CN100453521C - Prepn and application of ethyl diisopropyl carboxylate - Google Patents

Abstract

The present invention is preparation process and application of ethyl diisopropyl carboxylate. Diisopropyl malonate and ethyl chloroacetate as the initial material are one-step reacted under the action of strong alkali and catalyst to synthesize ethyl diisopropyl carboxylate. After reaction, the reaction product is filtered, water washed to eliminate inorganic salt and decompression distilled to obtain the product. Ethyl diisopropyl carboxylate is colorless or yellowish transparent liquid, and has structure similar to that of tri citrate, plasticizing efficiency and cold resistance similar to that of DOP and compatibility higher than that of DOP. The present invention is used as plasticizer.

Description

The preparation method of ethyl diisopropyl carboxylate and application thereof

Technical field

The present invention relates to the preparation method and the application thereof of ethyl diisopropyl carboxylate.

Background technology

Along with the raising of countries in the world environmental consciousness, plastics such as medicine and food product pack, daily necessities, toy have proposed higher purity and hygienic requirements to primary plasticizer dioctyl phthalate (DOP) DOP etc.There is the potential carcinogenic danger in DOP, has begun in the world to take appropriate measures, and the use range of restriction DOP: U.S. environment protection general bureau has stopped the industrial production of 6 kinds of phthalic ester plasticizers according to the result of study of National Cancer Institute; Switzerland's government decided bans use of DOP in toy for children; Germany bans use of DOP in all plastics relevant with human body, wholesome food; In Japan, DOP only limits to use in the industrial plastic goods as additives for plastics.China is Asia area plasticizer production amount and the maximum country of consumption, but at present the primary plasticizer produced of domestic enterprise on many performances particularly aspect such as health, hypotoxicity all be difficult to satisfy environmental protection requirement.Therefore, accelerate the research and development dynamics of non-toxic plasticizer product, particularly accelerate exploitation, popularization and the propaganda of the high new plasticizer of hygienic requirements become the task of top priority of state internal plasticizer enterprise.

The citrate series products is present universally acknowledged nontoxic " green " environmentally-friendly plastic softening agent, be widely used in food and medical instrumentation package, makeup, daily necessities, toy, military supplies etc., have that consistency is good, plasticizing efficiency is high, nontoxic, easily by advantage such as biological degradation and volatility be little, photostabilization and having excellent water-resistance, and shock resistance is arranged in resin, do not grow advantages such as mould.The prior synthesizing method of citric acid ester plasticizer is to use citric acid and corresponding alcohol to prepare in the presence of as the sulfuric acid of catalyzer, its raw material citric acid is main at present to adopt microbe fermentation method to prepare, this method technological process is longer, particularly produce a large amount of organic pollutants and solid waste, these pollutents are contaminate environment not only, and quantity discharged is big.Therefore environmental problem always is the principal element of restriction citric acid industry development for a long time, and then has also influenced the extensive promotion and application of citric acid ester plasticizer.If can or have the compound of similar structures by the direct synthesizing citric acid ester of chemical process, will greatly promote the marketing and the widespread use of citric acid ester plasticizer.

Summary of the invention

The object of the present invention is to provide the close compound of a kind of structure and citric acid three ester: ethane-2-carboxylic acid, ethyl ester-1, (2-ethyl 1 for 1-dicarboxylic acid isopropyl ester, 1-diisopropyl ethane-1,1,2-tricarboxylate, synthetic method EDETC) and as the application of new plasticizer.

Purpose of the present invention is achieved through the following technical solutions:

With Diisopropyl malonate and chlorine (or bromine) ethyl acetate is starting raw material, under highly basic and catalyst action, Diisopropyl malonate and halogenated acetic acids ethyl ester be through the synthetic EDETC of single step reaction, after reaction finishes after filtration or washing remove inorganic salt, promptly get product through underpressure distillation again.The gained material is colourless or slightly yellowy transparent liquid, and EDETC is structurally similar to citric acid three ester.Plasticising performance contrast experiment by EDETC and DOP can find, plasticizing efficiency and the DOP of novel compound EDETC are on close level, consistency all is better than DOP, winter hardiness and the DOP of EDETC are on close level, these The performance test results show that EDETC meets the every requirement as softening agent fully, are a kind of softening agent of new texture.

