CN1188502C - 可生物降解的植物油组合物 - Google Patents

可生物降解的植物油组合物 Download PDF

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Publication number
CN1188502C
CN1188502C CNB018118666A CN01811866A CN1188502C CN 1188502 C CN1188502 C CN 1188502C CN B018118666 A CNB018118666 A CN B018118666A CN 01811866 A CN01811866 A CN 01811866A CN 1188502 C CN1188502 C CN 1188502C
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Prior art keywords
oil
composition
acid
carbon atoms
modification
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CN1439045A (zh
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威廉·W·加米尔
亚当·W·罗托多
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Renewable Lubricants Inc
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Renewable Lubricants Inc
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Abstract

一种组合物，包括：A)至少一种(I)式的甘油三酯油，其中R1、R2和R3是含有约7～约23个碳原子的脂肪烃基；B)降凝剂包括(1)烷基化聚苯乙烯或(2)聚烷基甲基丙烯酸酯；和C)一种抗氧化剂，其包括(II)式的胺，其中R4为(III)，R5为氢、烷芳基或芳烷基，R6为一种芳基、烷芳基或芳烷基，条件是当R5为氢时，R4为一种芳基。可选择地，A)、B)和C)组合物可以进一步包括D)其它油。

Description

可生物降解的植物油组合物
技术领域
本发明涉及可生物降解润滑剂组合物，其由植物油甘油三酯以及降凝剂和胺类抗氧化剂制成。这些润滑剂组合物可以用于润滑发动机、变速器、齿轮箱以及用于液压。这种组合物提供了抗氧稳定性以及低温性能。这些组合物也可用作要求具有氧化稳定性和耐低温性的生物可降解油脂或其它可降解润滑剂组合物的基本原料，如用于渗透组合物和金属加工组合物。
背景技术
植物油是一种可由可再生资源大量获得的并且普遍具有容易生物降解或“环保”的特征的一类物质。所以，这类油在广泛应用方面具有潜在的吸引力。
植物油用于润滑并不是十分理想。许多植物油不具有关于倾点、氧化稳定性以及与其它辅助剂的兼容性这一系列的理想特征。然而，植物油也有许多用作润滑剂的优良特征。特别是，植物油普遍具有良好的边界润滑性、良好的粘度、高粘度指数以及高闪点。除此之外，植物油一般是无毒的和易于生物降解的。例如，在标准测试条件(如OCED 301D测试方法)下，普通的植物油在28天内将有可达80％的部分降解成二氧化碳和水，而其它普通石油基润滑液体的降解率为25％或更少。
美国专利4,783,274(Jokinen等，1998年11月8日)涉及一种无水油性润滑剂，这种润滑剂以植物油为基础代替矿物润滑油，并且其主要成份甘油三酯是饱和和/或不饱和的C10～C20直链脂肪酸和甘油醇的酯类。这种润滑剂的特征在于其含有至少70％重量的甘油三酯，其中甘油酯的碘价至少为50，并且不超过125，其粘度指数至少为190。润滑油也可以含有由所述甘油三酯或相应的甘油三酯通过热聚合而制得的聚合物，该聚合物可以替代上述的甘油三酯或与其一同作为润滑油的基本组份。润滑油可以含有辅助剂如溶剂、脂肪酸衍生物，特别是它们的金属盐、有机的或无机的，天然的或合成的聚合物，以及惯用的润滑辅助剂。
美国专利5,298,177(Stoffa，1994年3月29日)公开了一种官能液，其包括：
(A)至少一种甘油三酯；
