CN1270618A - 基于聚新戊基多元醇酯的冷却剂和改进的添加剂组合物 - Google Patents

基于聚新戊基多元醇酯的冷却剂和改进的添加剂组合物 Download PDF

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CN1270618A
CN1270618A CN98809160A CN98809160A CN1270618A CN 1270618 A CN1270618 A CN 1270618A CN 98809160 A CN98809160 A CN 98809160A CN 98809160 A CN98809160 A CN 98809160A CN 1270618 A CN1270618 A CN 1270618A
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composition
acid
ester
polyol ester
lubricant
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CN1114682C (zh
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迈克尔·A·麦克亨利
戴尔·D·卡尔
托马斯·G·谢弗
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Kauffman Holdings
Lanxess Solutions US Inc
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Hatco Corp
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Abstract

一种合成润滑剂组合物,其是一种与有效量的抗氧化剂、黄铜缓蚀剂和锈抑制剂相混合的多元醇酯的混合物。该多元醇酯混合物包括主要组分的聚新戊基多元醇酯混合物,该混合物是由聚季戊四醇部分酯化的酯与至少一种C7－C12羧酸反应形成的,该C7－C12羧酸与具有至少2个羟基和至少一种C8－C10羧酸的多元醇反应形成的酯相混合。优选的是,该酸是直链的并能避免在使用中产生气味的酸。有效的添加剂包括仲芳基胺抗氧化剂、三唑衍生物黄铜缓蚀剂和氨基酸衍生物及取代的伯和仲胺和/或二胺锈抑制剂。

Description

基于聚新戊基多元醇酯的冷却剂和改进的添加剂组合物
本发明涉及合成酯组合物，且特别涉及以聚新戊基多元醇酯和一种具有至少2个羟基的多元醇酯的混合物为基础的组合物，其能用添加剂的独特组合物所抑制。该组合物特别适合用做旋转螺杆空气压缩机中的冷却剂/润滑剂。在该冷却剂/润滑剂组合物中将由气味很大的酸形成的酯的用量减到最小，但仍提供了延长寿命、更高的操作温度、极好的反乳化性、生物降解性、防锈性和水解稳定性的组合的性能，该性能组合是现有的合成压缩机冷却剂/润滑剂组合物所不能达到的。
众所周知，在旋转螺杆压缩机中使用的是烃类润滑油。这类油可密封转动件、润滑轴承、冷却压缩气体和将由压缩气体冷凝产生的水除去。高温和压力及水的存在将使得烃类油在相当短的时间内分解并产生淤渣。
为延长用于空气压缩机的冷却剂的使用寿命的努力是使用合成酯作为基础原料。典型的操作温度在约80-104℃(170-220°F)之间，虽然这些温度对合成润滑剂来说并不高，然而环境是高氧化的，致使矿物油在经过约1000小时使用后有分解的趋势并必须更换。目前使用的几种合成冷却剂/润滑剂将更换润滑剂的间歇时间延长到8000小时。
以己二酸和苯二甲酸的二酯为基础的合成酯冷却剂已经被用于包括旋转螺杆压缩机在内的各种压缩机中的时间已超过了25年。使用的其他合成冷却剂是以合成烃类或聚α-烯烃(PAO’s)、聚亚烷基二醇(PAG’s)、聚硅氧烷、及合成烃类和二元酸酯的混合物。当与在高氧化的环境中在压缩机中使用的以石油为基础的冷却剂相比时，所有这些产品延长了润滑剂的寿命。然而没有一种可用的润滑剂能提供全部所需的性能，特别是在避免难闻气味的同时，提供生物降解性和水解稳定性、防锈性，及反乳化性的组合性能。
