技术领域technical field
本发明涉及一种碳氮材料固载杂多酸催化剂以及利用该催化剂的烯烃环氧化合成的方法。The invention relates to a carbon-nitrogen material immobilized heteropolyacid catalyst and a method for olefin epoxidation synthesis using the catalyst.
背景技术Background technique
最近几年，有关碳氮材料的报道越来越多，一方面是由于组成碳氮材料的主要元素是碳和氮以及少量的氢，对环境无污染，符合绿色化学要求；另一方面，由于碳氮材料的热稳定性好，并且在一系列的反应中表现出优秀的催化性能。2007年，有文献报道(J.Solid.State.Chem.2007,125-133.)用三聚氰胺和三氯甲基硅烷为原料，通过高温煅烧制得一种含有硅的多孔碳氮材料；2009年，Vinu报道了(Angew.Chem.2009,121,8024-8027.)用具有较大比表面积的碳氮材料作为酯交换催化剂，并且当该碳氮材料负载金催化剂后，能够将苯甲醛，哌啶和苯乙炔通过偶联反应制得相应的炔丙基胺。2010年，Ye报道了(J.Phys.Chem.C.2010,114,4100-4105.)钽酸掺杂在碳氮材料中作为光催化剂，成功的从甲醇溶液中制得氢气。2011年，Wang报道了(J.Am.Chem.Soc.,2011,2362-2365.)一种多孔的碳氮材料，然后用来负载金属钯，用该催化剂做苯酚加氢反应。本发明以三聚氰胺和杂多酸为原料，通过高温煅烧制得碳氮材料固载杂多酸催化剂，并应用该碳氮材料固载杂多酸催化剂催化烯烃的环氧反应得到脂肪族环氧树脂。In recent years, there have been more and more reports on carbon-nitrogen materials. On the one hand, because the main elements of carbon-nitrogen materials are carbon, nitrogen and a small amount of hydrogen, they have no pollution to the environment and meet the requirements of green chemistry; on the other hand, because Carbon-nitrogen materials have good thermal stability and exhibit excellent catalytic performance in a series of reactions. In 2007, it was reported in literature (J.Solid.State.Chem.2007,125-133.) that melamine and trichloromethylsilane were used as raw materials to prepare a silicon-containing porous carbon-nitrogen material through high-temperature calcination; in 2009 , Vinu reported (Angew.Chem.2009,121,8024-8027.) with a carbon-nitrogen material with a larger specific surface area as a transesterification catalyst, and when the carbon-nitrogen material supports gold catalyst, benzaldehyde, piperazine can be Pyridine and phenylacetylene are prepared by coupling reaction to the corresponding propargylamine. In 2010, Ye reported (J.Phys.Chem.C.2010, 114, 4100-4105.) that tantalum acid was doped in carbon-nitrogen materials as a photocatalyst, and hydrogen was successfully produced from methanol solution. In 2011, Wang reported (J.Am.Chem.Soc., 2011, 2362-2365.) a porous carbon-nitrogen material, which was then used to support metal palladium, and the catalyst was used for phenol hydrogenation reaction. The present invention uses melamine and heteropolyacid as raw materials to obtain a carbon-nitrogen material-immobilized heteropolyacid catalyst through high-temperature calcination, and uses the carbon-nitrogen material-immobilized heteropolyacid catalyst to catalyze the epoxy reaction of olefins to obtain an aliphatic epoxy resin .
环氧树脂是一种重要的热固性树脂品种，其广泛应用于化工、轻工、水利、交通、机械、电子、家电、汽车及航天航空等工业领域。而作为新一代环氧树脂，脂肪族双环氧化合物具有热稳定性好，耐候性高，电绝缘性能优异，耐紫外光以及抗电子辐射性能而适于户外使用，并可广泛应用于抗紫外线涂料以及LED等电子产品上。目前工业上主要采用过酸氧化法和催化氧化法合成烯烃环氧化合物。过酸氧化法采用高浓度的过氧乙酸作氧化剂，在生产过程中存在很大的安全隐患，并且在生产过程中产生大量的乙酸，造成产品分离困难，因此该方法在国内无法实现大规模生产。而催化氧化法采用具有氧化性的金属化合物为催化剂，并以双氧水或烷基过氧化物为氧源，来合成脂肪族环氧化合物。1983年，Venturello报道的用钨酸钠和磷酸等合成的相转移催化剂，以双氧水为氧源，该体系为水-油两相反应体系，并且对直链端烯有较好的环氧化催化活性(J.Org.Chem.,1983,48,3831-3833.)。1988年，Ishii对Venturello进行了改进，但活性物质并没有改变(J.Org.Chem.,1988,53,3587-3593.)。2001年，奚祖威的反应控制相转移催化体系，很好的解决了均相催化剂的回收的问题(分子催化.,2001,2，113-118.)。2008年，公开号为CN101143919的发明专利中提出了一种催化剂可回收循环是用的催化环氧化工艺，但是，该工艺存在着催化剂难以回收以及在产物中残留的问题。Epoxy resin is an important thermosetting resin variety, which is widely used in chemical industry, light industry, water conservancy, transportation, machinery, electronics, home appliances, automobiles, aerospace and other industrial fields. As a new generation of epoxy resin, aliphatic diepoxy compounds have good thermal stability, high weather resistance, excellent electrical insulation performance, UV resistance and electronic radiation resistance, and are suitable for outdoor use, and can be widely used in UV resistance Paint and LED and other electronic products. At present, peracid oxidation and catalytic oxidation are mainly used in industry to synthesize olefin epoxy compounds. The peracid oxidation method uses high-concentration peracetic acid as the oxidant, which has great potential safety hazards in the production process, and produces a large amount of acetic acid in the production process, resulting in difficulty in product separation. Therefore, this method cannot achieve large-scale production in China . The catalytic oxidation method uses an oxidizing metal compound as a catalyst, and uses hydrogen peroxide or alkyl peroxide as an oxygen source to synthesize aliphatic epoxy compounds. In 1983, Venturello reported a phase transfer catalyst synthesized with sodium tungstate and phosphoric acid, using hydrogen peroxide as the oxygen source. This system is a water-oil two-phase reaction system, and has a good epoxidation catalysis for linear terminal alkenes. Activity (J. Org. Chem., 1983, 48, 3831-3833.). In 1988, Ishii improved Venturello, but the active substance did not change (J.Org.Chem., 1988, 53, 3587-3593.). In 2001, Xi Zuwei's reaction-controlled phase-transfer catalytic system solved the problem of homogeneous catalyst recovery (Molecular Catalysis., 2001, 2, 113-118.). In 2008, the invention patent with the publication number CN101143919 proposed a catalytic epoxidation process for recyclable catalysts. However, this process has the problems of difficult recovery of catalysts and residues in the product.
