羧酸酯插入式乙氧基化反应研究
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摘要
聚乙二醇单烷基醚羧酸酯是一类重要的精细化学品，合成该类化合物的传统方法主要分两步进行，即先制备乙二醇单烷基醚，再将之与羧酸或其衍生物经酯化反应得目标产物。新开发的环氧乙烷对羧酸酯的插入式反应将上述两步反应缩减为一步反应，并使原子经济性达到100%。已见报道的催化羧酸酯与环氧乙烷的插入乙氧基化反应的催化剂主要有DBU（1,8-diazabicyclo [5.4.0] undec-7-ene）及其类似物、Lewis酸与有机胺的复合物、烷氧基碱土金属盐和铝镁复合氧化物等，其中铝镁复合氧化物催化活性高、产物分布性窄、安全性好以及性价比高等优点使其更具开发价值。
以铝镁复合氧化物为催化剂，包括本实验室在内的国内外研究团队已经成功开发了乙酸乙酯、长链脂肪酸甲酯和油脂的插入式乙氧基化反应。但是，该催化技术能否推广到含不饱和结构的原料如丙烯酸甲酯、丙烯酸苯酯、乙酸苯酯和乙酸乙烯酯等羧酸酯原料中仍未知，突破上述原料限制的关键在于深入了解羧酸酯的残基结构影响插入式乙氧基化反应的内在规律。因此本文首要解决的问题是考察羧酸酯的残基结构如何影响插入式乙氧基化反应，研究对不同结构的羧酸酯实施插入式乙氧基化反应的可能性和可行性。
虽然本实验室和其他研究团队利用各自的催化技术已经开发了多个具有显著工业化潜能的羧酸酯插入式乙氧基化产物，但迄今为止该技术仍未得到大规模推广。阻碍该技术进一步产业化的关键技术在于催化剂的工业放大，这是因为工业催化剂制备过程中保持高催化活性与追求高生产效率构成矛盾。因此本文要解决的第二个关键问题是探索合适的催化剂制备工艺，在保持高催化活性的前提下追求高生产效率，以推进羧酸酯插入式乙氧基化反应的工业化进程。
针对上述两大瓶颈问题，本文主要研究具有不同残基结构羧酸酯的插入式乙氧基化反应，探索残基结构影响该类反应的内在规律，在此基础上进一步考察其它促进羧酸酯一步法乙氧基化反应的因素；同时研究对合成铝镁复合氧化物催化剂最有益的制备工艺，在此基础上进一步优化催化剂制备的工艺条件，并进行催化剂制备扩试试验。在本文实验范围内，得到以下主要结果和结论。
考察了羧酸酯原料中不同残基的空间效应和电子效应，研究其对插入式乙氧基化反应的引发反应温度、反应表观活化能、产物选择性和多种酯基共存体系中的反应竞争性等影响。由实验结果得到以下结论：原料或中间体羧酸酯的残基结构是影响其乙氧基化反应的反应速率、反应竞争性和产物选择性的根本要素；受残基电子效应和空间效应的影响，羧酸酯的乙氧基化反应总体表现出酯键键长较长或反应位受位阻影响较小的羧酸酯更易于发生插入式乙氧基化反应，具体表现为引发反应温度低、反应速率快和活化能小。本文的研究结论可以较好解释以下实验结果：（1）对多种酯基共存的羧酸酯原料而言，插入式乙氧基化反应优先发生在化学键长较长的酯基位，因此4-乙酰氧基苯甲酸甲酯与环氧乙烷反应的产物主要是4-(2-乙酰氧基乙氧基)苯甲酸甲酯。（2）在含不同键长的羧酸酯的反应体系中，乙氧基化反应优先发生在键长较长的羧酸酯酯分子中，因此乙酸苯酯的乙氧基化反应产物主要是乙二醇苯醚乙酸酯，对苯二酚二乙酸酯的乙氧基化反应产物主要是乙酸-4-(2-乙酰氧基乙氧基)苯酯。（3）由于羧酸酯插入式乙氧基化反应产物仍为羧酸酯，故新生成的羧酸酯还可以继续与环氧乙烷发生插入式乙氧基化反应。但是，产物羧酸酯与原料羧酸酯的酯基的键长和受空间位阻的影响具有一定差异，因此后续插入式乙氧基化反应速率随着乙氧基化反应的推进而不断变化：由于产物羧酸酯的位阻效应大于原料羧酸酯，故十二酸甲酯与环氧乙烷的反应速率随乙氧基化反应进行而不断下降；由于产物羧酸酯的位阻效应较原料羧酸酯削弱，故棕榈硬脂与环氧乙烷的反应先慢后快；由于产物羧酸酯的位阻效应较弱，故乙酸乙酯和甲基丙烯酸甲酯的乙氧基化反应速率随环氧乙烷加合数的增加变化不大；受中等环状化合物的环张力的影响，γ-丁内酯与环氧乙烷的乙氧基化反应速率先缓慢增加，在平均加合数在3.3左右时，反应速率迅速增大并达到恒定值。
