CN110776418A - Method for preparing maleic acid ester by catalyzing maleic anhydride with ionic liquid - Google Patents
Method for preparing maleic acid ester by catalyzing maleic anhydride with ionic liquid Download PDFInfo
- Publication number
- CN110776418A CN110776418A CN201911107060.2A CN201911107060A CN110776418A CN 110776418 A CN110776418 A CN 110776418A CN 201911107060 A CN201911107060 A CN 201911107060A CN 110776418 A CN110776418 A CN 110776418A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- maleic anhydride
- catalyzing
- maleic
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种离子液体催化马来酸酐制备马来酸酯的方法，其特征在于，包括如下步骤：将离子液体与马来酸酐和脂肪醇混合，加热至80～140℃，反应0.5～4h，获得马来酸酯，所述离子液体用量为马来酸酐的0.1％～10％mol，脂肪醇和马来酸酐的摩尔比为2～12。制备出以完全酯化的马来酸酯为主要产物的高附加值化学品。本发明工艺简单，条件温和，环境友好，双酯化程度高，离子液体活性高且不易失活，可实现循环使用。The invention discloses a method for catalyzing maleic anhydride to prepare maleate by ionic liquid, which is characterized by comprising the following steps: mixing ionic liquid, maleic anhydride and fatty alcohol, heating to 80-140° C., and reacting 0.5-140° C. 4h, maleic acid ester is obtained, the dosage of the ionic liquid is 0.1%-10% mol of maleic anhydride, and the molar ratio of fatty alcohol and maleic anhydride is 2-12. High value-added chemicals with fully esterified maleate as the main product are prepared. The invention has the advantages of simple process, mild conditions, environmental friendliness, high degree of diesterization, high activity of the ionic liquid and not easy to be deactivated, and can realize recycling.
Description
技术领域technical field
本发明涉及化工产品制备技术领域，具体涉及一种离子液体催化马来酸酐制备马来酸酯的方法。The invention relates to the technical field of chemical product preparation, in particular to a method for catalyzing maleic anhydride to prepare maleate by an ionic liquid.
背景技术Background technique
马来酸酐是一种常用的重要基本有机化工原料。是世界上仅次于醋酐和苯酐的第三大酸酐原料。马来酸酐来源广泛，可由苯氧化法、丁烯氧化法、丁烷氧化法及苯酐副产法等以化石原料为基础合成的方法制备，也可通过生物质原料(如：纤维素)发酵、催化转化得到。以马来酸酐为平台化合物，可用于生产1,4-丁二醇，四氢呋喃，γ-丁内酯，马来酸酯等多种高附加值的化学产品。因此，马来酸酐的转化研究受到了学术界和工业界的广泛关注。Maleic anhydride is a common and important basic organic chemical raw material. It is the third largest acid anhydride raw material in the world after acetic anhydride and phthalic anhydride. Maleic anhydride has a wide range of sources, and can be prepared by benzene oxidation, butene oxidation, butane oxidation and phthalic anhydride by-product synthesis methods based on fossil raw materials, or by fermentation of biomass raw materials (such as cellulose), Catalytic conversion is obtained. Using maleic anhydride as a platform compound, it can be used to produce a variety of high value-added chemical products such as 1,4-butanediol, tetrahydrofuran, γ-butyrolactone, and maleate. Therefore, the conversion of maleic anhydride has received extensive attention from academia and industry.
作为有机合成中间体，马来酸酯主要是在双键上进行加成反应。如与丁二烯、环戊二烯等进行Diels-Alder反应，将氢、腈、硫醇、胺等含活泼氢的化合物加成，如通过亚硫酸氢钠的加成而制得著名的表面活性剂琥珀酸二烷基酯磺酸盐。其他氨、胺类与马来酸酯进行加成的同时，由于发生氨解而进行酰胺化(酰亚胺化)反应，即起着酰化剂的作用。马来酸二乙酯的应用极广，也用作生产高效杀虫剂马拉松等农药及医药的中间体，也可用于高分子化合物的生产；马来酸二甲酯、二丁酯、二辛酯是PVC的优良增塑剂；并可与氯乙烯、乙酸乙烯等单体共聚，用作涂料、粘接剂，造纸、织物等浸渍剂、分散剂、润滑剂等；马来酸二异辛酯和马来酸二壬酯是良好的石油降凝剂。As an intermediate in organic synthesis, maleate is mainly subjected to an addition reaction on the double bond. Such as Diels-Alder reaction with butadiene, cyclopentadiene, etc., addition of active hydrogen-containing compounds such as hydrogen, nitriles, mercaptans, amines, etc., such as the addition of sodium bisulfite to obtain the famous surface Active agent dialkyl succinate sulfonate. At the same time as other ammonia and amines are added to maleate, amidation (imidization) reaction occurs due to aminolysis, that is, it acts as an acylating agent. Diethyl maleate is widely used, and is also used as an intermediate for the production of high-efficiency pesticides such as marathon and medicine, as well as for the production of polymer compounds; dimethyl maleate, dibutyl, dioctyl Ester is an excellent plasticizer for PVC; it can be copolymerized with vinyl chloride, vinyl acetate and other monomers, used as coatings, adhesives, impregnants, dispersants, lubricants, etc. in papermaking, fabrics, etc.; diisooctyl maleate Esters and dinonyl maleate are good petroleum pour point depressants.