除这些性能外，还要求具有一定的物理性能，例如提供有效的冷却、低温启动、转动件的密封，和轴承的润滑。特别是所需的物理性能包括在100℃(220°F)时的粘度至少为8cst、粘度指数至少为140，闪点至少为260℃(500°F)和倾点最大为-50℃(-58°F)。
对于冷却剂来说很需要其具有宽的操作温度范围。为了使低温启动成为可能，润滑剂的倾点需要小于-50℃(-58°F)。需要有适合的高温粘度性能和低挥发性来使得在更高的操作温度下允许有适当的润滑作用。因此，该冷却剂组合物应具有从安全角度考虑的一些生产者所需要的260℃以上的闪点。
所有的螺杆压缩机冷却剂/润滑剂将与压缩空气冷凝产生的水接触。所以，任何的润滑剂必须具有好的水解稳定性和防锈性及防腐性能。提供具有好的反乳化性能的润滑剂是一个增加的优点，这将允许从用过的润滑剂中分离水，并且易于处理和回收用过的润滑剂。
提高生物降解性也是很希望的。此外，从环保的观点来看，除去在一些商品化的冷却剂中使用的重金属也是希望的。
避免有害气味也是很希望的。因此，希望避免将使用的由具有少于7个碳原子的羧酸形成的酯的用量减到最小。最后，还希望有足够的可调整的综合性能。
现有以石油基础和合成的空气压缩机冷却剂/润滑剂是不能提供现代旋转螺杆压缩机所需的所有特性和物理性能。通常，改变合成润滑剂的一种组分将使某一特定的所需性能得到改善，但其是以其他性能的牺牲为代价的。例如，以PAO’s为基础的冷却剂的生物降解性差；以己二酸二酯为基础的冷却剂不能提供粘度或闪点性能；以苯甲酸二酯为基础的冷却剂具有较差的生物降解性和粘度指数；以聚硅氧烷为基础的冷却剂具有较差的生物降暨解性和防锈性；以聚亚烷基二醇为基础的冷却剂的反乳化性较差且防锈性也不好；以及以PAO’s和二酯的混合物为基础的冷却剂不能提供所需的生物降解性。
下表综合了目前的各种旋转螺杆压缩机冷却剂/润滑剂通常所需的性能。几种不同类型的产品可被注意到在具有另人满意的特殊性能的同时，其在可接受的范围内将存在变化，其中的一些可能对使用者来说是重要的。“×”代表相关类型的商品化可得到的冷却剂/润滑剂能提供所需的性能，而“O”代表其性能不能被完全接受。
                                        表1
                   旋转螺杆压缩机冷却剂/调滑剂组合物所需的重要性能所需性能     所需组成    矿物油   PAO(聚α-烯烃) 二酯  PAO/酯   PAG聚亚烷基二醇  聚硅氧烷   磷酸酯    PAG/酯倾点＜-50℃     ×         O            ×                  O      ×                          ×                       ×                   O        ×闪点＞260℃     ×         O            O         ×            O             ×                       ×                    ×                ×优良的防锈性    ×                   ×                        ×                  ×            ×                          O            O          O        O优良的反乳化性  ×                   ×                        ×                  ×            ×                          O            ×                   O        O优良的水解稳定性×                   ×                        ×                  O      ×                          ×                        ×                    O       ×生物降解性      ×                   O            O         O      O              O            O          O       O粘度指数＞140   ×                   O            ×                  O      ×                           ×                        ×                   O       ×*根据本发明制备的以聚新戊基多元醇酯为基础的组合物具有全部所需的性质。