The plasticising performance compares:

The available following general formula of reaction of the present invention is represented:

The synthetic EDETC of the present invention comprises following concrete steps:

A, hydrocarbyl reaction

The Diisopropyl malonate that in the three-necked bottle that induction stirring, thermometer, reflux condensing tube (on add drying tube) are housed, adds 0.10mol, amount of methanol sodium (methyl alcohol) or sodium ethylate (ethanol) solution, after temperature reaction 5-60 minute, add little amount of catalyst potassiumiodide or iodine, begin to drip an amount of ethyl chloroacetate or ethyl bromoacetate then, the dropping time is 10-80 minute, dropwises 3-24 hour stopped reaction of back back flow reaction.

The separation of B, inorganic salt and the purifying of product

Separation and purifying can be undertaken by two kinds of methods, and a kind of method is that direct filtration goes out inorganic salt, and air distillation goes out methyl alcohol or ethanol and low-boiling point material, and the cut of boiling spread is collected in underpressure distillation then, promptly gets final product EDETC; Another kind method is the inorganic salt that are dissolved in water and separate out in the mixture behind hydrocarbyl reaction, separates oil reservoir, and dry back underpressure distillation is collected the boiling spread product and got the finished product.

The preparation method of ethyl diisopropyl carboxylate specifically may further comprise the steps:

1), in the three-necked bottle that induction stirring, thermometer, reflux condensing tube are housed, stirring and down Diisopropyl malonate being joined mass percent concentration is in 15.0%-32.0% methanol solution of sodium methylate or the alcohol sodium alcohol solution, the mol ratio of Diisopropyl malonate and sodium methylate or sodium ethylate is 1: 1.0-1.80 is warming up to 50-100 ℃ of reaction 5-60 minute;

2) add catalyzer potassiumiodide or iodine, the mass ratio of potassiumiodide or iodine and Diisopropyl malonate is 1: 40-300;

3) drip ethyl chloroacetate or ethyl bromoacetate, the mol ratio of ethyl chloroacetate or ethyl bromoacetate and Diisopropyl malonate is 1.00-1.02: 1, and the dropping time is 10-80 minute, 50-100 ℃ was reacted 3-24 hour, and reduced to room temperature then;

4) separation and purifying can be undertaken by two kinds of methods, and a kind of method is that direct filtration goes out inorganic salt, and air distillation goes out methyl alcohol or ethanol and low-boiling point material, and the cut of boiling spread is collected in underpressure distillation then, promptly gets final product EDETC; Another kind method is the inorganic salt that are dissolved in water and separate out in the mixture behind hydrocarbyl reaction, separates oil reservoir, and dry back underpressure distillation is collected the boiling spread product and got final product EDETC.

With synthetic the comparing of background technology citric acid three ester class softening agent, advantage of the present invention is:

(1) reaction conditions gentleness, the reaction times is shorter;

(2) do not use citric acid to be starting raw material, be not subjected to the restriction of citric acid market supply;

(3) do not have obvious waste discharge, having only NaCl or NaBr is by product;

(4) last handling process is simple;

(5) do not use the material of containing benezene, and traditional citrate synthetic often uses toluene etc. to be the band aqua.

Embodiment

Embodiment 1:

1) under the stirring Diisopropyl malonate being joined mass percent concentration is in 19.0% alcohol sodium alcohol solution, and the mol ratio of Diisopropyl malonate and sodium ethylate is 1: 1.05, is warming up to 85 ℃ of reactions 25 minutes;

2) add the catalyzer potassiumiodide, the mass ratio of potassiumiodide and Diisopropyl malonate is 1: 130;

3) dripping bromine ethyl acetate, the mol ratio of ethyl bromoacetate and Diisopropyl malonate are 1.01: 1, and the dropping time is 25 minutes, and 85 ℃ were reacted 4 hours, and reduced to room temperature;

4) inorganic salt that are dissolved in water and separate out are isolated underpressure distillation behind the oil reservoir, collect the boiling spread product, reclaim unreacted raw material and etoh solvent simultaneously.In the Diisopropyl malonate productive rate is 87%.