马来酸酐酯化主要分两步进行，第一步是单酯化反应，如方程(1)，该步反应较容易进行，在无任何催化剂、室温下即可转化；第二步是双酯化反应，如方程(2)，为可逆反应，需在酸性催化剂下才能进一步转化。Maleic anhydride esterification is mainly carried out in two steps. The first step is a monoesterification reaction, such as equation (1), which is easy to carry out and can be converted at room temperature without any catalyst; the second step is a diester. The transformation reaction, such as equation (2), is reversible and requires an acidic catalyst for further transformation.
传统的马来酸酯的生产方法中主要采用硫酸作催化剂，虽然硫酸的催化活性高、价格便宜，但存在副反应多、产品容易异构化成富马酸酯、设备腐蚀严重、后续处理复杂等缺点；专利CN106631784A、CN206204188U中使用强酸性离子交换树脂作为固体催化剂，该类催化剂虽然对设备腐蚀较小，但离子交换树脂的再生过程繁琐，易产生二次污染，且难于完全再生，树脂的重复使用性低。In the traditional production method of maleate, sulfuric acid is mainly used as a catalyst. Although the catalytic activity of sulfuric acid is high and the price is cheap, there are many side reactions, the product is easily isomerized into fumarate, the equipment is seriously corroded, and the follow-up treatment is complicated. Disadvantages: Strong acid ion exchange resin is used as solid catalyst in patents CN106631784A and CN206204188U. Although this type of catalyst is less corrosive to equipment, the regeneration process of ion exchange resin is cumbersome and prone to secondary pollution, and it is difficult to completely regenerate, and the repetition of resin Low usability.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种离子液体催化马来酸酐制备马来酸酯的方法，以实现高效催化合成马来酸酯的高效节能过程。The object of the present invention is to provide a method for catalyzing maleic anhydride to prepare maleate by ionic liquid, so as to realize the high-efficiency and energy-saving process of catalyzing and synthesizing maleate with high efficiency.
本发明提供一种离子液体催化马来酸酐制备马来酸酯的方法，包括如下步骤：将离子液体与马来酸酐和脂肪醇混合，加热至80～140℃，反应0.5～4h，获得马来酸酯，所述离子液体用量为马来酸酐的0.1％～10％mol，脂肪醇和马来酸酐的摩尔比为2～12，其中，离子液体的结构式为(1)～(5)中任意一种：The invention provides a method for catalyzing maleic anhydride to prepare maleate by ionic liquid, comprising the following steps: mixing ionic liquid, maleic anhydride and fatty alcohol, heating to 80-140° C., and reacting for 0.5-4 h to obtain maleic anhydride. Ester, the dosage of the ionic liquid is 0.1%～10%mol of maleic anhydride, and the molar ratio of fatty alcohol and maleic anhydride is 2～12, wherein, the structural formula of the ionic liquid is any one of (1)～(5) kind:
n为0～8的整数；X为Cl、Br、I中任意一种。n is an integer from 0 to 8; X is any one of Cl, Br, and I.
与现有技术相比，本发明的有益效果在于：本发明采用的是离子液体催化制备马来酸酐酯，有效解决传统液体酸设备腐蚀、后续处理复杂，以及固体离子交换树脂再生困难的问题。在离子液体催化下，马来酸酐保持较好的转化率和双酯化选择性，马来酸酐的转化率为90～99％，马来酸酯的产率达到80～95％。且该方法只需要将产物进行简单的减压蒸馏即可将产品与离子液体分离，实现离子液体的再生。Compared with the prior art, the present invention has the beneficial effects that: the present invention adopts ionic liquid to catalyze the preparation of maleic anhydride ester, which effectively solves the problems of corrosion of traditional liquid acid equipment, complicated follow-up treatment and difficult regeneration of solid ion exchange resin. Under the catalysis of ionic liquid, maleic anhydride maintains good conversion rate and diesterization selectivity, the conversion rate of maleic anhydride is 90-99%, and the yield of maleic acid ester reaches 80-95%. In addition, the method only needs to perform simple vacuum distillation on the product to separate the product from the ionic liquid, thereby realizing the regeneration of the ionic liquid.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.
