JP2006111551A - Method for producing 3,4-dihydroxy-1-butene and derivatives using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing the butene derivative at a high yield and low cost under mild reaction conditions.
SOLUTION: 3-hydroxy-4-acetoxy-1-butene (hereinafter abbreviated as 3,4-HABE) and / or 3-acetoxy-4-hydroxy-1-butene (hereinafter abbreviated as 3,4-AHBE). ) And water in the presence of an acid catalyst to produce 3,4-dihydroxy-1-butene (hereinafter abbreviated as 3,4-DHBE), , 4-HABE, and at least one selected from the group consisting of 3,4-AHBE is a reaction product obtained by acetoxylation of 1,3-butadiene and acetic acid in the presence of molecular oxygen and a palladium-based catalyst. A method for producing 3,4-DHBE, which is obtained by separating a mixture containing at least one of 3,4-HABE and 3,4-AHBE by distillation.
[Selection figure] None

Description

  The present invention relates to a method for producing 3,4-dihydroxy-1-butene and vinyl ethylene carbonate (hereinafter collectively referred to as butene derivatives). More specifically, the present invention relates to a method for industrially advantageously obtaining the butene derivative by using a by-product in the production of 1,4-diacetoxy-2-butene by reaction of 1,3-butadiene and acetic acid.

  Conventionally, 3,4-dihydroxy-1-butene can be obtained by hydrolyzing 3,4-epoxy-1-butene using an appropriate hydrolyzing agent. For example, a method by solvolysis using an acid catalyst such as sulfuric acid is disclosed (see Non-Patent Document 1). Further, a method of hydrolyzing with water in the presence of rhenium oxide (see Patent Document 1) or a mixture of hydroiodic acid and an organic solvent-soluble iodide salt has been proposed (see Patent Document 2).

  In either method, 3,4-dihydroxy-1-butene can be easily obtained from 3,4-epoxy-1-butene in a high yield under mild conditions. However, in these methods, the raw material 3,4-epoxy-1-butene reacts in a gas phase with 1,3-butadiene and oxygen in the presence of a silver-based catalyst (see Patent Document 3). Poor property and requires large capital investment. In addition, 3,4-epoxy-1-butene still has problems in industrially inexpensive production, for example, lacking stability and requiring attention in handling.

  Next, conventionally, as a method for producing vinyl ethylene carbonate, for example, peracetic acid generated from hydrogen peroxide and glacial acetic acid is used to hydroxyacetate or diacetate butadiene through an oxirane ring, and then hydrolyze 3-butene. A method of synthesizing -1,2-diol and transesterifying it with diethyl carbonate using a sodium catalyst is disclosed (see Non-Patent Document 2). Although this method is useful as a laboratory method, it has a low yield and is problematic in terms of economics. In addition, industrial methods such as the use of peracetic acid, which requires extreme caution when handling highly explosive materials, are used. Is not preferred.

As another method, various methods for producing vinylethylene carbonate by reacting epoxybutene and carbon dioxide in the presence of a catalyst have been proposed. As the catalyst used in that case, an organic tertiary phosphine compound, chromium, manganese, ruthenium, rhodium, cadmium metal halide, an organic tertiary phosphine compound, and the like have been proposed (see Patent Document 4). However, in these methods, the reaction is carried out at a high temperature and high pressure of 180 ° C. or higher and 50 Kg / cm ² or higher. Therefore, the cost of equipment such as a reactor is increased, which is not economically advantageous. In addition, there is a method using a catalyst composed of a combination of tetrakistriphenylphosphine palladium and triphenylphosphine (see Non-Patent Document 3). However, this method uses a palladium catalyst that is expensive and unstable with respect to air as a catalyst, so that sufficient attention must be paid to its recovery and reuse.

In response to such industrial disadvantages, alkenyl-substituted alkylene oxide and carbon dioxide are produced under mild conditions by reacting in the presence of an alcohol with an alkali metal bromide and / or chloride as a catalyst. A method has been proposed (see Patent Document 5). However, in this method, since a halogen compound is used, there are restrictions on the apparatus and there is a problem in industrial implementation. In addition, there are still problems in manufacturing inexpensively industrially, such as the use of epoxy butene which is not stable and requires care in handling.
Neil W. Boaz, “The Stereochemistry of Solvolysis of an Acyclic Allylic Epoxide”, Tetrahedron: Asymmetry, Vol.6 No.1, 1995, 15-16 German Patent No. 4,429,700 JP-T-2002-514164 Japanese Patent Laid-Open No. 03-502330 Asai, “Polymerization of vinyl ethylene carbonate and reaction of the produced polymer”, Production Research, July 1973, Vol. 25, No. 7, p. 297 Japanese Patent Publication No. 48-22702 Japanese Patent Laid-Open No. 8-59557 Tatuo Fujinami, “Chemistry Letters” (Japan), No. 2; 1985, p. 199-200

  An object of the present invention is to provide a method capable of producing the butene derivative at a high yield and low cost under mild reaction conditions as compared with the conventional method using epoxybutene as a starting material. is there.

