CN1174879A - 可生物降解的双循环发动机油组合物的酯基料 - Google Patents

可生物降解的双循环发动机油组合物的酯基料 Download PDF

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CN1174879A
CN1174879A CN97111489A CN97111489A CN1174879A CN 1174879 A CN1174879 A CN 1174879A CN 97111489 A CN97111489 A CN 97111489A CN 97111489 A CN97111489 A CN 97111489A CN 1174879 A CN1174879 A CN 1174879A
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base stocks
ester
acid
eater base
basically
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CN1057113C (zh
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S·C·拉克斯
H·G·斯托沛尔
B·J·贝麦史
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Henkel Corp
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Henkel Corp
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Abstract

提供用于水冷却的或空气冷却的双循环发动机的包括可生物降解的酯基料的润滑剂组合物。

Description

可生物降解的双循环 发动机油组合物的酯基料
本发明涉及双循环发动机油组合物及其组分酯基料。本发明的组合物不需要任何增强混溶性溶剂并易于生物降解。
双循环(二冲程)发动机作为以下一些机械上的动力源很受欢迎：外装马达、扫雪机、机动自行车和各种绿化装置。例如，割草机，链锯、弦线式修剪机和鼓风机。双循环发动机的广泛应用主要是由于它们简单的设计和轻质量的构造，提供高能量输出并在低温下快速发动动的能力和相对低的花费。
双循环发动机使用按规定比例的汽油和润滑油混合物进行运转。润滑油必须在苛刻的操作条件下提供满意的运转性能，用于双循环发动机的润滑油通常是由矿物油或合成的碱性液体，运转添加剂和溶剂(通常相对低沸点的石油馏出液)组成，以增强汽油/润滑油的混溶性。
最新发展的用于减少四循环轿车和卡车发动机废气排出的技术不能成功地适应于双循环发动机。因此，公众更加关注从这些小型发动机中排出的高水准的碳氢化合物，因为碳氢化合物不容易生物降解。
碳氢化合物排放是发动机基本设计的结果。例如，在一典型的双循环发动机动力冲程中，空气、石油和燃料被吸入到曲柄箱中作为合并的进料被压入活塞上的空间。在排气冲程中，燃烧过的气体从排气口排出，新的易燃物料从曲柄箱中被转移到活塞上的空间。因为排气口在新的易燃物料的转移进行之前打开，之后并闭，所以高达20％的新的易燃物料未燃烧就被排出了。结果碳氢化合物排放远远高于可比较的四循环发动机的排放标准。
水冷却外装马达将废气直接排到水中，引起污染，其它前面提到的装有空气冷却双循环发动机的设备产生的废气造成了严重的空气污染问题。例如，加利福尼亚空气研究会(the California Air Re-search Board)曾测定过，许多双循环发动机每马力小时产生的污染高达卡车发动机的五十倍。
当润滑油中存在挥发性的有机溶剂时，上述污染问题更加重了。更严重的是，一些作为混溶性增强剂的溶剂，例如干洗溶剂汽油，具有相当低的闪点，因此产生了潜在的火灾危险，需要在储存和运输这些物质时给以特别的留心。