本发明实施例提供一种离子液体催化马来酸酐制备马来酸酯的方法，包括如下步骤：将离子液体与马来酸酐和脂肪醇混合，加热至80～140℃，反应0.5～4h，获得马来酸酯，所述离子液体用量为马来酸酐的0.1％～10％mol，脂肪醇和马来酸酐的摩尔比为2～12，其中，离子液体的结构式为(1)～(5)中任意一种：The embodiment of the present invention provides a method for catalyzing maleic anhydride to prepare maleate by ionic liquid, comprising the following steps: mixing ionic liquid, maleic anhydride and fatty alcohol, heating to 80-140° C., and reacting for 0.5-4 h to obtain Maleic acid ester, the dosage of the ionic liquid is 0.1%～10%mol of maleic anhydride, and the molar ratio of fatty alcohol and maleic anhydride is 2～12, wherein, the structural formula of the ionic liquid is in (1)～(5) Either:
n为0～8的整数；X为Cl、Br、I中任意一种。n is an integer from 0 to 8; X is any one of Cl, Br, and I.
具体地，所述加热为微波加热。所述的脂肪醇为甲醇、乙醇、正丁醇、异丁醇、正辛醇、异辛醇、正壬醇、1,4-二丁醇中的至少一种。优选地，所述的脂肪醇为甲醇、乙醇和丁醇中的至少一种。Specifically, the heating is microwave heating. The fatty alcohol is at least one of methanol, ethanol, n-butanol, isobutanol, n-octanol, isooctanol, n-nonanol and 1,4-dibutanol. Preferably, the fatty alcohol is at least one of methanol, ethanol and butanol.
优选地，所述离子液体用量为马来酸酐的0.5％～2％mol。所述脂肪醇和马来酸酐的摩尔比为3～6。Preferably, the dosage of the ionic liquid is 0.5% to 2% mol of maleic anhydride. The molar ratio of the fatty alcohol and maleic anhydride is 3-6.
更优选地，加热至110～130℃，反应45min～1.5h。More preferably, it is heated to 110-130° C., and the reaction is carried out for 45 minutes to 1.5 hours.
具体地，离子液体(1)、(2)中磺酸功能化的离子液体需经过两步制得：a.将甲基咪唑或吡啶溶于乙醇中，放入70℃的油浴锅中预热，在磁力搅拌下逐滴加入磺酸内酯，磺酸内酯稍微过量，滴加完后，继续搅拌8h，得到中间产物(磺酸功能化的内盐)。反应完后，用乙醚冲洗中间产物3～5次，以除去未反应完的原料，再放入真空干燥箱中，80℃干燥12h。b.将中间产物加入到圆底烧瓶中，用适量去离子水溶解，在70℃下预热，然后将浓硫酸逐滴加入到烧瓶中，继续搅拌10h，用丙酮洗涤3～5次，以除去未反应完的内盐，在80℃真空干燥12h，得到磺酸功能化的硫酸氢根酸性离子液体。离子液体(3)和(5)经一步反应即可制得：将甲基咪唑加入到圆底烧瓶中，用适量去离子水溶解，在70℃下预热，然后将卤素酸(如盐酸)或浓硫酸逐滴加入到烧瓶中，进行中和反应，继续搅拌10h，用丙酮洗涤3～5次，以除去未反应完的原料，在80℃真空干燥12h，得到阳离子含质子的酸性离子液体。离子液体(4)可以通过两步法制得：a.取3～4g 1-R基-3-甲基咪唑卤盐(如1-乙基-3-甲基咪唑氯盐)至烧瓶中，用去离子水溶解，用阴离子交换树脂将氯离子置换成氢氧根离子，得到含中间产物的水溶液；用邻苯二甲酸氢钾为滴定剂，酚酞为指示剂，滴定水溶液中中间产物的浓度。b.取适量a中得到的水溶液，将等摩尔量的浓硫酸缓慢滴加到溶液中，继续搅拌10h，旋蒸除去溶剂，在80℃真空干燥12h，得到阴离子为硫酸氢根的酸性离子液体。Specifically, the ionic liquids functionalized with sulfonic acid in ionic liquids (1) and (2) need to be prepared in two steps: a. Methylimidazole or pyridine is dissolved in ethanol, and placed in an oil bath at 70° C. Heat, add sultone dropwise under magnetic stirring, the sultone is slightly excessive, after the dropwise addition, continue stirring for 8h to obtain an intermediate product (sulfonic acid-functionalized inner salt). After the reaction, the intermediate product was washed with ether for 3 to 5 times to remove the unreacted raw materials, and then put into a vacuum drying box and dried at 80°C for 12 hours. b. Add the intermediate product into the round-bottomed flask, dissolve it with an appropriate amount of deionized water, preheat at 70 °C, then add concentrated sulfuric acid dropwise into the flask, continue stirring for 10 hours, wash with acetone 3 to 5 times, The unreacted inner salt was removed, and vacuum dried at 80 °C for 12 h to obtain a sulfonic acid-functionalized hydrogen sulfate acidic ionic liquid. The ionic liquids (3) and (5) can be prepared by one-step reaction: add methylimidazole to a round-bottomed flask, dissolve in an appropriate amount of deionized water, preheat at 70°C, and then add a halogen acid (such as hydrochloric acid) Or concentrated sulfuric acid was added dropwise to the flask for neutralization reaction, continued stirring for 10 hours, washed with acetone for 3 to 5 times to remove unreacted raw materials, and vacuum dried