  The present inventors made 1,4-diacetoxy-2-butene (1,4-butanediol and tetrahydrofuran) by subjecting 1,3-butadiene and acetic acid to an acetoxylation reaction in the presence of molecular oxygen and a palladium-based catalyst. 3-Hydroxy-4-acetoxy-1-butene (hereinafter abbreviated as 3,4-HABE) and 3-acetoxy-4-hydroxy-1-butene (hereinafter referred to as 3,4), which are by-products when producing the raw material -AHBE), and at least one of the desired 3,4-dihydroxy-1-butene (hereinafter referred to as 3,4-DHBE) by hydrolysis reaction in the presence of an acid catalyst. (Abbreviation) was obtained, and the present invention was completed. This method is beneficial and economical because it is an effective use of by-products.In addition, it uses a raw material that is stable, low in toxicity, and easy to handle, instead of the conventional raw material epoxybutene. Useful for.

That is, the gist of the present invention is as follows.
(1) A method for producing 3,4-DHBE by hydrolysis reaction using 3,4-HABE and / or 3,4-AHBE and water in the presence of an acid catalyst, At least one selected from the group consisting of -HABE and 3,4-AHBE is obtained from a reaction product obtained by acetoxylation reaction of 1,3-butadiene and acetic acid in the presence of molecular oxygen and a palladium-based catalyst. A method for producing 3,4-DHBE, which is obtained by separating a mixture containing at least one of 3,4-HABE and 3,4-AHBE by distillation.
(2) The method for producing 3,4-DHBE according to (1), wherein the mixture of (1) contains 60% by weight or more of 3,4-diacetoxy-1-butene.
(3) The method for producing 3,4-DHBE according to (1) or (2), wherein the acid catalyst of (1) is a solid acid catalyst.
(4) A process for producing 4-DHBE, wherein 1,2-butanediol contained in 3,4-DHBE produced by the above (1) to (3) is separated by extractive distillation.
(5) 3,4-DHBE obtained by the above (1) to (4) and a low molecular carbonate compound are subjected to a transesterification reaction in the presence or absence of a basic catalyst. Manufacturing method.

According to the production method of the present invention, it is possible to produce various butene derivatives at high yield and low cost under mild reaction conditions by using a by-product in producing 1,4-butanediol as a raw material. it can.

Hereinafter, the present invention will be described in detail.
(1) Method for producing 3,4-DHBE <A mixture containing at least one selected from the group consisting of 3,4-HABE and 3,4-AHBE>
The mixture containing at least one selected from the group consisting of 3,4-HABE and 3,4-AHBE used as a starting material in the present invention comprises 1,3-butadiene and acetic acid as molecular oxygen and a palladium-based catalyst. It is a by-product that is simultaneously formed when 1,4-diacetoxy-2-butene is produced by an acetoxylation reaction in the presence. From the main product 1,4-diacetoxy-2-butene, 1,4-butanediol and tetrahydrofuran, which are the basic compounds of the chemical industry, are produced.
The acetoxylation reaction is performed at a high temperature and a high pressure in the presence of a catalyst, for example, by the method described in JP-A-8-3110. Preferable examples of the catalyst include palladium and / or a platinum-containing catalyst (particularly a supported catalyst). Moreover, when using as a catalyst composition, in addition to palladium or platinum, other metals, such as Te, Cu, Sb, Se, or Bi, may be included. In particular, a supported catalyst using a combination of palladium and tellurium and 0.15 to 0.5 gram atom of tellurium per 1 gram atom of palladium is preferable. As the carrier, silica, alumina, activated carbon and the like are preferable.
The reaction temperature is usually in the range of 20 to 150 ° C., and the reaction pressure is usually preferably in the range of 0.49 to 9.81 MPa.

  Molecular oxygen must be present in the reaction system. The molecular oxygen does not necessarily need to be pure oxygen, and oxygen diluted with an inert gas such as helium, nitrogen, or argon can be used. For example, air may be used. The amount of oxygen used is not particularly limited as long as it is greater than or equal to the stoichiometric amount, but is preferably within a range that does not cause an explosive composition industrially for safety reasons.

  As a method for separating a mixture containing at least one of 3,4-HABE and 3,4-AHBE from the acetoxylation reaction mixture, distillation is generally used. In particular, it is preferable to operate at a reduced pressure in order to prevent a decomposition reaction or a conversion reaction. When a general distillation tower is used, the bottom temperature is usually 110 ° C. or higher, preferably 120 ° C. or higher, and usually 190 ° C. or lower, preferably 150 ° C. or lower. The pressure is usually 0.1 kPa or more, preferably 1 kPa or more, and usually 20 kPa or less, preferably 5 kPa or less.

