CN1173197A - 可生物降解支链合成酯基料和由其制成的润滑剂 - Google Patents

可生物降解支链合成酯基料和由其制成的润滑剂 Download PDF

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CN1173197A
CN1173197A CN95197399A CN95197399A CN1173197A CN 1173197 A CN1173197 A CN 1173197A CN 95197399 A CN95197399 A CN 95197399A CN 95197399 A CN95197399 A CN 95197399A CN 1173197 A CN1173197 A CN 1173197A
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acid
biodegradable
lubricant
additive
agent
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C·B·当肯
L·K·米德
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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Abstract

一种包括下面基料混合物的可生物降解的合成酯基料:(A)下面物质的反应产物:(1)具有通式R(OH)n的直链或支链醇,其中R是具有约2—20个碳原子的脂族或环脂族基团和n至少是2;和(2)包括约30—80%(摩尔)碳数在约C5-C12范围的直链酸,和约20—70%(摩尔)的至少一种碳数在约C5-C10范围的支链酸的混合酸,并且其中不大于10%的用于形成所述的可生物降解的合成酯基料的所述支链酸含有季碳;其中所述的酯基料显示出下面的性质:通过改进的Sturm试验测定,在28天至少60%生物降解;倾点低于-25℃;和-25℃的粘度低于7500cps;和(B)通过改进的Sturm试验测定在28天至少60%生物降解的另一个基料;由此,该混合产物的通过改进Sturm试验测定的在28天的生物降解性比单独的(A)或(B)更大。

Description

可生物降解支链合成酯基料和由其制成的润滑剂
本申请是1991年12月8日申请的序列号为08/351990申请的部分连续申请。
本发明总的涉及使用支链合成酯以改善可生物降解润滑剂基料的低温流动性和分散剂溶解性,而不损失生物降解作用或润滑作用。在沿着酯的酰基和/或醇部分的链支化的情况下可达到至少60%生物降解作用(用改进的Sturm试验测定)。这些支链合成酯特别适用于形成可生物降解润滑剂,该可生物降解润滑剂用于二冲程发动机油、弹射器油、水力流体、钻孔液体、水轮机油、润滑脂、压缩机油、齿轮油和其他需要或要求有生物降解生的工业和发动机应用中。特别是,本发明涉及独特的可生物降解润滑剂基料与其他酯基料的混合物,以便得到比各自基料具有更高生物降解百分比的混合基料。
本发明的背景
开发可用于分散在水路中,如河、海和湖中的可生物降解润滑剂已引起了环保界和润滑剂制造者的广泛关注。非常希望合成一种润滑剂,该润滑剂保持其低温流动性和添加剂溶解性而不损失生物降解作用或润滑作用。
用于生物降解润滑剂(例如二冲程内燃机油、放送器油、水力流体、钻孔液态、水轮机油、润滑脂和压缩机油)的基料一般应满足5个标准:(1)与分散剂和其他添加剂如聚酰胺的溶解性;(2)好的低温流动性(例如,低于-40℃的倾点;在-25℃下低于7500cps);(3)足够的生物降解性,以弥补配制的润滑剂的任何分散剂和/或其他添加剂的低生物降解性;(4)在无抗磨剂下具有好的润滑性能;和(5)高闪点(大于260℃,用COC(Cleveland开杯)用ASTM试验号D-92测定的闪点和燃点)。
经济合作和发展组织(OECD)于1979年颁布了关于降解和累积试验的试验指南草案。专家组建议应使用下列试验来确定有机化学品的“迅速生物降解性”:改进的OECD筛分试验,改进的MITIS试验(I),封闭瓶试验,改进的Sturm试验和改进的AFNOR试验。专家组还建议在28天内得到的生物降解的“合格度”可作为“迅速生物降解”的一个好的证据:对上述试验分别为(溶解的有机碳(DOC))70%;(生物需氧量(BOD))60%;(总有机碳(TOD))60%;(CO2)60%;和(DOC)70%。因此,用改进的Sturm试验在28天内得到的生物降解的“合格度”至少为(CO2)60%。
因为设定28天的试验期间的主要目的是使微生物适应化学品(滞后相)有足够的时间,所以这将使缓慢降解的化合物在相当短的适应期之后不能通过该试验。因此应检查生物降解的速度。生物降解的“合格度”(60%)必须在生物降解开始的10天内达到。当已放出10%理论上的CO2时就认为生物降解已经开始,即在28天内迅速生物降解流体应产生至少60%的CO2,并且该合格度必须在生物降解的10天内超过10%。这被称作“10天窗口(Window)”
对用改进的Sturm试验(OECD301B,1981年5月12日采用,它被引入本文作为参考)检测“迅速生物降解性”的OECD指南包括,测定被检测的试验化合物所产生的CO2量并用理论CO2(TCO2)的百分数表示,理论CO2应是由试验化合物的碳含量计算出来的,因此生物降解性表示为TCO2的百分数。改进的Sturm试验是这样进行的,即用试验物质示踪化学定义的液体介质,主要是无其他有机碳源的液体介质,并用污水微生物接种。释放的CO2作为BaCO3被捕集。参考适合的空白对比试验后,确定试验期的试验化合物产生的CO2总量,并以总CO2的百分数计算,总CO2是试验物质基于碳成分可理论产生的。见G.van der Waal和D.Kenbeek,“Testing,Application,and Future Development of Environmentally FriendlyEster Based Fluids”,Journal of Synthetic Lubrication,10卷,期号1,1993年4月,67-83页,该文献引入本文作为参考。
目前使用的一种基料是菜子油(即脂肪酸的甘油三酯,例如7%饱和的C12-C18酸,50%油酸,36%亚油酸和7%亚麻酸),该菜子油具有下列性质:40℃下的粘度为47.8cSt,倾点为0℃,闪点为162℃和生物降解性为85%(用改进的Sturm试验测定)。尽管它具有好的生物降解性,但由于其差的低温性和差的稳定性,而使它在可生物降解润滑剂中的应用受到限制。
如果由直链酸和直链醇合成的酯不具有足够低的分子量,那么它们将具有差的低温性能。即使当由直链酸和高支链的醇合成酯时,也很难得到具有好的低温性能的高粘度酯。此外,支链酸的季戊四醇酯显示出差的与分散剂如聚酰胺的溶解性,并且低分子量的(即具少于14个碳原子)支链酸的三羟甲基丙烷酯没有提供足够的润滑性能。从支链醇的己二酸酯也可看到这种低质量的润滑性能。因为低分子量的支链酯也具有低的粘度,因此在保持好的低温流动性的同时,还要求有一些支化度以生产粘性。然而,当酯的醇和酸部分是高支链时,例如在高支链含氧酸的多元醇酯的情况下,得到的分子将显示出差的由改进的Sturm试验(OECD试验号301B)测定的生物降解作用。
在Randles和Wright的文章“Environmentally Considerate EsterLubricants for the Automotive and Engineering Industries”,Journalof Synthetic Lubrication,第9-2卷,145-161页中,说明了减慢或降低微生物破坏的主要因素是支化的程度,支化的程度降低了β-氧化作用,和抑制酯水解的程度。在R.D.Swisher的书中的“SurfactantBiodegradation”,Marcel Dekker,Inc.,第二版,1987,415-417页中进一步论述了由于沿碳链的支化而对生物降解性的不利影响。在他的书中,Swisher指出“结果清楚地表明随着支化的增加抗生物降解作用增加…,虽然在另外直链分子中单个甲基支链的作用几乎没有引人注意,但是通常观察到随着支化的增加抗生物降解作用也增加,并且当在分子的所有链端发生季支化时抵抗力变的特别大”。烷基支化对生物降解性的不利影响在下列文章中也有论述:N.S.Battersby,S.E.Pack,和R.J.Watkinson,A Correlation Between the Biodegradability of OilProducts in the CEC-L-33-T-82 and Modified SturmTests,Chemosphere,24(12),1989-2000页(1992)。
起初认为支链多元醇酯的差的生物降解作用是支化的结果,支化使分子在水中的不溶性降低到更小的程度。然而,本发明人近来的研究表明这些支链酯的非生物降解性比微生物不能破坏叔和季碳的能力具有更强的位阻作用。因此,通过减轻围绕酯键的位阻现象,可用支链酯更容易地产生生物降解作用。
支链合成多元醇酯已广泛地用于非生物降解应用中,例如冷冻润滑剂应用,并已证明如果将3,5,5-三甲基己酸以25摩尔%或更多的量引入到分子中时是非常有效的,然而,用改进的Sturm试验(OECD 301B)测定时三甲基己酸不是可生物降解的,并且即使以25摩尔%引入3,5,5-三甲基己酸也将会由于其中所含的季碳而大大地降低多元醇酯的生物降解作用。
同样,将三烷基乙酸(即新酸)引入到多元醇酯中产生了非常有效的冷冻润滑剂,然而,用改进的Sturm试验(OECD 301B)测定时这些酸不能生物降解,因此不能用来生产用于可生物降解的多元醇酯。所有支链酸的多元醇酯同时也可用作冷冻油。然而,如改进的Sturm试验(OECD 301B)测定的它们不能迅速生物降解,因此,不希望将它们用于可生物降解的应用中。