at 80 °C for 12 hours to obtain a cationic proton-containing acidic ionic liquid . The ionic liquid (4) can be prepared by a two-step method: a. Take 3-4 g of 1-R group-3-methylimidazolium halide (such as 1-ethyl-3-methylimidazolium chloride) into a flask, use Dissolve in deionized water, replace chloride ions with hydroxide ions with anion exchange resin, and obtain an aqueous solution containing intermediate products; use potassium hydrogen phthalate as titrant and phenolphthalein as indicator to titrate the concentration of intermediate products in the aqueous solution. b. Take an appropriate amount of the aqueous solution obtained in a, slowly drop an equimolar amount of concentrated sulfuric acid into the solution, continue stirring for 10 hours, remove the solvent by rotary evaporation, and vacuum dry at 80 °C for 12 hours to obtain an acidic ionic liquid with hydrogen sulfate as the anion .
优选地，所述离子液体的结构为(1)和(2)，Preferably, the structures of the ionic liquid are (1) and (2),
n为0～8的整数。n is an integer of 0-8.
当催化剂为离子液体(1)和(2)时，(1)中的磺酸甲基咪唑硫酸氢根离子液体和(2)中磺酸吡啶硫酸氢根离子液体中的阳离子均经磺酸基团酸化，同时阴离子也是酸性较强的硫酸氢根，离子液体酸性更强，更有利于反应的进行。马来酸酐酯化得到马来酸二甲酯需经两步酯化，第一步开环反应较为容易，马来酸酐与甲醇混合放置一段时间即可部分开环，但在第二步酯化中，需要经催化剂催化才能进一步酯化。强酸性催化剂有利于降低第二步酯化反应的活化能，加快反应速率。在n值取值时，优先n为3或4，因为丙基磺酸内酯及丁基磺酸内酯较六元或更多元的内酯更易开环，环张力较大。When the catalysts are ionic liquids (1) and (2), the cations in the sulfonic acid methylimidazole hydrogen sulfate ionic liquid in (1) and the sulfonic acid pyridine hydrogen sulfate ionic liquid in (2) are all converted by sulfonic acid groups At the same time, the anion is also a strong acid hydrogen sulfate, and the ionic liquid is more acidic, which is more conducive to the reaction. The esterification of maleic anhydride to obtain dimethyl maleate requires two-step esterification. The first step of the ring-opening reaction is relatively easy. The maleic anhydride and methanol are mixed and placed for a period of time to partially open the ring, but in the second step of esterification , it needs to be catalyzed by a catalyst for further esterification. The strong acid catalyst is beneficial to reduce the activation energy of the second-step esterification reaction and speed up the reaction rate. When the value of n is selected, n is preferably 3 or 4, because propyl sultone and butyl sultone are easier to open the ring than the lactone with six or more members, and the ring tension is larger.
实施例1：Example 1:
1-丙基磺酸-3-甲基咪唑硫酸氢盐离子液体催化马来酸酐与甲醇反应制备马来酸二甲酯1-Propylsulfonic acid-3-methylimidazole hydrogen sulfate ionic liquid catalyzed the reaction of maleic anhydride and methanol to prepare dimethyl maleate
1-丙基磺酸-3-甲基咪唑硫酸氢盐离子液体的制备：Preparation of 1-propylsulfonic acid-3-methylimidazole hydrogen sulfate ionic liquid:
在150mL的三口烧瓶中加入甲基咪唑4.106g(0.05moL)和乙醇(50mL)，放入70℃的油浴锅中预热，在磁力搅拌下逐滴将1,3-丙基磺酸内酯6.107g(0.05mol)加入到烧瓶中，滴加完后，继续搅拌8h，得到中间产物即阳离子磺酸功能的1-丙基磺酸-3-甲基咪唑。反应完后，用乙醚冲洗中间产物3～5次，以除去未反应完的原料，再放入真空干燥箱中，80℃干燥12h。Add 4.106g (0.05moL) of methylimidazole and ethanol (50mL) to a 150mL three-necked flask, put it in a 70°C oil bath to preheat, and add 1,3-propyl sulfonic acid dropwise under magnetic stirring. 6.107 g (0.05 mol) of the ester was added to the flask, and after the dropwise addition, stirring was continued for 8 h to obtain an intermediate product, 1-propylsulfonic acid-3-methylimidazole with cationic sulfonic acid function. After the reaction, the intermediate product was washed with ether for 3 to 5 times to remove the unreacted raw materials, and then put into a vacuum drying box and dried at 80°C for 12 hours.