(B)至少一种清洁剂—抑制剂辅助剂；和
(C)至少一种粘度改性辅助剂，并进一步含有
(D)至少一种合成油。
美国专利5,388,471(Lal，1994年8月16日)涉及具有至少60％的单一不饱和成分的植物油，以及进行过酯交换并且含有至少一种降凝剂的植物油。除了降凝剂，植物油和酯交换产品也含有一种性能助剂，其目的在于提高植物油和酯交换产品在用作液压流体，两循环(两冲程)内燃机，齿轮油和客车发动机用油时性能。
美国专利5,399,275(Lange等，1995年3月21日)涉及具有粘度系数改进特征的甘油三酯，其中，甘油三酯油具有有至少60％的单一不饱和成分。含有该粘度改进剂的甘油三酯油可用作客车发动机用油(PCMO)、齿轮油、汽车变速器流体(ATF)、液压流体、链条润滑剂、用于机械操作的导轨润滑剂、柴油机用润滑剂以及拖拉机用流体。
美国专利5,413,725(Lal等，1995年5月9日)涉及具有至少60％的单一不饱和成分以及含有至少一种降凝剂的植物油。除降凝剂外，植物油也可含有一种性能助剂，其目的在于提高植物油和酯交换产品在用作液压流体，两循环(两冲程)内燃机，齿轮油和客车发动机用油时性能。
美国专利5,538,654(Lawate等，1996年7月23日)描述了一种食品等级的润滑剂组合物，该组合物可以用作液压油、齿轮油以及用于食品服务工业设备的压缩机用油。这种组合物包括(A)主要为基因改性的植物油和(B)少量性能助剂。在其它实施例中，该组合物含有(C)一种磷化合物或(D)一种非基因改性的植物油。
美国专利5,641,734(Naegely，1997年7月24日)描述了一种用于链条锯的链条润滑剂的润滑剂组合物，其包括：
(A)至少一种甘油三酯，其中油酸部分：亚油酸部分为约2到约90；
(B)至少一种粘度改进助剂；和
(C)至少一种增粘剂。
可选择地，组合物也可包含
(D)至少一种降凝剂和；
(E)至少一种耐磨剂。
发明内容
一种组合物，包括：
(A)至少一种下式的甘油三酯
其中R1、R2和R3是含有约7～约23个碳原子的脂肪烃基；
(B)降凝剂，包括
(1)烷基化聚苯乙烯或
(2)聚烷基甲基丙烯酸酯；和
(C)一种抗氧化剂，其包括下式的胺
其中R4为
Figure C0181186600072
R5为氢、烷芳基或芳烷基，R6为一种芳基、烷芳基或芳烷基，其满足当R5为氢时，R4为芳基。
可选择地，(A)、(B)和(C)组合物可以进一步包括
(D)其它油，其包括：
(1)一种合成酯基油或
(2)一种聚α-烯烃。
具体实施方式
(A)甘油三酯油
在本发明的实践中，基油是一种合成的甘油三酯或下式的天然油
Figure C0181186600081
其中，R1、R2和R3是含有约7～约23个碳原子的脂肪族烃基。此处使用的“烃基”表示有一个碳原子直连接在分子剩余部分的自由基。脂肪烃基包括如下：
(1)脂肪族烃基；即，烷基如庚基、壬基、十一烷基、十三烷基、十七烷基；含有一个双键的烯烃基如庚烯基、壬烯基、十一烯基、十三烯基、十七烯基、二十一烯基；含有2或3个双键的烯烃基如8，11-十七二烯基和8，11，14-十七三烯基。也包括所有上述物质的异构体，但是优选为直链基。
(2)取代脂肪烃基；即非烃取代基。在本发明中，非烃取代物基没有改变主要的烃基的特性。业内技术人员可以领会到适当的取代物；取代物的例子如羟基、烷氧羰基(carbalkoxy)(特别是低链烷氧羰基carbalkoxy)和烷氧基(特别是低链烷氧基)，“低链”表示含有不大于7个碳原子的基团。
(3)杂基，即，在本发明范围内的主要具有脂肪烃特性时，可以在本由脂肪族碳原子组成的链或环上含有非碳的原子。对于业内人士杂原子的选择是比较容易的，如氧、氮和硫。
适合于本发明使用的甘油三酯油是植物油和改性的植物油。植物油甘油三酯是天然产生的油类。“天然产生”意味着是从其中获得油的种子没有经过任何的基因改变。进一步，“天然产生”意味着所获得的油没有进行过改变其双-或三-不饱和特性的氢化处理和任何化学处理。本发明所利用的天然产生的植物油包括至少一种大豆油、油菜籽油、葵花油、椰子油、lesquerella油、芥末油、花生油、玉米油、棉籽油、棕榈油、红花油、meadowfoam或蓖麻油。
甘油三酯油也可以是改性的植物油。甘油三酯油可以通过化学或基因进行改性。对天然产生的甘油三酯的氢化是化学改性的主要方法。天然产生的甘油三酯具有不同的脂肪酸组成。天然产生的葵花油的脂肪酸组成为
