CN107418651B - 一种羧基化柠檬酸三庚酯钙盐润滑油清净剂及其制备方法 - Google Patents
一种羧基化柠檬酸三庚酯钙盐润滑油清净剂及其制备方法 Download PDFInfo
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- 239000010687 lubricating oil Substances 0.000 title claims description 28
- 238000002360 preparation method Methods 0.000 title abstract description 11
- NGBJYZDRPVGDJI-UHFFFAOYSA-N triheptyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCCOC(=O)CC(O)(C(=O)OCCCCCCC)CC(=O)OCCCCCCC NGBJYZDRPVGDJI-UHFFFAOYSA-N 0.000 claims abstract description 38
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical group [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
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Abstract
一种羧基化柠檬酸三庚酯钙盐清净剂及其制备方法。本发明清净剂的原料组成包括：羧基化柠檬酸三庚酯5‑25mol％、氧化钙15‑40mol％、分散剂2‑10mol％、溶剂10‑40mol％、促进剂0.5‑5mol％、助溶剂1‑5mol％，二氧化碳10‑40mol％，其中羧基化柠檬酸三庚酯具有如下式I的分子结构。本发明提供的清净剂具有优良的耐高温性能。
Description
技术领域
本发明属于精细化工领域，具体涉及到一种羧基化柠檬酸三庚酯钙盐润滑油清净剂及其制备方法。
背景技术
润滑油是用在各种类型汽车、机械设备上以减少摩擦，保护机械及加工件的液体或半固体润滑剂，主要起润滑、冷却、防锈、清洁、密封和缓冲等作用。但是在发动机润滑油的使用过程中，由于工况使用条件苛刻、高温氧化以及外界的氮氧化合物、二氧化硫的酸性气体的吸入等因素往往导致润滑油容易发生氧化降解，且产生一定量的酸性腐蚀物，如硫酸、硝酸、酸性油泥等，使润滑油的润滑作用下降且加剧对设备的腐蚀。因此，需要加入润滑油清净剂来持续中和润滑油使用过程中产生的酸性物质，阻止其对发动机造成腐蚀，从而达到延长润滑油的使用寿命、保护发动机的目的。
润滑油金属清净剂是一种广泛使用的润滑油添加剂，它的加入能够持续的中和发动机机油在使用过程中所发生氧化降解生成的酸性物质，从而阻止其对发动机造成的腐蚀，同时由于清净剂皂盐对有害颗粒物的乳化作用，可以达到减慢油品变质、延长使用时间的目的。目前关于润滑油清净剂的制备方法均是采用传统的有机酸与碱性氧化物发生反应将胶体碳酸盐分散在稀释油中，有机酸盐及胶体碳酸盐体系与稀释油属于物理相容范畴，稀释油主要就是润滑油基础油，又称为中性油或者溶剂油等，如CN 101195785A、CN102899132A、CN 103265995A等均需要使用这类稀释油作为主要组分。
然而，往往在高温使用过程中，会破坏原有的物理相容体系，产生胶体碳酸盐及有机酸盐析出物，从而减少了润滑，增加了摩擦。
发明内容
为此，本发明的目的之一在于提供一种羧基化柠檬酸三庚酯钙盐润滑油清净剂，该清净剂配方中不需要使用稀释油，耐高温性能优良。
为达上述目的，本发明采用如下技术方案：
一种羧基化柠檬酸三庚酯钙盐润滑油清净剂，其原料组成包括：
其中羧基化柠檬酸三庚酯具有如下式I的分子结构：
作为优选，所述清净剂原料组成包括：
针对现有技术的不足，本发明提供的羧基化的柠檬酸三庚酯钙盐清净剂原料采用羧基化的柠檬酸三庚酯，其自身带有合成酯基础油的特征官能团及羧基化的有机酸，能够自身起到过碱化反应及稀释油分散的双重作用，获得清净剂内的碱性有机酸盐、胶体碳酸盐与稀释油是分子内的结合，属于化学相容的范畴，在高温条件下相容性体系不易被破坏，耐高温性能优良。
作为优选，羧基化柠檬酸三庚酯的合成过程如下：
(1)柠檬酸与正庚醇反应后脱除多余的正庚醇后得到柠檬酸三庚酯；