The mixture containing at least one of 3,4-HABE and 3,4-AHBE separated by distillation usually contains 3,4-diacetoxy-1-butene (hereinafter abbreviated as 3,4-DABE). It is. The content of 3,4-DABE is usually 60% by weight or more, preferably 70% by weight, and usually 95% by weight or less, preferably 90% by weight or less, based on the total weight of the mixture.
In addition to the above 3,4-DABE, 3,4-HABE and 3,4-AHBE, 1,2-diacetoxybutane (hereinafter abbreviated as 1,2-DAB), 1-hydroxy-2- There are small amounts of acetoxybutane (hereinafter abbreviated as 1,2-HAB) and 1-acetoxy-2-hydroxybutane (abbreviated as 1,2-AHB).

<Acid catalyst>
As the acid catalyst used in the present invention, any general Lewis acid or Bronsted acid may be used. From the viewpoint of hydrolysis rate, hydrochloric acid, sulfuric acid and solid acid catalyst having strong acid strength can be used.
In particular, the use of a solid acid catalyst is preferable in that it can be easily handled including post-treatment, and the acetic acid produced by hydrolysis can be easily recovered. Examples of the solid acid catalyst to be used include silica-alumina, activated earth, silica, cation exchange resin, and the like. Cation exchange resins are preferable because they have a high hydrolysis rate and few by-products. The cation exchange resin is preferably a sulfonic acid type strongly acidic ion exchange resin based on a copolymer of styrene and divinylbenzene, and may be a gel type resin or a porous type resin. Specific examples thereof include SK1B, SK104, SK108, PK208, PK216, PK228, etc. manufactured by Mitsubishi Chemical Corporation.
In general, the basic catalyst is more advantageous than the acid catalyst in terms of hydrolysis rate. As the basic catalyst, alkali or alkaline earth metal hydroxides such as sodium hydroxide, potassium lithium hydroxide, calcium hydroxide are generally used. In addition, methoxide, sodium methoxide, potassium methoxide, etc. Metal alkoxides, alkali metal simple substances such as sodium and potassium.

  However, in the case of these basic catalysts, in order to form a salt with the acetic acid produced | generated by hydrolysis, it may be required more than the total equivalent of acetic acid. This is industrially disadvantageous because acetic acid cannot be easily recovered. However, since the acid catalyst has a hydrolysis rate inferior to that of the basic catalyst, it is conceivable that a part of the basic catalyst is used together for the purpose of pushing out the hydrolysis reaction.

<Reaction conditions>
3,4-DHBE is produced by hydrolyzing a mixture containing at least one of 3,4-HABE and 3,4-AHBE obtained above and water in the presence of an acid catalyst.
The hydrolysis reaction is usually carried out at 30 ° C or higher, preferably 40 ° C or higher, and usually 110 ° C or lower, preferably 90 ° C or lower. If the temperature is too low, the reaction rate is remarkably slow and a large amount of catalyst is required, which is industrially disadvantageous. On the other hand, if the temperature is too high, side reactions increase and the yield may be adversely affected. The reaction pressure is not particularly limited, but is usually in the range of normal pressure to 1 MPa. The reaction time varies depending on the reaction temperature, the amount of acid catalyst and water used, and the reaction mode, but is usually 1 hour or longer, preferably 2 hours or longer, and usually 50 hours or shorter, preferably 20 hours or shorter. If the reaction time is too short, the hydrolysis reaction may be insufficient. On the other hand, if the reaction time is too long, side reactions may occur depending on the reaction temperature, and this is also disadvantageous industrially.
The ratio of the mixture containing at least one of 3,4-HABE and 3,4-AHBE obtained above and water is not only the stoichiometric amount because water is the reaction raw material and also the solvent. Used. Usually 1 or more, preferably 2 or more, usually 100 or less, preferably 50 or less per 1 equivalent of acetoxy group contained in a mixture containing at least one of 3,4-HABE and 3,4-AHBE. Used in the following ranges.
The amount of the acid catalyst varies depending on the acid strength, reaction type, reaction temperature, and time of the catalyst to be used. However, when the batch reaction is performed under the above conditions, at least one of 3,4-HABE and 3,4-AHBE is used. In the range of usually 0.01 equivalent or more, preferably 0.03 equivalent or more, usually 1 equivalent or less, preferably 0.5 equivalent or less, per 1 equivalent of acetoxy group contained in the mixture containing one kind. is there. If the amount of the acid catalyst is too small, the hydrolysis reaction may be insufficient. On the other hand, if the amount of the acid catalyst is too large, a side reaction may occur depending on the reaction temperature.

<Reaction format>
The hydrolysis reaction is carried out by an arbitrary method such as a batch method or a continuous method. When an ion exchange resin is used, the reaction may be carried out in a suspended state or the reaction raw material may be passed through a packed bed of ion exchange resin, and the fixed bed continuous method is industrially advantageous.
<Removal of water and acetic acid>
In order to remove acetic acid and water produced by hydrolysis, a method of distilling off under reduced pressure is generally used. As conditions in that case, industrially, it can carry out in the range whose temperature is normally 60 to 90 degreeC, and a pressure is normally 2 kPa to 20 kPa.