因此，需要有一种双循环发动机油组合物，它被配制后以便通过阻止有害碳氢化合物排放到环境中来防止污染，并减少含有溶剂的润滑油的潜在危险，特别是在储存和运输时的危险。这些目标必须要实现，然而，同时满足严格的运转标准，例如，优良的润滑性和去污力，特别是在活塞环上的润滑性和去污力，优异的抗滞塞性能和高的抗凝胶/絮凝作用和在操作条件的适宜范围内提供最佳的润滑油和燃料的混溶性。
根据本发明，提供了一种生物可降解的酯基料和含有同样基料的适用于水冷却和空气冷却双循环发动机的双循环发动机油组合物。本发明的油组合物被配制后以便不需要普通的溶剂，因而实际上不仅减少了用它润滑的双循环发动机的潜在污染，而且减少了含有溶剂的配制料的固有的危险。
根据本发明的一个实施方案，提供了一种用于双循环发动机油组合物的酯基料。它基本上是由(a)和(b)的混合物组成，其中(a)第一种多羟基化合物的酯，包括作为它的反应成分的新戊基多元醇和C6-C20支链饱和单羧酸，以及(b)第二种多羟基化合物的酯，包括作为它的反应成分的新戊基多元醇和选自至少一种C5-C10直链饱和单羧酸或至少一种C16-C20直链或支链不饱和单羧酸的羧酸。
根据本发明的另一实施方案，提供了用于双循环发动机油组合物的一种酯基料，它基本上是由(a)和(b)的混合物组成，其中(a)第一种多羟基化合物的酯，它包括作为它的反应成分的新戊基多元醇和C8-C10直链饱和单羧酸，以及(b)第二种复杂多羟基化合物的酯，包括作为它的反应成分的新戊基多元醇，C6-C12二元羧酸和C5-C10直链或支链饱和单羧酸。
如果需要，可将溶剂替代物任意地引入到本发明的酯基料中。适于这种目的的是任何不同的较低分子量的酯类，它包括作为它的反应成分的C8-C13直链或支链一元醇和C5-C12直链或支链羧酸。
本发明的酯基料的特征在于与迄今使用的双循环发动机润滑油基料相比，它们具有优越的生物可降解性，闪点和粘度性能。本发明的酯基料的生物降解能力按CEC-L-33-T-82测定高于80％。本发明的每一种酯基料具有至少175℃的闪点。本发明的酯基料的动力学粘度在100℃时低于15厘沲。
本发明的双循环发动机油组合物是由上述的基料或任何现有技术中已知的运转添加剂包装料组成，优选无尘去污/分散添加剂，例如多胺和较长链脂肪酸的反应产物。除了具有上面提到的所需要的生物可降解能力。闪点和粘度性质外，本发明的双循环发动机油组合物具有优良的与汽油的混溶性(燃料/油比例在16∶1到100∶1之间)。
A.酯基料
本发明优选的双循环发动机油基料是基本上由通过新戊基多羟基化合物与C6-C20支链饱和单羧酸反应形成的第一种多羟基化合物酯，和通过新戊基多羟基化合物与选自由(i)至少一种C5-C10直链饱和单羧酸或(ii)至少一种C16-C20直链或支链不饱和单羧酸的羧酸反应而形成的第二种多羟基化合物酯所组成的混合物。
适宜的用于制备上述酯混合物的新戊基多羟基化合物包括：三羟甲基乙烷、三羟甲基丙烷、双三羟甲基丙烷、季戊四醇、二季戊四醇、新戊基二醇和两种或多种这些新戊基多羟基化合物的混合物。在刚才提到的优选的酯混合物的两种组分中，三羟甲基丙烷作为新戊基多羟基化合物反应物是特别优选的。
可以用于形成第一种多羟基化合物酯的优选的酸类包括C16-C18的“异酸类”，异硬脂酸是特别优选的。异硬脂酸作为通过使天然的不饱和C18脂肪酸聚合而生产聚合脂肪酸时所得到的副产物，是很容易得到的商业产品，它可从Henkel corporation，EmeryGroup，Cincinnati，Ohio以商品牌号Emersol871和Emersol875得到。为了描述聚合脂肪酸的制备，可参考美国专利2,793,219和2,955,121。由不饱和脂肪酸聚合得到的聚合脂肪酸主要是由二聚酸和三聚酸构成；但也可能存在一些高级酸和未反应的单体。一部分C18单体酸在聚合过程中重排产生支链C18单羧酸产物，然后它通过蒸馏被分离出来。虽然这种C18支链产物的精确结构未被完全阐明，但其主要成分是甲基支化的异构体。
按刚才描述的方法制备的异硬脂酸可包含至多35％(重量)的饱和的和一些不饱和直链C8-C18脂肪酸。优选地，这些直链酸将组成异硬脂酸反应物的25％或更少。这些直链酸一般存在于从聚合过程中得到的异硬脂酸中，但附加的直链酸可与异硬脂酸混合只要不超过上述界限。