考察了反应温度、反应压力、溶剂和添加剂等因素对一步法插入反应的影响，以寻求羧酸酯插入式乙氧基化反应的其它促进因素。实验结果表明：（1）反应温度和反应压力提高，能有效地提高羧酸酯插入式乙氧基化反应的速率。（2）加入溶剂使体系的黏度降低，因此也大大提高羧酸酯的乙氧基化反应速率。（3）不同添加剂对催化剂有不同辅助作用，故对羧酸酯的插入式乙氧基化反应的影响也不尽相同：由于碱性添加剂或酸性添加剂可分别与催化剂表面的酸碱性活性位点发生相互作用，导致催化剂表面总活性位点数减少，因此添加十二酸、十六烷基三甲基溴化铵、六次甲基四胺和十二醇等添加剂降低了十二酸甲酯乙氧基化反应的速率；添加三氯化铝和三乙胺等添加剂使甲基丙烯酸甲酯乙氧基化反应速率急剧降低；由于无机盐与催化剂的酸碱性活性位点无明显相互作用，因此添加碘化钾对十二酸甲酯乙氧基化反应速率无明显影响；研究添加剂对丙烯酸苯酯单EO加合数产物乙二醇苯醚丙烯酸酯（GPA）选择性的影响时发现，添加BF_3、AlCl_3等Lewis酸或[MIMPS]_3PW_(12)O_(40)离子液体降低了GPA的收率；添加NaOH、Na_2CO_3、NaHCO_3、NH3等无机碱，N(Et)_3、六次甲基四胺等有机碱，MIMPS、BMIMCl等离子液体或卤化钾等添加剂均不同程度地提高了GPA收率。
以共沉淀法制备的铝镁复合氧化物具有高比表面积、中等强度碱性及布朗斯特酸性的双活性中心，可催化以十二醇为代表的脂肪醇的乙氧基化反应和羧酸酯的插入式乙氧基化反应。以影响催化剂放大的关键瓶颈因素，催化剂前体的过滤速率，表征催化剂的制备效率，以十二酸甲酯插入式乙氧基化反应表征催化剂的催化活性，探索了工艺扩试试验中催化剂的制备工艺，并优化了催化剂的制备工艺条件。以NH3-(NH4)2CO_3和NaOH-Na_2CO_3的复合物为沉淀剂，可在保持原优化工艺条件下催化剂高活性的同时，大大提高催化剂制备效率。以摩尔比4:6的NH3-(NH4)2CO_3与NaOH-Na_2CO_3为沉淀剂，催化剂前体悬浮液的过滤速率较NaOH-Na_2CO_3为沉淀剂快3.1倍，所得催化剂的催化活性为2.3gEO/gCat/min。优化的催化剂制备工艺条件为：将铝镁混合溶液（200g/L）和沉淀剂以10mL/min的加料速率同时流加到带有慢速机械搅拌（300r/min）的2L三口烧瓶中，共沉淀反应结束后在70oC下的老化6h，该优化工艺条件下所制备催化剂的活性为2.4gEO/gCat/min。
考察了不同工艺对催化剂制备效率和催化剂活性的影响。由实验结果得到以下结论：在适当的且稳定的pH环境下，大比例返混物料和弱剪切力条件下有效控制铝镁离子形成晶核和晶体生长速率可在工艺扩试规模上保持催化剂高催化活性的同时大大提高催化剂的制备效率。本文的研究结论可以较好解释以下实验结果：（1）在混合乳化泵-釜式混合工艺中，随着返混物料比例的增加，催化剂的制备效率和催化活性均得到提高；（2）由于后继批次的返混比例更大，双物料连续流加工艺和静态混合-釜式混合工艺中后继批次催化剂的制备效率和催化活性均大于前一批次；（3）因混合剪切力显著增强，混合乳化泵-釜式混合工艺制备催化剂的效率和催化活性显著低于弱剪切力的其它工艺。
The (poly) ethylene glycol monoalkyl ether carboxylic acid esters (PEGMAECAEs)are vital fine chemicals, and are widely used in many fields due to the different acyl groups,(poly) ethylene glycol or alkoxy blocks in the molecules. Usually, PEGMAECAEs areprepared via a two-step synthetic route with ethylene glycol, alcohol, and carboxylic acidas starting materials. Novel one pot synthetic strategy with carboxylic esters and ethyleneoxide as raw materials is more atomic economy than the multi-step procedures. The onepot procedure was catalyzed by DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) and theanalogues, the composite of Lewis acid and organic base, alkoxy alkaline earth metal saltor Al/Mg composite oxide. In which, Al/Mg composite oxide was one of the potentialindustrial development value due to the higher catalytic activity, narrower productdistribution, security and higher cost performance of products.