虽然用于冷冻应用的由纯直链C5-C10酸制备的多元醇酯在改进的Sturm试验下是可生物降解的,但是它们在水力或二冲程发动机应用中不能作为润滑剂,因为它们的粘度太低,需要抗磨添加剂。开发能够显示出所有可生物降解润滑剂所要求的各种性能(即高粘度、低倾点、氧化稳定性和由改进的Sturm试验测定的生物降解性)的润滑剂基料是极其困难的。
1989年5月2日颁布的US4826633(Carr等人)公开了由至少一种三羟甲基丙烷和单季戊四醇与脂族单羧酸的混合物反应形成的合成酯润滑剂基料。酸的混合物包括含有5-10个碳原子的直链酸和含有6-10个碳原子的异构酸,优选异壬酸(即3,5,5-三甲基己酸)。该基料与常规酯润滑剂添加剂配料混合形成具有粘度为至少5.0厘沲(在99℃(210°F)下)、和倾点至少为-54℃(-65°F)的润滑剂。该润滑剂在燃气轮机中特别有用。由于下述两个原因Carr等人的专利与本发明不同。首先,它优选使用其在每个酸分子中含有季碳的支链酸3,5,5-三甲基己酸。在3,5,5-三甲基己酸中引入季碳抑制了多元醇酯产物的生物降解作用。另外,如用高压差扫描量热器(HPDSC)所测定的,因为Carr等人的润滑剂显示出高的稳定性,即读数为约35-65分钟,所以微生物不能将润滑剂拉开。相反的是,本发明的润滑剂具有低的稳定性,即它具有HPDSC的读数为约12-17分钟。较低的稳定性使得微生物能够破坏多元醇结构的C-C键,从而有效地使酯生物降解。本发明润滑剂具有低稳定性的一个原因是用于形成含季碳的润滑剂酯基料的支链酸不多于10%。
因此,本发明人发现,使用具有好的低温流动性、好的与分散剂的溶解性和好的润滑性能的可生物降解基料的高度可生物降解的润滑剂可通过将支链酸引入到酯分子中而得到。用于本发明的支链酸需要生产粘性,并且在这些酸中的多种异构体有助于达到低温性能。也就是说,支链酸使化学工作者不用提高分子量将可使化合物产生粘性。此外,支链可生物降解润滑剂比所有直链可生物降解润滑剂具有下列附加的优点:(1)较低的倾点;(2)提高的其他添加剂的溶解性;(3)提高的润滑油的清净性/分散性;和(4)在水力流体和弹射器油应用提高的氧化稳定性。
本发明人还发现,本文公开的独特的可生物降解酯基料与其他可生物降解酯基料的混合物提供了比单独的各个基料更高百分比的生物降解作用。
1994年5月3日颁布的US5308524(Miyaji等人)公开了用于二冲程或旋转式发动机的可生物降解的润滑油,Miyaji等人公开的例子之一是季戊四醇的酯基料与异C8一元脂肪酸和正C10一元脂肪酸的混合物,其显示出运动粘度为39.9cSt(在40℃下)和CEC试验下的生物降解性为98%。应注意的是,在测定生物降解性方面CEC试验不象改进的Sturm试验那样可靠。因为季戊四醇和异C8酸的粘度在40℃下为约50cSt,季戊四醇和正C10酸的粘度在40℃下为约38.6cSt,所以为了得到在40℃下39.9cSt的粘度,Miyaji等人所公开的季戊四醇和异C8酸和正C10酸的酯将仅包括约10%或更少的异C8酸。本领域普通技术人员知道,正如Miyaji等人所公开的,含有少量,即10%或更少支链酸的酯是可生物降解的,然而本发明涉及含有混合酸的可生物降解使基料,该混合酸包括约30-80摩尔%含碳原子数为约C5-C12直链酸和约20-70摩尔%至少一种含碳原子数为约C5-C10支链酸。本领域技术人员无法知道使用这种大百分比的支链酸,其仍能产生显示出至少60%生物降解作用(在28天内,用改进的Sturm试验测定)。普通常识将告诉我们不要在可生物降解酯基料的合成中使用20-70摩尔%的支链酸。此外,含有10%异C8酸的Miyaji等人的酯基料将不能满足本发明的低温性能要求,即倾点小于-25℃,优选小于-40℃,粘度小于7500cps(在-25℃下)。也就是说,Miyaji等人公开的酯基料在-25℃或更低的温度下将是固体。
本发明人所编辑的数据和下面实施例中所列的数据表明用可生物降解的合成酯基料配制的可生物降解润滑剂能够最好地满足上面所列的所有性能,该可生物降解的合成酯基料引入了高度支链酸和直链酸。这些数据还表明该基料和其他可生物降解的酯基料的混合物比其各自基料显示出增强的生物降解作用。
本发明的概况
可生物降解的合成基料优选包括支链或直链醇和混合酸的反应产物,该支链或直链具有通式:R(OH)n,其中R具有约2-20个碳原子的脂族或环脂族基团,n是至少2和高达约10,该混合酸包括约30-80摩尔%,更优选约35-55摩尔%具有碳数(即,碳数是指在酸或可能情况下醇中的碳原子总数)为约C5-C12,更优选约C7-C10的直链酸,和约20-70摩尔%,更优选约35-55摩尔%具有碳数为约C5-C13,更优选约C7-C10的至少一种支链酸;其中酯显示出下列性能:至少60%生物降解性(在28天内,用改进的Sturm试验测定);倾点小于-25℃;粘度小于7500cps(在-25℃下);和氧化稳定性高达45分钟(用HPDSC测定)。
在最优选的实施方案中,希望所含的支链酸包括多种异构体,优选多于3种异构体,最优选多于5种异构体。直链酸优选是具有通式RCOOH的烷基单或二羧酸,通式中R是具有约4-11个碳原子,优选约7-10个碳原子的正烷基。还优选不多于10%的用于形成可生物降解合成酯基料的支链酸含有季碳。
上述可生物降解的的合成酯基料可另外地与其他可生物降解性稍弱的酯混合,其中混合的产物比单独的各组分具有更好的生物降解作用。当两种酯需要达到特殊的粘度、低温性能或其他物理性能时,这是特别重要的。此外,混合基料可作为用于环境敏感区域的润滑剂的基料,该区域要求高水平的生物降解以减少环境中形成油沉积。
这些可生物降解的合成基料在可生物降解的润滑剂配方中特别有效,例如,在二冲程发动机、可生物降解的弹射器油、可生物降解的水力流体、可生物降解的钻孔液体、可生物降解的水轮机油、可生物降解的润滑脂、可生物降解的压缩机油、官能流体,例如齿轮油,和其他需要或要求有生物降解性的工业和发动机应用中。
根据本发明配制的可生物降解的润滑剂包括约60-99.5%(重量)至少一种上述可生物降解润滑剂合成基料,约1-20%(重量)润滑剂添加剂配料,和约0.5-20%溶剂。
本发明可生物降解的润滑剂还显示出下列性能:(1)非常低的毒性;(2)增强的氧化稳定性;和(3)对密封膨胀是中性的。
对附图的简更描述
图1是标绘出各种含酯基料的配制的水力流体对每种流体稳定性(用HPDSC@200℃测定)的图表;
图2是标绘出各种天然和合成基料对每种基料的稳定性(PHDSC)和生物降解性(RBOT)的图表;
图3是标绘出各种酯基料对各种用于制备密封垫的材料,即腈、丙烯酸酯、氟代、氯丁橡胶和硅氧烷在密封膨胀中的百分数增加的图表;
优选实施方案的描述
用于本发明的各种可生物降解的润滑剂和油配方中的支链合成酯基料优选由工业级季戊四醇与约45-70摩尔C8-C10直链酸(“C810”直链酸)和约30-55摩尔%异C8(例如Cekanoic8)支链酸的反应产物制得,所述的工业级季戊四醇包括约86-92%单季戊四醇,6-12%季戊四醇而后1-3%三季戊四醇。
新戊二醇(NPG)可被2-乙基己酸或异C8酸完全酯化并仍保持由改进的Sturm试验测定的约90%生物降解作用。两种支链酸加到支链多元醇后,酯键开始在支链醇的季碳周围变得密集。另外的支链酸加到支链醇开始降低分子的生物降解作用,以致通过第4次加入支链酸到支链醇,得到的分子的生物降解作用由约80%降到小于15%(由改进的Strum试验测定)。
将直链酸引入到分子中降低了支链醇的季碳周围的空间密集性。因此,例如通过在季戊四醇上带有两个支链酸和两个直链酸,酶接近到酯,就可发生生物降解的第一阶段,即酯的水解。在每个季戊四醇酯中,羟基被各种支链和直链酸酯化。
                            醇
可与本发明的支链和直链酸反应的醇是,例如,由下通式表示的多元醇(即多羟基化合物):
                           R(OH)n其中R是任何脂族或环脂族烃基(优选烷基),n是至少2。烃基可含有约2-约20个或更多个碳原子,烃基还可含有取代基如氯、氮和/或氧原子。多羟基化合物通常含有约2到约10个羟基,更优选约2-约6个羟基。多羟基化合物可含有一个或多个氧化烯基,因此,多羟基化合物包括象多醚多元醇这样的化合物。用于形成羧酸酯的多羟基化合物中所含的碳原子数(即碳数)和羟基基团的数量(即羟基数)可在宽的范围内变化。
下列醇作为多元醇是特别有效的:新戊二醇、2,2-羟甲基丁烷、三羟甲基乙烷、三羟甲基丙烷、三羟甲基丁烷、单季戊四醇、工业级季戊四醇、二季戊四醇、乙二醇、丙二醇和聚二醇(例如,聚乙二醇、聚丙二醇、聚丁二醇等,和它们的混合物如乙二醇和丙二醇的聚合混合物)。
优选的支链或直链醇选自:工业级季戊四醇、单季戊四醇、二季戊四醇、新季戊四醇、三羟甲基丙烷、三羟甲基乙烷和丙二醇、1,4-丁二醇、山梨醇等,和2-甲基丙二醇。最优选的醇是工业级(即88%单,10%二和1-2%三)季戊四醇。
                        支链酸
支链酸优选是具有碳数为约C5-C13,更优选约C7-C10的单羧酸,其中甲基支链是优选的。优选的支链酸是其中少于或等于10%支链酸含有季碳的那些酸。单羧酸是至少一种选自如下的酸:2-乙基己酸、异庚酸、异辛酸、异壬酸、异癸酸和α支链酸。最优选的支链酸是异辛酸,例如Cekanoic8酸。支链酸主要是具有每分子平均支化为约0.3-1.9的双支链或α支链酸。
希望支链酸含有多个异构体,优选多于3个异构体,最优选多于5个异构体。
                         直链酸
优选的直链单和/或二羧酸是具有碳数为约5-12,优选7-10的任何直链饱和羧酸,最优选的直链酸是单羧酸。
直链酸的一些例子包括正庚酸、正辛酸、正癸酸和正壬酸,选择的二酸包括己二酸、壬二酸、癸二酸和十二双酸。为了改进得到的酯产物的粘度,总酸混合物的高达20%的酸可由直链二酸组成。
                  可生物降解的润滑剂
支链合成酯基料可与选择的润滑剂添加剂一起用于可生物降解的润滑剂配方中。下面所列的添加剂一般以这样的量使用以便能提供它们通常带有的功能,各个组分的典型量也在下面列出。优选的可生物降解的润滑剂含有约80%(重量)或更多的基料和20%(重量)下列添加剂的任何混合物:
                  (宽的)    (优选的)