刚才描述的优选的酯基料中的第二种多羟基化合物酯的酸组分(i)优选从己酸、辛酸、壬酸、癸酸和两种或更多此类直链饱和单羧酸的混合物中选择。特别优选的第二种多羟基化合物酯的酸组分(i)是壬酸，或辛酸(C8)和癸(C10)酸的混合物，后者从Henkel Cor-poration，Emery Group，Cincinnati，Ohio以商品牌号Emery658很容易买到。如果需要的话，也可使用较低分子量的脂肪酸(如E-mery1210)的混合物作为酸组分(i)。
前述第二种多羟基化合物酯的酸组分(ii))优选从棕榈油酸、油酸和这样的不饱和单羧酸的混合物中选择。油酸特别优选作为酸组分(ii)。
本发明的酯基料混合物是使用传统的混合机械和技术制得的。一般，在刚才描述过的优选的酯基料中的第一种多羟基化合物酯的含量应占酯基料总重量的约10％-约65％，而混合物中存在的第二种多羟基化合物酯的含量应占酯基料总重量的约35％-约90％。
根据本发明的其它优选的酯基料是基本上由通过新戊基多羟化合物和C8-C10直链饱和单羧酸反应得到的第一种多羟基化合物酯和通过新戊基多羟基化合物、C6-C12的二元羧酸和C5-C10的直链或支链饱和单羧酸反应得到的第二种混合多羟基化合物酯的混合组成。
在制备本发明的这些另外的实施方案的酯基料时所使用的优选的新戊基多羟基化合物类基本上与那些前面提到的化合物相同。在本实施方案中，TMP是最优选的新戊基多羟基化合物。
这些另外的实施方案的第一种多羟基化合物酯的优选酸组分包括壬酸或辛酸和癸酸的混合物(例如Emery658)，壬酸(例如E-mery1202)是特别优选的。
用在制备本以明最后提到的基料的混合多羟基化合物酯类是优选使用辛酸和癸酸的混合物(如Emery658)作为混合酯的单羧酸组分和使用己二酸作为混合酯的二元酸组分。典型的辛酸-癸酸与己二酸的重量比例为约2.5∶1.0至约3.0∶1.0。
这些另外的实施方案的酯基料中的第一种多羟基化合物酯的量通常应为基料总重量的约25％-约85％，第二种多羟基化合物酯组分的量应为基料总重的约15％-约75％。
前面提到的酯基料可由相当纯试剂或工业级试剂制得，例如：混合多元醇或混合酸，试剂混合物是更经济实惠的，因为可使用商业上可买到的产品而不需要在提纯上耗资作为先决条件。
前述的酯类利用普通的酯化过程制得的。典型地，最初加到反应混合物中的酸的量要足以提供比与之反应的醇的当量过量约1.1-1.2％当量的酸。酸的当量对于本说明书来说被定义为含有一克当量的羧基的量，而醇的当量是含有1克当量的羟基的量。如果反应混合物中即包含一价的又包含二价的酸，过量的部分优选是由一价酸组成，酯化反应在升高的温度下进行，并同时除水。该反应可在共沸溶剂，如甲苯或二甲苯中回流反应物进行，以便于除水。可以使用酯化反应催化剂，但对于该反应不是必需的。反应完成后，过量的酸和溶剂可以方便在通过真空汽提或蒸馏从酯产物中分离出来。
这样制备的酯产物可直接使用，或者它用碱精制或另外被处理以减少酸值，除去催化剂残留物，减少灰分含量或其它一些不需要的杂质。如果酯产物经过碱精制，那么在根据本发明将酯作为基料和(或)润滑剂使用之前，得到的产品应该用水洗涤以除去任何未反应的过量的碱和少量的从过量的、被中和的脂肪酸形成的皂。
如果需要的话，本发明的酯基料可以任意包括较低分子量的酯作为溶剂替代物以增强燃料/油的混溶性。溶剂替代物-酯可以由选自辛醇、壬醇、癸醇、十一烷醇、十二烷醇、十三烷醇以及它们的支链异构体的一元醇与选自戊酸、己酸、庚酸、辛酸、壬酸、癸酸、十一烷酸、月桂酸以及它们的支链异构体的羟酸的反应来制得。
B.双循环油组合物
在配制本发明的双循环油组合物时，不同的去污/分散添加剂包装料可与前述的酯基料合并。无灰的或含灰分的添加剂可用于此目的，无灰添加剂是优选的。
适宜的无灰添加剂包括聚酰胺、链烯基琥珀酰亚胺硼酸改性的链烯基琥珀酰亚胺、酚胺和琥珀酸酯衍生物，或是此类添加剂的两种或多种的结合。