<Purification treatment>
As a purification method suitable for 3,4-DHBE, purification by distillation is usually used. The conditions at that time can be carried out by distillation under reduced pressure at a temperature of usually 80 ° C. to 120 ° C. and a pressure of usually 0.6 kPa to 6.0 kPa.
<Extraction solvent>
The generated 3,4-DHBE usually contains 1,2-butanediol (hereinafter abbreviated as 1,2-BG). 1,2-BG has a very close boiling point to 3,4-DHBE and cannot be easily separated by ordinary distillation. For this reason, the separation is generally performed by extractive distillation in which a third solvent (hereinafter abbreviated as an extractant) is added. The extract is not particularly limited as long as each component can be efficiently separated.
When 3,4-DHBE is recovered from the top of the column, preferred extractants that can be used include an infinite dilution activity coefficient (γ∞, BG) in 1,2-BG extractant and 3,4-DHBE. The ratio (separation coefficient, S = γ∞, BG / γ∞, DHBE) to the infinite dilution activity coefficient (γ∞, DHBE) in the extract is usually 0.9 or less, preferably 0.8 or less More preferably, it is 0.7 or less. The standard boiling point is usually 150 ° C. or higher, preferably 200 ° C. or higher, and usually 400 ° C. or lower, preferably 300 ° C. or lower. These solvents may be used alone or in combination. For example, particularly preferred extractants include decane, undecane, dodecane, tetradecane, pentadecane, cyclodecane, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, cyclodecene, octanol, nonanol, decanol, undecanol, dodecanol, butanediol, heptanediol. , Dipentyl ether, dihexyl ether, decanone, undecanone, dodecanone, diethylene glycol monobutyl ether, ethyl octoate, dioctyl phthalate, dinonyl phthalate, tributylamine, and tripentylamine. The solvent in which S is 0.9 or more is 3,4-DHB
The separation of E and 1,2-BG tends to be very poor. Moreover, the solvent whose boiling point is outside the above range does not function as an extractant because it is far from the boiling point of 3,4-DHBE.
On the other hand, when 3,4-DHBE is recovered together with the extractant from the bottom of the column, the preferable extractant that can be used has a ratio of infinite dilution activity coefficient of 1.1 or more, preferably 1 as described above. .2 or more, more preferably 1.4 or more. The standard boiling point is usually 150 ° C. or higher, preferably 200 ° C. or higher, and usually 400 ° C. or lower, preferably 300 ° C. or lower. These solvents may be used alone or in combination. For example, particularly preferred extractants include gamma-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl phthalate, methoxyphenol, methylphenol and the like. A solvent in which S is 1.1 or less tends to cause extremely poor separation of 3,4-DHBE and 1,2-BG. Moreover, the solvent whose boiling point is outside the above range does not function as an extractant because it is far from the boiling point of 3,4-DHBE.

In the present specification, the infinite dilution activity coefficient means A. Klamt, “Journal of Physical Chemistry” (Journal of Physical Chemistry).
Chemistry), (USA), American Chemical Society, 1995, Vol. 99, p. The method described in 2224, that is, the charge density on the surface of the molecule is calculated by quantum chemical calculation, and the interaction between different molecules is calculated as an activity coefficient.

In more detail, the calculation method is described as follows.
(1) Empirical molecular orbital method AM1 + Monte Carlo method was used to obtain the most stable structure of solute molecules in terms of energy.
(2) The obtained molecular structure was subjected to density functional theory (DFT) calculation using a COSMO-RS (COnductor like Screening Model for Real Solvent) model to determine the charge density on the molecular surface.
(3) The chemical potential between the solute and the solvent in the solution was estimated according to statistical thermodynamics expressed as an interaction by contact of molecular surfaces having different charge densities.
(4) The activity coefficient of the solute in the infinitely diluted solution was determined based on the calculated chemical potential.

Software used:
(1) Spartan
(2) TURBOMOLE
(3), (4) COSMOtherm / COSMObase

<Extraction distillation>
The following (1) and (2) can be considered as methods for separating 3,4-DHBE from the purified mixture by extractive distillation. The format may be either batch distillation or continuous distillation, but the case of continuous distillation is shown below. Here, the extract (1) is an extract having an infinite dilution activity coefficient ratio of 1 or less, and the extract (2) is an extract having an infinite dilution activity coefficient ratio of 1 or more.
(1) About the mixture, extractive distillation is performed using (1) as the extractant, and 3,4-DHB is obtained from the top of the column.
A method in which E and (1) are distilled, a mixture of 1,2-BG and (1) is withdrawn from the bottom of the column, and the distilled mixture is subjected to ordinary distillation to separate 3,4-DHBE.
(2) About the mixture, extractive distillation is performed using (2) as an extractant, 1,2-BG and (2) are distilled from the top of the column, and 3,4-DHBE and (2) are distilled from the bottom of the column. A method of extracting 3,4-DHBE by extracting the mixed solution and subjecting the bottom mixed solution to normal distillation.

