剂的HFC化合物中的优良溶解度。所述油类的原材料可以用经济上有利的羰基合成法(临氢重整)制造。这些油类的性质可以很容易地得到改进，取决于所用的酯的多元醇的不同比例(BEPD的量可以是多元醇总量的100至5mol-％)，酯化羧酸和/或各酯化羧酸之间的比例。通过采用分支酸，溶解度可以改进，而通过使用二元酸，粘度可以提高。
在下面，将借助于详细描述和应用一些操作实例对本发明加以检验。
本发明的酯含有2-丁基-2-乙基-1，3-丙二醇的多元醇或复合酯。“多元醇酯”意指具有含一个一元羧酸或其酐的羧基的酯。对于本发明来说，术语“多元醇酯”通常也包含“复合酯”，它是其中至少一部分酯化酸是二元的酯。通常这些酸的两羧基与一种醇反应，得到齐聚酯化合物，它们含有至少两个醇残基和一个羧酸残基。复合酯也包括具有羧酸残基的酯，羧酸残基是由含有羟基和羧基二者的羟基酸生成的。羧基与多元醇反应，而羟基与另一个羧酸的羧基反应。
“多元醇”代表具有至少两个羟基的化合物。按照本发明，BEPD可以单独酯化或与另外的多元醇一起酯化。这些多元醇是，例如，NPG(新戊基二醇)，HPHP(羟基新戊酸羟基新戊酰基酯)，ETHD(2-乙基-1，3-己二醇)，TMP(三羟甲基丙烷)，TME(三羟甲基乙烷)，PE(季戊四醇)，TMPD(2，2，4-三甲基-戊二醇)和CHDM(1，4-二羟甲基-环己烷)。
优选的多元醇酯混合物是通过把多元醇混在一起并通过将形成的混合物就地酯化而生成的。
按照本发明的第一个优选实施方案，被提供的制冷液体组合物含有一种多元醇的酯，它完全或几乎完全(95mol-％或甚至100％)由BEPD的酯组成。
按照本发明的另一个优选实施方案，所提供的制冷液体组合物除含有BEPD的多元醇酯外，还含有任何比例的NPG，HPHP，ETHD，TMP，TME，PE，BEPD或TMPD的酯，典型的是5∶95～100∶0。优选BEPD构成酯混合物的多元醇基的主要部分，即其摩尔量为50％～99.9％，通常为50～95％。
BEPD或BEPD和其他多元醇的混合物用线型或分支C4～C18羧酸或其酐进行酯化。作为可以用于制备上述酯的脂族、线型或分支、饱和或不饱和C4～C18羧酸的特定实例，可以是如下所指出的：
-饱和、线型C4～C18羧酸：丁酸、戊酸、己酸、庚酸、辛酸、癸酸、十二酸(月桂酸)和十六酸(棕榈酸)和它们的混合物。
-饱和、支化C4～C16羧酸：异丁酸、2-乙基己酸、异壬酸和3，5，5-三甲基己酸。
-不饱和、线型C4～C18羧酸：3-丁烯酸(乙烯基乙酸)；和
-不饱和、分支C4～C18羧酸。
在混合酯中，各种线型和分支羧酸的比例可以在很大范围内变化。一般，线型羧酸存在量为1～100mol-％，优选约10～90mol-％羧酸量。相应地，分支羧酸的量为99～1mol-％，优选约90～10mol-％。特别是有可能制备含10～50mol-％的至少一种线型羧酸和90～50mol-％的一种分支羧酸的多元醇酯。
当BEPD的多元醇酯制出后，最好选择含4～14个碳原子的线型或分支酸作为酯化羧酸。辛酸，2-乙基己酸和月桂酸可以作为上面指出的实例。
酯化羟基酸是，例如，羟基新戊酸(HPAA)，乳酸，柠檬酸和二羟甲基丙酸(DMPA)。
除了前面指出的以外，所用的酯化羧酸可以含有二元羧酸，如草酸、丙二酸、二甲基丙二酸、丁二酸、戊二酸、己二酸、癸二酸、庚二酸、辛二酸和壬二酸。也可能应用环酐，如丁二酸酐或其烷基衍生物，或1，2，4-苯三酸酐。少量芳香酐，如邻苯二甲酸酐也是可以的。
多元醇的酯化度为50～100％，优选尽可能高，至少约90％。在复合酯中一元和二元羧酸之间的比例是50∶50～99∶1。
