酯类系列润滑材料的合成及其性能研究
蔡国星
学位类型博士
导师吾满江·艾力
2014-05-22
学位授予单位中国科学院大学
学位授予地点北京
学位专业有机化学
关键词合成酯类 合成酯类 润滑油 润滑油 抗磨 抗磨 粘度改性剂 粘度改性剂 无溶剂酯化 无溶剂酯化
其他摘要

本论文的研究工作是基于新戊基多元醇、二元脂肪酸、一元脂肪酸和丙烯酸及丙烯酸酯为基础的酯类系列润滑材料的研究和开发,并对多元醇酯的无溶剂酯化反应工艺进行了研究。设计与合成了一系列新戊基多元醇酯、多元醇复合酯、丙烯酸多元醇聚合酯及分子量可控的具有粘度指数改进功能的抗磨型聚丙烯酸酯类润滑产品。对所合成的润滑产品理化参数进行了测试,并考察了产品的的氧化安定性和热氧化稳定性,对抗磨型粘度指数改进剂进行了抗磨性能和剪切稳定性测试。结果表明,本文合成的系列酯类是一类性能优异的润滑产品。主要内容和结论如下:
(1)以新戊二醇、三羟甲基丙烷、季戊四醇、单元脂肪酸(庚酸、正辛酸、异辛酸、壬酸、癸酸和油酸)为主要原料,在对甲苯磺酸的作用下,在真空无溶剂条件下直接酯化,合成了一系列多元醇酯润滑基础油,并优化了工艺条件。傅立叶红外吸收光谱确定这类合成酯的结构与目标产物的结构一致。通过对这些合成酯的理化参数的测定,证明这类合成酯是一类性能优异的润滑油基础油。通过产品的理化指标检测结果可以得到结论:相同多元醇和一元羧酸酯化后的产品性能受到羧酸分子结构的影响,奇数碳原子数的羧酸酯化后的产品低温流动性优于相邻两个偶数碳的羧酸酯产品;分子中增加支链会提高产品的粘度指数和降低倾点;相同脂肪酸和不同多元醇酯化反应,产品粘度由大到小依次为季戊四醇酯>三羟甲基丙烷酯>新戊二醇酯,而低温流动性则相反。
(2)以三羟甲基丙烷、单元脂肪酸和二元羧酸为主要原料,在对甲苯磺酸的作用下,经过两步酯化反应,合成了一系列复合酯类润滑基础油,并通过傅立叶红外光谱分析确定了合成酯的结构与目标产物的结构一致。对其物理性能进行测试,结果表明,当原料中一元脂肪酸的碳链增加时,得到的复合酯类产品的粘度和闪点有所升高;原料中一元脂肪酸的碳链数为偶数时,得到的产品粘度指数和倾点指标均不如相邻奇数碳链一元脂肪酸酯得到测产品越;当原料中二元羧酸的碳链长度增加时,得到的复合酯产品粘度、粘度指数和闪点均增加,而倾点有所升高,氧化安定性变化不大,有提高趋势;当复合酯分子结构中含有双键时,产品的氧化安定性能不高。
(3)以三羟甲基丙烷、庚酸和丙烯酸为主要原料,在对甲苯磺酸催化剂条件下,经过两步酯化反应,合成了三羟甲基丙烷-二庚酸-单丙烯酸酯单体,对合成条件进行了优化。将三羟甲基丙烷-二庚酸-单丙烯酸酯单体,在乙酸乙酯中聚合得到聚酯,结合单体聚合前后的红外光谱图,确定了聚合反应进行彻底。通过对产品氧化诱导期、剪切下降率测试,结果表明该聚酯产品有良好的氧化安定性和剪切稳定性,同时TG 曲线表明聚酯的热稳定性较聚合前有明显提高,润滑性能测试结果表明该聚酯产品可以作为润滑基础油或添加剂使用。
(4)以丙烯酸丁酯和丙烯酸异辛酯为单体,以 s、s’-二(α,α’-甲基-α’’-乙酸)三硫代碳酸酯为链断裂转移剂,通过RAFT 自由基聚合,进行分子设计,得到不同分子量大小的聚合物,将含硫基团引入聚合物分子内,用正丁醇对不同分子量的聚酯的端基进行酯化处理,得到具有抗磨性的的聚酯类粘度指数改进剂,并对聚酯进行润滑性能和对TMP-庚酸酯的影响进行分析。结果如下:聚合物分子量大小与RAFT 试剂的加入量有直接的关系,RAFT 试剂加入量越大,产品分子量越小,可以通过加入RAFT 试剂的量来控制聚合物的分子量大小;聚合物分子中硫含量增加会提高聚合物氧化安定性、剪切稳定性和抗磨性能;基于RAFT试剂的聚酯具有很好的物理指标和很高的粘度指数,是一类多功能的润滑油添加剂;相同分子量条件下,聚丙烯酸异辛酯类粘度指数改进剂的剪切稳定性、氧化安定性和抗摩擦性能聚较聚丙烯酸丁酯有所降低,但粘度指数有所提高。
(5)对无溶剂酯化反应-蒸馏一体化工艺进行了研究,采用均相催化剂和非均相催化剂对TMP-庚酸酯的合成进行了评价,结果表明:均相催化剂对甲苯磺酸的酯化效率高,但产品需要精制处理,精制后酸值低,而固体催化剂树脂D001的酯化率低,但所得产品无需精制,脱酸后可直接应用,且收率高,损失小。