聚酰胺去污/分散添加剂，例如通常使用的四亚乙基五胺异硬脂酸盐，可通过脂肪酸同聚亚烷基多胺的反应制备，如美国专利3,169,980中所描述的那样，它的整个公开作为参考引入本说明书，就好象本文详细陈述的。这些聚酰胺可包括可测定量的环状咪唑啉，它是通过在升高的温度连续加热下将直链聚酰胺内缩合而制成的。另一种有用的聚酰胺添加剂种类是从聚亚烷基多胺和C19-C25科赫酸按照R.Hartle等人，JAOCS，57(5)：156-59(1980)中的方法得到。
链烯基琥珀酰亚胺可由下面的逐步反应过程得到，其中烯烃例如聚丁烯( Mw1200)与马来酸酐反应生成聚丁烯基琥珀酸酐加成物，然后与胺例如烷基胺或多胺反应，生成所需要的产物。
酚胺由众所周知的Mannich反应制备(C.Mannich和W.Krosche，Arch.Pharm.，250：674(1912))，包括聚亚烷基取代苯酚，甲醛和聚亚烷基多胺。
琥珀酸酯衍生物由以下的反应制得，首先是烃(例如聚丁烯( Mw1200 700-300))同马来酸酐反应生成聚丁烯基琥珀酸酐加成物，然后进一步与多羟基化合物(例如季戊四醇)反应，生成需要的产物。
适宜的含灰分去污/分散添加剂包括碱土金属(例如，Mg、Ca、Ba)，碳酸盐，磷酸盐或酚盐，或者任何两种或多种此类添加剂的结合。
上述去污/分散添加剂可引入到本文描述过的润滑剂组合物中，其用量占组合物总重量的约5％-约20％，更优选约10％-约16％。
随意地，各种其它的添加剂可引入到本发明的润滑剂组合物中，它们包括烟抑制剂(例如聚异丁烯)，极限压力添加剂(例如二烷基二硫代磷酸盐或酯)，消泡剂(例如硅油)，倾点下降剂(例如聚甲基丙烯酸酯)，防腐防蚀剂(例如三唑衍生物、棓酸丙酯或碱金属酚盐或磺酸盐)；氧化抑制剂(例如取代二芳胺，吩噻嗪、受阻酚或其它类似物)。某些此类添加剂是多功能的，例如聚甲基丙烯酸酯，它可作为消泡剂，还可作为倾点下降剂。
这些其它的添加剂可以以基于该润滑剂组合物总重量的约0.01-约15％的用量引入到该润滑剂组合物中，优选约0.01-约6％。在该特定范围内选择的用量应使得它不影响该润滑剂的所需运转性能。由此类添加剂产生的影响可容易地通过例行试验测定。
本发明的酯基料/润滑剂组合物的生物降解能力是≥80％，按照Co-ordinating European Counsel标准试验方法L-33-T-82(双冲程循环外装动机油在水中的生物降解能力)测定，该方法提供了与标准校准原料的生物降解能力对照来相对评双循环外装发动机润滑剂的生物降解能力的程序。在进行该试验程序时，包含有矿物培养基，该试验油和细菌培养液(取自城市污水处理厂的污水)的试验烧瓶以及包含有被污染的空白试样的烧瓶被培养0-21天。包含有校准油的烧瓶平行进行试验。该试验是一次三份在25±1℃和黑暗中进行。
在培养期结束后，将烧瓶中的内容物进行超声波振荡、酸化水和用四氯化碳或1，1，2-三氯三氟乙烷苹取。然后该苹取液用红外光谱分析，测得CH3-CH2-键的最大吸收在2930cm-1。
生物降解能力以％被表达为在被污染的烧瓶和相对应的试验烧瓶之间残余油含量的差别。
详细的参考次料和标准泣滑剂可在CEC Handbook ofReference/Standardization Oils for Engine/Rig Tests中找到。
按上面提到的同样CEC标准测试方法测定，本发明的酯基料的生物降解能力优选≥90％。按前述CEC标准方法，酯基料生物降解能力数值低于80％，则不认为是容易生物降解的。
本发明的酯基料/润滑剂组合物具有的闪点≥175℃，优选≥250℃。这样的闪点性质比含有增强混溶性溶剂的现有技术的酯基料(例如干洗溶剂汽油)有了决定性的改进。后者具有的闪点为约40℃。
本发明的酯基料/润滑剂组合物在100℃时具有所希望的小于15厘沲的较低粘度。在100℃的粘度优选在7-9厘沲的范围。当在100℃粘度高于15厘沲时，则在-25℃与之对应的粘度使得在汽油中酯基料/润滑剂的混溶性降低。
本发明的双循环发动机油组合物与汽油的混溶性，当燃料/油比例为16∶1-100∶1时相对于对比油一般是≤110％，这是通过ASTM-4682对于如SAE J1536中所列的Category3，使用Citgo-93738作为对比油测得的。