最广泛使用的高性能旋转螺杆压缩机冷却剂之一是Carswell等人在美国专利4,302,343中描述的PAG/酯合成润滑剂，Carswell的PAG/酯润滑剂是一种聚亚烷基二醇与具有3-8个羟基和5-10个碳原子的脂族多元醇的受阻链烷酸酯的具有抑制作用的混合物。当将其与添加剂适当共混和混合时，发现得到的合成冷却剂/润滑剂能满足高温粘度的需要和表现出对热、空气和水环境的稳定性。然而，发现亚铁金属的耐腐蚀性和反乳化性能不太令人满意。重金属钡的存在在处理上也需要考虑。
Timony在美国专利4,175,045中描述的压缩机润滑剂是由具有约4-13个碳原子的羧酸的多元醇酯形成的。使用的多元醇为季戊四醇、二季戊四醇、三羟甲基丙烷、或其混合物。该润滑剂是季戊四醇酯和二季戊四醇酯的混合物。其在提供了令人满意的使用寿命和温度特性的同时，在100℃(212°F)时的粘度和倾点不能满足上述表1中所列出的希望值。此外，该润滑剂是以由戊酸形成的基本量的酯为基础，所以其在使用时表现出人们不希望的气味问题。对防锈性和反乳化性的改进也是需要的。
正如所注意到的那样，现有技术描述了以不同多元醇酯为基础的多种合成润滑剂和将其与不同的添加剂混合以使性能得到改善的混合物。在目前将这些合成的旋转螺杆压缩机冷却剂/润滑剂广泛应用的同时，仍希望能提供具有如表1所示的全部所需性能的改进的冷却剂/润滑剂组合物，特别是具有增强的氧化稳定性、改进的反乳化性、改进的防锈性、增强的生物降解性和使用时的低气味性。
总的来说，根据本发明，提供了一种用于旋转螺杆压缩机的独特地以多元醇酯基础原料和适合的添加剂为基础的具有优良性能改进了的合成冷却剂/润滑剂组合物，该组合物中的酯部分是主要量的聚新戊基多元醇酯和少量的由具有至少2个羟基的多元醇形成的多元醇酯的混合物。该组合物包括抗氧剂、黄铜缓蚀剂、锈抑制剂、水解稳定性改进剂和可包括消泡添加剂。发现这种使用聚季戊四醇酯为基础来制备的独特方法是必要的，以便可以获得全部所需的性能，特别是延长的寿命、低倾点、高闪点、好的反乳化性和降低的气味的组合性能。这种方法不同于专利文献中所描述的和当今所使用的合成冷却剂/润滑剂组合物。
所述的聚新戊基多元醇酯组分是用至少一种一元羧酸或具有约6至12个碳原子的酸的混合物将季戊四醇、二季戊四醇、三季戊四醇、四季戊四醇等进行部分酯化形成的聚季戊四醇酯。该聚季戊四醇酯的形成是首先将季戊四醇与选择的羧酸或酸的混合物反应，其中羟基较羧基过量以便形成部分酯化的酯。在优选的实施方案中，所述的羧酸是具有7-12个碳原子的直链酸。
所述的多元醇酯组分是被用来平衡聚季戊四醇酯的性能，特别是在不会反向影响任何其他所需性能的情况下来降低倾点和改进生物降解性。它是用具有5-8个碳原子和至少2个羟基的受阻多元醇与具有7-12个碳原子的一元羧酸反应来制备的。在优选的实施方案中，所述的多元醇是三羟甲基丙烷，且所述的酸为具有7-12个碳原子的直链酸。
所述的冷却剂/润滑剂组合物的形成是通过将约50-80wt％的聚新戊基多元醇酯和20-50wt％的多元醇酯混合，且添加有效量的添加剂，如约-0.5-10wt％的抗氧化剂、黄铜缓蚀剂、锈抑制剂和消泡剂来完成的。
因此，本发明的目的是，提供一种改进的旋转螺杆压缩机冷却剂/润滑剂。
本发明的另一目的是，提供一种由聚新戊基多元醇酯和传统的多元醇酯混合形成的改进的旋转螺杆压缩机冷却剂/润滑剂。
本发明的再一目的是，提供一种与传统的合成压缩机润滑剂相比具有增强的氧化稳定性、改进的反乳化性、改进的防锈性、增强的生物降解性、和降低的挥发性的改进的旋转螺杆压缩机冷却剂/润滑剂。
本发明的又一目的是，提供一种改进的添加剂组合物，该组合物为合成酯的旋转螺杆压缩机冷却剂/润滑剂提供了改进的反乳化性、提高的防锈性和改进的水解稳定性。