将中间产物加入到150mL圆底烧瓶中，用适量去离子水溶解，在70℃下预热，然后将等摩尔量的浓硫酸逐滴加入到烧瓶中，继续搅拌10h，用丙酮洗涤3～5次，以除去未反应完的内盐，在80℃真空干燥12h，得到1-丙基磺酸-3-甲基咪唑硫酸氢盐离子液体。The intermediate product was added to a 150 mL round-bottomed flask, dissolved in an appropriate amount of deionized water, preheated at 70 °C, and then an equimolar amount of concentrated sulfuric acid was added dropwise to the flask, continued stirring for 10 h, and washed with acetone for 3-5 Second, to remove the unreacted inner salt, vacuum dry at 80 °C for 12 h to obtain 1-propylsulfonic acid-3-methylimidazolium hydrogen sulfate ionic liquid.
马来酸酐的酯化：分别称取马来酸酐0.9806g(0.01mol)、甲醇1.9236g(0.06mol)、1-丙基磺酸-3-甲基咪唑硫酸氢盐离子液体0.0605g(0.2mmol)于玻璃微波管中，设置反应温度120℃，反应1h，马来酸酐转化率达到97.78％，马来酸二甲酯产率达到94.59％。Esterification of maleic anhydride: respectively weigh 0.9806g (0.01mol) of maleic anhydride, 1.9236g (0.06mol) of methanol, 0.0605g (0.2mmol) of 1-propylsulfonic acid-3-methylimidazole hydrogen sulfate ionic liquid ) in a glass microwave tube, set the reaction temperature at 120°C, and react for 1 hour, the conversion rate of maleic anhydride reaches 97.78%, and the yield of dimethyl maleate reaches 94.59%.
实施例2：Example 2:
N-丁基磺酸吡啶硫酸氢盐离子液体催化马来酸酐与甲醇反应制备马来酸二甲酯Preparation of dimethyl maleate by reaction of maleic anhydride and methanol with N-butylsulfonic acid pyridine hydrogen sulfate ionic liquid
N-丁基磺酸吡啶硫酸氢盐离子液体的制备：Preparation of N-butylsulfonic acid pyridine hydrogen sulfate ionic liquid:
在150mL的三口烧瓶中加入吡啶3.933g(0.05mol)和乙醇(50mL)，放入70℃的油浴锅中预热，在磁力搅拌下逐滴将丁基磺酸内酯6.8085g(0.05mol)加入到烧瓶中，滴加完后，继续搅拌8h，得到中间产物即阳离子磺酸功能的N-丁基磺酸吡啶。反应完后，用乙醚冲洗中间产物3～5次，以除去未反应完的原料，再放入真空干燥箱中，80℃干燥12h。Add 3.933g (0.05mol) of pyridine and ethanol (50mL) to a 150mL three-necked flask, put it into a 70°C oil bath to preheat, and under magnetic stirring, dropwise 6.8085g (0.05mol) of butyl sultone ) was added to the flask, and after the dropwise addition was completed, stirring was continued for 8 h to obtain an intermediate product, namely, the N-butylsulfonic acid pyridine with cationic sulfonic acid function. After the reaction, the intermediate product was washed with ether for 3 to 5 times to remove the unreacted raw materials, and then put into a vacuum drying box and dried at 80°C for 12 hours.
将中间产物加入到150mL圆底烧瓶中，用适量去离子水溶解，在70℃下预热，然后将等摩尔量的浓硫酸逐滴加入到烧瓶中，继续搅拌10h，用丙酮洗涤3～5次，以除去未反应完的内盐，在80℃真空干燥12h，得到N-丁基磺酸吡啶硫酸氢盐离子液体。The intermediate product was added to a 150 mL round-bottomed flask, dissolved in an appropriate amount of deionized water, preheated at 70 °C, and then an equimolar amount of concentrated sulfuric acid was added dropwise to the flask, continued stirring for 10 h, and washed with acetone for 3-5 Second, to remove the unreacted inner salt, vacuum dry at 80 °C for 12 h to obtain N-butylsulfonic acid pyridine hydrogen sulfate ionic liquid.