发明内容Contents of the invention
本发明的目的是为了改进现有技术的不足而提供一种碳氮材料固载杂多酸催化剂，本发明的另一目的还提供了催化烯烃环氧化合物合成的方法，通过本发明制得的催化剂可以循环多次使用，并且能够用来进行安全大规模的生产烯烃环氧化合物。The object of the present invention is to provide a kind of carbon-nitrogen material immobilized heteropolyacid catalyst in order to improve the deficiencies in the prior art, and another object of the present invention also provides the method for the synthesis of catalyzed olefin epoxy compound, prepared by the present invention The catalyst can be recycled many times and can be used for safe large-scale production of olefin epoxy compounds.
本发明的技术方案为：一种碳氮材料固载杂多酸催化剂，由以下方法制备得到，其具体步骤如下：将杂多酸和三聚氰胺分别溶解到50℃～60℃的热水中，然后按杂多酸和三聚氰胺的摩尔比为1:（1～4）将杂多酸溶液加入到三聚氰胺溶液中，经过搅拌，过滤，烘干，得到白色固体粉末，然后将该固体粉末在惰性气体氛围下高温煅烧使其固化，即得碳氮材料固载杂多酸催化剂。The technical scheme of the present invention is: a carbon-nitrogen material immobilized heteropolyacid catalyst, which is prepared by the following method, and its specific steps are as follows: respectively dissolving the heteropolyacid and melamine into hot water at 50°C to 60°C, and then According to the molar ratio of heteropolyacid and melamine as 1: (1~4), add the heteropolyacid solution into the melamine solution, stir, filter, and dry to obtain a white solid powder, and then put the solid powder in an inert gas atmosphere Calcining at high temperature to make it solidify to obtain the carbon-nitrogen material immobilized heteropolyacid catalyst.
优选所述的杂多酸为H3PW12O40、H4SiW12O40或H4PW11VO40。优选所述的高温煅烧的温度为350℃～450℃，升温速率范围为5℃/分～10℃/分；煅烧时间为4小时～6小时。Preferably, the heteropoly acid is H3 PW12 O40 , H4 SiW12 O40 or H4 PW11 VO40 . Preferably, the temperature of the high-temperature calcination is 350° C. to 450° C., the heating rate ranges from 5° C./min to 10° C./min; the calcination time is 4 hours to 6 hours.
本发明还提供了利用上述的碳氮材料固载杂多酸催化剂的烯烃环氧化合成的方法，其具体步骤为：将催化剂和烯烃底物加入到有机溶剂中，并加入双氧水，在加热下不断搅拌直至反应结束；然后将固液两相分开，液相除去有机溶剂得到产品，固相催化剂经洗涤干燥后回收。The present invention also provides a method for olefin epoxidation synthesis using the above-mentioned carbon-nitrogen material immobilized heteropolyacid catalyst, the specific steps of which are: adding the catalyst and the olefin substrate into an organic solvent, adding hydrogen peroxide, and heating Stir continuously until the reaction is over; then separate the solid and liquid phases, remove the organic solvent from the liquid phase to obtain the product, and recover the solid phase catalyst after washing and drying.
优选所述的催化剂用量为催化剂中钨的摩尔量为烯烃底物摩尔量的3.2～10%。Preferably, the amount of the catalyst used is that the molar amount of tungsten in the catalyst is 3.2-10% of the molar amount of the olefin substrate.
优选所述的双氧水的质量浓度范围为20%～50%，双氧水和烯烃底物的摩尔比为2～3:1。Preferably, the mass concentration range of the hydrogen peroxide is 20%-50%, and the molar ratio of the hydrogen peroxide to the olefin substrate is 2-3:1.
优选加热温度为70～80℃，反应时间为6～8h。Preferably, the heating temperature is 70-80° C., and the reaction time is 6-8 hours.
在溶剂的选择上，腈，卤代烃，酯，酮，芳香烃，醇等有机溶剂均可用作本发明的合成反应溶剂，优选所述的溶剂为卤代烃、腈、酯或酮；更优选溶剂是乙腈、二氯乙烷、氯仿、乙酸乙酯、甲苯、甲醇、乙醇、异丙醇、叔丁醇、丙酮、丁酮等中的一种；最为优选的是乙腈、二氯乙烷、氯仿和乙酸乙酯。On the choice of solvent, organic solvents such as nitrile, halogenated hydrocarbon, ester, ketone, aromatic hydrocarbon, alcohol can be used as the synthetic reaction solvent of the present invention, and preferably described solvent is halogenated hydrocarbon, nitrile, ester or ketone; More preferred solvent is a kind of in acetonitrile, dichloroethane, chloroform, ethyl acetate, toluene, methyl alcohol, ethanol, Virahol, tert-butanol, acetone, methyl ethyl ketone etc.; alkanes, chloroform and ethyl acetate.
上述烯烃包括一般烯烃结构化合物，特别适用于具有如下结构特征的双环烯烃化合物，由于双环氧化二烯烃化合物具有重要的工业应用价值，本发明的一系列测试结果是基于表1所列举的双烯烃底物以及生成的相应的双环氧化合物：The above-mentioned olefins include general olefin structure compounds, and are particularly suitable for bicyclic olefin compounds with the following structural characteristics. Because double epoxidized diene compounds have important industrial application value, a series of test results of the present invention are based on the diolefin bases listed in Table 1. and the resulting corresponding diepoxides:
表1Table 1
优选所述的烯烃底物为环己烯、环辛烯、双环戊二烯、3-环己烯甲酸-3，-环己烯甲酯或6-甲基-3-环己烯甲酸-6，-甲基-3，-环己烯甲酯。Preferably, the alkene substrate is cyclohexene, cyclooctene, dicyclopentadiene, 3-cyclohexenecarboxylate-3,-cyclohexene methyl ester or 6-methyl-3-cyclohexenecarboxylate-6 ,-Methyl-3,-cyclohexene methyl ester.
本发明中催化剂和溶剂的回收是在体系反应完全后，待体系冷却至室温，通过过滤将固体和液体分开，液体通过静置将有机相收集，通过减压蒸馏得到有机溶剂，并得到相应的环氧产品；过滤得到的固体，经过洗涤、干燥、恒重后，按照上面所述工艺条件重新用于合成环氧树脂。回收使用的催化剂依然保持很好的选择性。The recovery of catalyst and solvent in the present invention is after the reaction of the system is complete, the system is cooled to room temperature, the solid and the liquid are separated by filtration, the liquid is collected by standing still, the organic solvent is obtained by distillation under reduced pressure, and the corresponding Epoxy product; the solid obtained by filtration, after washing, drying, and constant weight, is reused for synthesizing epoxy resin according to the above-mentioned process conditions. The recovered catalyst still maintains good selectivity.
有益效果：Beneficial effect:
本发明中合成的催化剂所使用的原料便宜易得，并且制备方法简单、安全，催化剂活性高，最重要的是本发明中的催化剂可以多次重复使用，并保持高活性、高选择性。通过本发明合成的催化剂不仅能降低合成成本，而且使催化剂寿命延长，和以往的均相催化剂相比，性价比更高。在倡导绿色化学的今天，这样一种催化剂是完全适合工业化大规模生产的。The raw materials used in the catalyst synthesized in the present invention are cheap and easy to obtain, and the preparation method is simple and safe, and the catalyst activity is high. Most importantly, the catalyst in the present invention can be repeatedly used and maintain high activity and high selectivity. The catalyst synthesized by the invention can not only reduce the synthesis cost, but also prolong the service life of the catalyst. Compared with the previous homogeneous catalyst, the cost performance is higher. In today's advocacy of green chemistry, such a catalyst is completely suitable for large-scale industrial production.
本发明中的所有的环氧化反应均是以市售双氧水为氧源，不同于以往的方法使用危险的、易爆的过氧醋酸。双氧水价格便宜，来源广，且生产过程中有较少水，避免了产物的分解。与现有的技术相比，本发明还有一个优点，采用本发明的生产工艺，无需通过加入缓冲剂来调节pH值，使生产工艺更加方便、简洁。All of the epoxidation reactions in the present invention are based on commercially available hydrogen peroxide as the oxygen source, which is different from the use of dangerous and explosive peracetic acid in previous methods. Hydrogen peroxide is cheap, has a wide range of sources, and there is less water in the production process, which avoids the decomposition of the product. Compared with the existing technology, the present invention has another advantage. The production process of the present invention does not need to adjust the pH value by adding a buffer, making the production process more convenient and simple.
在上述内容的基础上，按照本领域的普通技术知识和惯用手段，在不脱离本发明上述基本技术思想前提下，还可以做出多种方式的修改、替换或变更。On the basis of the above content, according to the common technical knowledge and conventional means in this field, without departing from the above-mentioned basic technical idea of the present invention, various modifications, replacements or changes can also be made.
以下通过实施形式的具体实施方式，对本发明的上述内容再作进一步的详细说明。但不应将此理解为本发明上述主题的范围仅限于以下的实例。凡基于本发明上述内容所实现的技术均属于本发明的范畴。The above-mentioned content of the present invention will be further described in detail below through the specific implementation manners of the implementation forms. However, this should not be construed as limiting the scope of the above-mentioned subject matter of the present invention to the following examples. All technologies realized based on the above contents of the present invention belong to the category of the present invention.
具体实施方式Detailed ways
实施例1催化剂A的合成The synthesis of embodiment 1 catalyst A
将288mL溶有28.8克(10mmol)H3PW12O40的50℃热水溶液，在不断搅拌的情况下加入到126mL溶有1.26克(10mmol)三聚氰胺的50℃热水中，继续剧烈搅拌24h，充分反应后，使反应混合物冷却，过滤，滤饼依次经水洗，乙醇洗后，真空干燥至恒重，得到催化剂前驱体[C3H6N6H3]PW12O40。Add 288 mL of 50°C hot water solution containing 28.8 g (10 mmol) of H3 PW12 O40 into 126 mL of 50° C. hot water containing 1.26 g (10 mmol) of melamine under constant stirring, and continue vigorously stirring for 24 hours. After fully reacting, the reaction mixture was cooled, filtered, and the filter cake was washed with water and ethanol in sequence, and vacuum-dried to constant weight to obtain the catalyst precursor [C3 H6 N6 H3 ]PW12 O40 .
称取20克上面制得的催化剂前驱体，在研钵中充分研磨，研磨成很细的粉末，将研好的粉末固体加入到石英器皿中，然后将其置于程序升温炉子中，在惰性气体氛围下进行煅烧。升温速率控制在5℃/分，目标温度设置在350℃，在350℃下持续煅烧时间为4h，降温时间控制为1h，得到黑色催化剂A固体粉末。Take by weighing 20 grams of the catalyst precursor prepared above, fully grind in a mortar, grind into a very fine powder, add the ground powder solid into a quartz vessel, then place it in a temperature-programmed furnace, in an inert Calcination is carried out under gas atmosphere. The heating rate was controlled at 5°C/min, the target temperature was set at 350°C, the continuous calcination time at 350°C was 4h, and the cooling time was controlled at 1h to obtain black catalyst A solid powder.
实施2催化剂B的合成Implementation 2 Synthesis of Catalyst B
将288mL溶有28.8克(10mmol)H3PW12O40的60℃热水溶液，在不断搅拌的情况下加入到200mL溶有3.78克(30mmol)三聚氰胺的60℃热水中，继续剧烈搅拌24h，充分反应后，使反应混合物冷却，过滤，滤饼依次经水洗，乙醇洗后，真空干燥至恒重，制得催化剂前驱体[C3H6N6H][PW12O40]1/3。Add 288 mL of 60°C hot water solution containing 28.8 g (10 mmol) of H3 PW12 O40 into 200 mL of 60° C. hot water containing 3.78 g (30 mmol) of melamine under constant stirring, and continue to stir vigorously for 24 hours. After fully reacting, the reaction mixture was cooled, filtered, and the filter cake was washed with water and ethanol in turn, and then vacuum-dried to constant weight to obtain the catalyst precursor [C3 H6 N6 H][PW12 O40 ]1/3 .
称取20克上面制得的催化剂前驱体，在研钵中充分研磨，研磨成很细的粉末，将研好的粉末固体加入到石英器皿中，然后将其置于程序升温炉子中，在惰性气体氛围下进行煅烧。升温速率控制在10℃/分，目标温度设置在400℃，在400℃下持续煅烧时间为5h，降温时间控制为1.5h，得到黑色催化剂B固体粉末。Take by weighing 20 grams of the catalyst precursor prepared above, fully grind in a mortar, grind into a very fine powder, add the ground powder solid into a quartz vessel, then place it in a temperature-programmed furnace, in an inert Calcination is carried out under gas atmosphere. The heating rate was controlled at 10 °C/min, the target temperature was set at 400 °C, the continuous calcination time at 400 °C was 5 h, and the cooling time was controlled at 1.5 h to obtain black catalyst B solid powder.
实施3催化剂C的合成Implementation 3 Synthesis of Catalyst C
将300mL溶有28.8克(10mmol)H4SiW12O40的55℃水溶液，在不断搅拌的情况下加入150mL溶有1.67克(13.3mmol)三聚氰胺的55℃热水中，继续剧烈搅拌24h，充分反应后，使反应混合物冷却，过滤，滤饼依次经水洗，乙醇洗后，真空干燥至恒重，制得催化剂前驱体[C3H6N6H3][SiW12O40]3/4。Add 300 mL of 55°C aqueous solution containing 28.8 g (10 mmol) of H4 SiW12 O40 into 150 mL of 55°C hot water containing 1.67 g (13.3 mmol) of melamine under constant stirring, and continue vigorously stirring for 24 hours to fully After the reaction, the reaction mixture was cooled, filtered, and the filter cake was washed with water and ethanol in turn, and dried in vacuum to constant weight to obtain the catalyst precursor [C3 H6 N6 H3 ][SiW12 O40 ]3/4 .
称取20克上面制得的催化剂前驱体，在研钵中充分研磨，研磨成很细的粉末，将研好的粉末固体加入到石英器皿中，然后将其置于程序升温炉子中，在惰性气体氛围下进行煅烧。升温速率控制在5℃/分，目标温度设置在350℃，持续煅烧时间为4h，降温时间控制为1h，得到黑色催化剂C固体粉末。Take by weighing 20 grams of the catalyst precursor prepared above, fully grind in a mortar, grind into a very fine powder, add the ground powder solid into a quartz vessel, then place it in a temperature-programmed furnace, in an inert Calcination is carried out under gas atmosphere. The heating rate was controlled at 5 °C/min, the target temperature was set at 350 °C, the continuous calcination time was 4 h, and the cooling time was controlled at 1 h to obtain black catalyst C solid powder.
实施4催化剂D的合成Implementation 4 Synthesis of Catalyst D
将300mL溶有28.8克(10mmol)H4SiW12O40的60℃水溶液，在不断搅拌的情况下加入到250mL溶有4.9克(40mmol)三聚氰胺的60℃热水中，继续剧烈搅拌24h，充分反应后，使反应混合物冷却，过滤，滤饼依次经水洗，乙醇洗后，真空干燥至恒重，制得催化剂前驱体[C3H6N6H][SiW12O40]1/4。Add 300mL of 60°C aqueous solution containing 28.8g (10mmol) of H4 SiW12 O40 into 250mL of 60°C hot water containing 4.9g (40mmol) of melamine under continuous stirring, and continue vigorously stirring for 24h to fully After the reaction, the reaction mixture was cooled, filtered, and the filter cake was washed with water and ethanol in sequence, and vacuum-dried to constant weight to obtain a catalyst precursor [C3 H6 N6 H][SiW12 O40 ]1/4 .
称取20克上面制得的催化剂前驱体，在研钵中充分研磨，研磨成很细的粉末，将研好的粉末固体加入到石英器皿中，然后将其置于程序升温炉子中，在惰性气体氛围下进行煅烧。升温速率控制在10℃/分，目标温度设置在450℃，持续煅烧时间为6h，降温时间控制为2h，得到黑色催化剂D固体粉末。Take by weighing 20 grams of the catalyst precursor prepared above, fully grind in a mortar, grind into a very fine powder, add the ground powder solid into a quartz vessel, then place it in a temperature-programmed furnace, in an inert Calcination is carried out under gas atmosphere. The heating rate was controlled at 10 °C/min, the target temperature was set at 450 °C, the continuous calcination time was 6 h, and the cooling time was controlled at 2 h to obtain black catalyst D solid powder.
实施5催化剂E的合成Implementation of 5 Synthesis of Catalyst E
将310mL溶有31克(10mmol)H4PW11VO4的55℃热水溶液，在不断搅拌的情况下加入到150mL溶有1.67克(13.3mmol)三聚氰胺的55℃热水中，继续剧烈搅拌24h，充分反应后，使反应混合物冷却，过滤，滤饼依次经水洗，乙醇洗后，真空干燥至恒重，制得催化剂前驱体[C3H6N6H3][PW11VO4]3/4。Add 310mL of 55°C hot water solution with 31g (10mmol) of H4 PW11 VO4 into 150mL of 55°C hot water with 1.67g (13.3mmol) of melamine dissolved under constant stirring, and continue vigorously stirring for 24h , after fully reacting, the reaction mixture was cooled, filtered, the filter cake was washed with water and ethanol in turn, and dried in vacuum to constant weight to obtain the catalyst precursor [C3 H6 N6 H3 ][PW11 VO4 ]3 /4 .
称取20克上面制得的催化剂前驱体，在研钵中充分研磨，研磨成很细的粉末，将研好的粉末固体加入到石英器皿中，然后将其置于程序升温炉子中，在惰性气体氛围下进行煅烧。升温速率控制在10℃/分，目标温度设置在450℃，持续煅烧时间为4h，降温时间控制为2h，得到黑色催化剂E固体粉末。Take by weighing 20 grams of the catalyst precursor prepared above, fully grind in a mortar, grind into a very fine powder, add the ground powder solid into a quartz vessel, then place it in a temperature-programmed furnace, in an inert Calcination is carried out under gas atmosphere. The heating rate was controlled at 10 °C/min, the target temperature was set at 450 °C, the continuous calcination time was 4 h, and the cooling time was controlled at 2 h to obtain black catalyst E solid powder.
实施6催化剂F的合成Implement 6 Synthesis of Catalyst F
将310mL溶有31克(10mmol)H4PW11VO4的60℃热水溶液，在不断搅拌的情况下加入到250mL溶有4.9克(40mmol)三聚氰胺的60℃热水中，继续剧烈搅拌24h，充分反应后，使反应混合物冷却，过滤，滤饼依次经水洗，乙醇洗后，真空干燥至恒重，制得催化剂前驱体[C3H6N6H][PW11VO4]1/4。Add 310 mL of 60°C hot water solution containing 31 grams (10 mmol) of H4 PW11 VO4 into 250 mL of 60° C. hot water containing 4.9 grams (40 mmol) of melamine under continuous stirring, and continue vigorously stirring for 24 hours. After fully reacting, the reaction mixture was cooled, filtered, and the filter cake was washed with water and ethanol in sequence, and then vacuum-dried to constant weight to obtain the catalyst precursor [C3 H6 N6 H][PW11 VO4 ]1/4 .
称取20克上面制得的催化剂前驱体，在研钵中充分研磨，研磨成很细的粉末，将研好的粉末固体加入到石英器皿中，然后将其置于程序升温炉子中，在氮气的氛围下进行煅烧。升温速率控制在10℃/分，目标温度设置为450℃，持续煅烧时间为6h，降温时间控制为2h，得到黑色催化剂F固体粉末。Take by weighing 20 grams of the catalyst precursor prepared above, fully grind in a mortar, grind into a very fine powder, add the ground powder solid into a quartz vessel, then place it in a temperature-programmed furnace, under nitrogen Calcined in an atmosphere. The heating rate was controlled at 10 °C/min, the target temperature was set at 450 °C, the continuous calcination time was 6 h, and the cooling time was controlled at 2 h to obtain a black catalyst F solid powder.
实施7122催化氧化合成Implementation of 7122 Catalytic Oxidative Synthesis
将66克(0.5mol)双环戊二烯和5克催化剂A（钨的物质量为0.02mol）加入到100克乙腈中，在80℃下滴入165mL20%（1.1mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品二氧化环戊二烯76克，产率94%。Add 66 g (0.5 mol) of dicyclopentadiene and 5 g of catalyst A (0.02 mol of tungsten) into 100 g of acetonitrile, drop 165 mL of 20% (1.1 mol) hydrogen peroxide at 80°C, and react for 8 hours. Cool to room temperature, filter, and evaporate acetonitrile by rotary evaporation to obtain 76 g of the product cyclopentadiene dioxide, with a yield of 94%.