当与适宜的燃料混合后，本发明的双循环发动机油组合物特别适用于运转外装马达、扫雪机、机动自行车、割草机、链锯、弦线式修剪机，等等。
下面的例子描述了实施本发明的特定的酯基料和润滑剂组合物。下面例举的基料和组合物代表了本发明者设想的实施本发明的最佳方法。这些实施例仅为说明目的而提供的，而决不限制本发明的范围。
实施例1
根据本发明，无溶剂可生物降解的酯基料混合物是由三异硬脂酸三羟甲基丙酯(约42％(wt))和三壬酸三羟甲基丙酯(约8％(wt))制得。所得混合物具有的曲型特性在下表I中列出，同时确定了测定这些特定的特性的方法。
                                             表1
               性  能     特  性         方  法
  粘度，厘沲100℃40℃粘度指数粘度，赛波特通用粘度计流出秒数(SUS)210℃100℃粘度，厘泊-25℃闪点，℃倾点，℃酸值，mg KOH/gm羟值，mg KOH/gmNoack挥发性，％损失生物降解能力比重，60/60°F密度，英磅/加仑，60°F(15.6℃) 6.937.114849.5188.92425265-370.72.52.2客易生物降解0.93197.76     ASTM D-445ASTM D-2270ASTM D-2161ASTM D-2983ASTM D-92ASTM D-97ASTM D-974Emery 116.02CEC-L-40-T-87ASTM D-1298CEC-L-33-T-82
*根椐CEC-L-33-T-82标准试验方法高于80％
当约20％-约60％(wt)的三异硬脂酸三羟甲基丙酯与约40％-约80％(wt)的三壬酸三羟甲基丙酯混合时，可获得具有大致与表I所列相同的性质的酯基料。
具有突出的运转性能的双循环发动机油组合物是通过将85％(重量)的本文所描述的特定酯基料混合物与15％(重量)可从Lubri-zolCorp.在Luvrizol400 Additive System商品名下购得的无灰去污/分散添加剂进行结合而制得。
所得润滑剂组合物的典型特性和这些特性的评价标准列在下表II中。
                           表2
          性  能     特 性       方  法
    粘度，厘沲100℃40℃粘度指数闪点，℃倾点，℃Noack挥发性，％损失酸值，mg KOH/gm羟值，mg KOH/mg颜色，GTBN，mg KOH/mg％氮氯，ppm生物降解能力 9.0455.5143257-364.70.598.0122.940.166≥80％     ASTM D-445ASTM D-2270ASTM D-92ASTM D-97CEC-L-40-87TASTM D-974AOCS Cd 13-60AOCS Td 1a-64TASTM D-2896ASTM D-3228ASTM D-1317CEC-L-33-T-82
在the Southwest Research Institute成功地完成了验证试验方法之后，本文描述的特定的润滑剂组合物已被the National Ma-rine Manufactures Association(NMMA)证明为TC-W3TM。这些测试方法和所得结果总结在下表III中。
                                  表3
A.小型试验        结果试样(对比样)/评价 试验方法    评价标准
浊点，℃相容性Brcokfield@-25℃(流体)厘泊混溶性(转化@-25℃)锈试验，％过滤性，％变化   -29澄清5130/通过75(95)/通过3.16(4.04)/通过+6.5/通过+6.5/通过 ASTM D-2500独立地与每一种对比油(*，**)混合后均匀并存放48小时ASTM D-2983低于7500厘泊比对比油(*)更多的转化不超过10％NMMA方法，等于或大于对比(*)NMMA方法，流动性降低不超过20％
                                       表3(续)