本发明的又一目的是，提供一种用完全以多元醇酯为基础的冷却剂/润滑剂来润滑旋转螺杆压缩机的方法。
本发明的又一目的是，提供一种合成酯的旋转螺杆压缩机冷却剂/润滑剂，该冷却剂/润滑剂在不含大量的具有令人不愉快气味的酸为基础的酯的情况下就能得到全部所需的性能。
本发明的再一目的是，提供一种用以聚新戊基多元醇酯和多元醇酯的混合物为基础的一种冷却剂/润滑剂组合物来润滑旋转螺杆压缩机的方法。
本发明的又一目的是，提供一种新的添加剂组合物，该组合物能使合成酯润滑剂的防锈性、水解稳定性和反乳化性得到改进。
本发明的其他目的和优点在说明书部分将是显而易见的和明显的。
因此，本发明包括的一种组合物，其具有的特征、性能、和相关的组分将在随后描述的组合物中得到证实，且本发明的范围将在权利要求书中示出。
根据本发明制备的基于多元醇酯的压缩机冷却剂/润滑剂组合物包括一种多元醇酯的混合物和设计能提供改进的反乳化性、生物降解性、极好的亚铁金属防锈性和改进的水解稳定性的性能符合要求的添加剂。在该组合物中没有有气味的重金属组分或金属。
所述的润滑剂中的合成酯部分是聚新戊基多元醇酯和多元醇酯的混合物。该润滑剂包括约50-80wt％聚新戊基多元醇酯和约20-50wt％的多元醇酯。优选的是，聚新戊基多元醇酯存在的量在约55-75wt％之间，且在最优的实施方案中，其存在的量在约65-70wt％之间。其中的重量百分数是以具有平衡的多元醇酯和添加剂的组合物的总重量为基础来计算的。
优选的是，聚新戊基多元醇酯是由季戊四醇与具有约6-12个碳原子的至少一种一元羧酸在羟基较羧基过量的情况下反应形成的季戊四醇、二季戊四醇、三季戊四醇、四季戊四醇等的酯的混合物。最优选的是，所述的酸是具有7-10个碳原子且是直链酸。本发明最优选的是，聚新戊基多元醇酯的酸组分是直链一元羧酸，或具有5wt％或更少的支链酸的混合物。
具有少于7个碳原子的酸不在本发明的范围内，因为其可能会在使用中给出有害的气味。合适的酸非限制性包括庚酸、辛酸、壬酸和癸酸。优选的是，所述的直链酸是庚酸(C7)和辛-癸酸(C8-C10)的混合物。该辛-癸酸通常是6和10个碳原子的酸的混合物，但实际上包括C6-C12的酸，其中包括微量的C6酸(少于约5wt％)。仅使用直链酸来制备酯使得冷却剂/润滑剂组合物的生物降解性和粘度指数有所增加。
在反应的开始阶段是按照Leibfried在美国专利3,670,013中描述的方式来形成聚新戊基多元醇酯的。在此，将季戊四醇(272w)和戊酸(217v)的反应混合物放入反应器中，该反应器具有存有额外的戊酸(38v)冷凝器以保证反应混合物中的戊酸处于恒定的水平。将该混合物加热到171℃并加入用水(2v)稀释的浓缩硫酸(1.0w)。将该反应混合物加热至192℃并保持到直至在约1.4小时后50.5v的水被除去为止。其分析产物为季戊四醇、二季戊四醇、三季戊四醇和四季戊四醇，它们的重量比为34∶38∶19∶8。
将所述的新戊基多元醇和所选择的酸或酸的混合物在强酸催化剂的存在下混合并加热。该反应继续进行直至反应混合物达到所需粘度为止。在此当开始的新戊基多元醇是季戊四醇时，该混合物包括部分酯化的季戊四醇、二季戊四醇、三季戊四醇、四季戊四醇及其类似物。为了完成酯的部分酯化，需在反应混合物中加入过量的酸，然后加热，将反应的水除去并让酸返回到反应器中。
在本发明的优选实施方案中，所述的聚新戊基多元醇部分酯化的酯是由季戊四醇形成的聚季戊四醇。该聚季戊四醇的是通过将季戊四醇和具有7-12个碳原子的直链一元羧酸的混合物进行反应，并将有效量的酸催化剂原料加入Liebfried描述的反应区中，其中羧基与羟基的起始摩尔比为约0.25∶1至0.5∶1。
所述的酸催化剂至少是一种酸酯化催化剂。酸酯化催化剂的实例包括无机酸，优选硫酸、盐酸等，酸盐，例如硫酸氢钠、亚硫酸氢钠等，磺酸，例如苯磺酸、甲苯磺酸、聚苯乙烯磺酸、甲磺酸、乙磺酸等。将该反应混合物加热到150-200℃之间，并同时除去酸蒸汽和水蒸气从而得到部分酯化的聚季戊四醇酯产物。
在酯化之前，所述的部分酯化产物包括季戊四醇的各种缩合产物。该混合物包括的季戊四醇的量较明显地比存在于商品化的二季戊四醇的量多10-15wt％。根据羧基与羟基的起始比例和反应条件的选择，该部分酯化的产品可能包括下表所示的重量范围的下述组分。
季戊四醇组分                                  wt％