  When performing the extractive distillation of (1) and (2) above, a distillation column having a theoretical plate number of usually 10 or more, preferably 20 or more is used. The reflux ratio is usually about 0.5 or more and 30 or less. If the reflux ratio is too small, the separation efficiency tends to deteriorate. On the other hand, if the reflux ratio is too large, the column system becomes large, which may be industrially disadvantageous. Usually, the extractant is supplied to the upper side of the distillation column, and the mixture is supplied to the lower side of the middle column of the distillation column. In any case, the amount of the extractant used is usually equal to or greater than that of the mixture, and the tower top pressure is usually 0.001 MPa or more and usually 0.05 MPa or less.

Next, a more specific embodiment will be described with reference to the drawings with respect to a method for separating and obtaining 3,4-DHBE from a mixture containing 2,4-DHBE and 1,2-BG.
FIG. 1 shows a method for separating 3,4-DHBE from a mixture containing two kinds of 3,4-DHBE and 1,2-BG using an extractant (1). In FIG. 1, a mixture containing two kinds of 3,4-DHBE and 1,2-BG is sent from the line 1 to the distillation column D1, and the extractant (1) is sent from the line 2 to the distillation column D1. Extraction distillation is performed in the distillation column D1, and a mixture of 3,4-DHBE and the extractant (1) is extracted from the top of the column through the line 3 and sent to the distillation column D2. A mixture of 2-BG and extractant (1) is extracted and sent to the distillation column D3. In distillation column D2, 3,4-DHBE and extractant (1) are separated by distillation, and 3,4-DHBE is extracted from the top of the column through line 5 and extractant (1) is extracted from the bottom of the column through line 6. . On the other hand, the distillation tower D3 is supplied with a mixture of 1,2-BG and the extractant (1) through the line 4 to perform distillation separation. 1,2-BG is extracted through line 8 from the top of the column. The extract (1) is extracted from the bottom of the tower.

FIG. 2 shows a method for separating 3,4-DHBE from a mixture containing 2,4-DHBE and 1,2-BG using an extractant (2). In FIG. 2, a mixture containing two kinds of 3,4-DHBE and 1,2-BG is sent from the line 1 to the distillation column D1, and the extractant (2) is sent from the line 2 to the distillation column D1. In the distillation column D1, extractive distillation is performed, and a mixture of 1,2-BG and the extractant (2) is extracted from the top of the column through the line 3 and sent to the distillation column D3. A mixture of 4-DHBE and extractant (2) is withdrawn and sent to distillation column D2. In the distillation column D2, 1,2-BG and the extractant (2) are distilled and separated, and 1,2-BG is extracted from the tower top through the line 7, and the extractant (2) is extracted from the tower bottom through the line 8. . On the other hand, the distillation tower D2 is supplied with a mixture of 3,4-DHBE and the extractant (2) through the line 4 to perform distillation separation. 3,4-DHBE is extracted from the top of the column through line 5. Extractant (2) is extracted from the bottom of the tower.
(2) Method for producing vinyl ethylene carbonate

<Low molecular carbonate compound>
The low molecular carbonate compound used as a starting material in the present invention means a compound having a number average molecular weight of usually 300 or less. Specific examples include the following dialkyl carbonates, alkylene carbonates, and diaryl carbonates.

First, as a dialkyl carbonate, carbon number of an alkyl group part is a thing of 1-6 normally. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and t-butyl group. Two alkyl groups may be the same or different.
Next, examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate and the like.

Finally, examples of the diaryl carbonate include diphenyl carbonate and dinaphthyl carbonate. Further, the two aryl groups may be the same or different.
Among these low molecular carbonate compounds, dialkyl carbonate is preferable from the viewpoint of easy handling, and dimethyl carbonate is most preferable from the viewpoint of reactivity and economy.

<Basic catalyst>
The 3,4-DHBE obtained in the above (1) and a low molecular carbonate compound are subjected to a transesterification reaction in the presence or absence of a basic catalyst.
As the basic catalyst used here, a general transesterification catalyst can be used, but a strong basic catalyst is preferable. Specific examples include metal alkoxides such as lithium methoxide, sodium methoxide, and potassium methoxide. Further, as a metal alkoxide source, an alkali metal simple substance such as Li, Na, and K, an alkaline earth metal simple substance such as Mg, n-butyl lithium, t-butyl lithium, Examples include organic lithium compounds such as phenyl lithium, metal amides such as sodium amide, metal hydrides such as sodium hydride, potassium hydride, calcium hydride, and LiBH ₄ .

Among these, when alkali metal simple substance, alkaline earth metal simple substance, organolithium compound, metal amide, metal hydride is used, the basicity is too strong, so the presence of 3,4-DHBE and low molecular carbonate compounds If used directly in the reaction system, there may be side reactions to carbonyl groups. Moreover, although sodium hydroxide, potassium hydroxide, etc. are applicable at the point of basic strength, these have low catalyst activity compared with a metal alkoxide etc., and depending on the quantity to be used, reaction may take a long time.
Therefore, as the basic catalyst, alkoxides of alkali metals and alkaline earth metals are preferable, and sodium methoxide is most preferable from the viewpoint of ease of handling and economy. Two or more of these basic catalysts may be used in combination.