马来酸酐的酯化：分别称取马来酸酐0.9806g(0.01mol)、甲醇1.9236g(0.06mol)、N-丁基磺酸吡啶硫酸氢盐离子液体0.0627g(0.2mmol)于玻璃微波管中，设置反应温度120℃，反应1h，马来酸酐转化率达到97.19％，马来酸二甲酯产率达到91.80％。Esterification of maleic anhydride: Weigh 0.9806 g (0.01 mol) of maleic anhydride, 1.9236 g (0.06 mol) of methanol, and 0.0627 g (0.2 mmol) of N-butylsulfonic acid pyridine hydrogen sulfate ionic liquid into a glass microwave tube. , the reaction temperature was set at 120° C. and the reaction was performed for 1 h, the conversion rate of maleic anhydride reached 97.19%, and the yield of dimethyl maleate reached 91.80%.
实施例3：Example 3:
1-丙基磺酸-3-甲基咪唑硫酸氢盐离子液体催化马来酸酐与乙醇反应制备马来酸二乙酯1-Propylsulfonic acid-3-methylimidazole hydrogen sulfate ionic liquid catalyzed the reaction of maleic anhydride and ethanol to prepare diethyl maleate
1-丙基磺酸-3-甲基咪唑硫酸氢盐离子液体的制备：过程同实施例1。Preparation of 1-propylsulfonic acid-3-methylimidazole hydrogen sulfate ionic liquid: the process is the same as that in Example 1.
马来酸酐的酯化：分别称取马来酸酐0.9806g(0.01mol)、乙醇2.7642g(0.06mol)、1-丙基磺酸-3-甲基咪唑硫酸氢盐离子液体0.0605g(0.2mmol)于玻璃微波管中，设置反应温度120℃，反应1h，马来酸酐转化率达到97.87％，马来酸二乙酯产率达到88.39％。Esterification of maleic anhydride: Weigh 0.9806g (0.01mol) of maleic anhydride, 2.7642g (0.06mol) of ethanol, 0.0605g (0.2mmol) of 1-propylsulfonic acid-3-methylimidazole hydrogen sulfate ionic liquid respectively ) in a glass microwave tube, set the reaction temperature to 120°C, and react for 1 hour, the conversion rate of maleic anhydride reaches 97.87%, and the yield of diethyl maleate reaches 88.39%.
实施例4：Example 4:
N-丁基磺酸吡啶硫酸氢盐离子液体催化马来酸酐与乙醇反应制备马来酸二乙酯Preparation of Diethyl Maleate by the Reaction of Maleic Anhydride with Ethanol Catalyzed by N-Butanesulfonic Acid Pyridine Hydrogen Sulfate Ionic Liquid
N-丁基磺酸吡啶硫酸氢盐离子液体的制备：过程同实施例2。Preparation of N-butylsulfonic acid pyridine hydrogen sulfate ionic liquid: the process is the same as that in Example 2.
马来酸酐的酯化：分别称取马来酸酐0.9806g(0.01mol)、乙醇2.7642g(0.06mol)、N-丁基磺酸吡啶硫酸氢盐离子液体0.0627g(0.2mmol)于玻璃微波管中，设置反应温度120℃，反应1h，马来酸酐转化率达到99.90％，马来酸二乙酯产率达到84.68％。Esterification of maleic anhydride: Weigh 0.9806 g (0.01 mol) of maleic anhydride, 2.7642 g (0.06 mol) of ethanol, and 0.0627 g (0.2 mmol) of N-butylsulfonic acid pyridine hydrogen sulfate ionic liquid into a glass microwave tube. , the reaction temperature was set at 120° C., and the reaction was performed for 1 h. The conversion rate of maleic anhydride reached 99.90%, and the yield of diethyl maleate reached 84.68%.
实施例5：Example 5:
1-丙基磺酸-3-甲基咪唑硫酸氢盐离子液体催化马来酸酐与正丁醇反应制备马来酸二丁酯1-Propylsulfonic acid-3-methylimidazole hydrogen sulfate ionic liquid catalyzed the reaction of maleic anhydride with n-butanol to prepare dibutyl maleate
1-丙基磺酸-3-甲基咪唑硫酸氢盐离子液体的制备：过程同实施例1。Preparation of 1-propylsulfonic acid-3-methylimidazole hydrogen sulfate ionic liquid: the process is the same as that in Example 1.
马来酸酐的酯化：分别称取马来酸酐0.9806g(0.01mol)、正丁醇4.4472g(0.06mol)、1-丙基磺酸-3-甲基咪唑硫酸氢盐离子液体0.0605g(0.2mmol)于玻璃微波管中，设置反应温度120℃，反应1h，马来酸酐转化率达到97.72％，马来酸二丁酯产率达到84.11％。Esterification of maleic anhydride: respectively weigh 0.9806g (0.01mol) of maleic anhydride, 4.4472g (0.06mol) of n-butanol, 0.0605g ( 0.2 mmol) in a glass microwave tube, set the reaction temperature at 120° C., and react for 1 h, the conversion rate of maleic anhydride reaches 97.72%, and the yield of dibutyl maleate reaches 84.11%.