季戊四醇                                      30-45
二季戊四醇                                    30-45
三/四季戊四醇                                 20-35
其他                                          3-15
为制备所述的聚新戊基多元醇酯的优选的庚酸和辛-癸酸混合物的量可以在很宽的范围内变化。开始时，羟基较羧基过量以形成部分酯化的季戊四醇、二季戊四醇、三季戊四醇、四季戊四醇等等。该羟基的过量是必需的，以便在反应中促进多元醇缩合成部分酯化的酯，酸混合物与多元醇的摩尔比根据所需的缩合度和润滑剂最终所需的粘度而变化的。在形成部分酯化的酯后，通常将过量10-25wt％的庚酸和C6-C10酸的混合物加入反应器中并加热，收集反应中的反应水同时使酸返回到反应器中。真空的存在将有利于反应的进行。当羟基的量降低到足够低的水平时，通过真空蒸馏将大部分过量的酸除去，用碱来中和任何残留的酸。将得到聚新戊基多元醇酯干燥并过滤。
优选的多元醇酯是具有5-8个碳原子和至少2个羟基的多元醇与具有7-12个碳原子的直链一元羧酸得到的酯。在本发明中使用的多元醇的具体实例包括新戊基多元醇、季戊四醇、二季戊四醇、三季戊四醇、三羟甲基丙烷、四季戊四醇等等。也可使用任何上述多元醇的混合物。被用来制备聚新戊基多元醇酯的所述多元醇酯的酸组分可以相同或不同。因此，优选具有约7-12个碳原子的一元羧酸，例如庚(C7)酸和含有最小量C6和更低C6酸的辛-癸(C8-C10)酸。在最优选的实施方案中，利用的是一种被称为辛-癸酸的直链酸来形成多元醇酯。在该反应混合物中存在的酸量可以在宽范围内变化。因为希望的是使多元醇完全酯化，所以通常加入相对于化学数量的过量约10-25wt％的过量酸。
所述的多元醇酯是通过多元醇与过量的羧酸反应、除去反应水和将未反应的酸返回到加热反应器中来形成的。该反应器装备有机械搅拌器、热电偶、温度调节器、迪安-斯达克榻分水器、冷凝器、氮气分布器和真空源。酯化作用可在或不在酯化催化剂如草酸亚锡存在下进行，该酯化催化剂是现有技术中众所周知的。所述的多元醇优选三羟甲基丙烷，用C8-C10酸将其酯化以形成所需的三酯。将该三羟甲基丙烷-C8-C10的三酯与聚季戊四醇酯混合以形成所述的润滑剂，所以该三酯存在的量为润滑剂量的约20-50wt％，优选约25-40wt％。在优选的实施方案中使用的为约30-35wt％。
将多元醇和过量约10-15wt％的一元羧酸加入反应器中，加热该反应器并在反应中于分水器中收集反应水，将酸返回到反应器中，施以真空来维持反应的进行。当羟基的量降低到足够低的水平时，通过真空蒸馏来除去大部分过量的酸，残留的酸用碱来中和。最后，将得到的多元醇酯产物干燥和过滤。
为了改进作为冷却剂/润滑剂的根据本发明制备的基于聚新戊基多元醇的酯组合物的性能，加入有效量的各种添加剂。例如通过加入有效量的至少一种抗氧化剂能改进基于酯的冷却剂/润滑剂的氧化稳定性。可使用的合适的抗氧化剂的实例为仲芳基胺；和苯基萘基胺，即α和β-萘基胺；二苯胺；亚氨基二苄基胺；p，p’-二辛基-二苯基胺；以及相关的芳香胺。其他合适的抗氧化剂有受阻酚，例如2-叔丁基苯酚、2，6-二叔丁基苯酚和4-甲基-2，6-二叔丁基苯酚等。
通常，抗氧化剂在酯组合物中的量为约0.5-10wt％之间，优选含有约1-5wt％之间。优选的抗氧化剂是仲芳基胺的混合物，例如二辛基二苯基胺和苯基-α-萘基胺的混合物。当这后两种胺组合使用时，含有的每一种的量在约0.01-5wt％之间，且优选每一种的量为约0.1-0.5wt％之间。
含有的锈抑制剂是为了抑制亚铁金属的腐蚀，该种腐蚀是由来自于压缩气体的冷凝水引起的一个严重问题。传统的锈抑制剂是含有人们希望避免的重金属化合物，然而，带有取代的伯和仲胺的氨基酸的衍生物的混合物被发现可提供一种协合效应—其不仅能提供改进的亚铁金属防锈性和改进的水解稳定性，而且同时不会反向地影响反乳化性。发现合适的氨基酸衍生物是以KingIndustries的KCORR-100E(50％活性)的形式存在的，其是一种N-酰基-N-烷氧基取代的氨基酸酯和来自Akzo Nobel的被称为Duomeen TDO和Ethomeen T-12的取代的伯和仲胺的混合物。以混合物形式使用这些锈抑制剂以保持优良的反乳化性，和提供极好的防锈性和改进的水解稳定性。
