2，2，6，6-四甲基-3，5-庚二酮铈及其助剂的合成应用研究
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摘要
伴随着经济的发展，世界环境状况日趋恶化。由于汽车尾气排放是最大的污染源之一，提高汽油质量势在必行。使用汽油添加剂包括汽油辛烷值改进剂(抗爆剂)是提高车用汽油质量最有效和最经济的方法。目前市场应用最广的是甲基叔丁基醚(MTBE)。由于其对地下水有污染，将逐渐退出燃料添加剂市场。有学者认为以高效金属有机抗爆剂为基础的复合添加剂将是热点。在这种背景下，我们课题组展开了新型金属抗爆剂的研发，合成了高效的金属抗爆剂2，2，6，6-四甲基-3，5-庚二酮铈(Ce(thd)_4)及其助剂二异丁烯(DIB)。
以叔戊酸为原料经酯化、Claisen缩合制备了配体2，2，6，6-四甲基-3，5-庚二酮(Hthd)，然后与铈盐络合得到产品2，2，6，6-四甲基-3，5-庚二酮铈。主要研究了配体Hthd的合成方法。通过正交试验得到了优化实验条件：以乙醇钠的乙醇溶液为催化剂，酯酮摩尔比为1.2：1，反应温度90℃，溶剂用量10mL，反应时间5小时。产品Ce(thd)_4经熔点测定和质谱认证。探讨了Ce(thd)_4的抗爆机理。
在文献的基础上以国产强酸型阳离子交换树脂732为催化剂，叔丁醇为选择性改进剂合成了二异丁烯。正交试验得到的二异丁烯合成的优化工艺条件为：反应温度90℃，反应时间2小时；醇烯摩尔比0.5％：1，催化剂用量为1％。产品经标准品定性，气相色谱法定量。
油溶性和腐蚀性试验结果表明，产品2，2，6，6-四甲基-3，5-庚二酮铈符合要求，适宜作为汽油辛烷值改进剂。辛烷值应用性能检测表明：二异丁烯添加量为5％(体积分数)，铈添加量为0.016g／L，可将催化裂化汽油(FCC)升级为合格的90#车用汽油；二异丁烯添加量为10％时，铈添加量为0.08g／L，可将90#车用汽油升级为93#高级汽油。
Going with the development of economy, the world environment condition gets worse.Asthe automobile exhaust is one of the biggest pollutant source, improving the quality ofgasoline is imperative under the situation. Using gasoline additives including octane-improvement agents(anti-knock agents) is the most efficient and economical way to improvethe gasoline quality. MTBE has the most percentage in the present market, but it will quit thethis stage soon because of its pollution to underground water. Scholars believe that efficientcomposite additives based on organometallic antiknock agents will be hot spots. Under thisbackground, our team begin the research on new organometallic antiknock agents.(2, 2, 6, 6-tetramethyl-3, 5-heptanedionato)-cerium(Ⅳ)(Ce(thd)_4) is synthesized accompaniedwith its addition agent diisobutene(DIB).
Starting with triethylacetic acid, after esterification, claisen condensation and complexing,final product Ce(thd)_4 is obtained. Synthesis of Hthd is studied by orthogonal experiments.Optimized conditions are as follows:using ethanol solution of sodium ethylate as catalyst, themole ratio of ester to ketone is 1.2:1; the temperature is 90℃; the dosage of solvent is 10mLwith reaction time 5h. Final product is confirmed by melting point measuration andMS. Antiknock mechanism of Ce(thd)_4 is discussed.
Using strong acid cation exchange resin homemade as a catalyst, t-butanol as selectivityimprover, diisobutene is synthesized on the basis of literatures. Optimized conditions are got byorthogonal experiments:the temperature is 90℃, the time is 2h, the mole ratio of t-butanol toisobutene is 0.5%: 1, the dosage of catalyst is 1%. The product is determined by standard product and GC.
Test results of oil-solubility and corrosiveness indicate that both products are suitable asexcellent gasoline antiknock agents. Application test results indicate that FCC can be upgratedto 90# gasoline with 5%(volume) diisobutene and 0.016g/L Ce; 90# gasoline can be upgradedto 93# gasoline with 10% diisobutene and 0.08g/L Ce.
以叔戊酸为原料经酯化、Claisen缩合制备了配体2，2，6，6-四甲基-3，5-庚二酮(Hthd)，然后与铈盐络合得到产品2，2，6，6-四甲基-3，5-庚二酮铈。主要研究了配体Hthd的合成方法。通过正交试验得到了优化实验条件：以乙醇钠的乙醇溶液为催化剂，酯酮摩尔比为1.2：1，反应温度90℃，溶剂用量10mL，反应时间5小时。产品Ce(thd)_4经熔点测定和质谱认证。探讨了Ce(thd)_4的抗爆机理。
在文献的基础上以国产强酸型阳离子交换树脂732为催化剂，叔丁醇为选择性改进剂合成了二异丁烯。正交试验得到的二异丁烯合成的优化工艺条件为：反应温度90℃，反应时间2小时；醇烯摩尔比0.5％：1，催化剂用量为1％。产品经标准品定性，气相色谱法定量。
油溶性和腐蚀性试验结果表明，产品2，2，6，6-四甲基-3，5-庚二酮铈符合要求，适宜作为汽油辛烷值改进剂。辛烷值应用性能检测表明：二异丁烯添加量为5％(体积分数)，铈添加量为0.016g／L，可将催化裂化汽油(FCC)升级为合格的90#车用汽油；二异丁烯添加量为10％时，铈添加量为0.08g／L，可将90#车用汽油升级为93#高级汽油。
Going with the development of economy, the world environment condition gets worse.Asthe automobile exhaust is one of the biggest pollutant source, improving the quality ofgasoline is imperative under the situation. Using gasoline additives including octane-improvement agents(anti-knock agents) is the most efficient and economical way to improvethe gasoline quality. MTBE has the most percentage in the present market, but it will quit thethis stage soon because of its pollution to underground water. Scholars believe that efficientcomposite additives based on organometallic antiknock agents will be hot spots. Under thisbackground, our team begin the research on new organometallic antiknock agents.(2, 2, 6, 6-tetramethyl-3, 5-heptanedionato)-cerium(Ⅳ)(Ce(thd)_4) is synthesized accompaniedwith its addition agent diisobutene(DIB).
Starting with triethylacetic acid, after esterification, claisen condensation and complexing,final product Ce(thd)_4 is obtained. Synthesis of Hthd is studied by orthogonal experiments.Optimized conditions are as follows:using ethanol solution of sodium ethylate as catalyst, themole ratio of ester to ketone is 1.2:1; the temperature is 90℃; the dosage of solvent is 10mLwith reaction time 5h. Final product is confirmed by melting point measuration andMS. Antiknock mechanism of Ce(thd)_4 is discussed.
Using strong acid cation exchange resin homemade as a catalyst, t-butanol as selectivityimprover, diisobutene is synthesized on the basis of literatures. Optimized conditions are got byorthogonal experiments:the temperature is 90℃, the time is 2h, the mole ratio of t-butanol toisobutene is 0.5%: 1, the dosage of catalyst is 1%. The product is determined by standard product and GC.
Test results of oil-solubility and corrosiveness indicate that both products are suitable asexcellent gasoline antiknock agents. Application test results indicate that FCC can be upgratedto 90# gasoline with 5%(volume) diisobutene and 0.016g/L Ce; 90# gasoline can be upgradedto 93# gasoline with 10% diisobutene and 0.08g/L Ce.
引文
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