<Reaction conditions>
The obtained 3,4-DHBE and a low molecular carbonate compound can be transesterified in the presence or absence of a basic catalyst to produce vinyl ethylene carbonate.
Even if a basic catalyst is not used, the transesterification reaction can proceed by raising the reaction temperature or lengthening the reaction time. However, a side reaction occurs or the obtained 3,4-DHBE undergoes a polymerization reaction. Since problems such as raising the viscosity of the reaction solution may occur, it is preferable to use an appropriate amount of a basic catalyst.

The amount of the low molecular carbonate compound is usually 0.1 mol or more, preferably 1.0 mol or more, and usually 5 mol or less, preferably 3 mol or less, relative to 1 mol of 3,4-DHBE. Usually, the larger the amount of the low molecular carbonate compound used, the higher the yield. Further, under conditions where the reaction proceeds more rapidly, such as a large amount of catalyst used and / or a high reaction temperature, a high yield may be obtained even if the amount of low molecular carbonate compound used is small.

When a metal alkoxide is used as a basic catalyst, the activity may be reduced due to moisture contained in the reaction system.
In that case, it is considered that approximately the equivalent amount of water affects the activity of the basic catalyst.
Therefore, the amount of the basic catalyst used is preferably more than the total number of moles of water in the reaction system, and usually 0.001 mole or more, preferably 1 mole of 3,4-DHBE. Is 0.01 mol or more, more preferably 0.03 mol or more, usually 1 mol or less, preferably 0.2 mol or less, more preferably 0.1 mol or less. When the amount of the basic catalyst used is too small, the progress of the reaction tends to be slow. On the other hand, if too much, side reaction tends to occur easily depending on reaction conditions.

The reaction temperature depends on conditions such as the type and amount of the catalyst, but is usually 40 ° C. or higher, preferably 80 ° C. or higher, and is usually 190 ° C. or lower, preferably 150 ° C. or lower. When the reaction temperature is too low, the progress of the reaction tends to be slow. On the other hand, when the reaction temperature is too high, a side reaction may occur or the obtained vinyl ethylene carbonate may be polymerized to increase the viscosity of the reaction solution.
The reaction time depends on conditions such as the type and amount of the catalyst and the reaction temperature, but is usually 0.5 hours or longer, preferably 1 hour or longer, and usually 12 hours or shorter, preferably 4 hours or shorter.

  This reaction is usually carried out in the absence of a solvent, but it may be carried out in a suitable organic solvent as necessary. Examples of organic solvents that can be used in this case include hydrocarbon solvents such as n-hexane, cyclohexane and toluene, halogen solvents such as chlorobenzene, amide solvents such as DMF and DMAc, which are considered not to be involved in the reaction. Is mentioned. In this reaction system, an additive such as a benzoquinone derivative such as p-benzoquinone or a nitro compound such as diphenylpicrylhydrazyl may be used as a polymerization inhibitor for vinyl ethylene carbonate, if necessary.

<Reaction format>
The reaction mode in the present invention can be applied to batch equipment or continuous equipment. When the reaction liquid is in a large amount, it may be produced using continuous equipment such as plug flow.
<Purification treatment>
A purification method suitable for vinyl ethylene carbonate usually includes purification by distillation. The conditions at that time can be carried out by distillation under reduced pressure at a temperature of usually 80 ° C. to 140 ° C. and a pressure of usually 0.1 kPa to 4.5 kPa.

<Application>
Various butene derivatives obtained by the production method of the present invention are acrylic acid, methacrylic acid,
By copolymerizing with acrylic acid ester, methacrylic acid ester, vinyl acetate, vinyl chloride, styrene, vinyl pyrrolidone, ethylene, propylene, etc., it can be used for applications such as improving physical properties and imparting functionality.

  In addition, in the case of 3,4-DHBE, in addition to the above, it can be used for purposes such as improving physical properties and imparting functionality by adding it as a diol to constituent components such as polyester resins and polyurethane resins.

EXAMPLES Specific examples of the present invention will be described below in more detail with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist. In the following examples, the butene derivative was quantified by gas chromatography.
<Acetoxylation reaction>
4 g of a supported catalyst (spherical silica support) containing 5.0 wt% palladium and 1.56 wt% tellurium was charged into a stainless steel reaction tube having an inner diameter of 12 mm (effective cross-sectional area of 1.005 cm ² ), and a reaction pressure of 5.9 MPa. At a reaction temperature of 80 ° C., 1,3-butadiene 0.15 mol / hour, acetic acid 2.5 mol / hour, and nitrogen containing 6% were flowed at a flow rate of 100 Nl / hour, and the reaction was continuously carried out for 500 hours. did.
Subsequently, acetic acid and water were removed by distillation at a temperature of 135 ° C. and a pressure of 12 kPa to obtain 1510 g of an acetoxylation reaction mixture.