Embodiment 2:

1) stirring is that 19.5% methanol solution of sodium methylate joins in the Diisopropyl malonate with mass percent concentration down, and the mol ratio of Diisopropyl malonate and sodium methylate is 1: 1.1, is warming up to 80 ℃ of reactions 20 minutes;

2) add catalyst simple substance iodine, the mass ratio of iodine and Diisopropyl malonate is 1: 180;

3) drip ethyl chloroacetate, the mol ratio of ethyl chloroacetate and Diisopropyl malonate is 1.02: 1, and the dropping time is 20 minutes, and 80 ℃ were reacted 9 hours, and reduced to room temperature;

4) filter the inorganic salt of separating out, the boiling spread product is collected in underpressure distillation, reclaims unreacted raw material and solvent methanol simultaneously.In the Diisopropyl malonate productive rate is 85%.

Embodiment 3:

1) under the stirring Diisopropyl malonate being joined mass percent concentration is in 20.0% alcohol sodium alcohol solution, and the mol ratio of Diisopropyl malonate and sodium ethylate is 1: 1.08, is warming up to 75 ℃ of reactions 20 minutes;

2) add catalyst simple substance iodine, the mass ratio of iodine and Diisopropyl malonate is 1: 200;

3) drip ethyl chloroacetate, the mol ratio of ethyl chloroacetate and Diisopropyl malonate is 1.02: 1, and the dropping time is 30 minutes, and 80 ℃ were reacted 10 hours, and reduced to room temperature;

4) filter the inorganic salt of separating out, the boiling spread product is collected in underpressure distillation, reclaims unreacted raw material and etoh solvent simultaneously.In the Diisopropyl malonate productive rate is 87%.

The example that EDETC uses as plastic plasticizer is as follows:

With polyvinyl chloride (PVC) powder, EDETC, one package stabilizer and colorant were by mass ratio 100: 50: 3: 14 can be made into the leatheroid surface layer after mixing, and coat foaming layer again and promptly make leatheroid.

Claims (2)

1, a kind of preparation method of ethyl diisopropyl carboxylate is characterized in that may further comprise the steps:

1) in the three-necked bottle that induction stirring, thermometer, reflux condensing tube are housed, stirring and down Diisopropyl malonate being joined mass percent concentration is in 15.0%-32.0% methanol solution of sodium methylate or the alcohol sodium alcohol solution, the mol ratio of Diisopropyl malonate and sodium methylate or sodium ethylate is 1: 1.0-1.80 is warming up to 50-100 ℃ of reaction 5-60 minute;

2) add catalyzer potassiumiodide or iodine, the mass ratio of potassiumiodide or iodine and Diisopropyl malonate is 1: 40-300;

3) drip ethyl chloroacetate or ethyl bromoacetate, the mol ratio of ethyl chloroacetate or ethyl bromoacetate and Diisopropyl malonate is 1.00-1.02: 1, and the dropping time is 10-80 minute, 50-100 ℃ was reacted 3-24 hour, and reduced to room temperature then;

4) separation and purifying are undertaken by two kinds of methods, and the one, direct filtration goes out inorganic salt, and air distillation goes out methyl alcohol or ethanol and low-boiling point material, and the cut of boiling spread is collected in underpressure distillation then, promptly gets the final product ethyl diisopropyl carboxylate; Or the inorganic salt that are dissolved in water and separate out in the mixture behind hydrocarbyl reaction, separating oil reservoir, dry back underpressure distillation is collected the boiling spread product and is got the finished product ethyl diisopropyl carboxylate; Its structural formula is

2, the application of ethyl diisopropyl carboxylate according to claim 1, it is characterized in that: ethyl diisopropyl carboxylate uses as plastic plasticizer.