Using Al-Mg composite oxide as the catalyst, home or abroad, including ourresearching team had successfully developed one-step inserted ethoxylation of carboxylicesters such as ethyl acetate, the long-chain fatty acid methyl esters, oil and grease.However, whether the catalytic technologies could be extended to the raw materials suchas methyl methacrylate, phenyl acrylate, phenyl acetate, and vinyl acetate is still unknown.The key breakthrough of the above raw materials restrictions lies in the comprehensiveunderstanding the inherent laws of one-step inserted ethoxylation of carboxylic esterswhich was influenced by the building blocks in the molecules. Hence, the most importantquestion of this paper is to explore the relationship between the residue blocks and thereactivity of carboxylic esters.
Our laboratory and other research teams have been developed the insertedethoxylation techniques of many carboxylic esters with significant industrializationpotential, while such technology has not been promoted in a large-scale. The majorobstacle of the novel technology with industrialization potential was the catalystpreparation. Therefore, the second key problem is to explore suitable catalyst preparationprocess.
In response to those two bottlenecks problems, the inserted ethoxyaltion with thecarboxylic esters of different residue blocks was studied, the inherent laws of the affectionof the residue blocks was deduced. The promoting factors of the reaction were alsoinvestigated. At the same time, the most useful process for the synthesis of Al-Mgcomposite oxide catalyst was optimized. Based on the above-mentioned conditions, theprocess conditions of the catalyst preparation both in laboratory scale and the expansionpilot scale were also investigated. Within the scope of this study, the following main resultsand conclusions were reached.
The spatial effect and the electronic effect of the carboxylic ester feedstock withdifferent residues blocks were investigated by the initiating temperature, activation energy,product selectivity and the reaction competitive in the system with different ester groups.The main findings of the present study were as follows: The fundamental element of the ethoxylation rate, the reaction competitives and the product selectivity was the chemicalbond natures of the raw materials or the inermediates. By the influence of electronic effectsand spatial effects of the residues, the overall performance of the reaction was promotedwith the longer bond length or smaller steric effect of the esters. The promotedperformance of the reaction was manifested as lower initiating temperature, higher reactionrate and lower activation energy. The conclusions of the above can be better explain thefollowing experimental results:(1) In the carboxylic ester feedstock of different estergroups, the inserted ethoxylation reaction prefer to occurring in the bond of longer length,so the main product of the ethoxylation of methyl4-acetyloxybenzoate and ethylene oxidewas methyl4-(2-acetoxyethoxy) benzoate.(2) In the carboxylic ester feedstock withdifferent bond length, the inserted ethoxylation reaction prefer to occurring in themolecular with longer bond length, therefore the main product of the ethoxylation ofphenyl acetate was ethylene glycol phenyl ether acetate and the main product of theethoxylation of the hydroquinone diacetate was4-(2-acetoxyethoxy) phenyl acetate.(3)Since the ethoxylated product of carboxylic ester was still carboxylic ester, the novelintermediates could react with ethylene oxide by inserted ethoxylation strategy. However,the bond nature such as bond length and the steric effect, were different between thestarting material and the intermediates, therefore the subsequent inserted ethoxylation ratewas varying with the bond nature changed: due to the steric effect enhanced, the reactionrate of the ethoxylation of methyl laurate was declining; due to the steric effect weakened,the reaction rate of the ethoxylation of palm stearin was increasing; due to the weakersteric effect of both the starting material and the intermediates, the reaction rate of ethylacetate or methyl methacrylate with ethylene oxide was almost constant value; due to theintermediate’s bond length shorter than raw material, the reaction rate of phenyl acetatewas drastically decreasing; affected by the medium-tension of the ring of the cycliccompounds, the ethoxylation reaction rate of the γ-butyrolactone was very slow at first,then gradually increased as the reaction progressing, the reaction rate increased rapidly andreached a constant value after the average adduct number of about3.3.