实施8122催化氧化合成Implementation of 8122 Catalytic Oxidative Synthesis
将66克(0.5mol)双环戊二烯和5克催化剂B（钨的物质量为0.018mol）加入到100克乙腈中，在80℃下滴入165mL20%（1.1mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品二氧化环戊二烯72克，产率88%。Add 66 grams (0.5 mol) of dicyclopentadiene and 5 grams of catalyst B (0.018 mol of tungsten) into 100 grams of acetonitrile, drop 165 mL of 20% (1.1 mol) hydrogen peroxide at 80 ° C, and react for 8 hours. Cool to room temperature, filter, and evaporate acetonitrile by rotary evaporation to obtain 72 g of the product cyclopentadiene dioxide, with a yield of 88%.
实施9122催化氧化合成Implementation of 9122 Catalytic Oxidative Synthesis
将66克(0.5mol)双环戊二烯和5克催化剂C（钨的物质量为0.018mol）加入到100克乙腈中，在75℃下滴入110mL30%（1.1mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品二氧化环戊二烯70克，产率85%。实施10122催化氧化合成Add 66 grams (0.5 mol) of dicyclopentadiene and 5 grams of catalyst C (0.018 mol of tungsten) into 100 grams of acetonitrile, drop 110 mL of 30% (1.1 mol) hydrogen peroxide at 75 ° C, and react for 8 hours. Cool to room temperature, filter, and evaporate acetonitrile by rotary evaporation to obtain 70 g of the product cyclopentadiene dioxide, with a yield of 85%. Implementation of 10122 Catalytic Oxidative Synthesis
将66克(0.5mol)双环戊二烯和5克催化剂D（钨的物质量为0.016mol）加入到100克乙腈中，在75℃下滴入150mL30%（1.5mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品二氧化环戊二烯65克，产率79%。Add 66 g (0.5 mol) of dicyclopentadiene and 5 g of catalyst D (0.016 mol of tungsten) into 100 g of acetonitrile, drop 150 mL of 30% (1.5 mol) hydrogen peroxide at 75 ° C, and react for 8 hours. Cool to room temperature, filter, and evaporate acetonitrile by rotary evaporation to obtain 65 g of the product cyclopentadiene dioxide, with a yield of 79%.
实施11122催化氧化合成Implementation of 11122 Catalytic Oxidative Synthesis
将66克(0.5mol)双环戊二烯和15克催化剂E（钨的物质量为0.05mol）加入到100克乙腈中，在70℃下滴入63mL50%（1.05mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品二氧化环戊二烯78克，产率95%。Add 66 grams (0.5 mol) of dicyclopentadiene and 15 grams of catalyst E (0.05 mol of tungsten) into 100 grams of acetonitrile, drop 63 mL of 50% (1.05 mol) hydrogen peroxide at 70 ° C, and react for 8 hours. Cool to room temperature, filter, and evaporate acetonitrile by rotary evaporation to obtain 78 g of cyclopentadiene dioxide, a product with a yield of 95%.
实施12122催化氧化合成Implementation of 12122 Catalytic Oxidative Synthesis
将66克(0.5mol)双环戊二烯和15克催化剂F（钨的物质量为0.045mol）加入到100克乙腈中，在70℃下滴入63mL50%（1.05mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品二氧化环戊二烯76克，产率94%。Add 66 g (0.5 mol) of dicyclopentadiene and 15 g of catalyst F (0.045 mol of tungsten) into 100 g of acetonitrile, drop 63 mL of 50% (1.05 mol) hydrogen peroxide at 70°C, and react for 8 hours. Cool to room temperature, filter, and evaporate acetonitrile by rotary evaporation to obtain 76 g of the product cyclopentadiene dioxide, with a yield of 94%.
实施13CER-4221催化氧化合成Implementation of 13CER-4221 catalytic oxidation synthesis
将110克(0.5mol)3-环己烯甲酸-3，-环己烯甲酯和5克催化剂A（钨的物质量为0.02mol）加入到100克乙腈中，在80℃下滴入165mL20%（1.1mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品3,4-环氧-环己基甲酸-3，,4，-环氧环己基甲酯115克，产率81%。Add 110 grams (0.5 mol) of 3-cyclohexenecarboxylate-3,-cyclohexene methyl ester and 5 grams of catalyst A (the amount of tungsten is 0.02 mol) into 100 grams of acetonitrile, drop 165 mL of 20 % (1.1mol) hydrogen peroxide, reacted for 8 hours, cooled to room temperature, filtered, and evaporated acetonitrile by rotary evaporation to obtain 115 grams of the product 3,4-epoxy-cyclohexylcarboxylate-3,,4,-epoxycyclohexylmethyl ester , yield 81%.
实施14CER-4221催化氧化合成Implementation of 14CER-4221 catalytic oxidation synthesis
将110克(0.5mol)3-环己烯甲酸-3，-环己烯甲酯和5克催化剂B（钨的物质量为0.018mol）加入到100克乙腈中，在80℃下滴入165mL20%（1.1mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品3,4-环氧-环己基甲酸-3，,4，-环氧环己基甲酯105克，产率74%。Add 110 grams (0.5 mol) of 3-cyclohexenecarboxylate-3,-cyclohexene methyl ester and 5 grams of catalyst B (0.018 mol of tungsten) into 100 grams of acetonitrile, drop 165 mL of 20 % (1.1mol) hydrogen peroxide, reacted for 8 hours, cooled to room temperature, filtered, and evaporated acetonitrile by rotary evaporation to obtain 105 grams of the product 3,4-epoxy-cyclohexylcarboxylate-3,,4,-epoxycyclohexylmethyl ester , yield 74%.