              棕榈酸70％
              硬脂酸4.5％
              油酸  18.7％
              亚油酸67.5％
              亚麻酸0.8％
              其它酸1.5％
通过氢化方法对葵花油进行化学改性，意味着氢和不饱和脂肪酸如油酸、亚麻酸和亚油酸进行反应。目的不是去掉所有的不饱和键。进一步，其目的并不是氢化油酸组成来而使其还原为硬脂酸组成。通过氢化的化学改性的目的是使亚油酸组成的大部分还原或转化为油酸组成。天然产生的葵花油的亚油酸的含量占67.5％。化学改性的目的是对亚油酸进行氢化而使其含量降低到约25％。这意味着油酸的组成从约18.7％增加到约61％(原来18.7％的油酸组+从亚油酸氢化的42.5％的油酸)。
氢化是植物油和氢气在催化剂存在条件下的反应。最普遍使用的催化剂是镍催化剂。这种处理结果是将氢加成到油上，从而降低了亚油酸和亚麻酸的含量。仅仅不饱和脂肪酸组分参与了氢化反应。在氢化反应中，其他的反应也可能发生，如双键转移到新的位置并且由顺式纽转成具有更高熔点的反式。
表1显示了从天然选择的植物油的油酸(18∶1)、亚油酸(18∶2)和亚麻酸(18∶3)组成。可以通过氢化对甘油三酯的亚油酸组成大部分进行化学改性而使油酸组成提高到60％以上。
                  表1
油 18∶1  18∶2  18∶3
玉米油 25.4  59.6  1.2
棉籽油 18.6  54.4  0.7
花生油 46.7  32.0  --
红花油 12.0  77.7  0.4
大豆油 23.2  53.7  7.6
葵花油 18.7  67.5  0.8
基因的改进是对种子储备进行的。丰收的农作物含有一种甘油三酯，其榨取物中具有较高的油酸组成和较低的亚油酸组成时，。参照上面的表1，自然产生的葵花油具有18.7％的油酸。基因改性的葵花油具有81.3％的油酸组成和9.0％的亚油酸。也可以对表1所列的各种植物油进行基因改性来获得大于90％的油酸组成。化学改性的植物油包括至少一种化学改性的玉米油、化学改性的棉籽油、化学改性的花生油、化学改性棕榈油、化学改性蓖麻油、化学改性芥末油、化学改进油菜籽油、化学改进红花油、化学改进大豆油和化学改进葵花油的至少一种。
在优选的实施例中，脂肪族烃基R1、R2和R3是含有至少60％，优选为70％，更优选为80％的单一不饱和性的甘油三脂。在本发明中利用的甘油三酯通过基因改性而含有比一般油酸含量高的植物油来说明。一般的葵花油具有25-30％的油酸含量。通过对葵花种子的基因改性，获得的葵花油中油酸的含量从约60％提高到约90％。也就是说，R1、R2和R3基团是十七烯基，并且R1COO-、R2COO-和R3COO-是连接在1，2，3-丙三基CH2CHCH2上的油酸分子的残余部分。美国专利4,627,192和美国专利4,743,402公开的高油酸葵花油的制备在此一并引入作为参考。
例如，只包括油酸部分的甘油三酯具有100％的油酸含量和因而含有100％的单一性不饱成分。当甘油三酯是由70％的油酸、10％的硬脂酸、13％的棕榈酸和7％的亚油酸组成时，单一性的不饱和成分为70％。优选的甘油三酯油为高油酸，即基因改性的植物油(至少60％)的甘油三酯油。在本发明中，普通利用的高油酸植物油是高油酸红花油、高油酸芥末油、高油酸花生油、高油酸玉米油、高油酸油菜籽油、高油酸葵花油、高油酸棉籽油、高油酸lesquerlla油、高油酸棕榈油、高油酸蓖麻油、高油酸meadowfoam和高油酸大豆油。芥末油是含有1％芥酸的油菜籽油的一类油。优选的高油酸植物油是从Helianthus sp获得的高油酸葵花油。这种产品由AC Humko，Cordova，TN，38018生产如TriSunTM高油酸葵花油得到。另一种高油酸植物油是由Brassica campestris或Brassica napus生产，也由AC Humko生产如RS高油酸芥末油。RS80油表示一种芥末油，其中，其酸的部分含有80％的油酸。