作为锈抑制剂存在的所述氨基酸衍生物和取代的胺及二胺的量为润滑剂量的约0.05-10wt％，优选为约0.1-6wt％。在优选实施方案中，总共含有约0.50wt％的如KCORR-100E、Ethomeen T-12和Duomeen TDO的锈抑制剂。
还包括被称为黄铜缓蚀剂的亚铜金属减活化剂，例如咪唑、苯并咪唑、吡唑、苯并三唑、甲苯基三唑、2-甲基苯并咪唑、3，5-二甲基吡唑和亚甲基二苯并三唑。优选芳基三唑，例如使用甲苯基三唑。包括的这类黄铜缓蚀剂的有效量通常为润滑剂量的约0.001-0.5wt％，优选约0.01-0.2wt％。在优选实施方案中使用为约0.05wt％的作为黄铜缓蚀剂的甲苯基三唑。
除这些抗氧化剂、黄铜缓蚀剂和锈抑制剂外，希望的是包含有效量的消泡剂，该消泡剂将阻止当润滑剂在压缩机螺杆之间工作时产生不希望的泡沫。少量的聚硅氧烷流体的存在是有效的。通常有约0.001-10ppm的消泡剂就足够了，在优选的实施方案中其量为约1ppm。
所述的润滑剂是通过在装备有机械搅拌器、热电偶、温度调节器和氮气分布器的反应器中加入所需量的聚新戊基多元醇酯和多元醇酯混合物来形成的。将该混合物加热到约100℃(211°F)。此时，加入所述的抗氧化剂和黄铜缓蚀剂添加剂并搅拌直至其溶解。将该混合物冷却到50℃(122°F)以下，并加入氨基酸衍生物，和取代的伯和仲胺的混合物。将该混合物搅拌、过滤，然后加入消泡剂。
根据本发明制备的酯冷却剂/润滑剂是特别指明用于旋转螺杆空气压缩机的。因此，其指明的粘度在100℃(212°F)时为约5-15厘沲，且在100℃(212°F)时优选7-10厘沲，并且其指明的倾点范围为约-29至-54℃(-20至-65°F)。参考以下的实施例可更好地理解本发明。除指明是摩尔量以外，所述的所有百分数都是指重量百分含量。这些实施例仅用于说明发明的目的，而并非用于限制本发明的范围。
实施例1
根据本发明的一种基于聚新戊基多元醇酯的冷却剂/润滑剂的制备方法如下：
在装备有机械搅拌器、热电偶、温度调节器和氮气分布器的反应器中加入按照表2中所示量的聚季戊四醇和三羟甲基丙烷酯。将该酯的混合物加热至约100℃。当该混合物的温度达到100℃时，加入仲芳基胺和三唑衍生物并搅拌直至其溶解。然后将该混合物冷却至50℃以下并向其中加入氨基酸衍生物、及取代的伯和仲胺。充分搅拌混合物、过滤，且然后加入消泡剂。表2
组分                                            wt％聚季戊四醇酯                                        66三羟甲基丙烷酯                                      32二辛基二苯胺(仲芳基胺)                              0.9苯基-a-萘基胺(仲芳基胺)                             0.9甲苯基三唑(三唑)                                    0.05K-Corr 100E(氨基酸衍生物)                           0.25Ethomeen T-12(取代的伯和仲胺)                       0.17Duomeen TDO(取代的伯和仲胺)                         0.08聚硅氧烷流体(消泡剂)                                1ppm
实施例2
分析确定根据本发明的如实施例1所述方法制备的基于聚新戊基多元醇酯的冷却剂/润滑剂组合物的物理性能。使用同样的ASTM测试方法，同时测试被称为SSR Ultra(目前的工业标准)的商品化用的旋转螺杆压缩机润滑剂样品和测试认为是根据Carswell的美国专利4,302,343制备的样品。物理和化学性能及操作特性的比较结果如下表3所示。
                                      表III
                                物理和操作性能
                              实施例1    SSR ULTRA