BEPD的多元醇酯/混合酯/复合酯或BEPD和至少另一种多元醇可用于制备制冷剂组合物。这些酯含有作为制冷剂的一种或数种无氯的氟代烃(制冷剂)，在其中酯是溶解的。作为该组合物的制冷液体组分的特定实例，可以是如下所列出的：氟代烃134(1，1，2，2-四氟乙烷)，氟代烃134a，氟代烃143(1，1，2-三氟乙烷)，氟代烃143a(1，1，1-三氟乙烷)，氟代烃152(1，2-二氟乙烷)和氟代烃152a(1，1-二氟乙烷)。通常优选这些化合物中的氟代烃134a。氟代烃的混合物也可以应用。其实例包括氟代烃混合物407(氟代烃32，125和134a的混合物)和氟代烃混合物410(氟代烃32和125的混合物)。
取决于应用，按照ISO标准，酯的(运动)粘度要求在5～200cSt(厘斯托克斯)(40℃)。低(5～10)和中等(22～32)粘度是制冷器和其他小型制冷装置所需要的。高粘度组合物(46～68)是用于如空调器的冷却装置，而极高粘度是大型装置所需要的。
如在前面已经指出的，制得的酯的粘度可以用适当地选择酯化的羧酸组分和/或加入更多的多元醇到BEPD中而调节到所希望的大小。因此，通过应用常规的线型或分支羧酸(C4-C12)和，例如，己二酸，就有可能制备具有粘度为约15～22cSt(40℃)的酯。它们的粘度指数约为100，倾点低于-40℃。它们适合用于较小型冷却装置。通常增加分支羧酸的量，可以增加这些酯的溶解度。通过将二元羧酸加入到酯化反应中，尤其是将其与线型或分支酸一起应用，可以增加产物的粘度。在酯化之前将BEPD与另外的多元醇混合可以调节酯的性质，使其合乎要求。因而，指出一个例子，酯的粘度在许多情况下可以在不减低溶解度的情况下增加。粘度甚至可增长到高粘度范围。
作为特别有价值的酯的实例，可以是如下所指出的：
BEPD的多元醇酯，它含有30～60％线型羧酸和70～30mol-％分支羧酸。
BEPD的复合酯，它含有1～10mol-％二元羧酸和90～99mol-％线型和/或分支一元羧酸；和
BEPD与NPG的复合酯，它含有4～30mol-％二元羧酸和96～70mol-％线型和/或分支一元羧酸。
如上所述，BEPD的复合酯像BEPD和某种其他多元醇的复合酯一样已是可以用于不同目的的润滑剂组合物的新产品。
上述酯用作这些组合物的基油，并构成组合物的主要部分，即大于组合物的50％重量，优选约80～100％重量。为了改进组合物以使它们更好地适于各种应用，通常应用占组合物重量0～20％的添加剂。因此，上述酯不仅适用于制冷组合物，也适用于说明书导言中所指出的各种应用。
可用于制冷液体组合物的常规添加剂包括如下的一些：抗氧化剂、抗磨添加剂、洗涤剂、消泡剂和腐蚀抑制剂。
适合的抗氧化剂包括酚类，如2，6一二叔丁基-4-甲基酚和4，4′-亚甲基-双(2，6-二叔丁基酚)；芳香胺，如对，对-二辛基苯基胺，一辛基二苯基胺，吩噻嗪，3，7-二辛基吩噻嗪，苯基-1-萘胺，苯基-2-萘胺，烷基苯基-1-萘亚甲基胺，和烷基苯基-2-萘亚甲基胺，以及含硫的化合物，例如二硫代磷酸盐、亚磷酸盐、硫化物和二硫代金属盐，如苯并噻唑，二烷基二硫代磷酸锡，二芳基二硫代磷酸锌。
适合的抗磨添加剂包括，例如磷酸盐，磷酸酯，亚磷酸盐，硫代磷酸盐，例如二烷基二硫代磷酸锌，二芳基二硫代磷酸锌，磷酸三(甲苯酯)，氯化石蜡，硫化脂和烯烃，如硫代二丙酸酯，二烷基硫化物，二烷基多硫化物，烷基-硫醇，二苯基噻吩和2，2′-二硫代双(苯基噻唑)；有机铅化合物，脂肪酸、钼络合物，如二硫化钼，卤代有机硅化合物，有机硅化合物，硼酸盐和卤代磷化合物。
作为适合的洗涤剂的特定实例应是下面所指出的：