进一步注意，基因改性的植物油具有以双-和三-不饱和酸为代价的高油酸含量。正常的葵花油具有20-40％的油酸部分和50-70％亚油酸部分。这表明正常葵花油单-和双-不饱和部分(20+70)或(40+50)的含量为90％。本发明的基因改性的植物油产生一种低链的双或三-不饱和部分的植物油。本发明的基因改性油的油酸部分：亚油酸的比例为2-90左右。甘油三酯的60％的油酸部分和30％的亚油酸部分的比为2。由80％的油酸部分和10％的亚油酸部分组成的甘油三酯油的比为8。由90％的油酸部分和1％的亚油酸甘油三酯油部分组成的甘油三酯油的比为90。正常花生油的比为0.5(30％的油酸部分和60％的亚油酸部分)。
(B)降凝剂
在低温时，植物油存在一种自然变稠现象，特别是具有高度单一不饱性成分的植物油。这类似于在降低温度时蜂蜜或糖蜜的变稠现象。为了维持植物油在降低温度下“倾倒”或“流动”，就需要加入降凝剂。在本发明中的所用的降凝剂是烷化聚苯乙烯和聚甲基丙烯酸烷基酯。
在制备烷化聚苯乙烯时，可有两种不同的反应途径。第一途径是将烷基氯或烯烃与苯乙烯反应形成烷化苯乙烯。然后将烷化苯乙烯聚合形成烷化聚苯乙烯。第二条途径是将苯丙烯聚合形成聚苯乙烯，将丙烯或丁烯或其混和物聚合形成聚丙烯或聚丁烯或其混和物，也叫作聚烯烃。然后将聚苯乙烯与聚烯烃进行烷基化形成烷基化的聚苯乙烯。
在烷化聚苯乙烯类中，优选的降凝剂是Keil-FloTM150，由FerroCorporation-Petroleum Additives，3000 Sheffield Avenue，Hammond，Indiana46327生产。
有本发明中适用的聚烷甲基丙烯酸酯是通过C1-C30的甲基丙烯酸酯的聚合来制得。这些聚合物的制备可以进一步包括使用具有含氮官能团、羟基团和/或烷氧基团的丙烯酸单体，这些基团提供了聚烷甲基丙烯酸酯的其它特性如提高其分散性。聚烷基甲基丙烯酸酯优选为具有从10000-250000，更优选为从20000-200000数均分子量。聚烷基甲基丙烯酸酯也可以通过传统的自由基或阴离子聚合方法来制备。在聚烷基甲基丙烯酸酯类中，优选的降凝剂是RohMax，USA，Delran，NJ 08075生产的EF171。
(C)胺类抗氧化剂
本发明利用的抗氧化剂是下式的胺类抗氧化剂
其中R4为
和R5为氢、烷芳基或芳烷基，R6为芳基、烷芳基或芳烷基，条件为当R5为氢时，R4为芳基。
当R4为
R6优选为下式结构表示的烷芳基
Figure C0181186600131
和R7为含有1-4个碳原子的脂肪基。
R7优选为由结构 表示的含有2个碳原子的脂肪基团。
优选的胺类抗氧化剂为下式表示的苯乙烯化二苯基胺
Figure C0181186600133
如由Goodyear，Akron，OH44316生产的Wingstay@29。
在其它优选胺类抗氧化剂中，R5为氢时，R4一定为芳基。优选烷基具有结构
Figure C0181186600134
以及该优选的胺类抗氧化剂具有结构
Figure C0181186600135
这种结构为苯基-α-萘胺(PANA)。
(D)其它油类
本发明的(A)、(B)和(C)组合物可以进一步包括其它油，其包括(D)(1)合成酯基油，(D)(2)聚α-烯烃或(D)(3)未提炼的、提炼的、再提炼的油以及(D)(1)、(D)(2)、(D)(3)两种以上的混和物。合成酯基油(D)(1)包括下列酸与醇的反应，其中，酸包括：下式表示的单羧酸
R8COOH
下式表示的二羧酸
或下式表示的芳基羧酸
R10-Ar(COOH)p
其中，R8为一含有约4-约24个碳原子的羟基，R9为氢或含有约4-约50个碳原子的羟基，R10为氢或含有1-约24个碳原子的羟基，m为从0-约6的整数，p为从1-约4的整数；醇如下式所示，
Figure C0181186600142
其中，R11为含有1-约24个碳原子的脂肪基或含有6-约18个碳原子的芳基，R12为氢或含有1-约2个碳原子的烷基，t为0-约40，n为1-约6。
在单羧酸中，R8优选为含有约6-约18个碳原子。一个说明但并没有穷举的单羧酸可例举为丁酸、己酸、辛酸、壬酸、癸酸、十一酸、十二酸、棕榈酸或硬脂酸的异构体。
在二羧酸中，R9优选为含有约4-约24个碳原子，m为1-约3的整数。一个说明但并没有穷举的二羧酸可例举为丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、顺丁烯二酸或反丁烯二酸。
作为芳基羧酸，R10优选为含有约6-约18个碳原子，p为2。用到的芳基羧酸有安息香酸、甲苯甲酸、乙苯酸、邻苯二甲酸、对苯二甲酸、间苯二甲酸、苯连三酸、三聚酸和均苯四酸。