       性能                   制备       (目前的标准)    测试方法粘度，在100℃(212°F)             8.48          8.82        ASTM D 445(CST)在40℃(104°F)               48.4          48.5        ASTM D 445ISO粘度等级                       46            46          ASTM D 2422倾点，℃(°F)                     -51(-60)      -50(-58)    ASTM D 97闪点，℃(°F)                     274(525)      282(540)    ASTM D 92燃点，℃(°F)                     307(585)      299(570)    ASTM D 92重金属含量，％                    无            1,200 ppm钡 原子发射脂肪酸＜C7，wt％                 无*          12          GC130°F下的反乳化性，分钟          25            无分离(3天) ASTM D 1401生物降解性，％                    85.4          66.8        CEC
                                                        L-33-A-93亚铁金属腐蚀海水，24小时                      通过(无锈)    失败        ASTM D 665海水，48小时                      通过(无锈)    失败        B旋转高压气体贮罐氧化，            15.0          10.1        ASTM D 227225小时压力降，psi改进的旋转高压气体贮罐氧化15小时，10％H2O，压力降，psi     20            4415小时，0％H2O，压力降，psi      3             20水解稳定性                                                  ASTM D 2619于93.3℃(20°F)经48小时在40℃下的粘度变化％              -0.2          +1.4油酸变化，mgKOH/g                 +32           +.04水酸变化，mgKOH/g                 +.11          +.72在400°F下6.5小时的               1.34          5.58        ASTM D 972蒸发率，损失％在400°F下的挥发性，                                        Hatco方法损失％6小时                             0.1           0.421小时                            0.3           0.955小时                            0.9           0.483小时                            1.2           3.9*包括来自商品化C8-C10酸的微量C6酸。
化学和物理性能的比较显示根据本发明的如实施例1制备的冷却剂/润滑剂组合物能满足和/或超过了相应的用于压缩机冷却剂/润滑剂的每一个化学和物理性能。在实施例2中的操作特性测试结果表明实施例1的冷却剂/润滑剂的操作特性大大地超过了旋转螺杆空气压缩机用的润滑剂的被认为是重要的每一个操作特性。
实施例3
将根据实施例1制备的足够量的冷却剂/润滑剂放入三个不同的马力为5、7.5和30的旋转螺杆空气压缩机中。每隔500小时观察一次流体的状况。在30hp压缩机运转3000小时后，对冷却剂/润滑剂进行观察和测试，发现其超过了表1中所示的最小技术指标。