To find the other contributing factors of the inserted ethoxylation of carboxylic esters,some other factors such as reaction temperature, pressure, solvents, and additives were alsoinvestigated. Experimental results show that:(1) the reaction rate could be effectivelyimproved by the reaction temperature or pressure increasing;(2) the reaction rate couldalso be improved by using petroleum ether as solvent which reduced the viscosity of thereaction mixture;(3) the reaction performance was changed by inserting additives inreaction systems due to the different promoted role: The alkaline additives or acidicadditives could neutralize the active site of the catalyst respectively, leading to the decreasein the total active sites of the catalyst, therefore the addition of lauric acid, cetyl trimethylammonium bromide (CTAB), hexamethylenetetramine (HMTA), lauryl alcohol and otheradditives could reduce the reaction rate of methyl laurate; the addition of aluminumtrichloride and triethylamine could reduce the reaction rate of methyl methacrylatedrastically; due to the weak interaction between inorganic salt and the catalyst, the additionof potassium iodide almost no effect the reaction rate of methyl laurate; the influence of additives to the reaction selectivity of phenyl acrylate was also investigated, the resultwas that the addition of Lewis acid such as BF_3, AlCl_3or room temperature ionic liquidsuch as [MIMPS]_3PW_(12)O_(40)reduced the yield of GPA; the addition of inorganic basessuch as Na_2CO_3, NaHCO_3,NaOH, NH3, the organic bases such as N(Et)_3, hexamethylenetetramine, the room temperature ionic liquid such as MIMPS, BMIMCl, and potassiumhalide additives improved the yield of GPA.
Al–Mg composite oxide with higher specific surface areas, Bronsted acidic activesites and medium strength alkaline active sites, was prepared by coprecipitate procedure,which could catalyze the ethoxylation of ethylene oxide and fatty alcohol such asdodecanol and the inserted ethoxylation of ethylene oxide and the carboxylic ester. Todiscover a process in pilot scale of the catalyst preparation, and optimize the preparationconditions of the catalyst, the efficiency of the catalyst preparation was evaluated by thefiltration rate of the catalyst precursor. The catalytic activity of the catalyst wascharacterized by the inserted ethoxylation of methyl laurate. Using NH3-(NH4)2CO_3andNaOH-Na_2CO_3complex as the precipitating agent, the catalyst with high activity wasobtained by efficiency of the catalyst preparation procedure. With a molar ratio of4:6,NH3-(NH4)2CO_3NaOH-Na_2CO_3as precipitant, the catalyst precursors suspensionfiltration rate was3.1times faster than that of NaOH-Na_2CO_3as precipitant, the catalyticactivity of the resulting catalyst was2.3gEO/gCat/min. The optimized reactionconditions were as follows:200g/L Al-Mg salts mixture, a feed rate of10mL/min, slowmechanical stirring of300rounds/min, and aging at70oC for further6h. The catalystactivity under the optimized conditions was2.4gEO/gCat/min.
The effects of different process on catalyst activity and the efficiency of the catalystpreparation were studied. The main findings of the present study were as follows: in aproper and stable pH environment, a large proportion back mixing and weak shearing forcecould effective control the formation of nuclei and the crystal growth rate of Al-Mg ion,result in the higher catalytic activity on the expanded pilot scale, and the efficiency of thepreparation was greatly improved. The conclusions of this study could better explain thefollowing experimental results:(1) in the mixed pump-batch mixing process, with theincrease in the proportion of material back mixing, the preparation of the catalystefficiency and the catalytic activity was improved;(2) since the subsequent batches of agreater proportion of back mixing, the catalyst efficiency and the catalytic activity washigher than that in the previous batch by the continuously feeding-batch mixing processesand static mixing-the batch mixing process;(3) due to the mixing shear significantlyenhanced in the mixed pump, the catalyst efficiency and the catalytic activity by the mixedpump-batch mixing process was lower than the other procedure.