醇中，R11优选为含有约3-约18个碳原子，t为0-约20。醇可以是单羟基的、多羟基的或者烷氧化的单羟基和多羟基的醇。单羟基的醇可以包括如伯醇或仲醇。然而优选的单羟基醇是一级脂肪醇，特别是脂肪烃醇如烯醇和烷醇。优选的衍生成R11的单羟基醇是1-辛醇、1-癸醇、1-十二醇、1-十四醇、1-十六醇、1-十八醇、油醇、亚油醇、亚麻醇、叶绿醇、十四烷醇、十二烷醇、十四烷醇月桂醇、十六烷醇、十八烷醇、二十二醇。
多羟基醇的例子包括含有2-约6个羟基的醇。例如，烷撑二醇类说明如乙二醇、二乙二醇、三乙二醇、四乙二醇、二丙二醇、三丙二醇、二丁二醇、三丁二醇、和其它烷撑二醇。适合于本发明使用的优选的醇类是含有达到12个碳原子的多羟基醇。这类醇包括丙三醇、赤藓醇、季戊四醇、二季戊四醇、葡萄糖酸、甘油醛、葡萄糖、树胶醛醣、1，7-庚二醇、2，4-庚二醇、1，2，3-己二醇、1，2，4-己二醇、1，2，5-己二醇、2，3，4-己二醇、1，2，3-丁二醇、1，2，4-丁二醇、奎尼酸、2，2，6，6-四(羟甲基)环己醇、1-10-癸二醇、毛地黄烷醇等。
另一些适用于本发明的多羟基醇类为含有3-10碳原子的多羟基醇，特别是含有3-6个碳原子的至少具有三个羟基团的多羟基醇。这种醇的例子如丙三醇、赤藻糖醇、季戊四醇、甘露醇、山梨醇、2-羟甲基-2-甲基-1，3-丙二醇(三甲基丙醇)、双-三羟甲基丙烷、1，2，4-己三醇等。
烷氧化醇可以是烷氧化单羟基醇或烷氧化多羟基醇。烷氧醇一般是由过量的烯化氧处理醇而得到，烯化氧如环氧乙烷或环氧丙烷。例如，可用约6-约40摩尔的环氧乙烷或环氧丙烷可以和脂肪醇进行缩合。
在一个实施例中，脂肪醇含有约14-约24个碳原子，其可以从长链脂肪醇如十八醇或油醇衍生。
与羧酸反应来制备合成酯所用的烷氧醇在商业上可以获得，如UnionCarbide的“TRITON”和“TERGITOL”，Vista Chemical的“ALFONIC”，Shell Chemical Company的“NEODOL”。TRITON一般为聚乙氧化烷基苯酚，这些酚可以从直链或支链烷基苯酚衍生。TERGITOL为伯醇或仲醇的聚乙二醇醚类；ALFONIC为乙氧化的线性醇相同，其可以用一般的结构
                   CH3(CH2)xCH2(OCH2CH2)nOH
表示，其中x取4-16的值，n取3-11之间的值。具有上式特性的ALFONIC乙氧化物的具体例子包括ALFONIC1012-60，其中，x为约8-10，n为约为5.7的平均值；ALFONIC1012-70，其中，x为10-12，n为约为10.6的平均值；ALFONIC1412-60，其中，x为10-12，n为约为7的平均值；以及ALFONIC1218-70，其中，x为10-16，n为约为10.7的平均值；
NEODOL乙氧化物为乙氧化醇，其中醇类为含有9-约15个碳原子的线性和支链醇类的混和物。乙氧化物可以通过醇类和过量的环氧乙烯反应来制备，如每摩尔的醇与3-12摩尔或更多的环氧乙烯反应。例如，NEODOL乙氧化物23-6.5是一种含有12-13个碳原子以及含有平均约6.5个单元的乙氧单元的线性或支链醇化物的混和物。
如上所述，合成酯基油包括将上述任意酸或其混和物与上述任意醇或其混和物以1个COOH比1个OH的比例进行酯化反应，该反应利用了现有技术的酯化工序、条件和催化剂。
生产合成酯的公司和其商品名的非穷举例子为BASF的Glissofluild，Ciba-Geigy的Reolube，JCI的Emkarote，Oleofina的Radialube以及EmeryGroup of Henkel Coporation的Emery。
聚α-烯烃类(D)(2)如烯化氧聚合物和内聚合物及其衍生物，其中端羟烃基已经通过酯化或醚化等改性变成了另一类可以使用的油。这些可以通过环氧乙烯或环氧丙烯所制得的油类说明，这些聚氧化烯聚合物(如具有约1000的平均分子量的甲基聚异丙烯乙二醚，具有500-1000分子量聚乙二醇二苯醚，具有1000-1500分子量的聚丙二醇二乙基醚等)或者其的单-及聚羧酸酯如乙酸乙酯，C3到C8脂肪酸酯混合物，或四乙二醇的C13含氧酸二酯。
