KR100377504B1 - Process for the preparation of pyrrolidone derivatives - Google Patents

Abstract

The present invention relates to a method for preparing pyrrolidone derivatives by reacting gamma-butyrolactone, amine derivatives and water, wherein the molar ratio of gamma-butyrolactone, methylamine and water under an acidic silica-alumina acid catalyst is disclosed. Is 1: 1 to 7: 1 to 25, reaction temperature is 250 to 400 ° C., space velocity is 700hr ^{-1 to} 2000hr ^-1 , reaction pressure is normal gas phase catalyst reaction under the condition of normal pressure to 10 atm. The present invention relates to a method for preparing rolidone.

The method of the present invention has the effect of producing pyrrolidone derivatives at high selectivity and high yield under mild reaction conditions in the preparation of pyrrolidone derivatives from gamma-butyrolactone.

Description

Process for preparing the pyrrolidone derivatives from gamma-butyrolactone

The present invention relates to a process for preparing pyrrolidone derivatives from gamma-butyrolactone.

Specifically, gamma-butyrolactone is reacted with an amine derivative such as monomethyl amine or ethanol amine to react N-methyl-2-pyrrolidone (N-methyl-2). to a pyrrolidone derivative such as -pyrrolidone) or N-vinyl-2-pyrrolidone.

N-methyl-2-pyrrolidone is not only a very stable organic solvent with excellent colorlessness, low toxicity, low volatility, high polarity and heat resistance, but also has various uses as a starting material for various organic synthesis reactions. N-vinyl-2-pyrrolidone is a material that is useful for extracting semiconductor cleaners, acetylene and butadiene in the electronics and petrochemical industries. N-vinyl-2-pyrrolidone is well soluble in water or organic solvents. As a starting material for the synthesis of polymers, such as polyvinyl-2-pyrrolidone, which is essential for preparing a polymer, as well as a solvent for a polymerization process of a high functional resin, its use is various.

As a conventional method for preparing N-methyl-2-pyrrolidone from gamma-butyrolactone, a method for producing a high-temperature, high-pressure batch liquid phase reaction of gamma-butyrolactone and monomethylamine under a catalyst is known. As a method for producing N-vinyl-2-pyrrolidone, a method of preparing gamma-butyrolactone and ethanolamine by a tubular liquid phase reaction under a catalyst and a flow gaseous catalyst under a fixed bed catalyst bearing a metal oxide A method for producing by reaction is known.

Conventional method for preparing N-methyl-2-pyrrolidone from gamma-butyrolactone using a non-catalyzed liquid batch reaction of gamma-butyrolactone and various alkylamines for several hours under reaction conditions of 240 ° C. or higher and 50 atm or higher. The process for preparing N-alkyl-2-pyrrolidone (JP 01-19066, JP 01-186864, JP 01-186863, JP 51-042107), and the already-repeated Reppe Process process is 250 The reaction was carried out for several hours at a temperature of < RTI ID = 0.0 > C < / RTI > to produce N-methyl-2-pyrrolidone on a commercial scale in a yield of about 85% to 90%. (Chem. Ing.

In addition, the molar ratio of gamma-butyrolactone, monomethylamine, and water was in the range of 1: 1 to 2: 1 to 5, respectively, and was reacted at 240 ° C to 270 ° C for 1 hour to several hours, and N-methyl-2-pyrrolidone Techniques for preparing these are known (JP 10-158238, JP 49-20585, JP 47-21420). Such non-catalytic or catalytic liquid phase batch reactions often require harsh reaction conditions of more than 240 ° C. and more than 50 atmospheres, which, despite the simplicity of the process, poses a significant risk to process control.

In addition, as a technique for producing N-methyl-2-pyrrolidone by a gas phase catalytic reaction from gamma-butyrolactone and monomethylamine, a catalyst made of copper and various metal oxides is used at a reaction temperature of 270 ° C. JP 49-000259 is known to produce N-methyl-2-pyrrolidone in a yield of 60% by reaction for 3 hours, and gamma-butyrolactone and mono on chromium ion-exchanged ZSM-5 zeolite catalysts are known. A technique for producing N-methyl-2-pyrrolidone by continuously reacting methylamine at 300 ° C. for 4 hours (J. Org. Chem., 50 (1994), 3998) is known.