根据本发明获得的这些明显的结果是由于酯混合物和添加剂的协合效应所引起的，即主要量的聚新戊基多元醇酯与多元醇酯和氨基酸衍生物及取代胺锈抑制剂混合物的结合。这种对防锈性和水解稳定性的改进是不会对生物降解性、反乳化性或氧化稳定性有任何负面影响的。这些改进的达到是不需使用含有能使所用的润滑剂的处理变得非常容易的化合物的任何重金属。
因此，可见上述的目的在前面描述中显而易见已经有效地达到了，并且由于在不背离本发明的范围和精神的情况下可就上述的组合物进行一定的改变，所以上述所有描述都被理解为用于解释说明本发明而并不意味着限制本发明。
还需理解的是，下述的权利要求书试图覆盖本文所述的本发明的所有一般和特殊的特征，并且所有关于本发明范围的陈述，无论何种语言，都可被认为落入了其中。
特别需要理解的是，在所述的权利要求书中，以独特形式引用的组分或化合物试图包括无论何种情况下其意义都被允许的这类组分的相容混合物。

Claims (24)

1、一种合成冷却剂/润滑剂组合物，其包括下述酯的混合物：
约50-80wt％的聚新戊基多元醇酯，其由聚新戊基多元醇部分酯化的酯与至少一种具有7-12个碳原子的直链一元羧酸反应形成；和
约20-50wt％的多元醇酯，其由具有5-8个碳原子和至少2个羟基的多元醇与至少一种具有7-12个碳原子的直链一元羧酸反应形成；
所述的重量百分含量以所述的组合物的总重量为基础。
2、权利要求1的组合物，其中所述酯的混合物包括约55-75wt％的聚新戊基多元醇酯和约25-40wt％的多元醇酯。
3、权利要求1的组合物，其中所述的聚新戊基多元醇是聚季戊四醇。
4、权利要求1的组合物，其中所述的羧酸选自C7酸和C8-C10酸及其混合物。
5、权利要求4的组合物，其中所述的羧酸包括小于5wt％的支链酸。
6、权利要求1的组合物，其中所述的聚新戊基多元醇酯由含有约65-85摩尔％的C7酸的直链羧酸与平衡量的C8-C10酸反应形成。
7、权利要求1的组合物，其中所述的多元醇酯由具有3个羟基的多元醇反应形成。
8、权利要求1的组合物，其中所述的多元醇酯是三酯。
9、权利要求9的组合物，其中所述的多元醇是三羟甲基丙烷。
10、权利要求1的组合物，其中用于形成多元醇酯的所述羧酸是C8-C10直链酸。
11、权利要求1的组合物，其中所述的C8-C10直链酸包括小于5wt％的支链酸。
12、权利要求1的润滑剂组合物，其中所述的多元醇酯是由三羟甲基丙烷与C8-C10的直链酸反应形成的反应产物。
13、权利要求1的组合物，其中所述聚新戊基多元醇酯是由聚季戊四醇与C7和C8-C10的直链酸的混合物反应形成的反应产物。
14、权利要求1的组合物，其进一步包括有效量的每一种的抗氧化剂、锈抑制剂和黄铜缓蚀剂中的至少一种。
15、权利要求16的组合物，其中所述抗氧化剂是仲芳基胺，所述黄铜缓蚀剂是三唑衍生物，和所述锈抑制剂是氨基酸衍生物和取代的伯和仲胺和/或二胺的混合物。
16、权利要求14的组合物，其中所述锈抑制剂是氨基酸衍生物及取代伯和仲胺和/或二胺的混合物。
17、权利要求15的润滑剂组合物，其中所述伯胺和/或二胺是取代的丙基二胺。
18、权利要求15的润滑剂组合物，其中所述仲胺是取代的乙氧化胺。
19、权利要求15的润滑剂组合物，其中所述伯胺是用脂取代的。
20、权利要求15的润滑剂组合物，其中所述仲胺是用脂取代的。
21、一种润滑剂组合物，其包括至少一种新戊基多元醇酯，该新戊基多元醇酯与有效量的含有氨基酸衍生物和取代的伯和仲胺的混合物的锈抑制剂相混合。
22、一种用于改进新戊基多元醇酯润滑剂的防腐蚀性的添加剂组合物，其包括有效量的N-酰基-N-烷氧基烷基天冬氨酸酯和至少一种取代的伯和仲胺和/或二胺。
23、一种冷却和润滑压缩机的方法，其包括被冷却和润滑的压缩机的活动部件与有效量的合成润滑剂相接触，该合成润滑剂包括通过混合下列组分形成的酯的混合物：
(i)聚新戊基多元醇和至少一种具有7-12个碳原子的一元羧酸的反应产物，和(ii)具有至少2个羟基的多元醇和具有7-12个碳原子的至少一种一元羧酸的反应产物。
24、权利要求23的冷却和润滑压缩机的方法，其中所述的压缩机是旋转螺杆压缩机。
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