未提炼的、提炼的、再提炼的油(D)(3)以及它们中的两种或者多种的混合物可以作为本发明的润滑剂组合物。未提炼的油是直接从天然或合成来源获得的，没有进行进一步的提纯处理。例如，直接从干馏操作中获得的页岩油、直接通过蒸馏获得的石油、成品油，直接经过酯化处理获得的酯油以及没有经过处理所使用的物质是未提炼油。提炼的油与未提炼的油除了在经过一次或多次提纯步骤提高一项或多项特性之外，其它的特性相同。对于业内人士来说，已知的许多提纯技术，如蒸馏、溶剂萃取、酸或碱萃取、过滤以及渗透的方法。再提炼的油是通过使用类似于得到提炼油的提炼方法而获得的，该方法是应用于已经被使用的提炼油。这种再提炼油也被称作回收或再加工油，并且通常通过其它技术处理来去掉失效的助剂和油分解产物。
本发明的组合物包括组份(A)、(B)和(C)或者(A)、(B)、(C)和(D)，其用作可生物降解的润滑剂。
当组合物包括组份(A)、(B)和(C)时，下面表明了这些组份的重量范围。
  组份 一般  优选  更优选
  (A) 50-99  65-99  90-99
  (B) 0.1-5  0.5-4  0.75-3
  (C) 0.1-5  0.1-3  0.1-2
当组份包括组份(A)、(B)、(C)和(D)时，下面表明了这些组份的重量范围。
  组份 一般  优选  更优选
  (A) 40-90  40-80  45-75
  (B) 0.1-5  0.5-4  0.75-3
  (C) 0.1-5  0.1-3  0.1-2
  (D) 1-80  10-60  25-50
可以理解，除了(A)、(B)、(C)和(D)，还可以有其它组份包含在本发明的组合物里。
本发明的组份根据上述范围混合得到溶液。虽然加入的顺序没有要求，但一般是将(B)和(C)或(B)、(C)和(D)加到(A)中。
表2是一个旋转弹内氧化试验(RBOT)(ASTM D2272)的比较。在表2中，例1和例2是100％植物油组合物的基准。其它的例子含有不同量的其它助剂。例5-7介绍了本发明和剩余的例子，它们虽不属于本发明，但可以与例5-7进行比较。在三个例子中，非本发明的例子(11-13)最好与例子5-7比较。这是由于例11和13利用了本发明的组份，还有例12是一种矿物油配方而不是植物油配方。对在全新配制的例子中，可以注意到RBOT的改进。所有的均以重量份来计算的。
                表2
实施例                 组份
    (A) (B) (C) (D) RBOT
 1 100份TriSun 90 无 无 无 16
 2 100份RS 80 无 无 无 14
 3 98.0份TriSun 90+2.0份a 无 无 无 131
 4 98.0份TriSun90+2.0份b 无 无 无 138
5 28.66份TriSun 90+28.66份RS 80 1.28份Keil Flo 150 0.3份Wingstay 290.3份PANA 20.04份PAO20.04份合成酯 261
6 33.73份TriSun 90+33.73份RS 80 1.52份Keil Flo 150 0.35份Wingstay 290.35份PANA 15.16份PAO15.16份合成酯 273
 7 67.08份TriSun 90 2.03份Keil Flo 150 0.26份Wingstay 290.26份PANA 15.25份PAO15.25份合成酯 402
 8 98.75份TriSun 90+1.25份c 无 无 无 147
 9 67.2份TriSun 90+4.0份d 无 无 28.8份合成酯 197
 10 96.0份RS 80+4.0份d 无 无 无 139
11 98.27份TriSun 90+1.0份d 无 0.365份Wingstay290.365份PANA 无 276
 12 98.75.2份矿物油+1.25份c 无 无 无 262
13 48.17份RS80+1.25份c 2.0份Keil Flo 150 0.205份Wingstay290.205份PANA 48.17份再提炼油 237
           表2
实施例                   组份
    (A) (B) (C) (D) RBOT
14 99份TriSun 90+1.0份e 无 无 无 97
15 98份TriSun90+0.65份f，0.35份g，0.85份h 无 无 无 104
16 97.8份TriSun90+1.4份f，0.8份g 无 无 无 61
17 98.15TriSun90+0.2份i，0.4份j，1.25份c 无 无 无 94
18 98.0份TriSun90+1.0份b，1.0份g 无 无 无 110