以铝镁复合氧化物为催化剂，包括本实验室在内的国内外研究团队已经成功开发了乙酸乙酯、长链脂肪酸甲酯和油脂的插入式乙氧基化反应。但是，该催化技术能否推广到含不饱和结构的原料如丙烯酸甲酯、丙烯酸苯酯、乙酸苯酯和乙酸乙烯酯等羧酸酯原料中仍未知，突破上述原料限制的关键在于深入了解羧酸酯的残基结构影响插入式乙氧基化反应的内在规律。因此本文首要解决的问题是考察羧酸酯的残基结构如何影响插入式乙氧基化反应，研究对不同结构的羧酸酯实施插入式乙氧基化反应的可能性和可行性。
虽然本实验室和其他研究团队利用各自的催化技术已经开发了多个具有显著工业化潜能的羧酸酯插入式乙氧基化产物，但迄今为止该技术仍未得到大规模推广。阻碍该技术进一步产业化的关键技术在于催化剂的工业放大，这是因为工业催化剂制备过程中保持高催化活性与追求高生产效率构成矛盾。因此本文要解决的第二个关键问题是探索合适的催化剂制备工艺，在保持高催化活性的前提下追求高生产效率，以推进羧酸酯插入式乙氧基化反应的工业化进程。
针对上述两大瓶颈问题，本文主要研究具有不同残基结构羧酸酯的插入式乙氧基化反应，探索残基结构影响该类反应的内在规律，在此基础上进一步考察其它促进羧酸酯一步法乙氧基化反应的因素；同时研究对合成铝镁复合氧化物催化剂最有益的制备工艺，在此基础上进一步优化催化剂制备的工艺条件，并进行催化剂制备扩试试验。在本文实验范围内，得到以下主要结果和结论。
考察了羧酸酯原料中不同残基的空间效应和电子效应，研究其对插入式乙氧基化反应的引发反应温度、反应表观活化能、产物选择性和多种酯基共存体系中的反应竞争性等影响。由实验结果得到以下结论：原料或中间体羧酸酯的残基结构是影响其乙氧基化反应的反应速率、反应竞争性和产物选择性的根本要素；受残基电子效应和空间效应的影响，羧酸酯的乙氧基化反应总体表现出酯键键长较长或反应位受位阻影响较小的羧酸酯更易于发生插入式乙氧基化反应，具体表现为引发反应温度低、反应速率快和活化能小。本文的研究结论可以较好解释以下实验结果：（1）对多种酯基共存的羧酸酯原料而言，插入式乙氧基化反应优先发生在化学键长较长的酯基位，因此4-乙酰氧基苯甲酸甲酯与环氧乙烷反应的产物主要是4-(2-乙酰氧基乙氧基)苯甲酸甲酯。（2）在含不同键长的羧酸酯的反应体系中，乙氧基化反应优先发生在键长较长的羧酸酯酯分子中，因此乙酸苯酯的乙氧基化反应产物主要是乙二醇苯醚乙酸酯，对苯二酚二乙酸酯的乙氧基化反应产物主要是乙酸-4-(2-乙酰氧基乙氧基)苯酯。（3）由于羧酸酯插入式乙氧基化反应产物仍为羧酸酯，故新生成的羧酸酯还可以继续与环氧乙烷发生插入式乙氧基化反应。但是，产物羧酸酯与原料羧酸酯的酯基的键长和受空间位阻的影响具有一定差异，因此后续插入式乙氧基化反应速率随着乙氧基化反应的推进而不断变化：由于产物羧酸酯的位阻效应大于原料羧酸酯，故十二酸甲酯与环氧乙烷的反应速率随乙氧基化反应进行而不断下降；由于产物羧酸酯的位阻效应较原料羧酸酯削弱，故棕榈硬脂与环氧乙烷的反应先慢后快；由于产物羧酸酯的位阻效应较弱，故乙酸乙酯和甲基丙烯酸甲酯的乙氧基化反应速率随环氧乙烷加合数的增加变化不大；受中等环状化合物的环张力的影响，γ-丁内酯与环氧乙烷的乙氧基化反应速率先缓慢增加，在平均加合数在3.3左右时，反应速率迅速增大并达到恒定值。
考察了反应温度、反应压力、溶剂和添加剂等因素对一步法插入反应的影响，以寻求羧酸酯插入式乙氧基化反应的其它促进因素。实验结果表明：（1）反应温度和反应压力提高，能有效地提高羧酸酯插入式乙氧基化反应的速率。（2）加入溶剂使体系的黏度降低，因此也大大提高羧酸酯的乙氧基化反应速率。（3）不同添加剂对催化剂有不同辅助作用，故对羧酸酯的插入式乙氧基化反应的影响也不尽相同：由于碱性添加剂或酸性添加剂可分别与催化剂表面的酸碱性活性位点发生相互作用，导致催化剂表面总活性位点数减少，因此添加十二酸、十六烷基三甲基溴化铵、六次甲基四胺和十二醇等添加剂降低了十二酸甲酯乙氧基化反应的速率；添加三氯化铝和三乙胺等添加剂使甲基丙烯酸甲酯乙氧基化反应速率急剧降低；由于无机盐与催化剂的酸碱性活性位点无明显相互作用，因此添加碘化钾对十二酸甲酯乙氧基化反应速率无明显影响；研究添加剂对丙烯酸苯酯单EO加合数产物乙二醇苯醚丙烯酸酯（GPA）选择性的影响时发现，添加BF_3、AlCl_3等Lewis酸或[MIMPS]_3PW_(12)O_(40)离子液体降低了GPA的收率；添加NaOH、Na_2CO_3、NaHCO_3、NH3等无机碱，N(Et)_3、六次甲基四胺等有机碱，MIMPS、BMIMCl等离子液体或卤化钾等添加剂均不同程度地提高了GPA收率。