In addition, gamma-butyrolactone and various alkylamines were continuously reacted at atmospheric pressure and pressure for several hours at a reaction temperature of 270 ° C. or higher under various catalysts of Y-zeolites and sodium beta (Naβ) -zeolites in which various metals were ion-exchanged. Techniques for preparing N-methyl-2-pyrrolidone in yield (Bull. Chem. Soc. Japan, 50 (10) 1997, 2517. JP 01-0065589) are known.

A technique for producing N-methyl-2-pyrrolidone, which is similar to the liquid phase batch reaction and the gas phase catalytic reaction process, with nickel, palladium, cobalt-based catalysts supported on metal oxides and ammonia under high temperature and high pressure reaction conditions. A two-step liquid batch production technique (USP 4,814,464) is known, in which a first intermediate is prepared by reacting C _{1 to} C ₄ alcohols, and then N-methyl-2-pyrrolidone is known, a so-called 1-Vessel-2 step reaction. In the gas phase catalytic reaction known as copper, chromium-based oxide catalyst and sodium ion-exchanged X-zeolite catalysts, each packed in layers in one flow reactor to produce intermediates and N-methyl-2 under these fixed bed catalysts. Continuous reaction processes for producing pyrrolidone are known (USP 5,478,950).

However, when N-methyl-2-pyrrolidone was prepared using a zeolite catalyst as described above, it showed high activity at the beginning of the reaction, but it was confirmed that there was a problem in the industrial use due to the rapid decrease in activity.

N-vinyl-2-pyrrolidone may be prepared from gamma-butyrolactone by using N- (2-hydroxyethyl as an intermediate in the form of a liquid batch reaction under high temperature and high pressure of gamma-butyrolactone and monoethanolamine. ) To prepare N-vinyl-2-pyrrolidone by primary gas phase catalysis under an alkali and / or alkaline earth metal oxide supported catalyst of cesium, potassium, sodium and the like. Two-step manufacturing methods are known. (USP 5,801,252, JP 48-96584, JP 47-18862, JP 47-40792, JP 48-44251, JP 6-256306, USP 2,669,570)

A similar process is known for the production of N-vinyl-2-pyrrolidone from a 2-pyrrolidone and acetylene by flow gas phase catalysis under an alkali metal-supported metal oxide catalyst. (USP 96- 589517)

To summarize briefly the problems of known techniques, the preparation of N-methyl / vinyl-2-pyrrolidone by liquid batch reaction requires very harsh reaction conditions of high temperature and high pressure, whereas in the case of a process using a catalyst, Since the activity of the metal oxide supported catalyst is generally low, the production yield of N-methyl / vinyl-2-pyrrolidone is not industrially satisfactory, or the catalyst is easily deactivated even if the initial activity is high. The operation must be performed, and there is a problem such that the catalyst life is short despite such an operation.

An object of the present invention is to solve the problems caused by the harsh reaction conditions, yield reduction, degradation of catalyst long-term reaction stability, etc., which occur in the process of preparing a pyrrolidone derivative by reacting the gamma-butyrolactone and the amine derivative. It is to provide a method for producing a milder pyrrolidone derivative using the catalyst having excellent activity, high selectivity and long-term reaction stability.

In order to solve various problems of the prior art, the inventors of the present invention search for the performance of various catalysts, and the primary reactants of gamma-butyrolactone and monomethylamine, and gamma-butyrolactone and ethanolamine are acidic silica-alumina cray. Under the (Acid-Clay) catalyst, N-methyl / vinyl-2-pyrrolidone can be produced in high yield by continuously flowing gas phase catalytic reaction at a reaction temperature of 200 ° C to 400 ° C and a reaction pressure of atmospheric pressure to 20 atm. It was also confirmed that the catalytic activity is maintained for a long time and completed the present invention.

In the present invention, the reactants used in the production of N-methyl-2-pyrrolidone by flow gas phase reaction on silica-alumina cray catalyst are gamma-butyrolactone and monomethyl in aqueous solution of gamma-butyrolactone and monomethylamine. The molar ratio of amine and water was preferably 1: 1 to 7: 1 to 25. The reaction temperature is 230 ℃ ~400 ℃, preferably 250 ℃ ~350 ℃, space velocity is N- methyl-2 under the conditions of 500hr ^-1 ~3000hr ^-1, preferably 700hr ^-1 ~2000hr ^-1 Rollidone was prepared. The reaction pressure was carried out under relatively mild conditions of 20 atm or less, preferably 10 atm or less, to maximize the catalytic activity of the reactants.