磺酸盐，芳香磺酸，它是被具有长链烷基取代的，磷酸盐，硫代磷酸盐，响岩(phonolates)，烷基酚的金属盐，和烷基硫化物。
典型的消泡剂包括硅油，例如二甲基聚硅氧烷和有机硅化合物，如二乙基硅酸盐。
腐蚀抑制剂的实例是有机酸，胺，磷酸盐，醇，磺酸盐和亚磷酸盐。
按照本发明的酯是用常规的酯化方法制备的，其中多元醇或多元醇的混合物与一种酸性混合物在催化剂(或不用催化剂)存在下反应。各种酸，如硫酸、盐酸、对甲苯磺酸、丁基钛酸盐，氧化锡等是实施本发明的适合催化剂。特别有利的催化剂是氧化锡。
在反应过程中多元醇与酸组分的反应是应用当量的酸，不足量的酸或有多余量的酸，过量的酸量一般最大为10mol-％，优选约0.1～5mol-％，尤其是约1mol-％。反应温度是150～230℃，优选170～220℃，特别是190～210℃。
酯化可以按分批法或半分批法进行，例如下回加入剩余的酸。最典型的实施方案包括在熔融相进行酯化，但也可以应用烃型介质，如甲苯或二甲苯。将产物中和并洗涤。酯产物的酯化度优选高于85％，尤其是高于90％，而酯的酸值优选低于0.1mg KOH/g。
下面的一些实例说明本发明。然而，这些实例并不限制本发明的范围。
在表1～3中所用的下述缩写是：kV代表运动粘度，VI代表粘度指数，而PP代表倾点。
实施例1酯的溶解度测定
酯在氟化烃中的溶解度按如下测定：将1mL所研究的酯放入一个试管中，试管用塞子密封。将试管放在温度-30℃的冷却浴中。当试管和酯的温度达到-30℃(约5分钟后)时，加入一种氟化制冷剂，如R-134a，使总体积为10mL。
在可能的轻微非正规搅拌下，使酯-制冷剂混合物在-30℃的浴中静置。大约15分钟后，目视估价混合物并确定其含有一相或两相。如果该酯和制冷剂液体形成一相，则酯完全溶于制冷剂液体。如果在混合物中存在两相，则该酯在制冷剂液体中部分或完全不溶。
实施例2BEPD酯的制备
BEPD的酯的制备按如下叙述分别用BEPD和月桂酸及2-EHA的酯的制备，作为一个例子。
原料按下述配方称重后放入玻璃反应器中：BEPD 30g，月桂酸37.5g和2-EHA 27.5g。所用催化剂含0.16g氧化锡，在约200℃通过搅拌和使反应混合物氮化进行酯化。反应在7小时内完成。
来自反应混合物的过量酸用2.3g固体碳酸钠中和。除碳酸钠外，向反应混合物中加入0.3g助滤剂。在210℃和5小时内进行中和反应。通过过滤除去产物中的碳酸钠和氧化锡。最后在硫酸钠上干燥产物和过滤。
通过适当改变条件制备BEPD与其他线型和分支脂肪酸的酯。结果归纳于表1中。表1.BEPD的多元醇酯
样品   多元醇(mol-％)    酸(mol-％)  kV40℃(cSt)  kV100℃(cSt)   VI   PP(℃)  溶解度(在R-134a)
  1  BEPD(100)   C12(50)2-EHA(50)   19.5  4.1   108   -39   良好
  2  BEPD(100)   C12(40)2-EHA(60)   19.8  4.0   97   -48   良好
  3  BEPD(100)   C12(30)2-EHA(70)   20.0  4.1   99   -57   良好
  4  BEPD(100)   C12(20)2-EHA(80)   17.5  3.6   74   -57   良好
  5  BEPD(100)   C12(10)2-EHA(90)   21.3  4.1   82   -57   良好
  6  BEPD(100)   C12(40)C8(10)2-EHA(50)   19.8  4.8   173   -48   良好