以共沉淀法制备的铝镁复合氧化物具有高比表面积、中等强度碱性及布朗斯特酸性的双活性中心，可催化以十二醇为代表的脂肪醇的乙氧基化反应和羧酸酯的插入式乙氧基化反应。以影响催化剂放大的关键瓶颈因素，催化剂前体的过滤速率，表征催化剂的制备效率，以十二酸甲酯插入式乙氧基化反应表征催化剂的催化活性，探索了工艺扩试试验中催化剂的制备工艺，并优化了催化剂的制备工艺条件。以NH3-(NH4)2CO_3和NaOH-Na_2CO_3的复合物为沉淀剂，可在保持原优化工艺条件下催化剂高活性的同时，大大提高催化剂制备效率。以摩尔比4:6的NH3-(NH4)2CO_3与NaOH-Na_2CO_3为沉淀剂，催化剂前体悬浮液的过滤速率较NaOH-Na_2CO_3为沉淀剂快3.1倍，所得催化剂的催化活性为2.3gEO/gCat/min。优化的催化剂制备工艺条件为：将铝镁混合溶液（200g/L）和沉淀剂以10mL/min的加料速率同时流加到带有慢速机械搅拌（300r/min）的2L三口烧瓶中，共沉淀反应结束后在70oC下的老化6h，该优化工艺条件下所制备催化剂的活性为2.4gEO/gCat/min。
考察了不同工艺对催化剂制备效率和催化剂活性的影响。由实验结果得到以下结论：在适当的且稳定的pH环境下，大比例返混物料和弱剪切力条件下有效控制铝镁离子形成晶核和晶体生长速率可在工艺扩试规模上保持催化剂高催化活性的同时大大提高催化剂的制备效率。本文的研究结论可以较好解释以下实验结果：（1）在混合乳化泵-釜式混合工艺中，随着返混物料比例的增加，催化剂的制备效率和催化活性均得到提高；（2）由于后继批次的返混比例更大，双物料连续流加工艺和静态混合-釜式混合工艺中后继批次催化剂的制备效率和催化活性均大于前一批次；（3）因混合剪切力显著增强，混合乳化泵-釜式混合工艺制备催化剂的效率和催化活性显著低于弱剪切力的其它工艺。
The (poly) ethylene glycol monoalkyl ether carboxylic acid esters (PEGMAECAEs)are vital fine chemicals, and are widely used in many fields due to the different acyl groups,(poly) ethylene glycol or alkoxy blocks in the molecules. Usually, PEGMAECAEs areprepared via a two-step synthetic route with ethylene glycol, alcohol, and carboxylic acidas starting materials. Novel one pot synthetic strategy with carboxylic esters and ethyleneoxide as raw materials is more atomic economy than the multi-step procedures. The onepot procedure was catalyzed by DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) and theanalogues, the composite of Lewis acid and organic base, alkoxy alkaline earth metal saltor Al/Mg composite oxide. In which, Al/Mg composite oxide was one of the potentialindustrial development value due to the higher catalytic activity, narrower productdistribution, security and higher cost performance of products.
Using Al-Mg composite oxide as the catalyst, home or abroad, including ourresearching team had successfully developed one-step inserted ethoxylation of carboxylicesters such as ethyl acetate, the long-chain fatty acid methyl esters, oil and grease.However, whether the catalytic technologies could be extended to the raw materials suchas methyl methacrylate, phenyl acrylate, phenyl acetate, and vinyl acetate is still unknown.The key breakthrough of the above raw materials restrictions lies in the comprehensiveunderstanding the inherent laws of one-step inserted ethoxylation of carboxylic esterswhich was influenced by the building blocks in the molecules. Hence, the most importantquestion of this paper is to explore the relationship between the residue blocks and thereactivity of carboxylic esters.
Our laboratory and other research teams have been developed the insertedethoxylation techniques of many carboxylic esters with significant industrializationpotential, while such technology has not been promoted in a large-scale. The majorobstacle of the novel technology with industrialization potential was the catalystpreparation. Therefore, the second key problem is to explore suitable catalyst preparationprocess.
In response to those two bottlenecks problems, the inserted ethoxyaltion with thecarboxylic esters of different residue blocks was studied, the inherent laws of the affectionof the residue blocks was deduced. The promoting factors of the reaction were alsoinvestigated. At the same time, the most useful process for the synthesis of Al-Mgcomposite oxide catalyst was optimized. Based on the above-mentioned conditions, theprocess conditions of the catalyst preparation both in laboratory scale and the expansionpilot scale were also investigated. Within the scope of this study, the following main resultsand conclusions were reached.
The spatial effect and the electronic effect of the carboxylic ester feedstock withdifferent residues blocks were investigated by the initiating temperature, activation energy,product selectivity and the reaction competitive in the system with different ester groups.The main findings of the present study were as follows: The fundamental element of the ethoxylation rate, the reaction competitives and the product selectivity was the chemicalbond natures of the raw materials or the inermediates. By the influence of electronic effectsand spatial effects of the residues, the overall performance of the reaction was promotedwith the longer bond length or smaller steric effect of the esters. The promotedperformance of the reaction was manifested as lower initiating temperature, higher reactionrate and lower activation energy. The conclusions of the above can be better explain thefollowing experimental results:(1) In the carboxylic ester feedstock of different estergroups, the inserted ethoxylation reaction prefer to occurring in the bond of longer length,so the main product of the ethoxylation of methyl4-acetyloxybenzoate and ethylene oxidewas methyl4-(2-acetoxyethoxy) benzoate.(2) In the carboxylic ester feedstock withdifferent bond length, the inserted ethoxylation reaction prefer to occurring in themolecular with longer bond length, therefore the main product of the ethoxylation ofphenyl acetate was ethylene glycol phenyl ether acetate and the main product of theethoxylation of the hydroquinone diacetate was4-(2-acetoxyethoxy) phenyl acetate.(3)Since the ethoxylated product of carboxylic ester was still carboxylic ester, the novelintermediates could react with ethylene oxide by inserted ethoxylation strategy. However,the bond nature such as bond length and the steric effect, were different between thestarting material and the intermediates, therefore the subsequent inserted ethoxylation ratewas varying with the bond nature changed: due to the steric effect enhanced, the reactionrate of the ethoxylation of methyl laurate was declining; due to the steric effect weakened,the reaction rate of the ethoxylation of palm stearin was increasing; due to the weakersteric effect of both the starting material and the intermediates, the reaction rate of ethylacetate or methyl methacrylate with ethylene oxide was almost constant value; due to theintermediate’s bond length shorter than raw material, the reaction rate of phenyl acetatewas drastically decreasing; affected by the medium-tension of the ring of the cycliccompounds, the ethoxylation reaction rate of the γ-butyrolactone was very slow at first,then gradually increased as the reaction progressing, the reaction rate increased rapidly andreached a constant value after the average adduct number of about3.3.