B.发动机试验         结果试样(对比样)/评价 试验方法    评价标准
1.0MC发动机试验40马力试验(98小时)平均活塞光泽上活塞环卡住70马力试验(100时)平均活塞沉积第二活塞环卡住2.水星15马力试验(100小时)擦伤轴承粘滞性 9.2(8.9)/通过10.0(9.5)/通过6.5(5.0)/通过9.6(7.6)/通过通过通过通过 低于对比油(*)的同样额定值不少于0.6等于或大于对比油(***)的同样额定值)100小时没有卡住活塞环，外加：a)在充许的限度有擦伤(30％)b)不需很容易从活塞销下
                                     表3(续)
B.发动机试验          结果试样(对比样)/评价       试验方法    评价标准
压缩损失综合评价3.雅马哈发动机试验CE50S紧固/光滑试验扭矩降，英磅/英寸CE50S预燃试验(100小时)主预燃         通过通过5.18(5.43)/通过1(1)/通过   c)20psi最大值压缩损失(每5次试样试验，一对比样(***)试验)在90％准确度内等于或大于对比油(**)等于或大于对比油
*    Citgo-93738(TC-W II对比油)
**   XPA-3259
***  OR-71591
实施例2
具有与上述实施例相似特性的无溶剂、可生物降解酯基料是通过用三羟甲基丙烷与辛酸和癸酸的混合物(Emery658)反应得到的酯代替实施例1中的三壬酸三羟甲基丙酯。特别是由49％(重量)的三异硬脂酸三羟甲基丙酯与51％(重量)的上述替代酯组成的混合酯表现出很好的性能。
可从约15-约55wt％的三异硬脂酸三羟甲基丙酯与约45-约85wt％的由三羟甲基丙烷和壬酸-癸酸混合物反应得来的酯的混合物制得具有相似的特性的酯基料。
双循环发动机油组合物是从本文所描述的特定的酯基料和与上面实施例1中使用的相同量的同类添加剂制得。根据ASTM D-4682，含有本文所描述的特定的润滑组合物的燃料-油混合物表现出良好的混溶性。
实施例3
无溶剂、可生物降解的酯基料是从三异硬脂酸三羟甲基丙酯(约75％wt.％)和三油酸三羟甲基丙酯(约25wt.％)制得，这样得到的酯基料具有的特性列于表IV。
                                  表4
   性    能     特 性      方  法
 粘度，厘沲100℃40℃粘度，厘泊-25℃粘度指数闪点，℃倾点，℃生物降解能力 13.2288.8926，700149293-28＞90％     ASTM D-45ASTM D-2983ASTM D-2270ASTM D-92ASTM D-97CEC L-33-T-82
表现出大致类似于于上表IV中所列出性能的酯基料可从约35-约90％(重量)的三异硬酯酸三羟甲基丙酯和约10-约65％(重量)的三油酸三羟甲基丙酯的混合物制得。
双循环发动机油组合物是从本文所描述的特定的酯基料和与上面实施例1使用的相同添加剂制得。仍按ASTM D-4682，含有本文描述过的特定的润滑剂组合物的燃料-油混合物表现出很好的混溶性。
实施例4
具有所需的生物降解、闪点和粘度性能的无溶剂、可生物降解的酯基料是从约55wt.％的三异硬脂酸三羟甲基丙酯和约45wt.％的包括作为其活性组分的三羟甲基丙烷和C5-C9直链饱和单羧酸(Emery1210LMW酸)的酯掺混而制成。具有类似的生物降解能力，闪点和粘度性能的酯基料可以由约35-70％(重量)三异硬脂酸三羟甲基丙酯和约30-约65％(重量)的由三羟甲基丙烷与上面提到的C5-C9饱和单羧酸的混合物反应制得的酯的掺混物制得。
双循环发动机油组合物是从本文所描述的特点的酯基料和实施例1中所使用的同样的添加剂制得。所得到的润滑剂组合物在100℃具有的粘度小于10厘沲，并表现出与商品双循环发动机燃料满意的混溶性。
实施例5
一系列酯基料可通过掺混三壬酸三羟甲基丙酯和由三羟甲基丙烷、辛酸-癸酸混合物(Emery658)和己二酸反应得到的混合酯而制得，其各种不同的比例范围是约25wt.％-约85wt.％的三壬酸三羟甲基丙酯，和约15wt.％-约75wt.％的混合酯，如下所示：