                  重量%     重量%粘度指数增进剂        1-12       1-4腐蚀抑制剂            0.01-3     0.01-1.5氧化抑制剂            0.01-5     0.01-1.5分散剂                0.1-10     0.1-5润滑剂流动性改进剂    0.01-2     0.01-1.5清净剂和防锈剂        0.01-6     0.01-3倾点下降剂            0.01-1.5   0.01-1.5抗泡剂                0.001-0.1  0.001-0.01抗磨剂                0.001-5    0.001-1.5密封膨胀剂            0.1-8      0.1-4摩擦改进剂            0.01-3     0.01-1.5可生物降解的合成酯基料≥80%     ≥80%
当使用其他添加剂时,希望(虽然不是必须的)配制成包括分散剂(以上文所述的浓缩量)与一种或多种其他添加剂(当形成本文称为添加剂配料的添加剂混合物时为浓缩物)的浓缩溶液或分散体,从而使几种添加剂可同时加到基料中以形成润滑油组合物。可用溶剂和在温和加热下混合容易地将添加剂浓缩物溶解于润滑油中,但这不是重要的。当添加剂配料与预定量的基础润滑剂或基料混合时,浓缩物或添加剂配料通常配制成含有适当量的分散剂添加剂和任选的附加添加剂,以便在最终配方中提供所需的浓度。因此,本发明的可生物降解的润滑剂通常可使用高达约20%(重量)的添加剂配料,剩余的组分是可生物降解的酯基料和/或溶剂。
本文所表示的所有的重量百分数(除另有说明)是基于添加剂的活性组分(A.I.)的量,和/或任何添加剂配料的总重量,或是每个添加剂的A.I.重量加上总油或稀释剂重量的总和的配方的总重量。
用于可生物降解润滑剂的上述添加剂的例子陈述于下列文献中(这些文献在本文引入作为参考):1994年4月26日颁布的美国专利5306313(Emert等人);1994年5月17日颁布的美国专利5312554(Waddoups等人);1994年7月12日颁布的美国专利5328624(Chung);Benfaremo和Liu的文章,“Crankcase Engine Oil Additives”,Lubrication,Texaco Inc.,1-7页;和Liston的文章,“Engine Lubricant AdditiveWhat They are How They Function”,Lubrication Engineering,1992年5月,389-397页。
粘度改进剂给润滑油提供了高温和低温操作性并使润滑油在提高的温度下保持剪切稳定,同时还显示出在低温下可接受的粘度和流动性。这些粘度改进剂通常是包括聚酯的高分子烃类聚合物。粘度也可衍生以包括其他性能或功能,例如加入分散性能。适合的粘度改进剂的有代表性的例子是本领域已知的任何类型的粘度改进剂,包括聚异丁烯、乙烯和丙烯的共聚物、聚甲基丙烯酸酯、异丁烯酸酯共聚物、不饱和二羧酸和乙烯基混合物的共聚物、苯乙烯和丙烯酸酯的共聚物、苯乙烯/异戊二烯、苯乙烯/丁二烯,和异戊二烯/丁二烯的部分氢化共聚物、以及丁二烯和异戊二烯的部分氢化均聚物。
腐蚀抑制剂,作为防腐剂也是已知的,它降低了与润滑油组合物接触的金属部件的降解。腐蚀抑制剂的例子是磷酸硫化的(phosphosulfurized)烃和优选在烷基化酚或烷基酚硫酯存在下,还优选在二氧化碳存在下通过磷酸硫化烃与碱土金属氧化物或氢氧化物反应得到的产物。磷酸硫化烃是在约66-约316℃下通过适合的烃如萜烯、C2-C6烯烃聚合物如聚异丁烯的重质石油馏分与5-30%(重量)磷的硫化物反应0.5-15小时而制得。磷酸硫化烃的中和可以US1969324所介绍的方法进行。
氧化抑制剂,或抗氧化剂,降低了矿物油在使用中变质的倾向,这种变质可通过氧化的产物如淤渣和介绍表面上的漆膜状沉淀,和通过粘度的增加了证实。这样的氧化抑制剂包括优选具有C5-C12烷基侧链的烷基酚硫酯的碱土金属盐,例如壬基酚硫化钙、辛基苯基硫化钡、二辛基苯基胺、苯基-α-萘基胺、磷酸硫化烃或硫化烃等。
摩擦改进剂用来向润滑油组合物如自动传动液提供适合的摩擦性能。适合的摩擦改进剂的代表性例子是脂肪酸酯和酰胺、聚异丁烯基瑚珀酐-氨基链烷醇的钼配合物、二基脂肪酸的甘油酯、链烷膦酸盐、含油酰胺(oleaminde)的膦酸酯、S-羧亚烷基烃基瑚珀酰胺、N(羟烷基)链烯基瑚珀酰胺酸或瑚珀酰亚胺、二(低级烷基)亚磷酸盐和环氧化物、和磷酸硫化N(羟烷基)链烯基瑚珀酰亚胺的的烯化氧加合物。最优选的摩擦改进剂是烃基取代的琥珀酸或酸酐的瑚珀酸酯或其金属盐和硫代二链烷醇。
分散剂保持使用期间氧化生成的不溶物在流体的悬浮液中,这样就避免了淤渣絮凝和沉淀或在金属部件上沉积。适合的分散剂包括高分子量烷基瑚珀酰亚胺、油溶性聚异丁烯瑚珀酸酐与亚乙基胺如四亚乙基五胺的反应产物及其硼酸盐。
无灰型的其他分散剂也可用于润滑剂和燃料组合物中。一种这样的无灰分散剂是与至少一种胺、醇,包括多元醇氨基醇等混合的衍生的烃类组合物。优选的衍生烃类分散剂是下列反应的产物,即(1)少于500Mn的官能化烃,其中官能作用包括至少一个式-CO-Y-R3的基团,其中Y是O或S;R3是H、烃基、芳基、取代的芳基或取代的烃基,其中至少50摩尔%的官能团连接到叔碳原子上;与(2)亲核反应剂反应得到的产物;其中至少约80%最初存在于官能化烃中的官能团被衍生。
官能化烃或聚合物可用下式表示:
             POLY-(CR1R2-CO-Y-R3)n其中POLY是烃,包括具有数均分子量小于500的低聚物或聚合物主链,n是大于0所数,R1,R2和R3可以相同或不同,并且每个是H、烃基,但须R1和R2是这样选择的以致至少50摩尔%的-CR1R2基团,其中R1和R2不是H,或R3是芳基取代的烃基。
上述官能化的分散剂更完全地描述在共同未决的1994年6月17日申请的系列号为08/261558的美国专利申请中,该文献引入本文作为参考。
倾点下降剂,还称作润滑油流动改进剂,降低了流体将流动或可倾倒的温度。这种添加剂是公知的。通常最优化流体低温流动性的这种类型的添加剂是C8-C18二烷基富马酸乙烯基乙酸酯共聚物、聚甲基丙烯酸酯和蜡萘。泡沫控制可通过聚硅氧烷型防沫剂如硅油和聚二甲基硅氧烷提供。
抗磨添加剂,顾名思义,降低了金属部件的磨损。常规抗磨添加剂的代表性例子是二烷基二硫代硫酸锌和二烷基二硫代酸锌。
防沫剂用于控制润滑剂中的泡沫。泡沫控制可由高分子量二甲基硅氧烷和聚醚提供,聚硅氧烷类型的防沫剂的一些例子是硅油和聚二甲基硅氧烷。
清净剂和金属防锈剂包括磺酸、烷基酚、硫化烷基酚、烷基水杨酸、环烷酸和其他油溶性单和二羧酸所金属盐,高碱性金属盐,例如高碱性碱土金属磺酸盐(尤其是Ca和Mg盐)常用作清净剂。
密封膨胀剂包括引起发动机密封垫膨胀的那类矿物油,包括8-13个碳原子的脂族醇如十三醇,优选的密封膨胀剂的特征在于其是10-60个碳原子和2-4个键的油溶性、饱和的、脂族或芳族烃酯,例如邻苯二甲酸二己酯,如美国专利3974081所描述的,该文献引入本文作为参考。
               可生物降解的二冲程发动机油
支链合成酯基料可与选择的润滑剂添加剂一起用于可生物降解的二冲程发动机油的配方中。优选的可生物降解的二冲程发动机油通常用本发明制得的可生物降解合成酯基料与常规的二冲程发动机油添加剂配料一起配成。下面所列的添加剂一般以这样的量使用以便提供其带有的功能。添加剂配料可包括,但不限于,粘度指数改进剂、腐蚀抑制剂、氧化抑制剂、偶合剂、分散剂、极压剂、颜色稳定剂、表面活性剂、稀释剂、清净剂和防锈剂、倾点下降剂、防沫剂和抗磨添加剂。
本发明的可生物降解的二冲程发动机油通常可使用约75-80%的基料,约1-5%的溶剂和包括添加剂配料的剩余物。
用于可生物降解的润滑剂的上述添加剂的例子列于下列文献中(这些文献引入本文作为参考):1987年5月5日颁布的美国专利5663063(Davis);1994年7月19日颁布的美国专利55330667(Tiffany,III等人);1988年4月26日颁布的美国专利4740321(Davis等人);1994年6月14日颁布的美国专利5321172(Alexander等人);和1991年9月17日颁布的美国专利5049291(Miyaji等人)。
一种这样的可生物降解的二冲程发动机油包括:
(a)主要量的至少一种可生物降解合成酯基料,该基料包括支链或直链醇和混合酸的反应产物,所述的支链或直链醇具有通式R(OH)n,其中R是具有约2-20个碳原子的脂族或环脂族基团,n是至少2;所述的混合酸包括约30-80摩尔%具有碳数为约C5-C12的直链酸,和约20-70摩尔%具有碳数为约C5-C13的至少一种支链酸;其中酯基料显示出下列特性:用改进的Sturm试验测定的在28天内的至少60%的生物降解作用;倾点小于-25℃;和粘度小于7500cps(在-25℃下);
(b)以润滑剂组合物计,约3-约15%(重量)具有运动粘度为约20-约40cSt(在100℃下)的重质高粘度润滑油料;
(c)以润滑剂组合物计,约3-约15%(重量)具有数均分子量为约400-约1050的聚异丁烯;和
(d)约3-约15%(重量)具有数均分子量为约1150-约1650的聚异丁烯。
另一种这样的可生物降解的二冲程发动机油包括:
(a)主要量的至少一种可生物降解合成酯基料,该基料包括支链或直链醇和混合酸的反应产物,所述的支链或直链醇具有通式R(OH)n,其中R是具有约2-20个碳原子的脂族或环脂族基团,n是至少2;所述的混合酸包括约30-80摩尔%具有碳数为约C5-C12的直链酸,和约20-70摩尔%具有碳数为约C5-C13的至少一种支链酸;其中酯基料显示出下列特性:用改进的Sturm试验测定的在28天内的至少60%的生物降解作用;倾点小于-25℃;和粘度小于7500cps(在-25℃下);和