To find the other contributing factors of the inserted ethoxylation of carboxylic esters,some other factors such as reaction temperature, pressure, solvents, and additives were alsoinvestigated. Experimental results show that:(1) the reaction rate could be effectivelyimproved by the reaction temperature or pressure increasing;(2) the reaction rate couldalso be improved by using petroleum ether as solvent which reduced the viscosity of thereaction mixture;(3) the reaction performance was changed by inserting additives inreaction systems due to the different promoted role: The alkaline additives or acidicadditives could neutralize the active site of the catalyst respectively, leading to the decreasein the total active sites of the catalyst, therefore the addition of lauric acid, cetyl trimethylammonium bromide (CTAB), hexamethylenetetramine (HMTA), lauryl alcohol and otheradditives could reduce the reaction rate of methyl laurate; the addition of aluminumtrichloride and triethylamine could reduce the reaction rate of methyl methacrylatedrastically; due to the weak interaction between inorganic salt and the catalyst, the additionof potassium iodide almost no effect the reaction rate of methyl laurate; the influence of additives to the reaction selectivity of phenyl acrylate was also investigated, the resultwas that the addition of Lewis acid such as BF_3, AlCl_3or room temperature ionic liquidsuch as [MIMPS]_3PW_(12)O_(40)reduced the yield of GPA; the addition of inorganic basessuch as Na_2CO_3, NaHCO_3,NaOH, NH3, the organic bases such as N(Et)_3, hexamethylenetetramine, the room temperature ionic liquid such as MIMPS, BMIMCl, and potassiumhalide additives improved the yield of GPA.
Al–Mg composite oxide with higher specific surface areas, Bronsted acidic activesites and medium strength alkaline active sites, was prepared by coprecipitate procedure,which could catalyze the ethoxylation of ethylene oxide and fatty alcohol such asdodecanol and the inserted ethoxylation of ethylene oxide and the carboxylic ester. Todiscover a process in pilot scale of the catalyst preparation, and optimize the preparationconditions of the catalyst, the efficiency of the catalyst preparation was evaluated by thefiltration rate of the catalyst precursor. The catalytic activity of the catalyst wascharacterized by the inserted ethoxylation of methyl laurate. Using NH3-(NH4)2CO_3andNaOH-Na_2CO_3complex as the precipitating agent, the catalyst with high activity wasobtained by efficiency of the catalyst preparation procedure. With a molar ratio of4:6,NH3-(NH4)2CO_3NaOH-Na_2CO_3as precipitant, the catalyst precursors suspensionfiltration rate was3.1times faster than that of NaOH-Na_2CO_3as precipitant, the catalyticactivity of the resulting catalyst was2.3gEO/gCat/min. The optimized reactionconditions were as follows:200g/L Al-Mg salts mixture, a feed rate of10mL/min, slowmechanical stirring of300rounds/min, and aging at70oC for further6h. The catalystactivity under the optimized conditions was2.4gEO/gCat/min.
The effects of different process on catalyst activity and the efficiency of the catalystpreparation were studied. The main findings of the present study were as follows: in aproper and stable pH environment, a large proportion back mixing and weak shearing forcecould effective control the formation of nuclei and the crystal growth rate of Al-Mg ion,result in the higher catalytic activity on the expanded pilot scale, and the efficiency of thepreparation was greatly improved. The conclusions of this study could better explain thefollowing experimental results:(1) in the mixed pump-batch mixing process, with theincrease in the proportion of material back mixing, the preparation of the catalystefficiency and the catalytic activity was improved;(2) since the subsequent batches of agreater proportion of back mixing, the catalyst efficiency and the catalytic activity washigher than that in the previous batch by the continuously feeding-batch mixing processesand static mixing-the batch mixing process;(3) due to the mixing shear significantlyenhanced in the mixed pump, the catalyst efficiency and the catalytic activity by the mixedpump-batch mixing process was lower than the other procedure.
引文
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