In addition, the process for preparing N-vinyl-2-pyrrolidone from gamma-butyrolactone and monoethanolamine is divided into two steps. First, the first step is a method known to gamma-butyrolactone. Monoethanolamine and water are added in the same molar ratio, and an intermediate N- (2-hydroxyethyl) -2-pyrrolidone is prepared by a liquid batch reaction under high temperature and high pressure for several hours.

In a two-step process, N- (2-hydroxyethyl) -2-pyrrolidone is 200 ° C. under the same acidic silica-alumina-Clay catalyst as the N-methyl-2-pyrrolidone preparation catalyst. N-vinyl-2-pyrrolidone is produced by a flow-type gas phase catalysis in a reaction temperature range of from -400 deg. C, preferably 250 deg. C-350 deg. C and a reaction pressure of atmospheric pressure -20 atm, preferably atmospheric pressure-5 atm. do. In addition, when preparing N-vinyl-2-pyrrolidone from N- (2-hydroxyethyl) -2-pyrrolidone, the space velocity of the reactant was 500hr ^- under acidic silica-alumina cray catalyst. ^{1 to} 3,000 hr ^-1 , preferably 700 hr ^{-1 to} 2,000 hr ^-1 .

Gamma-buty when preparing N-methyl-2-pyrrolidone or N-vinyl-2-pyrrolidone from gamma-butyrolactone and monomethyl or ethanolamine as described in the following Examples and Comparative Examples of the present invention Lolactone, aqueous monomethylamine solution, and N- (2-hydroxyethyl) -2-pyrrolidone are injected into the reactor together with an inert gas using a metering pump, and the inert gas used is nitrogen gas. The amount of nitrogen is adjusted to maintain the contact time in the range of 1 to 10 seconds, preferably 2 to 7 seconds.

Silica-alumina cray used in the preparation of N-methyl-2-pyrrolidone from gamma-butyrolactone and monomethylamine is preferably a cray compound having a silica to alumina ratio of 1: 0.35-1.10 and an acidic silica- In order to prepare an alumina cray compound, it may be effective to adjust the degree of acid treatment, but commercially available acid cray may be used as it is. As a result of the screening test, Engerhard's trade name Fitrol 113 showed good reactivity. When Fitrol 113 is used as the reaction catalyst, it is calcined for 1 to 10 hours at 250 ° C to 500 ° C, preferably 350 ° C to 450 ° C. In addition, in order to mold an acidic cray powder, it is molded by a compression method or by extrusion molding using 5 to 30% by weight of silica as a binder.

The following examples illustrate the invention in more detail and are not intended to limit the scope of the invention, and in the examples N-methyl-2-pyrrolidone and N-vinyl-2-pi from gamma-butyrolactone Each manufacturing method of a ralidone was shown.

Example 1

Preparation of N-methyl-2-pyrrolidone

Catalyst Preparation and Reaction

Commercially available acid-type silica-alumina cray (Fitrol 113) is ground, fractionated into 20-40 mesh sizes and fired at 400 ° C. for 4 hours. 7.0 ml of the calcined catalyst is charged into a 1/2 inch stainless steel reactor and nitrogen gas is injected.

Thereafter, 50 wt% gamma-butyrolactone aqueous solution and 40 wt% monomethylamine aqueous solution were injected from the top of the reactor so that the molar ratio of gamma-butyrolactone to monomethylamine was 1: 2.9 using different metering pumps. At this time, the space velocity (WHSV) of gamma-butyrolactone relative to the catalyst was adjusted to 0.16hr ⁻¹ .

Under the reaction conditions of 270 ℃ and 2 atmospheres, the reaction result was 99.1% of gamma-butyrolactone conversion and 99.4% of N-methyl-2-pyrrolidone 120 hours after the start of the reaction, and 300 ℃ after 2,500 hours. The conversion of gamma-butyrolactone was 99.8% and the selectivity of N-methyl-2-pyrrolidone was 99.5% under the reaction conditions of 2 atm. The initial specific surface area of the catalyst was 316m ² / g and the specific surface area was 77m ² / g after 2,500 hours of reaction.