19 98.1 5TriSun90+0.65份f，0.35份g，0.85份h 无 无 无 104
20 98.6份TriSun90+0.5份j，0.9份k 无 无 无 108
21 98.65份TriSun90+0.9份j，0.32份k 无 无 无 115
22 98.15份TriSun90+0.3份j，0.3份k，1.25份c 无 无 无 149
23 98.15份TriSun90+0.3份j，0.3份1，1.25份c 无 无 无 128
a：2，6-二叔丁酚
b：无烟酚类抗氧化剂
c：含有Lubrizol Corp生产的如LZ5186B耐磨剂和抗氧化剂的完整液压组件
d：含有Lubrizol Corp生产的如LZ7653耐磨剂和抗氧化剂和降凝剂的完整商业液压组件
e：Rhein Chemie生产如AdditinRC 9308的防锈和抗氧化剂
f：烷基化二苯胺
g：丁基化羟基甲苯
h：一种含有硫或磷的有机化学助剂的耐磨剂/抗氧化剂
i：二硫代氨基甲酸酯
J：甲苯基三唑烷
k：Ciba Geigy生产的如Irganox L 135的液态酚类抗氧化剂
l：对甲酚和二环戊二烯的丁基化反应产物
表3介绍了一种微型旋转粘度计(MRV)(ASTM D4684)。MRV是一种低剪切速率测量仪器。该仪器的关键特征为测试慢的样品冷却速率。对样品预热以使其包含一个具体的加热、缓慢冷却、均温的循环的热记录，其包括。MRV测量表观屈服应力，这个应力是使油流动的最小应力。MRV也测量在1到50s-1剪切速率下的表观粘度。该过程可被发展为用于预测野外使用马达的低温泵流性。
为了测量低温特性，在多个不同温度下对本发明的组合物进行评价。例如，当评价的温度为-25℃时，表示了15个冬用级规格。下面温度表示其对应的粘度级。
-40℃                  0W
-35                    5
-30                    10
-25                    15
-20                    20
-15                  25
无论组合物在什么温度下测量时，如果要要符合要求，则粘度测量值必须低于6000，厘泊(cP)， 并且该cP越低越好。MRV是一种比标准倾点程序(ASTMD97)更严格的评价。
在表3中，例1和2是100％植物油组合物的基准。在-25℃时，例1和2太粘稠而不能测量(TVTM)，结果不合格。其它的例子含有不同量的其他助剂。例3-6是含有降凝剂的植物油，这些降凝剂并不是本发明的部分。例3-6所有的都太粘稠而不能测量，结果不合格。例7-13是包括本发明的降凝剂的植物油组合物。例7-13不仅显示了MRV测量的合格结果，而且粘度也均很好的低于6000cP这一合格/不合格的分界点。
             表3
实施例                组份
       (A)   (B)   (C)   (D)    cP     ℃
  1   100份TriSun90   无   无   无   TVTM*     -15
  2   100份RS80   无   无   无   TVTM     -20
3   98.0份RS80+2.0份m 无 无 无 TVTM -25
4   34份TriSun9034份RS80+2份n 无 无 30份合成酯 TVTM -30
5   34份TriSun90+34份RS80+2份m 无 无 30份合成酯 TVTM -25
6   68份TriSun90+2份n 无 无 30份合成酯 TVTM -25
  7   98份RS80   2份Keil Flo 150   无   无   1864     -25
  8   68份高油酸大豆油   2份Keil Flo 150   无   30份合成酯   9089     -30
  9   68份TriSun90   2份Keil F1o 150   无   30份合成酯   1861     -25
10 68份TriSun90 2份RohMax10-310 无 30份合成酯   19482730     -25-30
  11   34份TriSun90+34份RS80 2份Keil F1o 150 无 30份合成酯   15312687     -25-30