;

The research and development of series esters of lubricants were carried out based on neopentyl polyol, dicarboxylic acid, fatty acid, acrylic acid and acrylate. The esterification process of solvent-free was investigated. A series of neopentyl polyol esters, complex compound esters, acrylic polyol polyester and molecular weight controllable viscosity index improver with anti-wear function of polyacrylic esters were designed and synthesized. The physicochemical properties, such as viscosity, viscosity index, flash point and pour point were tested, and the oxidation stability and thermal oxidation stability of the products were investigated. The anti-wear property and shear stability of viscosity index improver with anti-wear function were tested. Results suggested that these synthetic esters can be used as lubricants base oil or base oil additives with excellent properties. The main content and conclusions of this thesis are as follows: ⑴ A series of esters as lubricant base oils were synthesized under solvent free conditions over toluene sulfonic acid catalyst, with neopentyl glycol, trimethylolpropane, pentaerythritol, fatty acid (heptanoic acid, octanoic acid, octanoic acid, azelaic acid, decanoic acid, oleic acid) as the main materials, and the esterification process were further optimized. The data of Fourier Transforminfrared Spectroscopy (FT-IR) confirmed that the structures of the products were in agreement with the structures of esters designed. The physicochemical properties analysis demonstrated that these synthetic esters have excellent performance and could be used as lubricant base oil. The major conclusions are as follows: the performance of ester is affected by molecular structure of acids used when polyol structure was same. The carboxylic ester, which has odd number of carbon atoms, has better low temperature fluidity than those that have adjacent even carbon carboxylic esters. The viscosity index could be improved and pour point could be lower with the branched carbon chain. When esterificated with the same fatty acid, the order of the viscosity of neopentyl polyol esters is as followed: pentaerythritol ester > three trimethylolpropane ester > neopentyl glycol ester, and the low temperature fluidity variation is the opposite. ⑵Using trimethylolpropane, fatty acid and dicarboxylic acid as the main materials, a series of compound esters were synthesized via two-step esterification reaction under solvent free conditions, with toluene sulfonic acid as catalyst. The results of Fourier Transform infrared Spectroscopy (FT-IR) confirmed that the structures of these esters synthesized were in agreement with the structures of targeted products. The physicochemical properties analysis demonstrated that when the carbon chain of fatty acid material increases, the viscosity and flash point of compound ester products improved; The esters, which obtained from fatty acid that have odd number of carbon atoms, have superial low temperature fluidity and viscosity index than those of adjacent even carboxylic esters; When chain length of dicarboxylic acid in raw material was increased, the viscosity, viscosity index and flash point of products were improved, while the pour point was decreased and oxidative stability changed a little. When double bond is prezented in the molecular structure of the synthesized ester, the oxidation stabilitydecreased. ⑶ Using trimethylolpropane,heptanoic acid and acrylic acid as raw materials, TMP-diheptanoate- acrylate was synthesized via two-step esterification under the solvent free condition, with toluene sulfonic acid as catalyst, the esterification process were optimized. The polymerization was carried out in ethyl acetate. Results of Fourier Transform infrared Spectroscopy (FT-IR) of raw material and product confirmed that the polymerization reaction went to complete. RBOT (Rotary Oxygen Bomb Time) and Shear rate declining of the polyester suggested that the polyester has good oxi

文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/3423
专题新疆维吾尔自治区精细化工工程技术研究中心
作者单位中国科学院新疆理化技术研究所
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蔡国星. 酯类系列润滑材料的合成及其性能研究[D]. 北京. 中国科学院大学,2014.
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