实施例6：Example 6:
N-丁基磺酸吡啶硫酸氢盐离子液体催化马来酸酐与正丁醇反应制备马来酸二丁酯Preparation of Dibutyl Maleate by the Reaction of Maleic Anhydride with n-Butanol Catalyzed by N-Butanesulfonic Acid Pyridine Hydrogen Sulfate Ionic Liquid
N-丁基磺酸吡啶硫酸氢盐离子液体的制备：过程同实施例2。Preparation of N-butylsulfonic acid pyridine hydrogen sulfate ionic liquid: the process is the same as that in Example 2.
马来酸酐的酯化：分别称取马来酸酐0.9806g(0.01mol)、正丁醇4.4472g(0.06mol)、N-丁基磺酸吡啶硫酸氢盐离子液体0.0627g(0.2mmol)于玻璃微波管中，设置反应温度120℃，反应1h，马来酸酐转化率达到98.67％，马来酸二丁酯产率达到84.38％。Esterification of maleic anhydride: Weigh 0.9806 g (0.01 mol) of maleic anhydride, 4.4472 g (0.06 mol) of n-butanol, and 0.0627 g (0.2 mmol) of N-butylsulfonic acid pyridine hydrogen sulfate ionic liquid into glass In the microwave tube, the reaction temperature was set at 120° C. and the reaction was carried out for 1 h, the conversion rate of maleic anhydride reached 98.67%, and the yield of dibutyl maleate reached 84.38%.
以上实施例仅为本发明的示例性实施例，不用于限制本发明，本发明的保护范围由权利要求书限定。本领域技术人员可以在本发明的实质和保护范围内，对本发明做出各种修改或等同替换，这种修改或等同替换也应视为落在本发明的保护范围内。The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the protection scope of the present invention is defined by the claims. Those skilled in the art can make various modifications or equivalent replacements to the present invention within the spirit and protection scope of the present invention, and such modifications or equivalent replacements should also be regarded as falling within the protection scope of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911107060.2A CN110776418B (en) | 2019-11-13 | 2019-11-13 | Method for preparing maleic acid ester by catalyzing maleic anhydride with ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911107060.2A CN110776418B (en) | 2019-11-13 | 2019-11-13 | Method for preparing maleic acid ester by catalyzing maleic anhydride with ionic liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110776418A true CN110776418A (en) | 2020-02-11 |
| CN110776418B CN110776418B (en) | 2021-03-09 |
Family
ID=69390780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911107060.2A Active CN110776418B (en) | 2019-11-13 | 2019-11-13 | Method for preparing maleic acid ester by catalyzing maleic anhydride with ionic liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110776418B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269117A (en) * | 2020-02-28 | 2020-06-12 | 浙江工业大学 | Method for synthesizing diethyl maleate by catalysis of acidic ionic liquid |
| CN112321892A (en) * | 2020-09-28 | 2021-02-05 | 济南金彩阳新材料科技有限公司 | Foaming inhibitor and application thereof |
| CN112961129A (en) * | 2021-02-19 | 2021-06-15 | 上海昶法新材料有限公司 | Method for synthesizing alkenyl succinic anhydride by using microchannel reactor |
| CN113149834A (en) * | 2021-04-06 | 2021-07-23 | 中国科学院过程工程研究所 | Method for catalyzing esterification reaction of low-carbon alcohol by ionic liquid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985423A (en) * | 2009-12-18 | 2011-03-16 | 镇江高鹏药业有限公司 | Method for catalytic synthesis of salicylate alkyl ester by using ionic liquid under microwave promotion |
| CN103304415A (en) * | 2013-06-14 | 2013-09-18 | 河北科技大学 | Method for preparing maleic acid isopropyl ester |
| CN103752340A (en) * | 2013-12-30 | 2014-04-30 | 浙江工业大学 | Applications of acidic functionalized ion liquid in esterification reaction |
| CN105218368A (en) * | 2015-11-05 | 2016-01-06 | 黄山学院 | A kind of method of ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte |
| CN106349473A (en) * | 2015-12-17 | 2017-01-25 | 邯郸学院 | Method for preparing dipolyethylene glycol maleate by using ionic liquid |
-
2019
- 2019-11-13 CN CN201911107060.2A patent/CN110776418B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985423A (en) * | 2009-12-18 | 2011-03-16 | 镇江高鹏药业有限公司 | Method for catalytic synthesis of salicylate alkyl ester by using ionic liquid under microwave promotion |
| CN103304415A (en) * | 2013-06-14 | 2013-09-18 | 河北科技大学 | Method for preparing maleic acid isopropyl ester |
| CN103752340A (en) * | 2013-12-30 | 2014-04-30 | 浙江工业大学 | Applications of acidic functionalized ion liquid in esterification reaction |