<Separation and distillation of a mixture containing at least one selected from the group consisting of 3,4-HABE and 3,4-AHBE>
1500 g of the acetoxylation reaction mixture was placed in a 2 L three-necked flask, to which a stirrer, thermometer, and distillation tower (Older show; 75 mmφ, 30 stages in actual stage) were attached. When distillation under reduced pressure was performed at a pressure of 0.2 kPa for about 2 hours, 160 g of a distilled and purified product was obtained. When this was quantitatively analyzed by gas chromatography, the main components were as follows. (This mixture is referred to as mixture A)
3,4-DABE 73.6% by weight
3,4-HABE and 3,4-AHBE 18.4% by weight
1,2-DAB 3.1% by weight
1,2-HAB and 1,2-AHB 1.5% by weight
Other 3.4% by weight
Therefore, in 100 g of the obtained mixture, 3,4-DABE is 0.428 mol, 3,4-HABE and 3,4-AHBE are 0.142 mol, and the compound (3 , 4-DABE, 3,4-HABE, 3,4-AHBE, 1,2-DAB, 1,2-HAB and 1,2-AHB) was contained in an amount of 0.599 mol.

Example 1
In a stainless steel autoclave equipped with a stirrer having a capacity of 70 ml, 10.0 g of the mixture A,
9.4 g of demineralized water and 0.13 g of sulfuric acid (purity: 95%) were charged and the autoclave was sealed. Thereafter, the inside of the reactor was replaced with dry nitrogen to obtain atmospheric pressure, and then the temperature was raised to 100 ° C. The pressure increased slightly as the temperature rose and the reaction proceeded, but became constant at 0.3 MPa. This state was maintained and the hydrolysis reaction was continued for 4 hours. After the completion of the reaction, the contents were analyzed. The conversion of 3,4-DABE, 3,4-HABE and 3,4-AHBE to 3,4-DHBE was 72.8%.

Example 2
A four-necked flask with a capacity of 1 liter equipped with a stirrer, a thermometer, and a condenser tube was mixed with 250 g of mixture A, 470 g of demineralized water, strong acid ion exchange resin (manufactured by Mitsubishi Chemical Corporation: SK1BH, 2 as acid strength).
. 4 equivalents / 1000 g) and 144 g were charged, and the temperature was raised to 60 ° C. with stirring. After reaching 60 ° C., this temperature was maintained and the hydrolysis reaction was carried out for 4 hours. After the completion of the reaction, the contents were analyzed, and the conversion of 3,4-DABE, 3,4-HABE and 3,4-AHBE to 3,4-DHBE was 74.0%.

Example 3
After cooling the reaction liquid obtained in Example 2 to room temperature, SK1BH was removed by filtration, and the filtrate was a four-neck with a capacity of 1 l equipped with a stirrer, thermometer, and distillation tower (Oldershaw; actual stage 5 stages). Transfer to a flask and reduce pressure to 14-8 kPa at 60 ° C. to remove unreacted water and acetic acid.
To this, 144 g of SK1BH and 470 g of demineralized water are added, the hydrolysis reaction is again performed at 60 ° C. for 6 hours, and the reaction solution is cooled to room temperature, and then SK1BH is removed by filtration. Further, the filtrate was transferred again to a 4-liter flask having a volume of 1 l equipped with a stirrer, a thermometer, and a distillation tower (Oldershaw; actual stage 5 stages), and the pressure was reduced to 14 to 8 kPa at 60 ° C. to unreacted water. And acetic acid. The conversion of 3,4-DABE, 3,4-HABE and 3,4-AHBE to 3,4-DHBE is 85-95%. Subsequently, the desired 3,4-DHBE is obtained by distillation purification at a pressure of 0.8 to 1 kPa and a distillation temperature of 80 to 90 ° C. The 3,4-DABE obtained in this way includes 1,2-BG derived from 1,2-HAB, 1,2-AHB and 1,2-DAB contained in the mixture A which is a raw material. 5 parts by weight is included with respect to 95 parts by weight of 3,4-DHBE.

Example 4
In accordance with the composition of the 3,4-DHBE solution obtained in Example 2, extractive distillation was performed using undecanol as an extractant from a mixed solution consisting of 95% by weight of 3,4-DHBE and 5% by weight of 1,2-BG. About the method of distilling 1,2-BG by performing, the distillation simulation using the static simulator software ASPEN by ASPENTEC was performed.

In addition, the physical property model of simulation used what was calculated as a homogeneous system by NRTL which determined the parameter based on the infinite dilution activity coefficient calculated by the method described in the journal of physical chemistry described on page 12. Subsequent distillation simulation results were calculated in the same manner.
Each physical property value calculated in advance by a predetermined method is as follows.