实施例号        5(a)    5(b)    5(c)    5(d)    5(e)
wt％混合酯      15.0    26.2    31.0    43.0    52.7
wt％三壬三羟    85.0    73.8    69.0    57.0    47.3
甲基丙酯
这些特定的掺混物的某些特性在表V中列出，同时列出了测定这些特定的特性的方法。
尽管根据某些优选的实施方案已描述和例举过本发明的各个方面，但是各种其它实施方案对于本技术领域的熟练人员来说是清楚的。因而，本发明并不限于本文特作描述和例举的实施方案，但是在不脱离所附加的权利要求的范围的情况下是能够有所变化和改进的。
                           表5
    性  能                       特  性 方 法
5(a)      5(b)      5(c)        5(d)       5(e)
  粘度，厘沲100℃40℃-25℃，cp粘度指数浊点°F倾点°F闪点°F比重°60F 6.02      7.47      8.03       10.02      11.9929.89     39.4      43.86      60.60      76.111706      ---       4440       7248       9060153       159       158        152        154-70       ---       -75        Cl/pour    Cl/pour-65       ---       -65        -65        -65500       505       505        515        515.9558     ---       .9663      ---        .9805 ASTM D-445------ASTM D-2983ASTM D-2270ASTM D-2500ASTM D-97ASTM D-92ASTM D-1298

Claims (20)

1.一种用于双循环发动机油组合物的酯基料，该基料基本上由(a)和(b)的掺混物组成，其中(a)第一种多羟基化合物酯，它包括作为其反应组分的新戊基多羟基化合物和C16-C20支链饱和单羧酸和(b)第二种多羟基化合物酯，它包括作为其反应组分的新戊基多羟基化合物和选自至少一种C5-C10直链饱和单羧酸或者至少一种C16-C20的直链或支链不饱和单羧酸的羧酸，以及该酯基料还任意地含有较低分子量的酯，它包括作为其反应组分的C8-C13直链或支链一元醇和C5-C12直链或支链羧酸，该酯基料具有如下特征：
(i)生物降解能力≥80％，按CEC-L-33-T-82测定；
(ii)闪点≥175℃；和
(iii)动力学粘度在100℃时低于15厘沲。
2.权利要求1中要求的酯基料，其中第一种和第二种酯的新戊基多羟基化合物组分是选自三羟甲基丙烷、季戊四醇、双三羟甲基丙烷、二季戊四烷、新戊基二醇、三羟甲基乙烷和两种或多种该新戊基多羟基化合物的混合物。
3.权利要求2中要求的酯基料，其中第一种酯的酸组分是异硬脂酸，和第二种酯的酸组分选自(i)己酸、辛酸、壬酸、癸酸和两种或多种该直链饱和单羧酸的混合物，或(ii)棕榈油酸、油酸和该不饱和单羧酸的混合物。
4.权利要求1中要求的酯基料，它基本上是由约10％-约65％的第一种酯和35％-90％的第二种酯组成，以该酯基料的重量为基础。
5.一种用于双循环发动机油组合物的酯基料，其基本上由约20％-约60％的三异硬脂酸三羟甲基丙酯和约40％-约80％的三壬酸三羟甲基丙酯组成，以该酯基料的重量为基础。
6.权利要求5中要求的酯基料，其基本上是由42％的三异硬脂酸三羟甲基丙酯和约58％的三壬酸三羟甲基丙酯组成，以该酯基料的重量为基础。
7.一种用于双循环发动机油组合物的酯基料，其基本上由约15％-约55％的三异硬脂酸三羟甲基丙酯和约45％-约85％的包括作为其反应组分的三羟甲基丙烷和辛酸和癸酸的混合物的酯组成，以该酯基料的重量为基础。