  C8＝辛酸
  C12＝月桂酸(十二酸)
  2-EHA＝2-乙基己酸
实施例3
BEPD复合酯的制备
BEPD的复合酯的制备是用BEPD和2-EHA和己二酸的酯的制备作为例子阐明。
按下面配方将原料称重后放入玻璃反应器：BEPD 27.0g，2-EHA 44.6g和己二酸2.4g。所用催化剂含0.11g氧化锡。在搅拌和氮化反应混合物的情况下于约200℃进行酯化。反应在7小时内完成。
来自反应混合物的过量酸用1.9g固体碳酸钠中和。除碳酸钠外，向反应混合物中加入0.2g助滤剂。在约200℃进行中和5小时。过滤除去产物中的碳酸钠和氧化锡。最后将产物在硫酸钠上干燥和过滤。
通过适当改变条件制备其他的复合酯。结果归纳于表2中。表2.BEPD的复合酯
样品   多元醇(mol-％)    酸(mol-％)   kV40℃(cSt)   kV100℃(cSt)   VI   PP(℃)   溶解度(在R-134)
11 BEPD(100) 2-EHA(95)AA(5) 20.6 3.8 44 -48 良
  12   BEPD(100)   C12(38)2-EHA(58)AA(4)   27.6   5.2   117   -48     良
13 BEPD(100) C12(48)2-EHA(48)AA(4) 25.6 5.0 112 -42 良
  14   BEPD(100)   C5(95)AA(5)   8.9   2.4   83   -66     优
15 BEPD(100) C12(50)2-EHA(40)AA(10) 36.5 6.4 128 -42 良
16 BEPD(100) C12(47)C8(47)AA(3)DMMA(3) 17.7 4.0 129 -45 良
  17   BEPD(100)   C6(94)AA(6)   10.6   2.8   99   -63     优
  18   BEPD(100)   C5(85)AA(15)   20   4.2   111   -60     优
C5＝戊酸     C8＝辛酸    C6＝己酸    C12＝月桂酸(十二酸)2-EHA＝2-乙基己酸              AA＝己二酸DMMA＝二甲基丙二酸
实施例4
BEPD的多元醇/复合酯的制备
重复实施例3的方法制备BEPD和其他一些多元醇的混合物的复合酯。结果归纳于表3中。表3.BEPD的多元醇/复合酯
样品   多元醇(mol-％)   酸(mo1-％)  kV40℃(cSt)  kV100℃(cSt)   VI   PP(℃)   溶解度(在R-134a)
19 BEPD(90)NPG(10) C12(45)2-EHA(45)AA(10) 40.6 6.0 90 -42 良
20 BEPD(50)NPG(50) C12(21)Ci-9(43)Ci-4(18)丁二酸(18) 34.9 5.6 107 -48 良
21 BEPD(50)ETHD(50) C12(95)AA(5) 23.8 5.1 146 -37 良
22 BEPD(50)ETHD(50) 2-EHA(92)AA(8) 20.3 3.8 58 -49 良
  23   BEPD(90)   C5(95)AA(5)  9.6   2.6   92   -63     优
Ci-4＝异丁酸              C12＝月桂酸(十二酸)
C5＝戊酸                 2-EHA＝2-乙基己酸
Ci-9＝异壬酸              AA＝己二酸

Claims (17)

1.含有无氯的氟代烃基制冷剂的制冷剂组合物，此外混有含多元醇酯的润滑剂，其特征是多元醇酯含有2-丁基-2-乙基-1，3-丙二醇的酯，它构成至少是50mol-％润滑剂的多元醇残基。
2.按照权利要求1的制冷剂组合物，其特征是润滑剂含有至少一种次要的多元醇酯。
3.按照权利要求2的制冷剂组合物，其特征是次要的多元醇酯的多元醇残基得自新戊基二醇，羟基新戊酸羟基新戊酰酯，2-乙基-1，3-己二醇，三羟甲基丙烷，三羟甲基乙烷，季戊四醇或2，2，4-三甲基戊二醇。
4.按照权利要求2的制冷剂组合物，其特征是2-丁基-2-乙基-1，3-丙二醇和另外多元醇的摩尔比为50∶50～99.9∶0.1。
5.按照权利要求2的制冷剂组合物，其特征是多元醇酯的羧酸残基得自线型或分支C4～C18羧酸，或酐，或得自线型或分支C4～C18羧酸或它们的酐的混合物。
6.按照权利要求5的制冷剂组合物，其特征是羧酸残基得自2-乙基己酸，辛酸和/或月桂酸。
7.按照权利要求5的制冷剂组合物，其特征是酯的羧酸残基得自一元和二元羧酸混合物。
8.按照权利要求7的制冷剂组合物，其特征是一元羧酸残基是得自线型或分支C4～C18羧酸或酐或其混合物。
9.按照权利要求7的制冷剂组合物，其特征是二元羧酸残基得自乙二酸、丙二酸、二甲基丙二酸、丁二酸、戊二酸、己二酸、癸二酸、庚二酸、辛二酸或壬二酸，或环酐或其烷基衍生物，或1，2，4-苯三酸酐。
10.按照权利要求7～9的制冷剂组合物，其特征是一元和二元羧酸间的摩尔比是50∶50～99∶1。
11.按照权利要求1的制冷剂组合物，其特征是氟代烃基制冷剂是氟代烃134，氟代烃134a，氟代烃143，氟代烃143a，氟代烃152或氟代烃152a或各种氟代烃的混合物。
12.按照权利要求9的制冷剂组合物，其中所说的环酐或其烷基衍生物是丁二酸酐或其烷基衍生物。元羧酸二者的残基，一元和二元羧酸残基在酯中的摩尔比为50∶50～99∶1。
13.按照权利要求12的复合酯，其特征是一元羧酸残基得自线型或分支C4～C18羧酸或酐或它们的混合物。
14.按照权利要求12或13的复合酯，其特征是二元羧酸残基得自乙二酸、丙二酸、二甲基丙二酸、丁二酸、戊二酸、己二酸、癸二酸、庚二酸、辛二酸或壬二酸，或环酐，如丁二酸酐或其烷基衍生物，或1，2，4-苯三酸酐。
15.按照权利要求12～14的任一项的复合酯，其特征是它们以酯和/或另外的多元醇的复合酯的混合物形式。
16.按照权利要求15的复合酯，其特征是它们是以酯和/或NPG，ETHD或PE的复合酯的混合物的形式。
17.用于含按照权利要求12～16的酯润滑剂的基油。
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JP2001518971A (ja) 2001-10-16
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US6436309B1 (en) 2002-08-20
EP0973851A1 (en) 2000-01-26
KR20010006249A (ko) 2001-01-26
CA2285547A1 (en) 1998-10-22
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FI111711B (fi) 2003-09-15
CN1259986A (zh) 2000-07-12

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