(2)步骤(1)得到的柠檬酸三庚酯与癸二酸进行酯化反应，得到羧基化的羧基化柠檬酸三庚酯，其中癸二酸与柠檬酸三庚酯分子中的羟基反应。合成过程及分子结构为：
优选地，步骤(1)中柠檬酸与正庚醇的摩尔比为1:2-5，优选为1:3.5。
优选地，反应在钛酸丁酯催化下进行。
优选地，反应的温度为150-180℃，时间为2-6h。
多余的正庚醇可通过减压脱除。
优选地，步骤(2)中柠檬酸三庚酯与癸二酸的摩尔比为1:0.5-2，优选为1:1。
优选地，柠檬酸三庚酯酸值为125-130mgKOH/g。
优选地，酯化反应的温度为180-220℃，时间为1-5h。
本发明的一个优选实施例中，羧基化柠檬酸三庚酯由柠檬酸按照摩尔比1:3.5与正庚醇在钛酸丁酯催化下，150-180℃反应2-6h后，减压脱除多余的正庚醇后得到柠檬酸三庚酯，然后再加入与柠檬酸三庚酯摩尔比1:1的癸二酸与柠檬酸三庚酯分子中的羟基进行酯化反应，反应温度180-220℃，反应时间1-5h，得到羧基化的羧基化柠檬酸三庚酯。优选地，羧基化的柠檬酸三庚酯酸值为125-130mgKOH/g。
作为优选，所述分散剂为脂肪胺聚氧乙烯醚，优选江苏海安石油化工厂的AC-1812产品。
作为优选，所述溶剂为甲苯和/或二甲苯，优选为甲苯。
作为优选，所述促进剂为四甲基氢氧化铵溶液，优选为质量分数10-50％的四甲基氢氧化铵溶液，更优选为25％的四甲基氢氧化铵溶液。作为优选，所述助溶剂为乙醇和/或二乙胺，优选为乙醇。
作为优选，本发明所述的清净剂原料组成包括：
本发明的目的之一还在于提供一种本发明所述的羧基化柠檬酸三庚酯钙盐清净剂的制备方法，包括以下步骤：
(1)将原料羧基化柠檬酸三庚酯、氧化钙、分散剂、溶剂、促进剂、助溶剂混合在35℃-60℃中和1-5h；
(2)升温后通入二氧化碳气体；
(3)去渣，去溶剂即得到润滑油清净剂。
作为优选，步骤(1)中中和的时间为2-4h。
混合可在搅拌下进行。
作为优选，步骤(3)中去渣可通过离心或过滤去渣。
优选地，去溶剂可通过减压蒸馏去除。
作为优选，所述制备方法包括以下步骤：
A、配方量的羧基化柠檬酸三庚酯、氧化钙、分散剂、溶剂、促进剂、助溶剂加入反应器内，开启搅拌充分混合；
B、在35℃-60℃中和2-4.0小时；
C、然后升温至65-95℃，通入配方量的二氧化碳气体，通气速率为100-200mL/min；
D、离心或过滤去渣，减压蒸馏脱去溶剂即得到润滑油清净剂。
传统的润滑油清净剂基本都是使用单纯的有机酸，如十二烷基苯磺酸、水杨酸等，其中和及分散后的碱性产物由于是固体，必须借助润滑油基础油作为稀释油才能得到液体的润滑油清净剂；而本发明采用羧基化的柠檬酸三庚酯作为原料，该原料自身带有三个庚酯基团，是合成酯的结构，油溶性及流动性很好，羧基化后的柠檬酸三庚酯既可以起到有机酸原料的作用，又可以起到稀释油的作用，使用该原料制备钙盐清净剂不需要再额外使用稀释油。传统的使用稀释油制备的润滑油清净剂由于有机酸盐被分散在稀释油中，属于两种体系的物理融合，在一般的条件下基本没有问题，但是在苛刻的高温条件下，会出现分相析出等问题，导致一般的清净剂不适宜用于长期高温润滑油体系中；而本发明采用的合成酯稀释油与有机酸均属于同一分子内，有机酸盐被自身合成酯结构所分散，形成稳定的分子内均相体系，属于化学结构范畴，在苛刻的高温条件下，稳定性非常好，不会被高温等外界条件所破坏，导致有机酸盐析出，因此，耐高温性能非常优良。
具体实施方式
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅用于帮助理解本发明，不应视为对本发明的具体限制。
实施例1
一种羧基化柠檬酸三庚酯钙盐清净剂，其原料组成包括：羧基化柠檬酸三庚酯10mol、氧化钙30mol、脂肪胺聚氧乙烯醚(AC-1812)2mol、甲苯30mol、四甲基氢氧化铵2mol、乙醇1mol、二氧化碳25mol。制备方法如下：
A、配方量的羧基化柠檬酸三庚酯、氧化钙、分散剂、溶剂、促进剂、助溶剂加入反应器内，开启搅拌充分混合；
B、在35℃-55℃中和2-4小时；
C、然后升温至65-95℃，通入配方量的二氧化碳气体，通气速率为100-200mL/min；
D、离心或过滤去渣，减压蒸馏脱去溶剂即得到润滑油清净剂。
实施例2
一种羧基化柠檬酸三庚酯钙盐清净剂，其原料组成包括：羧基化柠檬酸三庚酯25mol、氧化钙15mol、脂肪胺聚氧乙烯醚(AC-1812)10mol、甲苯30mol、四甲基氢氧化铵5mol、乙醇5mol、二氧化碳10mol。
制备方法同实施例1。
实施例3
一种羧基化柠檬酸三庚酯钙盐清净剂，其原料组成包括：羧基化柠檬酸三庚酯20mol、氧化钙40mol、脂肪胺聚氧乙烯醚(AC-1812)7.5mol、甲苯10mol、四甲基氢氧化铵0.5mol、乙醇1mol、二氧化碳21mol。
制备方法同实施例1。
实施例4
一种羧基化柠檬酸三庚酯钙盐清净剂，其原料组成包括：羧基化柠檬酸三庚酯15mol、氧化钙21mol、脂肪胺聚氧乙烯醚(AC-1812)6mol、甲苯22mol、四甲基氢氧化铵3mol、乙醇3mol、二氧化碳30mol。
制备方法同实施例1。
上述实施例制得的产品外观为浅黄色透明液体，碱值：330-380mgKOH/g；粘度：25-40mm2/s。
对比例1
其它同实施例1，仅将羧基化柠檬酸三庚酯换成市售烷基苯磺酸，工业品，购自南京盛雄化工有限公司。
对比例2
其它同实施例1，仅将羧基化柠檬酸三庚酯换成市售精制环烷酸，工业品，购自济南博奥化工有限公司。
对比例3
其它同实施例1，仅将羧基化柠檬酸三庚酯换成市售烷基水杨酸，工业品，购自锦州圣大化学品有限公司。
对比例4
其它同实施例1，将羧基化柠檬酸三庚酯换成市售烷基苯磺酸，工业品，购自南京盛雄化工有限公司；同时添加稀释油(150SN)5mol，稀释油(150SN)购自苏州赛帕汉特种油品有限公司。
对比例5
其它同实施例1，将羧基化柠檬酸三庚酯换成市售精制环烷酸，工业品，购自济南博奥化工有限公司；同时添加稀释油(150SN)5mol，稀释油(150SN)购自苏州赛帕汉特种油品有限公司。
对比例6
其它同实施例1，将羧基化柠檬酸三庚酯换成市售烷基水杨酸，工业品，购自锦州圣大化学品有限公司；同时添加稀释油(150SN)5mol，稀释油(150SN)购自苏州赛帕汉特种油品有限公司。
对实施例和对比例制得的润滑油清净剂测定碱值、粘度、热稳定性及胶体物析出测试，测试方法如下，结果见下表1中所示。
测试方法：碱值测定依据SH/T 0251-1993石油产品碱值测定法(高氯酸电位滴定法)；粘度测定依据GB/T 265-88石油产品运动黏度测定法和动力黏度计算法；热稳定性及胶体物析出等依据SH/T0300-92曲轴箱模拟试验方法(QZX法)。
表1
本发明中由于羧基化柠檬酸三庚酯起到稀释油和有机酸皂分散的双重作用，可以不使用稀释油即可制得耐高温性能非常优良的清净剂产品，而市场上主要产品如烷基苯磺酸、环烷酸、烷基水杨酸等，如果不使用稀释油，因为结构中不含稀释油的酯类结构，不使用稀释油的话，产品碱值低，且粘度极大，耐热性极差，见对比例1-3与实施例1的比较，当它们使用稀释油的时候，碱值会上升，粘度会下降，同时耐热性也会逐渐提高，但是仍与本方案有一定的差距，见对比例4-6与实施例1的比较。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
1.一种羧基化柠檬酸三庚酯钙盐润滑油清净剂，其原料组成包括：
其中羧基化柠檬酸三庚酯具有如下式I的分子结构：
2.根据权利要求1所述的清净剂，其特征在于，羧基化柠檬酸三庚酯的合成过程如下：
(1)柠檬酸与正庚醇反应后脱除多余的正庚醇后得到柠檬酸三庚酯；
(2)步骤(1)得到的柠檬酸三庚酯与癸二酸进行酯化反应，得到羧基化的羧基化柠檬酸三庚酯。
3.根据权利要求2所述的清净剂，其特征在于，步骤(1)中柠檬酸与正庚醇的摩尔比为1:2-5；
反应在钛酸丁酯催化下进行；
反应的温度为150-180℃，时间为2-6h。
4.根据权利要求2或3所述的清净剂，其特征在于，步骤(2)中柠檬酸三庚酯与癸二酸的摩尔比为1:0.5-2；
酯化反应的温度为180-220℃，时间为1-5h。
5.根据权利要求1所述的清净剂，其特征在于，所述分散剂为脂肪胺聚氧乙烯醚。
6.根据权利要求1所述的清净剂，其特征在于，所述溶剂为甲苯和/或二甲苯。
7.根据权利要求1所述的清净剂，其特征在于，所述促进剂为四甲基氢氧化铵溶液。
8.根据权利要求1所述的清净剂，其特征在于，所述助溶剂为乙醇和/或二乙胺。
9.根据权利要求1所述的清净剂，其特征在于，所述的清净剂原料组成包括：
10.一种权利要求1-9任一项所述的羧基化柠檬酸三庚酯钙盐润滑油清净剂的制备方法，包括以下步骤：
(1)将原料羧基化柠檬酸三庚酯、氧化钙、分散剂、溶剂、促进剂、助溶剂混合在35℃-60℃中和1-5h；
(2)升温后通入二氧化碳气体，通入速率为50-350mL/min；
(3)去渣，去溶剂即得到润滑油清净剂。
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