(b)添加剂浓缩物包括:(1)约4-40%(体积)酰胺/咪唑啉或酰胺/酰亚胺/咪唑啉分散剂;(2)约5-50%(体积)瑚珀酰亚胺,分散剂(1)或(2)的至少一个被硼酸化;(3)约1-60%(体积)聚烯烃增稠剂,和任选的;(4)约0.1-5%(体积)硫化烷基苯(alkylphenyol sulphide);和(5)约0.1-5%(体积)含三价磷的抗磨剂。成品油中添加剂配料的处理比例为约5-约60(体积),优选约35-约50%(体积)浓缩物。(参见US5330667(Tiffany,III等人),该文献引入本文作为参考)。
另一种可生物降解的二冲程发动机油包括:
(a)主要量的至少一种可生物降解合成酯基料,该基料包括支链或直链醇和混合酸的反应产物,所述的支链或直链醇具有通式R(OH)n,其中R是具有约2-20个碳原子的脂族或环脂族基团,n是至少2;所述的混合酸包括约30-80摩尔%具有碳数为约C5-C12的直链酸,和约20-70摩尔%具有碳数为约C5-C13的至少一种支链酸;其中酯基料显示出下列特性:用改进的Sturm试验测定的在28天内的至少60%的生物降解作用;倾点小于-25℃;和粘度小于7500cps(在-25℃下);和
(b)至少一种由单羧酸酰化剂与聚胺反应制备的含酰胺/咪唑啉分散剂,和任选的,高分子量的酰化剂。这种分散剂还可包括当高分子量的酰化剂是适合的二酸或其酸酐时所形成的酰亚胺部分。
可与本发明可生物降解的基料形成配制的二冲程发动机油的另一个添加剂包括下列化合物的混合物:
(a)至少一种下式的烷基酚
                 (R)a-Ar-(OH)b其中每个R独立的是平均至少约10个脂族碳原子的基本饱和的烃基基团;a和b各自独立地是Ar中存在的芳核数量的1至高达3倍,其是整数,但须a和b的和不超过Ar的不饱和价;Ar是芳族部分,其是单环、稠环或具有0-3个任选取代基的连接的多核环,该取代基选自低级烷基、低级烷氧基、烷酯基羟甲基或基于取代的羟甲基、硝基、亚硝基、卤的低级烃和任选取代基的混合物;和
(b)至少一种氨基化合物,但须氨基化合物不是氨基苯基。(参见US4663063(Davis),该文献引入本文作为参考)。
优选用于二冲程发动机油配方中的分散剂包括主要量的至少一种润滑粘度的油和少量的官能化的和衍生的烃;其中官能作用包括至少一个式-CO-Y-R3的基团,其中Y是O或S;R3是芳基、取代的芳基或取代的烃基,和-Y-R3具有pKa为12或更小;其中至少50摩尔%的官能团连接到叔碳原子上;和其中所述的官能化烃含是由亲核反应剂衍生的。亲核反应剂选自醇和胺。
另一个二冲程发动机油分散剂添加剂基本上避免了在低温下胶凝附聚物的形成,但相应地提供了有效的发动机洁净度、清净性、润滑性和磨损抑制性。已经发现二冲程发动机油添加剂包括由(A)至少一种高分子量取代的羧酸酰化剂与(B)至少一种聚亚烷基聚胺和(C)至少一种单羧酸的反应制备的含氮化合物,其中单羧酸与高分子量取代的酰化剂的摩尔比是至少3∶1。该分散剂优选含有连接到极性部分的油溶性烃部分,该极性部分基本上由叔胺,优选咪唑啉杂环组成,其中叔胺与总胺的比为至少约0.7∶1。添加剂对胶凝附聚物的形成保持稳定,尤其在低温(0℃或更低)下延长储存期间。
                可生物降解的弹射器油
弹射器是用在海上航空母舰上的设备,它用来将飞机弹出航空母舰。支链合成酯基料可与选择的润滑剂添加剂一起用于可生物降解的弹射器油配方中。优选的可生物降解的弹射器油通常是用本发明制备的可生物降解合成酯基料与任何常规弹射器油添加剂配料一起配制的。下面所列的添加剂一般以这样的量使用以便提供其通常带有的功能。添加剂配料可包括,但不限于,粘度指数改进剂、腐蚀抑制剂、氧化抑制剂、极压剂、颜色稳定剂、清净剂和防锈剂、防沫剂、抗磨剂和摩擦改进剂。
本发明的可生物降解的弹射器油通常可使用约90-99%的基料,剩余物包括添加剂配料。
可生物降解的弹射器油优选包括常规的腐蚀抑制剂和防锈剂。如果需要的话,弹射器油可含有其他常规添加剂,例如防沫剂、抗磨剂、其他的抗氧化剂、极压剂、摩擦改进剂和其他的水解稳定剂。这些添加剂公开在Klamann,Lubricants and Related Products,Verlag Chemie,DeerfieldBeach,FL,1984中,该文献引入本文作为参考。
                可生物降解的水力流体
在可生物降解的水力流体的配方中可以将支链合成酯基料与选择的润滑剂添加剂一起使用。一般地,使用按照本发明形成的可生物降解的合成酯基料与常规的水力流体添加剂配料(package)一起配制优选的可生物降解的水力流体。一般以这样的量使用下面所列的添加剂,它使得提供其常规的附加功能。该添加剂配料可以包括,但不限于,粘度指数改进剂,腐蚀抑制剂,界面润滑剂,破乳剂,倾点下降剂,和防沫剂。
一般地,按照本发明的可生物降解的流体可以为约90-99%的基料,其余的包括添加剂配料。
其它的添加剂公开于1988年11月8日颁布的US4783274(Jokinen等人)中,该文献引入本文作为参考。
                  可生物降解的钻孔液体
在可生物降解的钻孔液体的配方中可以将支链合成酯基料与选择的钻孔液体添加剂一起使用。一般使用按照本发明形成的可生物降解的合成酯基料与常规的钻孔液体添加剂配料一起配制优选的可生物降解的钻孔液体。一般以这样的量使用下面所列的添加剂,它使得提供其常规的附加功能。该添加剂配料可以包括,但不限于,粘度指数改进剂,腐蚀抑制剂,润湿剂,水损失改进剂,生物杀伤剂,和钻头乳化剂。
一般地,按照本发明的可生物降解的钻孔液体可以为约60-90%的基料和约5-25%的溶剂,其余的包括添加剂配料。见1983年5月3日颁布的US4382002(Walker等人),该文献引入本文作为参考。
合适的烃溶剂包括:矿物油,特别是在200-400℃沸腾范围有良好的氧化稳定性的石蜡基础油,例如由Exxon Chemical Americas,Houston,Texas销售的Mentor28R;柴油和汽油;和重芳烃油。
                可生物降解的水轮机油
在可生物降解的水轮机油的配方中可以将支链合成酯基料与选择的水轮机油添加剂一起使用。一般使用按照本发明形成的可生物降解的合成酯基料与常规的水轮机油添加剂配料一起配制优选的可生物降解的水轮机油。一般以这样的量使用下面所列的添加剂,它使得提供其常规的附加功能。该添加剂配料可以包括,但不限于,粘度指数改进剂,腐蚀抑制剂,氧化抑制剂,增稠剂,分散剂,抗乳化剂,颜色稳定剂,洗涤剂和腐蚀抑制剂,和倾点下降剂。
一般地,以组合物的总重量计,按照本发明的可生物降解的水轮机油可以为约65-75%的基料和约5-30%的溶剂,其余的包括添加剂配料,一般在约0.01-约5.0%(重量)。
                可生物降解的润滑脂
在可生物降解的润滑脂的配方中可以将支链合成酯基料与选择的润滑油添加剂一起使用。在润滑脂中发现的主要组分是增稠剂或凝胶剂,和润滑脂的区别是常包括该组分。此外,通过可以使用的特别的润滑基料和各种添加剂可以影响增稠剂或凝胶剂,润滑脂的其它性质和特性。
一般地,使用按照本发明形成的可生物降解的合成酯基料与常规的润滑脂添加剂配料一起配制优选的可生物降解的润滑脂。一般以这样的量使用下面所列的添加剂,它使得提供其常规的附加功能。该添加剂配料可以包括,但不限于,粘度指数改进剂,氧化抑制剂,耐特压剂,洗涤剂和腐蚀抑制剂,倾点下降剂,金属减活剂,抗磨添加剂,增稠剂和凝胶剂。
一般地,按照本发明的可生物降解的润滑脂可以为约80-95%的基料和约5-20%的增稠剂或凝胶剂,其余的包括添加剂配料。
一般地,在润滑脂配方中使用的增稠剂包括:碱金属皂,粘土,聚合物,石棉,碳黑,硅胶,聚脲和铝络合物。皂增稠的润滑脂最普通的,锂和钙皂是最常用的。简单皂润滑脂是从长链脂肪酸的碱金属盐与12-羟基硬脂酸锂形成的,主要是从12-羟基硬脂酸,氢氧化锂一水合物和矿物油形成的。络合物皂润滑脂也是经常使用的,并且包括有机酸混合物的金属盐。一种在当今使用中发现的典型络合物皂是从12-羟基硬脂酸,氢氧化锂一水合物,壬二酸和矿物油制备的络合物锂皂润滑脂。该锂皂描述于和举例说明于很多专利中,包括1973年9月11日颁布的US3758407(Harting),1974年2月12日颁布的US3791973(Gilani),和1975年11月30日US3929651(Murray)中,所有这些文献和1983年7月12日颁布的US4392967(Alexander)一起引入本文作为参考。
在润滑脂中使用的添加剂,以及在其它可生物降解的产品中的上面所列的添加剂的描述可以在Boner,"Modem Lubricating Greases",1976,Chapter5(该文献引入本文作为参考)中找到。
                  可生物降解的压缩机油
在可生物降解的压缩机油的配方中可以将支链合成酯基料与选择的润滑油添加剂一起使用。一般地,使用按照本发明形成的可生物降解的合成酯基料与常规的压缩机油添加剂配料一起配制优选的可生物降解的压缩机油。一般以这样的量使用下面所列的添加剂,它使得提供其常规的附加功能。该添加剂配料可以包括,但不限于,氧化抑制剂,添加剂加溶剂,腐蚀抑制剂/金属钝化剂,金属减活剂,破乳剂,和抗磨添加剂。
一般地,按照本发明的可生物降解的压缩机油可以为约80-99%的基料和约1-15%的溶剂,其余的包括添加剂配料。
用于压缩机油的添加剂也列于1992年10月20日颁布的US5156759(Culpon)中,该文献引入本文作为参考。
                      实施例1
下面是作为可生物降解的润滑油使用并且不显示出令人满意性质的常规酯基料。在表1和2中列出的性质测定如下。使用ASTM#D-97测定倾点。使用ASTM#D-2983测定-25℃的Brookield粘度。使用ASTM#D-445测定的动力粘度(40℃和100℃)。使用ASTM#D-2270测定粘度指数(VI)。使用改进的Sturm实验(OECD实验301B)测定可生物降解性。通过混合需要的比例并查看雾状,浑浊,两相等确定与分散剂的溶解度。使用NMMA Yamaha CE50S润滑性实验确定发动机磨损。使用分别具有220℃和500psi(3.445MPa)空气的等温/等压条件的高压差示扫描量热计测定氧化诱导时间。使用分散水毒性试验测定水毒性。使用ASTM#D-664测定酸数。用红外光谱测定各样品的羟基数。
                                  表1
                  倾点   粘度@  粘度@   粘度@           *与分散
                  ℃     -25℃  40℃    100℃   生物    剂的溶  发动机基料                         (cPs)  (cSt)   (cSt)   降解%  解性    磨损天然油菜子油                0      固体   47.80   10.19   86.7    n/a     n/a全直链酯二(十一烷基)己二酸酯  +21    固体   13.92   2.80    n/a     n/a     n/a多元醇/直链或半直链酸TPE/C810/C7酸         n/a    固体   29.98   5.90    n/a     n/a     n/aTPE/DiPE/n-C7         -45    1380   24.70   5.12    82.31   H       破损TPE/C7酸              -62    915    24.0    4.9     83.7    H       破损TMP/n-C7,8,10       -85    350    17.27   4.05    61.7**  C       破损TMP/C7酸              -71    378    14.1    3.4     76.5    C       破损支链的己二酸酯二(十三烷基)己二酸酯  -62    n/a    26.93  5.33     65.99   C       破损全支链的TPE/Iso-C8酸          -46    n/a    61.60  8.2      13.33   C       n/a
*表示与分散剂的溶解度;H=雾状;C=清亮
**表示包括15.5%(重量)分散剂的该材料的生物降解性。
n/a表示得不到信息。
TPE表示工业级季戊四醇
TMP表示三羟甲基丙烷
C810表示主要是正辛酸和正癸酸,并可以包括少量正C6酸和正C12酸的混合物。C810酸的一般例子可以含有,例如,3-5%正C6酸,48-58%正C8酸,36-42%正C10酸,和0.5-1%正C12酸。
n-C7,8,10表示具有7,8和10个碳原子的直链酸的混合物,例如37%(摩尔)正C7酸,39%(摩尔)C8酸,21%(摩尔)C10酸和3%(摩尔)C6酸。
C7表示通过钴催化的己烯-1氧代反应生产的C7酸,它是70%直链和30%α-支链的。该组合物包括约70%正庚酸,22%的2-甲基己酸,6.5%的2-乙基戊酸,1%的4-甲基己酸,和0.5%的3,3-二甲基戊酸。
将按照本发明的支链酯基料的性质与各种常规可生物降解的润滑剂基料进行比较,结果列于下面表2。
                表2性质                         TPE/Ck8/C810  菜子油    DTDA      TMP/iC18倾点(℃)                     -45           0         -54       -20闪点(℃)                     274           162       221       n/a-25℃粘度(cps)               3600          固体      n/a       358,00040℃粘度(cSt)                38.78         47.80     26.93     78.34100℃粘度(cSt)               6.68          10.19     5.33      11.94粘度指数                     128           208       135       147氧化诱导时间*                15.96         2.12      3.88      4.29润滑性(Yamaha发动机)         合格          n/a       不合格    合格%生物降解性(改进的Sturm)    -85%         -85%     -60%     -65%毒性(LC50,ppm)              >5000        >5000    <1000    n/a与分散剂的溶解度             可溶解        n/a       可溶解    n/a酸数(mgKOH/g)                0.01          0.35      0.04      1.9羟基数(mgKOH/g)              1.91          n/a       1.49      n/a
*氧化诱导时间是使用高压差示扫描量热计(HPDSC)在特定的一套条件下分子氧化分解的时间(分钟)。其越长(分钟数越大),分子越稳定。它表明本发明的分子比目前所用的材料更氧化稳定几乎4倍。用于测定这些分子的条件是:220℃和500psi(3.447MPa)空气。-表示大约>表示大于<表示小于DTDA表示二(十三烷基)己二酸酯IMP/iC18表示三羟甲基丙烷混合异硬脂酸的三酯TPE表示工业级季戊四醇TMP表示三羟甲基丙烷C810表示3-5%正C6酸,48-58%正C8酸,36-42%正C10酸,和0.5-1%正C12酸。
Ck8表示Cekanoic酸,包括26%(重量)的3,5-二甲基己酸,19%(重量)的4,5-二甲基己酸,17%(重量)的3,4-二甲基己酸,11%(重量)的5-甲基庚酸,5%(重量)的4-甲基庚酸,和22%(重量)混合的甲基庚酸和二甲基己酸。
列于上面表2中的数据表明,在冷流动性质和稳定性方面,按照本发明的TPE/C810/Ck8可生物降解的酯基料优于菜子油。该数据还表明,在稳定性,可生物降解性,和水毒性方面,TPE/C810/Ck8可生物降解的酯基料优于二(十三烷基)己二酸酯。在冷流动性质,稳定性,和可生物降解性方面,按照本发明的酯基料也优于TMP/iso-C18。
菜子油,一种天然产物,是非常可生物降解的,但它具有非常差的低温性质,并且由于其不稳定性它不能很好地润滑。菜子油是非常不稳定的并且在发动机中分解引起沉积形成,淤泥和腐蚀问题。尽管二(十二烷基)己二酸酯是可生物降解的,但它具有非常差的低温性质。低分子量直链酸的多元醇酯不提供润滑性,和高分子量的直链或半直链酸的那些酯具有非常差的低温性质。另外,直链酸的季戊四醇酯与聚酰胺分散剂是不溶的。该二(十三烷基)己二酸酯仅勉强可生物降解,并且当与具有低的可生物降解性的分散剂混合时,该配制的油仅约45%可生物降解。另外,该二(十三烷基)己二酸酯不提供润滑性。较低分子量的支链己二酸酯,例如二(异癸基)己二酸酯,尽管其更可生物降解,但不提供润滑性并且可引起密封垫膨胀的问题。三羟甲基丙烷的多元醇酯或季戊四醇和支链的氧代酸由于前面讨论的立体位阻不容易生物降解。
                   实施例2
本发明人已经发现,通过将支链酸混入酯分子可以得到具有良好冷流动性质,良好与分散剂的溶解性,和良好润滑性的高度可生物降解的基料。在下面表3中列出的数据表明,用混入20-70%的高度支链的氧代酸和30-80%的支链酸的多元醇酯所有希望的基料性质均可以最好地满足。
                                     表3
                  倾点℃   粘度@    粘度@    粘度@             与分散   发动机
                           -25℃    40 ℃    100℃   生物      剂的溶   磨损基料                           (cPs)    (cSt)    (cSt)   降解性%  解度TPE/C810/Ck8          -36**    7455**   34.87    6.37    99.54     C        合格TPE/C810/Ck8和TMP/n-C7,8,10***    -56      610      24.90    5.10    81.0      C        合格TPE/C810/Ck8和TPE/1770****          -46      910      30.48    5.75    85.5      H        合格
*表示与分散剂的溶解度;H=雾状;C=清亮
**表示与分散剂一起的基料的倾点和-25℃的粘度性。
***表示50∶50%(重量)的TPE/C810/Ck8和TMP/7810。
****表示50∶50%(重量)的TPE/C810/Ck8和TMP/1770。
1770表示正C7酸(70%)和α-支链C7酸(30%)的70∶30混合物。该组合物包括约70%正庚酸,22%的2-甲基己酸,6.5%的2-乙基庚酸,1%的4-甲基己酸,和0.5%的3,3-二甲基庚酸。
TPE表示工业级季戊四醇
TMP表示三羟甲基丙烷
C810表示3-5%正C6酸,48-58%正C8酸,36-42%正C10酸,和0.5-1%正C12酸。
n-C7,8,10表示具有7,8和10个碳原子的直链酸的混合物,例如37%(摩尔)正C7酸,39%(摩尔)C8酸,21%(摩尔)C10酸和3%(摩尔)C6酸。
在上面表3中的数据表明,可以单独地或与其它低分子量的酯组合地将工业级的季戊四醇,异-C8和直链C810酸用作可生物降解的润滑剂。当对于各种可生物降解的润滑剂应用需要较低粘度时,这些酯是特别有用的。TPE/C810/Ck8酯提供了足够的润滑性致使甚至当用其它材料稀释时,它不加耐磨添加剂也可以满足润滑性的需要。当需要添加剂,例如聚异丁烯,EP(耐特压)耐磨添加剂,腐蚀抑制剂,或抗氧化剂时,可以降低最终产品的可生物降解性和增加其毒性。如果该基料不加添加剂就提供了所需的性质,或如果需要的添加剂是最小的,那么在这种情况下最终产品分别反映出该基料的高的可生物降解性和低的毒性。
                    实施例3
按照本发明制备酯基料的样品,其中将2201b(99.8kg)的C810和2051b(93kg)的Cekanoic8酸(50∶50摩尔比)装进反应器容器中并在大气压下加热至430F(221℃)。此后,将751b(34kg)的工业级季戊四醇加入到该酸混合物中和降低压力直到水开始析出。顶部取出水以便引起该反应。在约6小时反应时间后,顶部除去过量的酸直到该反应产物达到总酸数为0.26mgKOH/g。然后用两倍化学计量量的Na2CO3(以酸数计)和0.15%(重量)的混合物(以在反应器中的量计)在90℃中和和脱色该产物2小时。该混合物是80%(重量)的碳黑和20%(重量)的dicalite的混合物。在90℃2小时后,真空过滤该产物以便除去固体。
测定该产物的性质列于下面表4:
             表4总酸数              0.071mgKOH/g比重                0.9679倾点                -45℃ppm水               97闪点(COG)           285℃氧化诱导时间(min.)  15.96粘度@-25℃          3950cps粘度@40℃           38.88cSt粘度@100℃          6.66cSt粘度指数            127
为了确定分子上实际每种酸的量对该产物进行酸分析(皂化)。下面表5列出了在该产物酯上每种酸的摩尔量。
       表5Cekanoic8酸    43.35%n-C8酸        35.73%nC10酸        20.92%
然后将得到的酯产物与添加剂一起和没有添加剂地进行应用于水力流体市场的可生物降解试验。以2-5%(重量)的处理速度使用添加剂。结果列于下面表6。
                        表6产品                      生物降解%  标准偏差  满足10天窗口TPE/C810/Ck8(单独)        92.9        ±7.0     满足TPE/C810/Ck8+BIO SHP添    80.5        ±1.6     不满足加剂酯料*TPE/C810/Ck8+MGG 添加剂   75.4        ±6.9     不满足酯料***TPE/C810/Ck8+合成         76.8        ±14.7    不满足添加剂醌料**
*表示由Exxon Company,USA以商标名Univis BIO SHP Adpack销售的润滑剂添加剂配料。
**表示Exxon Company,Paramins Division以商标名Synestic Adpack销售的润滑剂添加剂配料。
***表示Exxon Company,USA以商标名MGG Adpack销售的润滑剂添加剂配料。
将按照实施例3形成的所得酯基料以50∶50%(重量)的比例与酯TMP/7810混合。将该混合物与添加剂一起和没有添加剂地进行应用于2循环发动机油市场的可生物降解试验。以14-16%(重量)的处理速度使用添加剂。结果列于下面表7。
                            表7产品                                      生物降解%  标准偏差TPE/C810/Ck8+TMP/7810(50∶50)             80.7        ±3.6TPE/c810/Ck8+TMP/7810+14.5wt.%分散剂*    76.1        ±4.6
                           实施例4
下面的表8含有对于全直链和半直链酯与按照本发明形成的可生物降解的合成酯基料的比较数据。我们提供了两个按照本发明的酯基料的例子,因为它们含有两个不同的Cekanoic8与C810的摩尔比。结果表明,如通过改进的Sturm试验所测定的,特定量的支链化没有很大地影响可生物降解性,并且事实上可以实际地改进可生物降解性,这与常识是相反的。
                 表8
              生物降解 标准偏差 10天窗口酯                %(28天)全直链酯TMP/7810          76.13    8.77     不满足TPE/Di-PE/n-C7   82.31    6.25     满足L9己二酸酯        89.63    6.28     满足MPD/Aa/C810       86.09    3.76     满足半直链酯TMP/异硬脂酸酯    63.32    1.91     不满足TMP/1770          76.46    1.58     不满足TMP/1770          83.65    6.89     不满足支链酯TPE/C810/Ck8*     92.90    7.00     满足TPE/C810/Ck8**    99.54    1.85     满足
注:TMP/7810表示三羟甲基丙烷和C7,C8和C10酸的三酯。
    TPE/Di-PE/n-C7表示工业级季戊四醇,二季戊四醇和n-C7酸的酯。
    MPD/AA/C810表示2-甲基-1,3-丙二醇(2摩尔),己二酸(1摩尔)和n-C8和C10酸(2摩尔)的复合酯。
菜子油是甘油和硬脂酸的三酯。
TMP/异硬脂酸酯表示三羟甲基丙烷和异硬脂酸(每酸链1甲基支链)的三酯。
TMP/1770表示三羟甲基丙烷和n-C7酸(70%)和α-支链的C7酸(30%)的70∶30混合物的三酯。1770组合物包括约70%的正庚酸,22%的2-甲基己酸,6.5%的2-乙基庚酸,1%的4-甲基己酸,和0.5%的3,3-二甲基庚酸。
TPE/1770表示工业级季戊四醇和n-C7酸(70%)和α-支链的C7酸(30%)的70∶30混合物的酯。1770组合物包括约70%的正庚酸,22%的2-甲基己酸,6.5%的2-乙基庚酸,1%的4-甲基己酸,和0.5%的3,3-二甲基庚酸。
*TPE/C810/Ck8表示工业级季戊四醇和45∶55摩尔比的异-C8酸和C810酸的酯。
**TPE/Ck8/C810表示工业级季戊四醇和30∶70摩尔比的异-C8酸和C810酸的酯。
                   实施例5
已经表明,按照本发明的支链的合成酯既显示出可生物降解性又显示出氧化稳定性。通过1摩尔的工业级季戊四醇与1.05-3.15摩尔的混合直链C6-C12酸(C810)和1.05-3.15摩尔的异-C8酸(Cekanoic)反应已经合成出了既可生物降解又氧化稳定的支链的合成酯,其中反应生成的酯称之为TPE/C810/Ck8。在由于设备寿命需要氧化稳定性的地方和在由于泄漏到环境中需要可生物降解的地方,可以将这些酯用作用于润滑剂例如水力流体的基料。
如在图1和2所表明的,可生物降解的可比较材料不具有在高温条件下保护设备所需要的稳定性。具有所需要的稳定性的其它材料是不可生物降解的。例如,图1的结果比较了基于200℃HPDSC结果的各种配制的水力流体与使用本发明可生物降解的基料形成的配制的水力流体。如图1所表明的,使用本发明可生物降解的基料形成的水力流体的稳定性是约73分钟,而下一个最好的配方的稳定性仅是15分钟。示于图1中的各种比较水力流体产品列于下表:
Mobil EAL 224H Biostar32 Biostar46 Synstar32 Synstar46
2%抗氧化剂 2%抗氧化剂 2%抗氧化剂 2%抗氧化剂 2%抗氧化剂
98%菜子油 90%菜子油 85%菜子油 65%TMP/C12-C18* 15%TMP/C12-C18*
8%添加剂酯料 9%添加剂酯料 33%植物油 83%植物油
4%Hv.聚合物
*平均碳数等于C16(TMP/C16 )**加氢精制的植物油。
图2是各种工业的天然和合成基料的稳定性(用HPDSC测定)和可生物降解性(用RBOT测定)与本发明的新多元醇酯的比较。图2表明,在可生物降解和氧化稳定性方面,本发明的可生物降解的基料远远优于任何其它的基料。
                    实施例6
通过将1摩尔工业级季戊四醇与1.05-3.15摩尔的混合直链C6-C12酸(例如,C810酸)和1.05-3.15摩尔的异C8酸(例如,Cekanoic8酸)反应制备低毒性基料。从该反应形成的酯对哺乳动物和水生生物具有非常低的毒性。由于其极好的润滑性,稳定性,低温性质,和可生物降解性,这些酯作为在环境敏感的地方,例如野生生物保护方面使用的润滑油基料是理想的。由于该基料的物理性质,用这些酯配制的润滑剂需要较少的添加剂,这进一步降低了润滑剂的毒性。
进行下面的研究以便确定通过将季戊四醇与n-C8/n-C10(C810)和异-C8(Cekanoic8)酸反应制备的多元醇酯基料对在半静止的体系中96小时的黑头呆鱼,Pimephales promelas的实际毒性。
方法产生的数据表明:使用乙醇作为载体,在50mg试验材料/ml乙醇浓度下,5.0mg/L是最大可达到的水溶解浓度。在低于5mg/L的浓度下在水溶液的表面上试验材料形成光泽。这表明该试验材料从溶液中出来了并且已经超过了该酯基料与该载体的最大水可溶浓度。
该试验的常规处理量是5.0mg/l,2.5mg/l,1.25mg/l,0.625mg/l和0.312mg/l。这些处理量的测定值是4.11mg/l,2.15mg/l,1.30mg/l,0.85mg/l和0.24mg/l。以0.1mg/l的浓度试验该载体作为对照。也试验实验室稀释水对照(BW1)。通过将1.5g的酯基料加入到30ML的乙醇中来制备料溶液(每毫升乙醇50mg本发明的酯基料)。通过将合适量的基料加入到实验室稀释水中制备处理溶液。将每处理的水容纳馏份(WAF)分进2个同样的仓内。使用在0天制备的料溶液每天制备新的处理和对照用于更新。从0天(“新”溶液)和第1天和第3天(“旧”溶液)的每个处理和对照中取出样品用气相色谱分析。
在任何处理量下在96小时的期间内没有出现死亡,因此LC50大于4.11mg/l(测定值),为在该试验方法条件下可以制备和试验的最高浓度。不引起死亡的最大负载浓度是5.0mg/l,为试验的最高浓度。没有引起100%死亡的最小负载浓度。
                         实施例7
使用DECD方法202进行该项研究以便确定对在静止体系中48小时在Daphnia,Daphnia magna中的多元醇酯基料的实际毒性。通过将工业级季戊四醇与Cekanoic8和C810脂肪酸反应制备按照本发明的多元醇酯基料。
EL50(有效负载50)是计算的在特定暴露时间期间内导致50%总数固定不动的处理量。48小时(EL50)值大于1000mg/L,为试验的最高浓度,以暴露于试验物质的水容纳馏份(WAF)计。试验结果概述于下面表9中。
表9
  负载量(mg/L)     固定百分数
    24小时     48小时
    控制     0     0
    62.5     0     5
    125     0     0
    250     0     0
    500     0     0
    1000     0     5
不能报道不引起固定不动的最大(负载)浓度,因为在最低浓度(62.5mg/l)下仅观察到5%的固定不动。没有引起100%固定不动的浓度。
                    实施例8
使用DECD方法202进行该项研究以便确定在海藻,selenastrumcapricomutum中的多元醇酯基料的实际毒性。通过将工业级季戊四醇与Cekanoic8和C810脂肪酸反应制备按照本发明的多元醇酯基料。
由于该本发明的多元醇基料的低水溶性,所以对5个暴露负载制备水容纳馏份(WAF)。用于该试验的正常负载量是10000mg/l,500mg/l,250mg/l,和62.5mg/l的该多元醇酯。每个负载量制备4个同样的仓并测定72和96小时的最终点数。
计算的72小时和96小时NOEL(没有观察到有效负载)值分别是1000mg/l,为试验的最高浓度,和62.5mg/l。它是基于1)生长曲线的面积和2)平均比生长速度的。由于如通过在生长曲线下面积减少或在下面表10中所示的平均比生长速度测定的,缺少令人满意明显效果,所以不能够计算这2个最终点数的72和96小时EL50(有效负载50)。
      表10
相对于对比的抑制性%
负载量(mg/L)     平均比生长曲线   在生长曲线下面的面积
    72小时     96小时     72小时     96小时
    62.5     8.3     4.1     28.3     20.9
    125     3.8     2.7     14.0     13.2
    250     5.3     3.0     20.6     16.4
    500     2.3     3.0     6.4     12.0
    1000     0.4     2.5     1.0     9.8
                      实施例9
使用MicrotoxR生物测定法进行该项试验以便确定在Photobacteriumphosphoreum中的多元醇酯基料的实际毒性。通过将工业级季戊四醇与Cekanoic8和C810脂肪酸反应制备按照本发明的多元醇酯基料。
由于该本发明的多元醇基料的低水溶性,所以对5个暴露负载制备水容纳馏份(WAF)。用于该试验的正常负载量是10000mg/l,500mg/l,250mg/1,和62.5mg/l的该多元醇酯。在5分钟和15分钟间隔下测定光读数。进行第2次试验以便验证第1次试验的结果。
有效负载(EL50)是在该多元醇酯负载量下由于毒性的结果损失一半的光(指标准发光试剂)。对于5分钟和15分钟EL50值的两个试验大于1000mg/l,为试验的最高浓度,以暴露于该多元醇酯的WAF计。这些试验的结果列于下面表11中。
表11
    负载量(mg/L)   平行测定        试验       试验
  5分钟   5分钟   5分钟   5分钟
    对照     1     82     67     72     62
    2     73     59     84     72
    3     77     64     79     69
    平均     77     63     78     68
    125     1     78     63     76     65
    2     76     63     77     65
    3     76     62     74     62
    平均     77     63     76     64
    250     1     70     58     71     60
    2     71     59     70     59
    3     73     60     74     63
    平均     71     59     72     61
    500     1     71     58     70     59
    2     69     58     70     59
    3     69     57     67     56
    平均     70     57     69     58
    1000     1     70     58     70     58
    2     71     58     70     57
    3     69     55     73     59
    平均     70     57     71     58
在已知很多酯破坏密封垫的地方,按照本发明制备的酯与其它酯基料相比表明基本上降低了密封垫膨胀。
按照本发明制备一个酯基料的样品,其中将2201b(99.8kg)的C810酸和2051b(93kg)的Cekanoic8酸(50∶50摩尔比)装进反应器容器中并在大气压下加热至430F(221℃)。此后,将751b(34kg)的工业级季戊四醇加入到该酸混合物中和降低压力直到水开始析出。顶部取出水以便引起该反应。在约6小时反应时间后,顶部除去过量的酸直到该反应产物达到总酸数为0.26mgKOH/g。然后用两倍化学计量量的Na2CO3(以酸数计)和0.15%(重量)的混合物(以在反应器中的量计)在90℃中和和脱色该产物2小时。该混合物是80%(重量)的碳黑和20%(重量)的dicalite的混合物。在90℃2小时后,真空过滤该产物以便除去固体。
如在所附的图3中所示的,表明按照本发明形成的酯基料与其它酯基料,例如季戊四醇/n-C7酯(PE/nC7),TMP/7810酯,异nonal醇/Cekanoic8酯(INA/Ck8),二异癸基己二酸酯(DIDA)和二(十三烷基)己二酸酯(DTDA)相比对密封垫是相对中性的。这在需要添加剂溶解性的酯配方中是特别重要的。另外,在密封垫膨胀对设备性能是关键的地方可以将这些酯用作基料。因为这些酯不破坏密封垫,所以密封垫的寿命应该增加。
                   实施例10
本发明的可生物降解的合成酯基料需要使用非常特定的支链C8与直链C810的比例,这样如通过改进的Sturm试验测定的,如下面表12中所示的,在28天可以得到的至少60%的生物降解。
表12
样品号 iso-C8∶n-C810比例 粘度@40℃cSt 改进的Sturm实验的生物降解性%
    1     30∶70     34.87     99
    2     40∶60     38.78     89
    3     45∶55     38.90     80
    4     55∶45     43.08     61
    5     65∶45     46.45     59
                    实施例11
将工业级季戊四醇(TechPE)的酯与1.05-3.15摩尔的C6-C12直链酸和1.05-3.15摩尔的异-C8(Cekanoic8)酸反应从而形成显示出下面性质的可生物降解的合成酯基料:如通过改进的Sturm试验测定的,在28天至少60%生物降解;倾点低于-25℃;25℃的粘度低于7500cps;和用HPDSC测定的氧化稳定性高达45分钟。通过将三羟甲基丙烷与直链C7,8,10酸反应制备第2个可生物降解的酯。这两个酯以50∶50的比例(TPE/C810/异-C8∶TMP/n-C7,8,10)混合在一起并且令人意想不到地生产出了比在下面表13中所示的单独一个组分都更可生物降解的混合产物。
表13
样品号 反应剂 改进的Sturm实验的生物降解性%
    1 TPE/C810/iso-C8     75.3%
    2 TMP/n-C7,8,10     76.1%
    3 TPE/C810/iso-Ci和TMP/n-c7,8,10     80.7%
TPE表示工业级季戊四醇
TMP表示三羟甲基丙烷
C810表示3-5%正C6酸,48-58%正C8酸,36-42%正C10酸,和0.5-1%正C12酸。
异-C8表示Cekanoic8酸,26%(重量)的3,5-二甲基己酸,19%(重量)的4,5-二甲基己酸,17%(重量)的3,4-二甲基己酸,11%(重量)的5-甲基庚酸,5%(重量)的4-甲基庚酸,和22(重量)混合的甲基庚酸和二甲基己酸。
n-C7,8,10表示具有7,8和10个碳原子的直链酸的混合物,例如37%(摩尔)正C7酸,39%(摩尔)C8酸,21%(摩尔)C10酸和3%(摩尔)C6酸。
                    实施例12
将工业级季戊四醇(TechPE)的酯与1.05-3.15摩尔的C6-C12直链酸和1.05-3.15摩尔的异-C8(Cekanoic8)酸反应从而形成显示出下面性质的可生物降解的合成酯基料:如通过改进的Sturm试验测定的,在28天至少60%生物降解;倾点低于-25℃;25℃的粘度低于7500cps;和用HPDSC测定的氧化稳定性高达45分钟。通过将三羟甲基丙烷与直链C7,8,10酸反应制备第2个可生物降解的酯。这两个酯以75∶25的比例(TPE/C810/异-C8∶TMP/n-C7,8,10)混合在一起并且令人意想不到地生产出了比在下面表14中所示的单独一个组分都更可生物降解的混合产物。
表14
样品号 反应剂 改进的Stum实验的生物降解性%
    1 TPE/C810/iso-C8     65.1%
    2 TMP/n-C7,8,10     62.9%
    3 TPE/C810/iso-C8和TMP/n-C7,8,10     72.6%
TPE表示工业级季戊四醇
TMP表示三羟甲基丙烷
C810表示3-5%正C6酸,48-58%正C8酸,36-42%正C10酸,和0.5-1%正C12酸。
异-C8表示Cekanoic8酸,26%(重量)的3,5-二甲基己酸,19%(重量)的4,5-二甲基己酸,17%(重量)的3,4-二甲基己酸,11%(重量)的5-甲基庚酸,5%(重量)的4-甲基庚酸,和22(重量)混合的甲基庚酸和二甲基己酸。
n-C7,8,10表示具有7,8和10个碳原子的直链酸的混合物,例如37%(摩尔)正C7酸,39%(摩尔)C8酸,21%(摩尔)C10酸和3%(摩尔)C6酸。
                   实施例13
将工业级季戊四醇(TechPE)的酯与1.05-3.15摩尔的C6-C12直链酸和1.05-3.15摩尔的异-C8(Cekanoic8)酸反应从而形成显示出下面性质的可生物降解的合成酯基料:如通过改进的Sturm试验测定的,在28天至少60%生物降解;倾点低于-25℃;25℃的粘度低于7500cps;和用HPDSC测定的氧化稳定性高达45分钟。按照常规的方法制备第2个可生物降解的二(异三癸基)己二酸酯。这两个酯以50∶50的比例(TPE/C810/异-C8∶DTDA)混合在一起并且令人意想不到地生产出了比在下面表15中所示的单独一个组分都更可生物降解的混合产物。
表15
样品号 反应剂 改进的Sturm实验的生物降解性%
1 TPE/C810/iso-C8  65.1%
2 DTDA  62.7%
3 TPE/C810/iso-C8和DTDA  79.9%
TPE表示工业级季戊四醇
C810表示3-5%正C6酸,48-58%正C8酸,36-42%正C10酸,和0.5-1%正C12酸。
异-C8表示Cekanoic8酸,26%(重量)的3,5-二甲基己酸,19%(重量)的4,5-二甲基己酸,17%(重量)的3,4-二甲基己酸,11%(重量)的5-甲基庚酸,5%(重量)的4-甲基庚酸,和22(重量)混合的甲基庚酸和二甲基己酸。

Claims (33)

1.一种包括下面基料混合物的可生物降解的合成酯基料:
(A)下面物质的反应产物:(1)具有通式R(OH)n的直链或支链醇,其中R是具有约2-20个碳原子的脂族或环脂族基团和n至少是2;和(2)包括约30-80%(摩尔)碳数在约C5-C12范围的直链酸,和约20-70%(摩尔)的至少一种碳数在约C5-C10范围的支链酸的混合酸,并且其中不大于10%的用于形成所述的可生物降解的合成酯基料的所述支链酸含有季碳;其中所述的酯基料显示出下面的性质:通过改进的Sturm试验测定,在28天至少60%生物降解;倾点低于-25℃;和-25℃的粘度低于7500cps;和
(B)通过改进的Sturm试验测定在28天至少60%生物降解的另一个基料;由此,该混合产物的通过改进Sturm试验测定的在28天的生物降解性比单独的(A)或(B)更大。
2.按照权利要求1的可生物降解的合成酯基料,其中所述的基料(B)是下面物质的反应产物:(1)具有通式R(OH)n的直链或支链醇,其中R是具有约2-20个碳原子的脂族或环脂族基团和n至少是2;和碳数在约C5-C12范围的直链酸。
3.按照权利要求2的可生物降解的合成酯基料,其中所述的基料(B)是包括37%(摩尔)n-C7酸,39%(摩尔)C8酸,21%(摩尔)C10酸和3%(摩尔)C6酸。
3.按照权利要求2的可生物降解的合成酯基料,其中所述的基料(B)是二(异三癸基)己二酸酯。
4.按照权利要求1的可生物降解的合成酯基料,其中所述的直链或支链醇选自:工业级季戊四醇,单季戊四醇,二季戊四醇,新季戊四醇,三羟甲基丙烷,乙二醇或丙二醇,丁二醇,山梨醇,和2-甲基丙二醇。
5.按照权利要求1的可生物降解的合成酯基料,其中所述的支链酸主要是每摩尔平均支链化在约0.3-1.9范围的双支链的或α支链的酸。
6.按照权利要求1的可生物降解的合成酯基料,其中所述的支链酸是至少一种选自:2-乙基己酸,异庚酸,异辛酸,异壬酸,和异癸酸。
7.一种可生物降解的润滑剂,它是从下面物质制备的:
至少一种包括下列基料混合物的可生物降解的合成酯基料:(A)下面物质的反应产物:(1)具有通式R(OH)n的直链或支链醇,其中R是具有约2-20个碳原子的脂族或环脂族基团和n至少是2;和(2)包括约30-80%(摩尔)碳数在约C5-C12范围的直链酸,和约20-70%(摩尔)的至少一种碳数在约C5-C10范围的支链酸的混合酸,并且其中不大于10%的用于形成所述的可生物降解的合成酯基料的所述支链酸含有季碳;其中所述的酯基料显示出下面的性质:通过改进的Sturm试验测定,在28天至少60%生物降解;倾点低于-25℃;和-25℃的粘度低于7500cps;和(B)通过改进的Sturm试验测定在28天至少60%生物降解的另一个基料;由此,该混合产物的通过改进Sturm试验测定的在28天的生物降解性比单独的(A)或(B)更大;和
一种润滑剂配料。
8.按照权利要求7的可生物降解的润滑剂,其中所述的基料(B)是下面物质的反应产物:(1)具有通式R(OH)n的直链或支链醇,其中R是具有约2-20个碳原子的脂族或环脂族基团和n至少是2;和碳数在约C5-C12范围的直链酸。
9.按照权利要求8的可生物降解的润滑剂,其中所述的基料(B)是包括37%(摩尔)n-C7酸,39%(摩尔)C8酸,21%(摩尔)C10酸和3%(摩尔)C6酸。
10.按照权利要求7的可生物降解的润滑剂,其中所述的基料(B)是二(异三癸基)己二酸酯。
11.按照权利要求7的可生物降解的润滑剂,其中所述的直链或支链醇选自:工业级季戊四醇,单季戊四醇,二季戊四醇,新季戊四醇,三羟甲基丙烷,乙二醇或丙二醇,丁二醇,山梨醇,和2-甲基丙二醇。
12.按照权利要求7的可生物降解的润滑剂,其中所述的支链酸主要是每摩尔平均支链化在约0.3-1.9范围的双支链的或α支链的酸。
13.按照权利要求7的可生物降解的润滑剂,其中所述的支链酸是至少一种选自:2-乙基己酸,异庚酸,异辛酸,异壬酸,和异癸酸。
14.按照权利要求7的可生物降解的润滑剂,其中所述的添加剂配料包括选自下面物质的添加剂:粘度指数改进剂,腐蚀抑制剂,氧化抑制剂,分散剂,润滑油流动改进剂,洗涤剂和防锈剂,倾点下降剂,防沫剂,耐磨剂,密封膨胀剂,和摩擦改性剂。
15.按照权利要求7的可生物降解的润滑剂,其中所述的可生物降解的润滑剂是弹射器油。
16.按照权利要求15的可生物降解的润滑剂,其中所述的添加剂配料包括至少一种选自下面物质的添加剂:粘度指数改进剂,腐蚀抑制剂,氧化抑制剂,偶联剂,分散剂,耐特压剂,颜色稳定剂,洗涤剂和防锈剂,防沫剂,耐磨剂,和摩擦改性剂。
17.按照权利要求7的可生物降解的润滑剂,其中所述的可生物降解的润滑剂是水力流体。
18.按照权利要求17的可生物降解的润滑剂,其中所述的添加剂配料包括至少一种选自下面物质的添加剂:粘度指数改进剂,腐蚀抑制剂,边界润滑剂,破乳剂,倾点下降剂,和防沫剂。
19.按照权利要求7的可生物降解的润滑剂,其中所述的可生物降解的润滑剂是钻孔液体。
20.按照权利要求19的可生物降解的润滑剂,其中所述的添加剂配料包括至少一种选自下面物质的添加剂:粘度指数改进剂,腐蚀抑制剂,悬浮剂,水损失改进剂,生物杀伤剂,和钻头乳化剂。
21.按照权利要求7的可生物降解的润滑剂,其中所述的可生物降解的润滑剂是水轮机油。
22.按照权利要求21的可生物降解的润滑剂,其中所述的添加剂配料包括至少一种选自下面物质的添加剂:粘度指数改进剂,腐蚀抑制剂,氧化抑制剂,增稠剂,分散剂,抗乳化剂,颜色稳定剂,洗涤剂和防锈剂,和倾点下降剂。
23.按照权利要求7的可生物降解的润滑剂,其中所述的可生物降解的润滑剂是润滑脂。
24.按照权利要求23的可生物降解的润滑剂,其中所述的添加剂配料包括至少一种选自下面物质的添加剂:增稠剂,粘度指数改进剂,腐蚀抑制剂,氧化抑制剂,耐特压剂,洗涤剂和防锈剂,倾点下降剂,金属碱活剂,和抗磨添加剂。
25.按照权利要求7的可生物降解的润滑剂,其中所述的可生物降解的润滑剂是压缩机油。
26.按照权利要求25的可生物降解的润滑剂,其中所述的添加剂配料包括至少一种选自下面物质的添加剂:氧化抑制剂,洗涤剂和防锈剂,金属碱活剂,添加剂加溶剂,破乳剂和抗磨添加剂。
27.按照权利要求7的可生物降解的润滑剂,该润滑剂还含有溶剂。
28.按照权利要求27的可生物降解的润滑剂,其中所述的可生物降解的合成酯基料存在的量是约50-99%(重量),所述的润滑剂添加剂配料存在的量是约1-20%(重量);和溶剂存在的量是约1-30%。
29.按照权利要求7的可生物降解的润滑剂,其中所述的可生物降解的润滑剂是2循环发动机油。
30.按照权利要求29的可生物降解的润滑剂,其中所述的添加剂配料包括至少一种选自下面物质的添加剂:粘度指数改进剂,腐蚀抑制剂,氧化抑制剂,偶联剂,分散剂,耐特压剂,颜色稳定剂,表面活性剂,稀释剂,洗涤剂和防锈剂,倾点下降剂,防沫剂,和抗磨添加剂。
31.按照权利要求29的可生物降解的润滑剂,其中所述的分散剂是官能化的和衍生的烃,其中官能作用包括至少一个式-CO-Y-R3的基团,其中Y是O或S;R3是芳基,取代的芳基或取代的烃基,和-Y-R3的pKa为12或更低;其中至少50%的官能团被连接到叔碳原子上;和其中所述的官能化烃是由亲核反应剂衍生的。
32.按照权利要求7的可生物降解的润滑剂,其中所述的可生物降解的润滑剂是齿轮油。
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