实施15CER-4221催化氧化合成Implementation of 15CER-4221 catalytic oxidation synthesis
将110克(0.5mol)3-环己烯甲酸-3，-环己烯甲酯和5克催化剂C（钨的物质量为0.018mol）加入到100克乙腈中，在75℃下滴入110mL30%（1.1mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品3,4-环氧-环己基甲酸-3，,4，-环氧环己基甲酯104克，产率73%。Add 110 grams (0.5 mol) of 3-cyclohexenecarboxylate-3,-cyclohexene methyl ester and 5 grams of catalyst C (0.018 mol of tungsten) into 100 grams of acetonitrile, drop into 110 mL30 at 75 °C % (1.1mol) hydrogen peroxide, reacted for 8 hours, cooled to room temperature, filtered, and evaporated acetonitrile by rotary evaporation to obtain 104 grams of the product 3,4-epoxy-cyclohexylcarboxylate-3,,4,-epoxycyclohexylmethyl ester , yield 73%.
实施16CER-4221催化氧化合成Implementation of 16CER-4221 catalytic oxidation synthesis
将110克(0.5mol)3-环己烯甲酸-3，-环己烯甲酯和5克催化剂D（钨的物质量为0.016mol）加入到100克乙腈中，在75℃下滴入150mL30%（1.5mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品3,4-环氧-环己基甲酸-3，,4，-环氧环己基甲酯103克，产率72%。Add 110 grams (0.5 mol) of 3-cyclohexenecarboxylate-3,-cyclohexene methyl ester and 5 grams of catalyst D (the amount of tungsten is 0.016 mol) into 100 grams of acetonitrile, drop into 150 mL30 at 75 ° C % (1.5mol) hydrogen peroxide, reacted for 8 hours, cooled to room temperature, filtered, and evaporated acetonitrile by rotary evaporation to obtain 103 grams of the product 3,4-epoxy-cyclohexylcarboxylate-3,,4,-epoxycyclohexylmethyl ester , yield 72%.
实施17CER-4221催化氧化合成Implementation of 17CER-4221 catalytic oxidation synthesis
将110克(0.5mol)3-环己烯甲酸-3，-环己烯甲酯和15克催化剂E（钨的物质量为0.05mol）加入到100克乙腈中，在70℃下滴入63mL50%（1.05mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品3,4-环氧-环己基甲酸-3，,4，-环氧环己基甲酯130克，产率91%。Add 110 grams (0.5 mol) of 3-cyclohexenecarboxylate-3,-cyclohexene methyl ester and 15 grams of catalyst E (the amount of tungsten is 0.05 mol) into 100 grams of acetonitrile, drop into 63 mL50 at 70 ° C % (1.05mol) hydrogen peroxide, reacted for 8 hours, cooled to room temperature, filtered, and evaporated acetonitrile by rotary evaporation to obtain 130 grams of the product 3,4-epoxy-cyclohexylcarboxylate-3,,4,-epoxycyclohexylmethyl ester , yield 91%.
实施18CER-4221催化氧化合成Implementation of 18CER-4221 catalytic oxidation synthesis
将110克(0.5mol)3-环己烯甲酸-3，-环己烯甲酯和15克催化剂F（钨的物质量为0.045mol）加入到100克乙腈中，在70℃下滴入63mL50%（1.05mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品3,4-环氧-环己基甲酸-3，,4，-环氧环己基甲酯125克，产率88%。Add 110 grams (0.5 mol) of 3-cyclohexenecarboxylate-3,-cyclohexene methyl ester and 15 grams of catalyst F (the amount of tungsten is 0.045 mol) into 100 grams of acetonitrile, drop into 63 mL50 at 70 ° C % (1.05mol) hydrogen peroxide, react for 8h, cool to room temperature, filter, and evaporate acetonitrile by rotary evaporation to obtain 125 grams of the product 3,4-epoxy-cyclohexylcarboxylate-3,,4,-epoxycyclohexylmethyl ester , yield 88%.
实施19Unox201催化氧化合成Implementation of 19Unox201 catalytic oxidation synthesis
将125克(0.5mol)6-甲基-3-环己烯甲酸-6，-甲基-3，-环己烯甲酯和5克催化剂A（钨的物质量为0.02mol）加入到100克乙腈中，在80℃下滴入165mL20%（1.1mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品4,5-环氧-2-甲基环己基甲酸-4，,5，-环氧-2，-甲基环己基甲酯124克，产率78%。125 grams (0.5mol) of 6-methyl-3-cyclohexene carboxylate-6,-methyl-3,-cyclohexene methyl ester and 5 grams of catalyst A (the amount of tungsten is 0.02mol) were added to 100 Add 165 mL of 20% (1.1 mol) hydrogen peroxide dropwise to 1 g of acetonitrile at 80°C, react for 8 hours, cool to room temperature, filter, and evaporate acetonitrile by rotary evaporation to obtain the product 4,5-epoxy-2-methylcyclohexyl formic acid -4,,5,-epoxy-2,-methylcyclohexyl methyl ester 124 g, yield 78%.
实施20Unox201催化氧化合成Implementation of 20Unox201 catalytic oxidation synthesis
将125克(0.5mol)6-甲基-3-环己烯甲酸-6，-甲基-3，-环己烯甲酯和5克催化剂B（钨的物质量为0.018mol）加入到100克乙腈中，在80℃下滴入165mL20%（1.1mol）的双氧水，反应7h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品4,5-环氧-2-甲基环己基甲酸-4，,5，-环氧-2，-甲基环己基甲酯115克，产率73%。125 grams (0.5mol) of 6-methyl-3-cyclohexene carboxylic acid-6,-methyl-3,-cyclohexene methyl ester and 5 grams of catalyst B (the amount of tungsten is 0.018mol) were added to 100 Add 165 mL of 20% (1.1 mol) hydrogen peroxide dropwise to 1 g of acetonitrile at 80°C, react for 7 hours, cool to room temperature, filter, and evaporate acetonitrile by rotary evaporation to obtain the product 4,5-epoxy-2-methylcyclohexyl formic acid -4,,5,-epoxy-2,-methylcyclohexyl methyl ester 115 g, yield 73%.