Comparative Example 1)

Catalyst Preparation and Reaction

Commercially available calcium ion exchange X zeolite (70% Ca ion exchange amount: hereinafter referred to as CaX-Zeolite) powder was prepared in the same manner as in Example 1), and 7 ml of catalyst was charged into the reactor. The following experimental method was also the same as in Example 1), and the reaction was carried out for 1300 hours to measure the long-term stability of the catalyst at a reaction temperature of 275 ° C to 300 ° C and a reaction pressure of 2 atm. The reaction result showed that the conversion of gamma-butyrolactone was 99.1% and the selectivity of N-methyl-2-pyrrolidone was 99.1% after 100 hours at 275 ° C. and atmospheric pressure. The selectivity dropped to 93.2%. After reactivation by slowly warming up to 400 ° C. under air flow and reacting at 300 ° C. and 2 atm for 1,300 hours, the conversion of gamma-butyrolactone was 95.6% and N-methyl-2-pyrroli. The selectivity of money was 99.2%. The initial specific surface area of the catalyst was 777 m ² / g but 4.7m ² / g after 1,300 hours of reaction.

Comparative example 2)

7 ml of a silica-alumina (SiO ₂ : Al ₂ O ₃ = 87: 13) catalyst was charged and reacted at 275 ° C. and atmospheric pressure as in Comparative Example 1) at WHSV = 0.16hr ⁻¹ . 100 hours after the start of the reaction, the conversion of gamma-butyrolactone was 95.6%, and the selectivity of N-methyl-2-pyrrolidone was 97.6%.

Example 2)

N-vinyl-2-pyrrolidone preparation

One Step Reaction: Preparation of N- (2-hydroxyethyl) -2-pyrrolidone

The molar ratios of gamma-butyrolactone, mono ethanolamine and water are equalized, and the mixture is placed in a high pressure reactor and reacted at 250 ° C. and 30 atm for 1 hour. A one-step reaction product, N- (2-hydroxyethyl) -2-pyrrolidone, was obtained with a high yield of at least 99%. This product was used as starting material for the two-step N-vinyl-2-pyrrolidone preparation without purification.

Two stage reaction-gas phase catalytic reaction

The same acidic silica-alumina cray powder as in Example 1) was prepared in the same manner, followed by fractionation and firing. 7 ml of the calcined catalyst is charged to a 1/2 inch size sus reactor and nitrogen gas is injected. Thereafter, the reaction product N- (2-hydroxyethyl) -2-pyrrolidone, which is a one-step reaction product, was injected from the top of the reactor with WHSV = 0.16 hr ^-1 using a metering pump. The space velocity of the reactants at this time was adjusted to 900hr ^-1 . The reaction was started at 300 ° C and atmospheric pressure and proceeded to 540 hours while the temperature was raised to 340 ° C. The reaction result was 95.2% conversion of N- (2-hydroxyethyl) -2-pyrrolidone and 74.5% selectivity to N-vinyl-2-pyrrolidone 100 hours after the start of the reaction at the reaction temperature of 300 ℃. The selectivity gradually increased over time, and after 540 hours, the conversion was 97.7% and the selectivity was 93.5% at 340 ° C.

Comparative Example 3)

The same procedure as in Comparative Example 2) was carried out except that a CaX-Zeolite catalyst commercially available as a two-stage reaction catalyst was used. The reaction result was 100 hours after the start of the reaction, the conversion of N- (2-hydroxyethyl) -2-pyrrolidone was 21.7% and the selectivity of N-vinyl-2-pyrrolidone was 42.8% at 340 ° C and atmospheric pressure. It was.

The method of the present invention has the effect of producing pyrrolidone derivatives at high selectivity and high yield under mild reaction conditions in preparing pyrrolidone derivatives from gamma-butyrolactone.

Claims (2)

A method for preparing pyrrolidone derivatives by reacting gamma-butyrolactone, amine derivatives and water, wherein the molar ratio of gamma-butyrolactone, methylamine and water under an acid type silica-alumina acid clay catalyst is 1: N-methyl-2-pyrrolidone by direct gas phase catalyst reaction under the conditions of 1 to 7: 1 to 25, reaction temperature of 250 to 400 ° C., space velocity of 700 hr ^{-1 to} 2000 hr ^-1 , and reaction pressure of normal pressure to 10 atm. How to manufacture. In the method for preparing a pyrrolidone derivative by reacting gamma-butyrolactone, amine derivative and water, gamma-butyrolactone, ethanolamine and water are reacted at 250 ° C. and 30 atm for about 1 hour to obtain N- (2 - distribution at the reaction temperature under the alumina catalyst cradle 200 ~ 400 ℃, a reaction pressure of normal pressure to 20 atm, a space velocity of 500hr ^-1 ~3000hr ^-1 condition-hydroxyethyl) -2-pyrrolidone to prepare a molded silica money and this acid A method for producing N-vinyl-2-pyrrolidone by a formula gas phase catalytic reaction.