Infinite dilution activity coefficient in undecanol (100 ° C)
1,2-BG: 1.52
3,4-DHBE: 2.30
Infinite activity coefficient ratio: 0.66
Standard boiling point of undecanol: 245 ° C (quoted from Dortmund Databank 2003)
As a result, 3,4-DHBE 19 kmol / Hr, 1,2-BG 1 kmol / h were obtained at the 56th stage from the top of the distillation column of 62 theoretical plates (the condenser at the top of the column and the reboiler at the bottom of the column were also one stage). When Hr was introduced and undecanol 200 kmol / Hr was introduced as the extractant in the third stage from the top, and extraction distillation was performed at a reflux ratio of 20 and a tower top pressure of 0.013 MPa, 1,2-BG0 was introduced from the tower top. A mixture of 3,4-DHBE and undecanol (3,4-DHBE 96.0 mol%, undecanol 3.5 mol%) containing 0.5% was obtained.

Further, the distillate from the top of the column was fed to the sixth column from the top of the 12-stage theoretical distillation column and subjected to normal distillation at a reflux ratio of 10 and a column top pressure of 0.013 MP. 3,4-DHBE containing 0.5% of 2-BG was obtained.
Example 5
According to the composition of the 3,4-DHBE solution obtained in Example 2, 3,4-DHBE9
About the method of distilling and purifying 3,4-DHBE from a mixed solution consisting of 5 wt% and 1,2-BG 5 wt% using propylene carbonate as an extractant, static simulator software manufactured by ASPENTEC Distillation simulation using ASPEN was performed.

The physical property values calculated by the method described in Journal of Physical Chemistry on page 12 are as follows.
Infinite dilution activity coefficient in propylene carbonate (100 ° C)
1,2-BG: 2.13
3,4-DHBE: 1.36
Infinite activity coefficient ratio: 1.57
Standard boiling point of propylene carbonate: 242 (quoted from Dortmund Data Bank 2003 edition)
As a result, 3,4-DHBE 19 kmol / Hr, 1,2-BG 1 kmol / h were obtained in the 16th column from the top of the distillation column having 62 theoretical plates (the condenser at the top of the column and the reboiler at the bottom of the column were also one). Hr was introduced, and 100 kmol / Hr of propylene carbonate was introduced as an extractant in the third stage from the top, and extraction distillation was performed at a reflux ratio of 20 and a top pressure of 0.013 MPa. A mixture of 3,4-DHBE and propylene carbonate containing BG 0.5% (3,4-DHBE 15.2 mol%, propylene carbonate 84.8 mol%) was obtained.

Further, the mixture obtained from the bottom of the column was supplied to the sixth column from the top of the 12-stage theoretical distillation column and subjected to normal distillation at a reflux ratio of 20 and a column top pressure of 0.013 MP. 3,4-DHBE containing 0.5% of 2-BG was obtained.
Example 6
A stainless steel autoclave equipped with a stirrer with a capacity of 70 ml is charged with 10.0 g of 3,4-DHBE obtained in Example 2, 12.3 g of dimethyl carbonate, and 0.06 g of sodium methoxide as a catalyst, and the autoclave is sealed. Thereafter, the inside of the reactor is replaced with dry nitrogen to obtain atmospheric pressure, and then the temperature is raised to 130 ° C. and the reaction is continued for 4 hours to obtain the intended vinyl ethylene carbonate. The conversion rate from 3,4-DABE to vinyl ethylene carbonate at the end of the reaction is 80-95%.

It is a flowchart showing the method of isolate | separating 3,4-DHBE from the mixture containing 2 types, 3,4-DHBE, and 1,2-BG using an extract (1). It is a flowchart showing the method of isolate | separating 3,4-DHBE from the mixture containing 2 types of 3, 4-DHBE and 1, 2-BG using an extractant (2).

Claims (5)

  3-hydroxy-4-acetoxy-1-butene (hereinafter abbreviated as 3,4-HABE) and / or 3-acetoxy-4-hydroxy-1-butene (hereinafter abbreviated as 3,4-AHBE) and water In which 3,4-dihydroxy-1-butene (hereinafter abbreviated as 3,4-DHBE) is produced by a hydrolysis reaction in the presence of an acid catalyst, which comprises 3,4-HABE and 3 , 4-AHBE is produced from a reaction product obtained by acetoxylation of 1,3-butadiene and acetic acid in the presence of molecular oxygen and a palladium-based catalyst. A method for producing 3,4-DHBE, which is obtained by separating a mixture containing at least one of HABE and 3,4-AHBE by distillation.   The method for producing 3,4-DHBE according to claim 1, wherein the mixture further contains 60% by weight or more of 3,4-diacetoxy-1-butene.     The method for producing 3,4-DHBE according to claim 1 or 2, wherein the acid catalyst is a solid acid catalyst.   The method for producing 3,4-DHBE according to any one of claims 1 to 3, wherein 1,2-butanediol contained in 3,4-DHBE produced by the reaction is separated by extractive distillation.   A vinyl characterized by transesterifying 3,4-DHBE obtained by the production method according to any one of claims 1 to 4 with a low-molecular carbonate compound in the presence or absence of a basic catalyst. A method for producing ethylene carbonate.

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