12   34份Trisun90+34份RS80 2份RohMax10-310 无 30份合成酯   15762581     -25-30
13 98份RS80+ 2份RohMax10-310 无 无   17913438     -25-30
*太粘稠而不能测量
m由Lubrizol Corp生产的LZ6662矿物油中顺丁烯二酐-苯乙烯共聚合物的酯
n由Lubrizol Corp生产的LZ7671矿物油中顺丁烯二酐-苯乙烯共聚合物的酯。
尽管以上优选的实施例对本发明作了解释，但可以理解在业内人士通过阅读说明书后是容易对其进行各种改进的。因此，这里公开的本发明就是要覆盖这样的改进以使其落入本发明的权利要求范围内。

Claims (20)

1.一种组合物，包括：
(A)至少一种下式的甘油三酯油
其中R1、R2和R3是含有约7～约23个碳原子的脂肪烃基；
(B)一种降凝剂，其包括
(1)烷基化聚苯乙烯或
(2)聚烷基甲基丙烯酸酯；和
(C)一种抗氧化剂，其包括下式的胺
Figure C018118660002C2
其中R4为
R5为氢、烷芳基或芳烷基团，R6为一种芳基、烷基芳基或芳烷基，其满足是当R5为氢时，R4为一种芳基。
2.根据权利要求1的组合物，其中在(A)中，甘油三酯油是一种天然产生的植物油。
3.根据权利要求1的组合物，其中在(A)中，甘油三酯油是一种改性的植物油。
4.根据权利要求2的组合物，其中天然产生的植物油包括至少一种大豆油、油菜籽油、葵花油、椰子油、莱斯奎拉油(lesquerella oil)、芥末油、花生油、玉米油、棉籽油、棕榈油、红花油、芒花油(meadowfoam oil)或蓖麻油。
5.根据权利要求3的组合物，其中，改性植物油是一种化学改性植物油或一种基因改性植物油。
6.根据权利要求5的组合物，其中，R1、R2和R3具有由油酸残余部分衍生的含有至少60％的单一性不饱和成分。
7.根据权利要求6的组合物，其中，化学改性的植物油包括化学改性的玉米油、化学改性的棉籽油、化学改性的花生油、化学改性的棕榈油、化学改性的蓖麻油、化学改性的芥末油、化学改性的油菜籽油、化学改性的红花油、化学改性的大豆油和化学改进葵花油的至少一种。
8.根据权利要求6的组物，其中，基因改性的植物油包括基因改性的红花油、基因改性的芥末油、基因改性的花生油、基因改性的玉米油、基因改性的油菜籽油、基因改性的葵花油、基因改性的棉籽油、基因改性的莱斯奎拉油(lesquerella oil)、基因改性的棕榈油、基因改性的蓖麻油、基因改性的芒花油(meadowfoam oil)和基因改芥末大豆油中的至少一种。
9.根据权利要求1的组合物，其中在(B)中，降凝剂是一种烷基化的聚苯乙烯。
10.根据权利要求1的组合物，其中在(C)中，R5和R6是烷芳基，其中的烷芳基是
Figure C018118660003C1
R7是含有1-4个碳原子的脂肪族基。
11.根据权利要求10的组合物，其中，R7含2个碳原子。
12.根据权利要求10的组合物，其中，R7是
Figure C018118660003C2
13.根据权利要求1的组合物，其中在(C)中，R5为氢，R4是α-萘基。
14.根据权利要求1的组合物进一步包括：
(D)其它油，其包括：
(1)一种合成酯基油或
(2)一种聚α-烯烃。
15.根据权利要求14的组合物，其中合成酯基油包括下列酸和醇的反应，其中，酸包括下式表示的单羧酸R8COOH
或下式表示的二羧酸
或下式表示的芳基羧酸
R10-Ar(COOH)p
其中，R8为一含有约4-约24个碳原子的羟基，R9为氢或含有约4-约50个碳原子的羟基，R10为氢或含有1-约24个碳原子的羟基，m为从0-约6的整数，p为从1-约4的整数；醇如下式所示，
其中，R11为含有1-约24个碳原子的脂肪基或含有6-约18个碳原子的芳基，R12为氢或含有1-约2个碳原子的烷基，t为0-约40，n为1-约6。
16.根据权利要求15的组合物，其中R8含有约6-约18个碳原子。
17.根据权利要求15的组合物，其中R9含有约4-约24个碳原子，m为0。
18.根据权利要求15的组合物，其中R9为氢，m为4。
19.根据权利要求15的组合物，其中R10含有约6-18个碳原子，p为2。
20.根据权利要求15的组合物，其中R11含有约3-约18个碳原子。
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