实施21Unox201催化氧化合成Implementation of 21Unox201 catalytic oxidation synthesis
将125克(0.5mol)6-甲基-3-环己烯甲酸-6，-甲基-3，-环己烯甲酯和5克催化剂C（钨的物质量为0.018mol）加入到100克乙腈中，在75℃下滴入110mL30%（1.1mol）的双氧水，反应6h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品4,5-环氧-2-甲基环己基甲酸-4，,5，-环氧-2，-甲基环己基甲酯113克，产率72%。125 grams (0.5mol) of 6-methyl-3-cyclohexenecarboxylic acid-6,-methyl-3,-cyclohexene methyl ester and 5 grams of catalyst C (the amount of tungsten is 0.018mol) were added to 100 Add 110 mL of 30% (1.1 mol) hydrogen peroxide dropwise to 1 g of acetonitrile at 75°C, react for 6 hours, cool to room temperature, filter, and evaporate acetonitrile by rotary evaporation to obtain the product 4,5-epoxy-2-methylcyclohexylcarboxylic acid -4,,5,-epoxy-2,-methylcyclohexyl methyl ester 113 g, yield 72%.
实施22Unox201催化氧化合成Implementation of 22Unox201 catalytic oxidation synthesis
将125克(0.5mol)6-甲基-3-环己烯甲酸-6，-甲基-3，-环己烯甲酯和5克催化剂D（钨的物质量为0.016mol）加入到100克氯仿中，在75℃下滴入150mL30%（1.5mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出氯仿，得到产品4,5-环氧-2-甲基环己基甲酸-4，,5，-环氧-2，-甲基环己基甲酯110克，产率70%。125 grams (0.5mol) of 6-methyl-3-cyclohexenecarboxylic acid-6,-methyl-3,-cyclohexene methyl ester and 5 grams of catalyst D (the amount of tungsten is 0.016mol) were added to 100 Add 150 mL of 30% (1.5 mol) hydrogen peroxide dropwise to 1 g of chloroform at 75°C, react for 8 hours, cool to room temperature, filter, and evaporate chloroform by rotary evaporation to obtain the product 4,5-epoxy-2-methylcyclohexylcarboxylic acid -4,,5,-epoxy-2,-methylcyclohexyl methyl ester 110 g, yield 70%.
实施23Unox201催化氧化合成Implementation of 23Unox201 catalytic oxidation synthesis
将125克(0.5mol)6-甲基-3-环己烯甲酸-6，-甲基-3，-环己烯甲酯和15克催化剂E（钨的物质量为0.05mol）加入到100克乙腈中，在70℃下滴入63mL50%（1.05mol）的双氧水，反应8h，冷却至室温，过滤，旋转蒸发蒸出乙腈，得到产品4,5-环氧-2-甲基环己基甲酸-4，,5，-环氧-2，-甲基环己基甲酯147克，产率94%。125 grams (0.5mol) of 6-methyl-3-cyclohexene carboxylic acid-6,-methyl-3,-cyclohexene methyl ester and 15 grams of catalyst E (the amount of tungsten is 0.05mol) were added to 100 Add 63 mL of 50% (1.05 mol) hydrogen peroxide dropwise to 1 g of acetonitrile at 70°C, react for 8 hours, cool to room temperature, filter, and evaporate acetonitrile by rotary evaporation to obtain the product 4,5-epoxy-2-methylcyclohexyl formic acid -4,,5,-epoxy-2,-methylcyclohexyl methyl ester 147 g, yield 94%.
实施24Unox201催化氧化合成Implementation of 24Unox201 catalytic oxidation synthesis
将125克(0.5mol)6-甲基-3-环己烯甲酸-6，-甲基-3，-环己烯甲酯和5克催化剂F（钨的物质量为0.045mol）加入到100克二氯乙烷中，在70℃下滴入63mL50%（1.05mol）的双氧水，反应7h，冷却至室温，过滤，旋转蒸发蒸出二氯乙烷，得到产品4,5-环氧-2-甲基环己基甲酸-4，,5，-环氧-2，-甲基环己基甲酯135克，产率86%。125 grams (0.5mol) of 6-methyl-3-cyclohexene carboxylic acid-6,-methyl-3,-cyclohexene methyl ester and 5 grams of catalyst F (the amount of tungsten is 0.045mol) are added to 100 Add 63 mL of 50% (1.05 mol) hydrogen peroxide dropwise to 1 g of dichloroethane at 70°C, react for 7 hours, cool to room temperature, filter, and evaporate dichloroethane by rotary evaporation to obtain the product 4,5-epoxy-2 -Methylcyclohexylcarboxylic acid-4,,5,-epoxy-2,-methylcyclohexyl methyl ester 135 grams, yield 86%.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310096442.6ACN103143381B (en) | 2013-03-22 | 2013-03-22 | Carbon-nitrogen material immobilized heteropoly acid catalyst and olefin epoxidation synthesis method |
| Application Number | Priority Date | Filing Date | Title |
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| CN201310096442.6ACN103143381B (en) | 2013-03-22 | 2013-03-22 | Carbon-nitrogen material immobilized heteropoly acid catalyst and olefin epoxidation synthesis method |
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| CN103143381A CN103143381A (en) | 2013-06-12 |
| CN103143381Btrue CN103143381B (en) | 2014-12-10 |
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