8.权利要求7中要求的酯基料，其基本上是由49％的三异硬脂酸三羟甲基丙酯和约51％的作为其反应组分的三羟甲基丙烷和辛酸和癸酸的混合物的酯组成，以该酯基料的重量为基础。
9.一种用于双循环发动机油组合物的酯基料，其基本上由约35％-约90％的三异硬脂酸三羟甲基丙酯和约10％-约65％的三油酸三羟甲基丙酯组成，以该酯基料的重量为基础。
10.权利要求9中要求的酯基料，其基本上是由75％的三异硬脂酸三羟甲基丙酯和约25％的三异硬脂酸三羟甲基丙酯和约25％的三油酸三羟甲基丙酯组成，以该酯基料的重量为基础。
11.一种用于双循环发动机油组合物的酯基料，其基本上是由约35％-约70％的三异硬脂酸三羟甲基丙酯和约30％-约65％的三羟甲基丙烷与C5-C9直链饱和单羧酸的混合物形成的酯组成，以该酯基料的重量为基础。
12.权利要求11中要求的酯基料，其基本上是由约55％的三异硬脂酸三羟甲基丙酯和约45％的三羟甲基丙烷与C5-C9直链饱和单羧酸的混合物形成的酯组成，以该酯基料的重量为基础。
13.一种用于双循环发动机油组合物的酯基料，该酯基料基本上由(a)和(b)的掺混物组成，其中(a)第一种多羟基化合物酯，它包括作为其反应组份的新戊基多羟基化合物和C8-C10直链饱和单羧酸和(b)第二种混合多羟基化合物酯，它包括作为其反应组分的新戊基多羟基化合物，C6-C12二元羧酸和C5-C10直链或支链饱和单羧酸；该酯基料还可任意地含有较低分子量的酯，它包括作为其反应组分的C8-C13直链或支链一元醇和C5-C12直链或支链羧酸，该酯基料具有如下特性：
(i)生物降解能力≥80％，按CEC-L-33-T-82测定；
(ii)闪点≥175℃；和
(iii)动力学粘度在100℃时低于15厘沲。
14.权利要求13中要求的酯基料，其中第一种和第二种酯的新戊基多羟基化合物是选自三羟甲基丙烷、季戊四醇、二三羟甲基丙烷、二季戊四醇、新戊基二醇、三羟甲基乙烷和两种或多种该新戊基多羟基化合物的混合物。
15.权利要求13中要求的酯基料，基本上由约25％-约85％的该第一种酯和约15％-约75％的该第二种酯组成，以该酯基料的重量为基础。
16.权利要求15中要求的酯基料，基本上由约85％的三壬酸三羟甲基丙酯和约15％的混合多羟基化合物酯组成，该混合多羟基化合物酯包括作为其反应组分的三羟甲基丙烷和基本上由辛酸和癸酸，和己二酸组成的酸混合物，其中辛酸和癸酸对己二酸的重量比在2.5∶1.0至3.0∶1.0的范围内，该百分数量以该酯基料的重量为基础。
17.权利要求15中要求的酯基料，基本上由约75％的三壬酸三羟甲基丙酯和约25％的混合多羟基化合物酯组成，该混合多羟基化合物酯包括作为其反应组分的三羟甲基丙烷和基本上由辛酸和癸酸，和己二酸组成的酸混合物，其中辛酸癸酸对己二酸的重量比在约2.5∶1.0至3.0∶1.0的范围内，该百分数量以该酯基料的重量为基础。
18.权利要求15中要求的酯基料，基本上由约70％的三壬酸三羟甲基丙酯和约30％的混合多羟基化合物酯组成，该混合酯包括作为其反应组分的三羟甲基丙烷和基本上由辛酸和癸酸，和己二酸组成的酸混合物，其中辛酸-癸酸对己二酸的重量比在2.5∶1.0到3.0∶1.0的范围内，该百分数量以该酯基料的重量为基础。
19.权利要求15中要求的酯基料，基本上由约55％的三壬酸三羟甲基丙酯和约45％的混合多羟基化合物酯组成，该混合酯包括作为其反应组分的三羟甲基丙烷和基本上由辛酸和癸酸，和己二酸组成的酸混合物，其中辛酸-癸酸对己二酸的重量比在2.5∶1.0到3.0∶1.0的范围内，该百分数量以该酯基料的重量为基础。
20.权利要求15中要求的酯基料，基本上由约45％的三壬酸三羟甲基丙酯和约55％的混合多羟基化合物酯组成，该混合酯包括作为其反应组分的三羟甲基丙烷和基本上由辛酸和癸酸，和己二酸组成的酸混合物，其中辛酸-癸酸对己二酸的重量比在2.5∶1.0到3.0∶1.0的范围内，该百分数量以该酯基料的重量为基础。
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