| CN105218368A (en) * | 2015-11-05 | 2016-01-06 | 黄山学院 | A kind of method of ionic liquid-catalyzed synthesis Momo-cyclohexyl fumarte |
| CN106349473A (en) * | 2015-12-17 | 2017-01-25 | 邯郸学院 | Method for preparing dipolyethylene glycol maleate by using ionic liquid |
Non-Patent Citations (2)
| Title |
|---|
| 潘小玉: "酸性离子液体合成及催化酯化反应应用研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 黎彧等: "微波协同1-丁基-3-甲基咪唑硫酸氢盐离子液体催化酯交换合成肉桂酸正丁酯的研究", 《中国酿造》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269117A (en) * | 2020-02-28 | 2020-06-12 | 浙江工业大学 | Method for synthesizing diethyl maleate by catalysis of acidic ionic liquid |
| CN112321892A (en) * | 2020-09-28 | 2021-02-05 | 济南金彩阳新材料科技有限公司 | Foaming inhibitor and application thereof |
| CN112961129A (en) * | 2021-02-19 | 2021-06-15 | 上海昶法新材料有限公司 | Method for synthesizing alkenyl succinic anhydride by using microchannel reactor |
| CN112961129B (en) * | 2021-02-19 | 2023-05-26 | 上海昶法新材料有限公司 | Method for synthesizing alkenyl succinic anhydride by micro-channel reactor |
| CN113149834A (en) * | 2021-04-06 | 2021-07-23 | 中国科学院过程工程研究所 | Method for catalyzing esterification reaction of low-carbon alcohol by ionic liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110776418B (en) | 2021-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110776418A (en) | Method for preparing maleic acid ester by catalyzing maleic anhydride with ionic liquid | |
| CN103611522B (en) | One formaldehyde and acetic acid are catalyst and its preparation method of Material synthesis acrylic acid (ester) | |
| CN104525260A (en) | Polymeric solid acid catalyst for esterification reaction and preparation method thereof | |
| CN103013682B (en) | Synthetic method for epoxy soybean oil acrylate | |
| CN102633929A (en) | Preparation method of acid ionic liquid mesoporous polymeric material | |
| CN103394370B (en) | Silica gel supported sulfonic acid dual-core ionic liquid catalyst, preparation method and application | |
| CN102060738A (en) | Ionic liquid combining B acid site and L acid site as well as preparation method and application thereof | |
| CN112774658A (en) | Acid-base bifunctional catalyst for synthesizing methyl acrylate from methyl acetate and formaldehyde and preparation method thereof | |
| CN112473736B (en) | Supported polyacid catalyst and application thereof in preparation of levulinate | |
| CN105148990A (en) | Preparation method and application of sulfated carbon nanotube/graphene oxide composite catalyst | |
| CN102850223A (en) | A kind of method of synthesizing ethyl methyl carbonate | |
| CN104892809B (en) | Synthesized biodiesel sulfonic acid funtionalized polymer catalyst, and preparation method thereof | |
| CN103951561B (en) | A kind of method for preparing L-menthol glyoxylate monohydrate by heteropolyacid catalysis | |
| CN101824627B (en) | Method for preparing dimethyl succinate | |
| CN107540520B (en) | Method for preparing pyromellitic acid or trimellitic acid from pinacol | |
| CN105646223B (en) | A kind of method that levulic acid catalysis oxidation esterification prepares succinate | |
| CN111875493A (en) | A kind of method that utilizes imidazole acidic ionic liquid to synthesize orthoborneol | |
| CN112645815A (en) | Preparation method for catalytically synthesizing methyl cinnamate based on eutectic solvent | |
| CN107188804B (en) | Method for catalytically synthesizing methyl oleate by using composite phosphotungstate | |
| CN119016105A (en) | Acidic ionic liquid catalyst, preparation method and application thereof in CO2 conversion | |
| CN108554451B (en) | A kind of transition metal natural polymer hybrid catalyst and its preparation method and application | |
| CN106279077A (en) | A kind of method that composite mixed phosphotungstate catalyzes and synthesizes 5 Hydroxymethylfurfural | |
| CN109748815A (en) | A kind of synthetic method of adipic dihydrazide | |
| CN104874421B (en) | Solid acid catalyst for glycerinum esterification and aldolization, and preparation method therefor | |
| CN115141685A (en) | Method for preparing biodiesel by catalysis of novel amino acid ionic liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |