JP2020169148A - Manufacturing method of alkapolyene - Google Patents

Abstract

To provide an efficient manufacturing method that is a method of manufacturing, with high yield, high-purity alkapolyene that is less in a mixing amount of aqueous monocarboxylic acid by-produced in the manufacturing process into the alkapolyene, and can effectively utilize the by-produced aqueous monocarboxylic acid.SOLUTION: A manufacturing method of alkapolyene includes the following processes of (1) to (5). (1) An esterification process for obtaining acyloxyalkapolyene by reacting an allyl alcohol compound substituted with an alkenyl group and aqueous monocarboxylic acid while distilling away by-produced water. (2) A deacyloxylation process for obtaining a distilled product containing a mixture of alkapolyene and aqueous monocarboxylic acid, by deacyloxylating the acyloxyalkapolyene obtained in the esterification process. (3) A separation process for separating and obtaining respectively an organic phase and aqueous phase, after phase separation into two phases of the organic phase containing alkapolyene and an aqueous phase containing aqueous monocarboxylic acid, by contacting water to the distilled product obtained in the deacyloxylation process. (4) A process for isolating the alkapolyene having a mixing rate of the aqueous monocarboxylic acid of 0.10 mass% or lower, from the organic phase separated and obtained in the separation process. (5) A recovering and reusing process for extracting the aqueous monocarboxylic acid by the allyl alcohol compound substituted with the alkenyl group from the aqueous phase separated and obtained in the separation process, and using thus obtained mixed solution (X) containing the allyl alcohol compound substituted with the alkenyl group and the aqueous monocarboxylic acid as a supply source of the allyl alcohol compound substituted with the alkenyl group and the aqueous monocarboxylic acid in the esterification process.SELECTED DRAWING: None

Description

The present invention relates to a method for producing an alkapoliene.

Alkapolienes such as 1,3,7-octatriene are useful as synthetic raw materials for various general-purpose or special-purpose organic compounds, and are also useful as polymer synthetic raw materials.
Specific examples of the synthetic raw material for the organic compound include a synthetic raw material for a silane coupling agent having a conjugated diene structure and a hydrolyzable silyl group (see, for example, Patent Document 1). Specific examples of the polymer synthetic raw material include a synthetic raw material of a 1,3,7-octatriene polymer produced in the presence of an alkali metal compound or an organic alkali metal compound (see, for example, Patent Document 2).

Among the alkapolienes, 2,7-octadien-1-all-acetate (hereinafter, 1-acetoxy-2,7-octadien) is used as a method for producing 1,3,7-octatriene, which is particularly attracting attention for its usefulness. Step 1 to obtain a product containing 1,3,7-octatriene and acetic acid from (referred to as) and step 2-A of contacting the product obtained in step 1 with water; or step 2-A. A method for producing 1,3,7-octatriene, which comprises step 2-B of distilling the obtained product with water, is disclosed (see Patent Document 3). It is described that the raw material 1-acetoxy-2,7-octadien used in the step 1 can be produced, for example, by reacting 2,7-octadien-1-ol with acetic anhydride (Patent Document 3). (See paragraph [0010]).

Japanese Unexamined Patent Publication No. 2014-152128 Special Publication No. 49-16269 Japanese Unexamined Patent Publication No. 2016-216385

However, in the method described in Patent Document 3, acetic acid, which has a boiling point close to 1,3,7-octatriene and is difficult to distill and separate due to deacyloxylation of 1-acetoxy-2,7-octadien, is the 1,3. Since an equimolar amount of acetic acid is produced as a by-product with 7-octatriene, even if water is brought into contact with these mixtures to try to remove acetic acid, the problem of disposal of a large amount of acetic acid aqueous solution produced as a by-product remains. In addition, even if acetic anhydride is produced from a large amount of acetic acid aqueous solution produced as a by-product and reuse as a raw material for 1-acetoxy-2,7-octadien is attempted, a device for separating acetic acid and water from the acetic acid aqueous solution and Since an apparatus for producing acetic anhydride from the separated acetic acid is required, it is difficult to keep the production cost low.
By the way, acetic acid causes problems such as inactivating the polymerization initiator used when carrying out the polymerization reaction of 1,3,7-octatriene. Therefore, the target product, 1,3,7-octatriene. It is desirable that it is not substantially contained therein. By going through step 2-B of Patent Document 3, that is, by distilling a mixed solution in which water is brought into contact with a distillate of 1,3,7-octatriene and acetic acid, it is true that 1,3,7-octa The amount of acetic acid mixed in the triene can be efficiently reduced. However, as a result of further studies by the present inventors, distillation of 1,3,7-octatriene with acetic acid produces a high boiling point compound, and the yield of 1,3,7-octatriene is reduced during the distillation. It was found that a very small amount of acetic acid remained in 1,3,7-octatriene even by the method through step 2-B, and the purity of 1,3,7-octatriene was further improved. It turned out that there was room.

Therefore, an object of the present invention is a method for producing a high-purity alkapolyene in a high yield with a small amount of water-soluble monocarboxylic acid mixed in the alkapoliene in the production process. It is an object of the present invention to provide an efficient production method capable of effectively utilizing a water-soluble monocarboxylic acid.

As a result of diligent studies by the present inventors, they have found that the above-mentioned problems can be solved by the manufacturing method described later, and have completed the present invention.

That is, the present invention relates to the following [1] to [11].
[1] A method for producing an alkapolyene, which comprises the following steps (1) to (5).
(1) An esterification step in which an allyl alcohol compound substituted with an alkenyl group and a water-soluble monocarboxylic acid are reacted while distilling off by-produced water to obtain acyloxyalcopolyene.
(2) A deacyloxylation step of deacyloxylating the acyloxyalkapolyene obtained in the esterification step to obtain a distillate containing a mixture of the alkapoliene and a water-soluble monocarboxylic acid.
(3) Water is brought into contact with the distillate obtained in the deacyloxylation step to separate the distillate into two phases, an organic phase containing alkapolyene and an aqueous phase containing a water-soluble monocarboxylic acid, and then the above. A separation step of separating and acquiring the organic phase and the aqueous phase, respectively.
(4) A step of isolating an alkapolyene having a water-soluble monocarboxylic acid mixing ratio of 0.10% by mass or less from the organic phase separated and obtained in the separation step.
(5) A water-soluble monocarboxylic acid is extracted from the aqueous phase separated and obtained in the separation step with an alkenyl group-substituted allyl alcohol compound, and the alkenyl group-substituted allyl alcohol compound thus obtained and the water-soluble monocarboxylic acid are contained. A recovery and reuse step of using at least one part of the mixed solution (X) to be used as a source of the allyl alcohol compound substituted with the alkenyl group and the water-soluble monocarboxylic acid in the esterification step.
[2] The method for producing an alkapoliene according to the above [1], wherein a high boiling point compound is produced as a by-product in the esterification step, and the acyloxyalkapolyene is subjected to a deacyloxylation step together with the high boiling point compound.
[3] The method for producing an alkapoliene according to the above [1] or [2], wherein in the esterification step, the conversion rate of the allyl alcohol compound substituted with the alkenyl group to acyloxyalcopolyene is 90 mol% or more.
[4] The method for producing an alkapolyene according to any one of [1] to [3] above, wherein the deacyloxylation step is carried out in the presence of a palladium compound and a tertiary phosphorus compound.
[5] The method for producing an alkapoliene according to any one of the above [1] to [4], wherein the conversion rate of the acyloxy alkapolyene to the alkapoliene to be subjected to the deacyloxylation step is 70 mol% or more.
[6] The content of the water-soluble monocarboxylic acid in the organic phase separated and obtained in the separation step is 0 to 0 of the amount of the water-soluble monocarboxylic acid in the distillate obtained in the deacyloxylation step. The method for producing an alkapoliene according to any one of the above [1] to [5], which is 10 mol%.
[7] The above [1] to the above [1] to which 40 mol% or more of the water-soluble monocarboxylic acid in the distillate obtained in the deacyloxylation step is contained in the mixed solution (X) used in the recovery and reuse step. The method for producing an alkapoliene according to any one of [6].
[8] The method for producing an alkapolyene according to any one of the above [1] to [7], wherein the purity of the alkapolyene isolated in the step (4) is 98.0% or more.
[9] The allyl alcohol compound substituted with the alkenyl group is at least one selected from the group consisting of 2,7-octadien-1-ol and 1,7-octadien-3-ol, and the alkapolyene. The method for producing an alkapoliene according to any one of the above [1] to [8], wherein is 1,3,7-octatriene.
[10] The method for producing an alkapolyene according to any one of the above [1] to [9], wherein the water-soluble monocarboxylic acid has 2 to 5 carbon atoms.
[11] The method for producing an alkapolyene according to any one of the above [1] to [10], wherein the water-soluble monocarboxylic acid is acetic acid or propionic acid.

According to the present invention, a method for producing high-purity alkapolyene in a high yield with a small amount of water-soluble monocarboxylic acid mixed in with alkapolyene in the production process, and water-soluble by-produced It is possible to provide an efficient production method capable of effectively utilizing a monocarboxylic acid. Therefore, the method for producing an alkapoliene of the present invention is industrially advantageous because the production cost can be kept low.

Hereinafter, all aspects in which the items described in the present specification are arbitrarily combined are also included in the present invention. Further, the lower limit value and the upper limit value of the numerical range are arbitrarily combined with the lower limit value or the upper limit value of other numerical ranges, respectively.

[Manufacturing method of alkapoliene]
The present invention is a method for producing an alkapolyene, which comprises the following steps (1) to (5).
(1) An esterification step [hereinafter, esterification step (1)] in which an allyl alcohol compound substituted with an alkenyl group and a water-soluble monocarboxylic acid are reacted while distilling off by-produced water to obtain an acyloxyalcopolyene. )].
(2) A deacyloxylation step of deacyloxylating the acyloxyalkapolyene obtained in the esterification step (1) to obtain a distillate containing a mixture of alkapoliene and a water-soluble monocarboxylic acid [hereinafter, deacyloxyxide]. It may be referred to as an esterification step (2)].
(3) Water was brought into contact with the distillate obtained in the deacyloxylation step (2) to separate the distillate into two phases, an organic phase containing alkapoliene and an aqueous phase containing a water-soluble monocarboxylic acid. After that, a separation step [hereinafter, may be referred to as a separation step (3)] in which the organic phase and the aqueous phase are separated and obtained.
(4) A step of isolating an alkapolyene having a water-soluble monocarboxylic acid mixing ratio of 0.10% by mass or less from the organic phase separated and obtained in the separation step (3) [hereinafter, isolation step (4)). May be called].
(5) A water-soluble monocarboxylic acid is extracted from the aqueous phase separated and obtained in the separation step (3) with an alkenyl group-substituted allyl alcohol compound, and the alkenyl group-substituted allyl alcohol compound thus obtained and the water-soluble monocarboxylic acid are extracted. At least one part of the acid-containing mixed solution (X) [hereinafter, may be simply referred to as the mixed solution (X)] is an allyl alcohol compound in which the alkenyl group is substituted in the esterification step (1) and the water-soluble mixture. A recovery / reuse step [hereinafter, may be referred to as a recovery / reuse step (5)] used as a source of the sex monocarboxylic acid.

First, each reagent used in the present invention will be described in detail in order.
(Allyl alcohol compound substituted with an alkenyl group)
The alkenyl group-substituted allyl alcohol compound used in the present invention (hereinafter, may be simply referred to as an allyl alcohol compound) is not particularly limited as long as it is a compound in which an alkenyl group is substituted for allyl alcohol. An allyl alcohol compound substituted with an "alkenyl group having 1 to 3 carbon-carbon double bonds" is preferable, and an allyl alcohol compound substituted with an "alkenyl group having one carbon-carbon double bond" is more preferable. Further, as the alkenyl group, an alkenyl group having 2 to 15 carbon atoms is preferable, an alkenyl group having 3 to 10 carbon atoms is more preferable, an alkenyl group having 3 to 7 carbon atoms is further preferable, and an alkenyl group having 4 to 6 carbon atoms is more preferable. The group is particularly preferable, and the alkenyl group having 5 carbon atoms is most preferable.
The alkenyl group is preferably substituted at the 1- or 3-position of allyl alcohol. Further, it is preferable that at least one of the carbon-carbon double bonds of the alkenyl group is at the molecular terminal of the allyl alcohol compound.
Examples of the allyl alcohol compound include 2,5-hexadiene-1-ol, 1,5-hexadiene-3-ol, 2,7-octadien-1-ol, and 1,7-octadien-3-ol, 2. , 9-Decadien-1-ol, 1,9-decadien-3-ol, 2,11-dodecadien-1-ol, 1,11-dodecadien-3-ol and the like. Among these, at least one selected from the group consisting of 2,7-octadien-1-ol and 1,7-octadien-3-ol is preferable from the viewpoint of usefulness of the obtained alkapolyene.
The allyl alcohol compound may be used alone or in combination of two or more.

(Water-soluble monocarboxylic acid)
The water-soluble monocarboxylic acid may be any monocarboxylic acid that can be dissolved in water, but a monocarboxylic acid that dissolves in water at an arbitrary ratio is preferable from the viewpoint of sufficiently dissolving in the aqueous phase in the separation step (3). .. Further, as the water-soluble monocarboxylic acid, a water-soluble monocarboxylic acid that is not easily decomposed by a palladium compound or the like preferably used in the deacyloxylation step (2) is preferable. Further, the water-soluble monocarboxylic acid in the deacyloxylation step (2) is a water-soluble monocarboxylic acid that can be distilled off at the same time as 1,3,7-octatriene, and the amount of water used in the separation step (3). It is preferable that the water-soluble monocarboxylic acid can reduce the amount of water. From the above viewpoint, the water-soluble monocarboxylic acid is preferably a water-soluble aliphatic monocarboxylic acid, and the water-soluble monocarboxylic acid (for example, a water-soluble aliphatic monocarboxylic acid) has 2 to 5 carbon atoms. It is preferably, 2 or 3, more preferably 2, and even more preferably 2. Further, a water-soluble monocarboxylic acid having 3 to 5 carbon atoms may be selected.
Examples of the water-soluble monocarboxylic acid include acetic acid (ethaneic acid), propionic acid (propionic acid), butyric acid (butanoic acid), barric acid (pentanoic acid), caprylic acid (hexanoic acid), and enanthic acid (heptanic acid). , Caprylic acid (octanoic acid), pelargonic acid (nonanoic acid), capric acid (decanoic acid) and the like. Among these, acetic acid and propionic acid are preferable, and acetic acid is more preferable.
One type of water-soluble monocarboxylic acid may be used alone, or two or more types may be used in combination, but a plurality of acyloxyalkapolyenes are produced in the deacyloxylation step (2) and their components. From the viewpoint of preventing a part of them from remaining in the reaction system without being distilled, it is preferable to use one of them alone.

(Acyloxyalkapolyene)
The acyloxyalkapolyene obtained in the esterification step (1) is a compound obtained by a dehydration condensation reaction between the hydroxyl group of the allyl alcohol compound and the carboxyl group of the water-soluble monocarboxylic acid. Therefore, the structure of the acyloxyalcoholene depends on the type of the allyl alcohol compound and the type of the water-soluble monocarboxylic acid, and the structure corresponds to them.
For example, when the allyl alcohol compound is 2,7-octadien-1-ol or 1,7-octadien-3-ol and the water-soluble monocarboxylic acid is acetic acid, the acyloxyalcapolyene is 1-acetoxy-2. , 7-Octadiene or 3-acetoxy-1,7-Octadiene.

(Alcapoliene)
The alkapoliene obtained in the deacyloxylation step (2) is a compound obtained by desorbing (deacyloxylating) an acyloxyanion and a proton from the acyloxyalkapolyene obtained in the esterification step (1). Therefore, the structure of the alkapoliene depends on the type of the acyloxyalcoholene, and thus on the type of the allyl alcohol compound and the type of the water-soluble monocarboxylic acid, and the structure corresponds to them. When the allyl alcohol compound is 2,7-octadien-1-ol or 1,7-octadien-3-ol and the water-soluble monocarboxylic acid is acetic acid, the alkapoliene is mainly 1,3,7-octa. Although it is a triene, when it contains an isomer, it may include 1,3,6-octatriene, 2,4,6-octatriene and the like.
The alkapolyene produced in the present invention is not particularly limited, but from the viewpoint of usefulness, 1,3,7-octatriene and 1,3,9-decatorien are preferable, and 1,3,7- Octatriene is more preferred. Examples of the isomer of 1,3,7-octatriene include 1,3,6-octatriene, 2,4,6-octatriene and the like, which are by-produced together with 1,3,7-octatriene. There is a possibility, but the by-product amount of these isomers may be small because the boiling points of these isomers are close to the boiling points of 1,3,7-octatriene, which makes it difficult to separate them by distillation. preferable. In this respect, according to the production method of the present invention, the ratio of 1,3,7-octatriene to all octatrienes including isomers (hereinafter referred to as the purity of 1,3,7-octatriene) is extremely high. The purity of 1,3,7-octatriene can be 95% or higher, 98.0% or higher, 98.5% or higher, 99.0. It can be% or more.
-1,3,7-How to measure the purity of octatriene-
The purity of 1,3,7-octatriene was determined according to the following method. The sum of the peak areas attributable to all octatrienes was calculated by analysis by gas chromatography, the percentage of the peak area of 1,3,7-octatriene to the sum was calculated, and the value was calculated as 1,3,7-octa. The purity of the trien. More specific methods such as measurement conditions for gas chromatography are as described in Examples. Here, the total octatriene is a double bond isomer of 1,3,7-octatriene and the 1,3,7-octatorien (for example, 1,3,6-octatriene, 2,4,6- It means all octatrienes (eg, octatrienes and 1,4,6-octatoriens).

Hereinafter, one aspect of each step included in the production method of the present invention will be described in detail.
<Esterification step (1)>
The esterification step (1) is a step of esterifying the allyl alcohol compound and a water-soluble monocarboxylic acid to obtain acyloxyalkapolyene, and the reaction is carried out while distilling by-produced water out of the reaction system. As a result, the esterification reaction proceeds efficiently. In particular, in this esterification step (1), not only the water-soluble monocarboxylic acid itself is used, but also in the recovery and reuse step (5) described later, a "alkenyl group-substituted allyl alcohol compound" mixed with water is used. And at least one part of the "mixture solution (X) containing water-soluble monocarboxylic acid" can be used as a source of raw materials (allyl alcohol compound substituted with an alkenyl group and water-soluble monocarboxylic acid). In order to obtain sufficient reaction efficiency, it is important to carry out the reaction while distilling water from the reaction system in the esterification reaction.
In the present specification, the total distillate distilled out of the reaction system in the esterification step (1) may be referred to as an esterification distillate. On the other hand, the total solution remaining in the reaction system in the esterification step (1) may be referred to as an esterification reaction solution.

(Amount of raw materials used)
In the esterification step (1), one hydroxyl group derived from the allyl alcohol compound reacts with one carboxyl group of the water-soluble monocarboxylic acid. Therefore, the amount of the raw material used may be appropriately set in consideration of this, and is not particularly limited. For example, the amount of the water-soluble monocarboxylic acid used in the esterification step (1) is 0.5 to 100 mol with respect to 1 mol of the hydroxyl group of the allyl alcohol compound in terms of the carboxyl group of the water-soluble monocarboxylic acid. Preferably, 1 to 100 mol is more preferable, 1.5 to 10 mol is further preferable, and 1.5 to 5 mol is particularly preferable from the viewpoint of increasing the volume efficiency.

(Organic solvent that can be used in the esterification step (1))
The esterification step (1) is carried out in the presence or absence of an organic solvent, but in the presence of an organic solvent from the viewpoint of promoting distilling of water from the reaction system and easiness of controlling the reaction temperature. It is preferable to carry out.
The organic solvent is not particularly limited as long as it is inert to the esterification reaction, and a known organic solvent that can be used in the known esterification reaction can be used. Examples of the organic solvent include saturated aliphatic hydrocarbons such as butane, isobutane, n-pentane, isopentane, 2,2,4-trimethylpentane, hexane, n-heptane, isoheptane, n-octane, isooctane, nonane and decane. Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, methylcycloheptane; benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, o-xylene, m-xylene, p-xylene, etc. Aromatic hydrocarbons; methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone. , Acetylacetone, 2-cyclohexene-1-one and other ketone compounds; dimethyl ether, methyl ethyl ether, diethyl ether, ethyl-n-propyl ether, di n-propyl ether, n-butyl methyl ether, tert-butyl methyl ether, di Acyclic monoethers such as n-butyl ether, din-octyl ether, ethylphenyl ether, diphenyl ether; 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-diisopropoxyetane, 1,2- Dibutoxyethane, 1,2-diphenoxyethane, 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2-diphenoxypropane, 1,3-dimethoxypropane, 1,3-diethoxypropane, Acyclic diethers such as 1,3-diisopropoxypropane, 1,3-dibutoxypropane, 1,3-diphenoxypropane, cyclopentylmethyl ethers; tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 2-methyl tetrahydrofuran and the like. Cyclic ethers; diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dibutylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, dibutylene glycol diethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tributylene glycol dimethyl ether, triethylene Recall diethyl ether, tripropylene glycol diethyl ether, tributylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, tetrabutylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetrapropylene glycol diethyl ether, tetrabutylene glycol diethyl ether, etc. Acyclic polyether; etc. can be used.
One type of organic solvent may be used alone, or two or more types may be used in combination, but from the viewpoint of simplifying the recovery operation of the organic solvent, it is preferable to use one type alone.

As the organic solvent, it is more preferable to use an organic solvent having a boiling point of 90 to 150 ° C. from the viewpoint of reducing the energy required for distilling off the organic solvent from the reactor after the esterification step (1). Examples of the organic solvent having a boiling point of 90 to 150 ° C. include saturated aliphatic hydrocarbons such as 2,2,4-trimethylpentane, n-heptane, n-octane, isooctane, nonane, and decane; methylcyclohexane, ethylcyclohexane, cyclo. Alicyclic hydrocarbons such as heptane and methylcycloheptane; aromatic hydrocarbons such as toluene, ethylbenzene, propylbenzene, butylbenzene, o-xylene, m-xylene and p-xylene; methylpropyl ketone and methyl isopropyl ketone (MILPK) ), Methylbutyl ketone, Methylisobutylketone, Methyl n-hexylketone, diethylketone, diisopropylketone, dibutylketone, diisobutylketone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetylacetone, 2-cyclohexene-1-one and other ketone compounds. ; Etc. can be mentioned.

As the organic solvent, the lower the solubility in water, the easier the wastewater treatment of water distilled off together with the organic solvent in the esterification step (1) (including the operation of separating from the organic solvent). From the above, ketone compounds are more preferable, and methylpropyl ketone, methyl isopropyl ketone (MIPK), methyl butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and methylcyclohexanone. , Acetylacetone, 2-cyclohexene-1-one are more preferred.
When an organic solvent is used, the amount used is not particularly limited, but it is preferably 1 to 75% by mass with respect to the total mass of the raw material liquid charged in the esterification step (1), and from the viewpoint of increasing the volumetric efficiency, 10 ~ 50% by mass is more preferable.

(Esterification reactor)
The esterification step (1) can be carried out by any of a batch type, a semi-batch type and a continuous type, and among these, the batch type is preferable. The type of reactor used in the esterification step (1) is not particularly limited, and a complete mixing tank type reactor, a tube type reactor, etc. can be used, and two or more of these reactors are connected in series or in parallel. You may. Among these, a complete mixing tank type reactor can be preferably used.

As one aspect of the complete mixing tank type reactor, a complete mixing tank type reactor including a reflux condenser and a stationary tank is preferable. An example of a preferred embodiment using a complete mixing tank type reactor including a reflux condenser and a stationary tank is not particularly limited, but for example, (a) in order to promote the esterification reaction. The esterification reaction is carried out while vaporizing water (preferably together with an organic solvent), and (b) the esterified distillate obtained by condensing the gas component obtained in the step (a) above is transferred to a stationary tank. , An organic phase containing an organic solvent, an allyl alcohol compound, and a water-soluble monocarboxylic acid, water produced as a by-product in the esterification reaction, and the mixed solution (X) used in the recovery and reuse step (5). The organic phase is separated into an aqueous phase containing water, and (c) the organic phase obtained in the step (b) is separated and obtained, and then circulated to the reactor again, while (d) obtained in the step (b). Esterization of the allyl alcohol compound with the water-soluble monocarboxylic acid while carrying out each step of separating and obtaining the obtained aqueous phase and then reusing the water-soluble monocarboxylic acid in the esterification reaction as needed. Examples thereof include a method of carrying out the reaction and obtaining an esterification reaction solution (a product containing acyloxyalkapolinene) remaining in the reactor after the reaction is completed.

From the viewpoint of increasing the conversion rate of the allyl alcohol compound and shortening the reaction time, molecular sieves or the like is provided in the middle of the line in which the organic phase obtained in the step (b) is separated and acquired and then circulated to the reactor again. An adsorption tower filled with the water adsorbent of the above may be attached.
Further, from the viewpoint of promoting the distilling of water from the reaction system, an exhaust pump for lowering the pressure inside the reactor is attached to at least one of the group consisting of the reflux condenser and the stationary tank. You can also do it.

(Esterification reaction conditions)
The esterification step (1) is not particularly limited, but from the viewpoint of not wasting the raw material unnecessarily, and suppressing the inhibition of the reaction between the allyl alcohol compound and the water-soluble monocarboxylic acid. From the viewpoint, it is preferable to carry out in the absence of the allyl alcohol compound or another substance capable of reacting with the water-soluble monocarboxylic acid.
The raw materials and the organic solvent used in the esterification step (1) are not particularly limited, but a method such as bubbling with an inert gas such as nitrogen, helium, or argon (hereinafter, simply referred to as an inert gas). It is preferable that the oxygen gas is sufficiently removed.
Although not particularly limited, all operations in the esterification step (1) are carried out in an inert gas atmosphere from the viewpoint of suppressing oxidation of various compounds due to the inflow of oxygen gas into the reaction system. It is preferable to do so. The inert gas that can be used in the present invention preferably has sufficient oxygen gas removed, and the same applies hereinafter.

The esterification step (1) is not particularly limited, but from the viewpoint of accelerating the esterification reaction, it is preferable to sufficiently distill off water from the reaction system, and for that purpose, an organic solvent and water are used. It is preferable to increase the amount of the gas vaporized by the ester introduced into the reflux condenser, and the purpose is achieved by, for example, aerating an inert gas from the lower part of the complete mixing tank type reactor to the reflux condenser. can do.
The esterification reaction pressure is not particularly limited, but from the viewpoint of promoting the distillation of water from the reaction system, the allyl alcohol compound and the water-soluble monocarboxylic acid are used at the reaction temperature at which the esterification reaction is carried out. , Preferably below the vapor pressure of the mixture consisting of water, organic solvent and acyloxyalcoholene. From the same viewpoint as described above, the esterification reaction pressure is more preferably 1 to 300 kPaA, still more preferably 10 to 200 kPaA. In addition, A of kPaA indicates that it is an absolute pressure, and the same applies hereinafter.
The esterification reaction temperature is preferably equal to or higher than the boiling point of water under the reaction pressure from the viewpoint of promoting the distillation of water from the reaction system, while the unreacted allyl alcohol compound is transferred to the reflux condenser. From the viewpoint of suppressing retention, it is preferably equal to or lower than the boiling point of the allyl alcohol compound under reaction pressure. The reaction temperature is preferably 70 to 200 ° C, more preferably 90 to 150 ° C.
The esterification reaction time is not particularly limited, but the conversion rate of the allyl alcohol compound to acyloxyalcoholene in the esterification reaction (hereinafter, may be referred to as esterification rate) is 90 mol% or more. Is preferable, and it is more preferable that the content is 95 mol% or more. Specifically, the esterification reaction time is preferably 1 to 200 hours, more preferably 2 to 100 hours. If the reaction time is within this range, the yield of acyloxyalkapolyene tends to be high.

By the esterification step (1), an esterification reaction solution containing acyloxyalkapolyene, an unreacted water-soluble monocarboxylic acid and an organic solvent as main components can be obtained from the reactor.
From the viewpoint of improving the volume efficiency in the deacyloxylation step (2) and reducing the load of water-soluble monocarboxylic acid recovery in the separation step (3), the esterification reaction solution is distilled to obtain a water-soluble monocarboxylic acid and an organic solvent. It is preferable to sufficiently reduce the content of. Specifically, acyloxyalkapolyene may be isolated by distillation purification of the esterification reaction solution and then used in the deacyloxylation step (2), or only the water-soluble monocarboxylic acid and the organic solvent may be used from the esterification reaction solution. The mixed solution from which the above is removed may be used in the deacyloxylation step (2). In the latter case, when the high boiling point compound is produced as a by-product in the esterification step (1), the acyloxyalkapolyene is subjected to the deacyloxylation step (2) together with the high boiling point compound. The high boiling point compound that can be produced as a by-product in the esterification step (1) tends to contain a high boiling point compound having a carboxyl group. According to the production method of the present invention, even if a high boiling point compound that can be produced as a by-product in the esterification step (1) is present in the reaction system of the deacyloxylation step (2), it has a great adverse effect on the reaction results. It is possible to carry out industrially. In the present invention, the high boiling point compound is, for example, a compound having a boiling point that cannot be detected under the gas chromatography analysis conditions described in Examples, that is, the boiling point is 200 ° C. or higher and exceeds 250 ° C. It may be, and it may be above 280 ° C.
The water-soluble monocarboxylic acid and the organic solvent obtained by these operations can be reused in the esterification step (1) after recovery.

<Deacyloxylation step (2)>
The deacyloxylation step (2) is a step of deacyloxylating the acyloxyalkapolyene obtained in the esterification step (1) to obtain a distillate containing a mixture of alkapoliene and a water-soluble monocarboxylic acid. In the present specification, the distillate in the deacyloxylation step (2) may be referred to as a deacyloxylation reaction solution.
The deacyloxylation step (2) is preferably carried out in the presence of a catalyst from the viewpoint of promoting the deacyloxylation of acyloxyalkapolyene. As the catalyst, a compound containing a metal having a high reaction activity per metal atom is preferable, and a palladium compound is more preferable. From the viewpoint of catalytic activity, the deacyloxylation step (2) is preferably carried out in the presence of a palladium compound and a tertiary phosphorus compound.
As an example of a preferred embodiment of the deacyloxylation step (2), for example, a palladium compound and a tertiary phosphorus compound are retained in the reactor, and the alkacpolyene produced while supplying the acyloxyalkapolyene to the reactor is used. Examples thereof include a method of distilling off the water-soluble monocarboxylic acid from the reaction system.

(Palladium compound)
The form and valence state of the palladium compound as a catalyst that can be used in the deacyloxylation step (2) are not particularly limited. Examples of the palladium compound include a zero-valent palladium compound and a divalent palladium compound.
Examples of the zero-valent palladium compound include bis (tert-butylisonitrile) palladium (0), bis (tert-amylisonitrile) palladium (0), bis (cyclohexylisonitrile) palladium (0), and bis (phenylisonitrile) palladium ( 0), bis (p-tolylisonitrile) palladium (0), bis (2,6-dimethylphenylisonitrile) palladium (0), tris (dibenzilidenacetone) dipalladium (0), (1,5-cyclooctadien) ) (Maleic anhydride) palladium (0), bis (norbornen) (maleic anhydride) palladium (0), bis (maleic anhydride) (norbornen) palladium (0), (dibenzilidenacetone) (bipyridyl) palladium (0) ), (P-benzoquinone) (o-phenanthroline) palladium (0), tetrakis (triphenylphosphine) palladium (0), tris (triphenylphosphine) palladium (0), bis (tritrylphosphine) palladium (0), Examples thereof include bis (trixysilylphosphine) palladium (0), bis (trimesitylphosphine) palladium (0), bis (tritetramethylphenyl) palladium (0), and bis (trimethylmethoxyphenylphosphine) palladium (0).
Examples of the divalent palladium compound include palladium (II) chloride, palladium (II) nitrate, tetraammine dichloropalladium (II), disodium tetrachloropalladium (II), palladium (II) acetate, and palladium (II) benzoate. Palladium α-picolinate (II), bis (acetylacetone) palladium (II), bis (8-oxyquinoline) palladium (II), bis (allyl) palladium (II), (η-allyl) (η-cyclopentadi) Enyl) Palladium (II), (η-Cyclopentadienyl) (1,5-cyclooctadiene) Palladium (II) Tetrafluoroborate, Bis (benzonitrile) Palladium (II) Acetate, Di-μ- Examples thereof include chloro-dichlorobis (triphenylphosphine) dipalladium (II), bis (tri-n-butylphosphine) palladium (II) acetate, and 2,2'-bipyridylpalladium (II) acetate.
Among these, tetrakis (triphenylphosphine) palladium (0), palladium acetate (II), and bis (acetylacetone) palladium (II) are preferable from the viewpoint of industrial availability and price, and from the viewpoint of price and availability. , Palladium acetate (II), bis (acetylacetone) palladium (II) are more preferred.

When a palladium compound is used, the palladium compound increases the conversion rate of acyloxyalkapolyene and suppresses the isomerization of alkapoliene with respect to the supply amount of acyloxyalkapolyene of 1 kg / hr in terms of palladium atom. It is preferably present in the reactor at 10 to 2,000 mmol, more preferably at 50 to 500 mmol.
If a decrease in the conversion rate of acyloxyalkapolyene is observed, a palladium compound may be further added to the reaction system. The amount of the palladium compound used in that case is not particularly limited, but is preferably 10 to 2,000 mmol / hr with respect to the supply amount of acyloxyalkapolyene of 1 kg / hr in terms of palladium atoms, and is preferably 50 to 500 mmol / hr. hr is more preferred.

(3rd grade phosphorus compound)
By allowing the tertiary phosphorus compound to be present in the reaction system together with the palladium compound, the reaction activity per atom of the palladium metal tends to be maintained for a long time, and a high conversion rate of acyloxyalkapolyene can be obtained in a long-term reaction. Easy to maintain.
Examples of the tertiary phosphorus compound include tertiary phosphine and tertiary phosphite.
Examples of the tertiary phosphine include triisopropylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine, tribenzylphosphine, triphenylphosphine, tris (p-methoxyphenyl) phosphine, and tris (p-N,). N-dimethylaminophenyl) phosphine, tris (p-fluorophenyl) phosphine, tri-o-toluylphosphine, tri-m-toluylphosphine, tri-p-toluylphosphine, tris (pentafluorophenyl) phosphine, bis (pentafluoro) Phine) phenylphosphine, diphenyl (pentafluorophenyl) phosphine, methyldiphenylphosphine, ethyldiphenylphosphine, cyclohexyldiphenylphosphine, dimethylphenylphosphine, diethylphenylphosphine, 2-furyldiphenylphosphine, 2-pyridyldiphenylphosphine, 4-pyridyldiphenylphosphine , M-diphenylphosphine benzenesulfonic acid or a metal salt thereof, p-diphenylphosphine benzoic acid or a metal salt thereof, p-diphenylphosphine phenylphosphonic acid or a metal salt thereof, and the like.
Examples of the tertiary phosphite include triethyl phosphite, triphenyl phosphite, tris (p-methoxyphenyl) phosphite, tris (o-methylphenyl) phosphite, tris (m-methylphenyl) phosphite, and tris. (P-Methylphenyl) phosphite, tris (o-ethylphenyl) phosphite, tris (m-ethylphenyl) phosphite, tris (p-ethylphenyl) phosphite, tris (o-propylphenyl) phosphite, tris (M-propylphenyl) phosphite, tris (p-propylphenyl) phosphite, tris (o-isopropylphenyl) phosphite, tris (m-isopropylphenyl) phosphite, tris (p-isopropylphenyl) phosphite, tris (O-tert-butylphenyl) phosphite, tris (p-tert-butylphenyl) phosphite, tris (p-trifluoromethylphenyl) phosphite, tris (2,4-dimethylphenyl) phosphite, tris (2) , 4-Di-tert-butylphenyl) phosphite, tris (2-tert-butyl-4-methylphenyl) phosphite and the like.
Among these, tertiary phosphine is preferable as the tertiary phosphorus compound, and from the viewpoint of industrial availability and price, triphenylphosphine, tri-o-toluic phosphine, tri-m-toluic phosphine, and tri. -P-Toluic phosphine is more preferred.

When a tertiary phosphorus compound is used, the amount used is not particularly limited, but from the viewpoint of maintaining the reaction activity per palladium metal atom, the phosphorus atom is converted with respect to 1 mol of the palladium atom. 1 to 1,000 mol is preferable, 1 to 500 mol is more preferable, 1 to 150 mol is further preferable, 2 to 50 mol is particularly preferable, and 2 to 15 mol is most preferable. Even if the amount of the tertiary phosphorus compound used is too large, the effect will reach a plateau, so it is preferable to adjust appropriately within the above range.
If a decrease in the conversion rate of acyloxyalkapolyene is observed, a tertiary phosphorus compound may be further added to the reaction system.

In the deacyloxylation step (2), as described above, even when a high boiling point compound is by-produced in the esterification step (1), the acyloxyalkapolyene is deacylated oxylated in the presence of the high boiling point compound. It was found by the examination of the present inventors.
However, since the high boiling point compound tends to contain a high boiling point compound having a carboxyl group, if the high boiling point compound stays in the reactor in the deacyloxylation step (2), the acidity in the reaction system increases. It is also conceivable that the conversion rate of acyloxyalkapolyene may decrease over time. Therefore, the deacyloxylation step (2) may be carried out in the presence of the nitrogen-containing compound to suppress the increase in acidity in the reaction system.

(Nitrogen-containing compound)
Examples of the nitrogen-containing compound include a tertiary amine compound and a nitrogen-containing heteroaromatic compound. Examples of the tertiary amine compound include triethylamine, tributylamine, tri-n-octylamine, N, N, N', N'-tetramethyl-1,2-diaminoethane, N, N, N', N. '-Tetramethyl-1,3-diaminopropane, N, N, N', N'-Tetramethyl-1,4-diaminobutane, N, N-diethylethanolamine, triethanolamine, N-methylpyrrolidine, N -Methylpyrrolidine, N-methylmorpholine and the like can be mentioned. Examples of the nitrogen-containing heteroaromatic compound include pyridine, picoline, lutidine, colidin, and quinoline. Among these, a tertiary amine compound is preferable as the nitrogen-containing compound, and triethylamine and tributylamine are more preferable from the viewpoint of industrial availability and price.

When a nitrogen-containing compound is used, the amount used may be appropriately adjusted according to the amount of carboxyl groups contained in the high boiling point compound that can be supplied to the deacyloxylation step (2) together with acyloxyalkapolyene. As a guide, the amount of the nitrogen-containing compound used may be 1 mol or less and 0.1 mol or less in terms of nitrogen atoms with respect to 1 mol of phosphorus atoms of the tertiary phosphorus compound. Within this range, a high conversion rate of acyloxyalkapolyene tends to be maintained in a long-term reaction.
If a decrease in the conversion rate of acyloxyalkapolyene is observed, a nitrogen-containing compound may be further added to the reaction system.

(Organic solvent that can be used in the deacyloxylation step (2))
The deacyloxylation step (2) is carried out in the presence or absence of an organic solvent, but is preferably carried out in the presence of an organic solvent. By using an organic solvent, the concentration of palladium atoms in the reaction system is kept constant when the supply of acyloxyalkapolyene to the reactor and the distillation of both alkapoliene and water-soluble monocarboxylic acid are simultaneously carried out. It tends to be easier to keep the reaction at, and the reaction tends to be easier to control.
The organic solvent is preferably one that is inert to the deacyloxylation reaction and has a higher boiling point than the alkapoliene and the water-soluble monocarboxylic acid. Examples of such organic solvents include saturated aliphatic hydrocarbons such as nonane and decane; alicyclic hydrocarbons such as ethylcyclohexane and methylcycloheptane; ethylbenzene, propylbenzene, butylbenzene, o-xylene, m-xylene and p. -Aromatic hydrocarbons such as xylene; ketone compounds such as dibutylketone, diisobutylketone, cyclopentanone, cyclohexanone, methylcyclohexanone; acyclic monoethers such as din-butyl ether, din-octyl ether, ethylphenyl ether, diphenyl ether 1,2-dibutoxyethane, 1,2-diphenoxyethane, 1,2-diethoxypropane, 1,2-diphenoxypropane, 1,3-diethoxypropane, 1,3-diisopropoxypropane, Acyclic diethers such as 1,3-dibutoxypropane, 1,3-diphenoxypropane, cyclopentylmethyl ether; diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dibutylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, dibutylene. Glycol diethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tributylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, tributylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, tetrabutylene glycol Acyclic polyethers such as dimethyl ether, tetraethylene glycol diethyl ether, tetrapropylene glycol diethyl ether, tetrabutylene glycol diethyl ether; and the like can be mentioned. One type of organic solvent may be used alone, or two or more types may be used in combination, but from the viewpoint of simplifying the recovery operation of the organic solvent, it is preferable to use one type alone.

When an organic solvent is used, the amount used is not particularly limited, but from the viewpoint of increasing the conversion rate of acyloxyalkapolyene and suppressing the retention of alkapoliene in the reaction system to suppress the isomerization of alkapoliene. Further, from the viewpoint of increasing the concentration of palladium atoms in the reaction system, it is preferable to make appropriate adjustments. As a guide, the amount of the organic solvent used is, for example, preferably 0 to 1 kg / hr, more preferably 0 to 500 g / hr with respect to the supply amount of acyloxyalkapolyene of 1 kg / hr.

(Deacyloxylation reactor)
In the deacyloxylation step (2), when the alkapoliene stays in the reaction system for a long time, the compound whose alkapoliene is difficult to distill and separate due to the palladium atom in the reaction system (for example, the target product is 1,3,7-octa). In the case of trienes, they can be isomerized to 1,3,6-octatrienes and 2,4,6-octatrienes), so the alkapolienes produced as the target product are rapidly distilled out of the reaction system. Is preferable. From this point of view, it is preferable that the deacyloxylation step (2) is carried out continuously using a complete mixing tank type reactor. The reactor is provided with a reflux condenser for condensing the distillate (deacyloxylation reaction solution) (containing a mixture of alkapolyene and a water-soluble monocarboxylic acid) distilled out of the reaction system. It is preferable to have. Further, in order to rapidly distill and condense the mixture of alkapoliene and the water-soluble monocarboxylic acid, it is preferable that the reactor is preferably equipped with an exhaust pump attached to the reflux condenser.

(Deacyloxylation reaction conditions)
The deacyloxylation step (2) is not particularly limited, but is preferably carried out in the absence of a substance capable of consuming, decomposing or inactivating the catalyst used in the preferred embodiment. Further, although not particularly limited, it is preferable that all the operations in the deacyloxylation step (2) are carried out in an inert gas atmosphere. Further, although not particularly limited, the raw material and the organic solvent used in the deacyloxylation step (2) are not particularly limited, but oxygen gas is sufficient by a method such as bubbling with an inert gas. It is preferable that the gas is removed. By doing so, for example, the oxidation of the palladium atom of the palladium compound can be easily suppressed, and the catalytic activity tends to be maintained for a long period of time.

In the deacyloxylation step (2), the conversion rate from acyloxyalkaliene to alkapolyene (hereinafter, may be referred to as deacyloxylation rate) is preferably 70 mol% or more, and from the viewpoint of increasing volumetric efficiency, it is preferable. More preferably, it is 80 mol% or more. In the deacyloxylation step (2) in the present invention, the deacyloxylation rate can be increased to 90 mol% or more, 95 mol% or more, or 98 mol% or more. Is.
Furthermore, in order to suppress the isomerization of alkapoliene (for example, in the case of 1,3,7-octatriene, isomerization to 1,3,6-octatriene and 2,4,6-octatriene), the reaction is carried out. It is preferable to suppress the retention of the target product, alkapolyene (for example, 1,3,7-octatriene) in the system. From this point of view, it is preferable to quickly distill the produced alkapoliene out of the reaction system. By increasing the amount of gas generated from the reaction system introduced into the reflux condenser, the distillate of the produced alkapoliene can be promoted. Therefore, the inert gas is aerated from the lower part of the complete mixing tank type reactor to the reflux condenser. You may.

The deacyloxylation reaction pressure may be appropriately adjusted depending on the type of water-soluble monocarboxylic acid. For example, when the water-soluble monocarboxylic acid is acetic acid, 0.5 kPaA to atmospheric pressure is preferable, and 1 kPaA to atmospheric pressure is more preferable. When the water-soluble monocarboxylic acid is, for example, a water-soluble monocarboxylic acid having 3 to 5 carbon atoms, it is preferably 0.02 kPaA to atmospheric pressure, more preferably 0.10 to 60 kPaA. When the water-soluble monocarboxylic acid is a water-soluble monocarboxylic acid having 4 or more carbon atoms, the conditions under which the water-soluble monocarboxylic acid can be easily distilled off may be appropriately selected by lowering the reaction pressure as necessary. In consideration of the above, the deacyloxylation reaction pressure is not particularly limited, but is preferably 0.001 kPaA to atmospheric pressure, and more preferably 0.01 kPaA to atmospheric pressure.
In order to maintain high volumetric efficiency and high conversion rate in the deacyloxylation step (2), it is preferable to rapidly distill off alkapoliene and water-soluble monocarboxylic acid from the reactor, and the reaction temperature and water-soluble monocarboxylic acid An appropriate reaction pressure may be set while considering the type of carboxylic acid and the like.

The deacyloxylation reaction temperature is preferably 50 to 150 ° C., and more preferably 70 to 120 ° C. from the viewpoint of maintaining a high deacyloxylation rate for a long time. The deacyloxylation rate tends to increase by increasing the reaction temperature, but if the reaction temperature is too high, the deacyloxylation rate tends to decrease over time as the metalization of the palladium atom progresses, and the isomerization of alkapoliene. Metalation (eg, isomerization of 1,3,7-octatriene to 1,3,6-octatriene) tends to proceed. From these viewpoints, the deacyloxylation reaction temperature is preferably in the above range.

As described above, from the viewpoint of suppressing isomerization, it is preferable to quickly distill off the alkapolyene and the water-soluble monocarboxylic acid generated by the deacyloxylation reaction to the outside of the reaction system, but at the same time, the amount of the internal liquid in the reaction system. From the viewpoint of maintaining the above, it is preferable to continuously distill off the amount of alkaliene and the water-soluble monocarboxylic acid to the outside of the reaction system in the same amount as the amount of acyloxyalkapolyene supplied to the reactor.
When the deacyloxylation step (2) is carried out continuously, the residence time as the reaction time is not particularly limited, but the deacyloxylation rate of the acyloxyalkapolyene is set to 70 mol% or more. Is preferable. The residence time may be appropriately adjusted depending on the amount of catalyst used, the amount of organic solvent used, the reaction temperature, etc., but from the viewpoint of reducing the deacyloxylation rate to 70 mol% or more, 0.1 to 20 hours is preferable, and 0 .5-10 hours are more preferred.

The distillate (deacyloxylation reaction solution) obtained in the deacyloxylation step (2) includes, in addition to alkapylene and water-soluble monocarboxylic acid, an unreacted raw material (acyloxyalkaliene) and a by-product [as a raw material]. An isomer of the acyloxyalkapolyene used (for example, 3-acetoxy-1,7-octadene when 1-acetoxy-2,7-octadene is used as a raw material)] may be included. This unreacted raw material (acyloxyalkapolyene) is separated into the organic phase side together with alkapoliene in the separation step (3) described later, and then, if necessary, alkapoliene by a known separation and purification means of the organic compound such as distillation. It can also be separated from the above and reused as a raw material in the deacyloxylation step (2).

<Separation process (3)>
In the separation step (3), water is brought into contact with the distillate (deacyloxylation reaction solution) obtained in the deacyloxylation step (2) to bring an "organic phase" containing alkapoliene and a water-soluble monocarboxylic acid. This is a step of separating and acquiring the organic phase and the aqueous phase after the two phases of the "aqueous phase" containing the above are separated.
The method of contacting the deacyloxylation reaction solution with water is not particularly limited. For example, the deacyloxylation reaction solution can be transferred to a separation device described later and water can be supplied to bring the deacyloxylation reaction solution into contact with each other. it can.

As the water to be brought into contact with the deacyloxylation reaction solution, the pH is preferably 6.5 to 7.5, more preferably 6.8 to 7.2, and substantially neutral water is used. It is more preferable to do so. The water is not particularly limited, but for example, distilled water, deionized water, purified water, RO (Reverse Osmosis) water and the like can be used. By using such water, esterification occurs when at least one part of the mixed solution (X) is used as a source of raw materials in the esterification step (1) in the recovery and reuse step (5). The reaction can proceed without any problem (for example, if the water mixed in the mixed solution (X) contains an alkali metal ion, it acts on the water-soluble monocarboxylic acid), which is industrially advantageous. Is.

The amount of water used is preferably such that the water-soluble monocarboxylic acid in the deacyloxylation reaction solution can be sufficiently recovered, and 90 mol% or more of the water-soluble monocarboxylic acid in the deacyloxylation reaction solution is recovered. It is more preferable that the amount is recoverable, 95 mol% or more is more preferable, 98 mol% or more is particularly preferable, and 99.0 mol% or more is recovered. Most preferably, it is an amount that can be used.
The amount of water used may be appropriately adjusted according to the type of water-soluble monocarboxylic acid, the method of separation operation, the desired recovery rate of the water-soluble monocarboxylic acid, etc., but specifically, the water-soluble monocarboxylic acid. From the viewpoint of achieving the recovery rate of the carboxylic acid, the mass ratio (water / distillate) to the deacyloxylation reaction solution is preferably 0.1 to 4, and more preferably 0.2 to 2. It is preferably 0.2 to 1.0, more preferably 0.3 to 0.8.

Since the aqueous phase obtained in the separation step (3) contains a water-soluble monocarboxylic acid which is a raw material of the esterification step (1), it is used in the recovery and reuse step (5) described later. All of the aqueous phase obtained in the separation step (3) may be used in the recovery and reuse step (5), or a part of the aqueous phase obtained in the separation step (3) may be recovered and reused in the recovery and reuse step (5). You may use it at. In any case, 40 mol% or more (more preferably 50 mol% or more, further preferably 60 mol% or more) of the water-soluble monocarboxylic acid in the deacyloxylation reaction solution is the recovery and reuse step (5). It is preferable that it is contained in the mixed solution (X) used in. For that purpose, for example, the amount of water to be brought into contact with the deacyloxylation reaction solution is adjusted within the range of the water / distillate ratio, and all the obtained aqueous phases are subjected to the recovery and reuse step (5). The method is simple and preferable.
If there is an aqueous phase that is not used in the recovery and reuse step (5), the aqueous phase may be mixed with water that is brought into contact with the deacyloxylation reaction solution in the [i] separation step (3). , [Ii] Water-soluble monocarboxylic acid and water may be separated by a known method to isolate the water-soluble monocarboxylic acid, and then the isolated water-soluble monocarboxylic acid may be stored, if necessary. It may be reused as a raw material in the esterification step (1), or it may be recovered and reused as a raw material in the esterification step (1) after concentration in [iii], or it may be discarded in [iv]. Alternatively, [v] it may be used for other purposes other than the above.

The organic phase obtained in the separation step (3) contains the target product, alkapoliene, but in addition to that, the acyloxyalkapolyene and the by-product [raw material] which were unreacted in the deacyloxylation step (2). (For example, when 1-acetoxy-2,7-octadene is used as a raw material, 3-acetoxy-1,7-octadene) may be mixed with the isomer of acyloxyalkapolyene used as a raw material. However, it is preferable that the organic phase does not contain a water-soluble monocarboxylic acid. Specifically, the content of the water-soluble monocarboxylic acid in the separated and obtained organic phase is determined in the deacyloxylation reaction solution. It is preferably 0 to 0.10 mol%, more preferably 0 to 0.05 mol%, still more preferably 0 to 0.01 mol% of the water-soluble monocarboxylic acid, substantially. It is particularly preferably 0 mol%. Under this condition, it is possible to avoid the formation of a high boiling point compound during the distillation of the organic phase, and it is possible to prevent the mixing of the water-soluble monocarboxylic acid into the alkapoliene. Polyenes tend to be obtained in high yield.

(Separator)
The embodiment of the separation step (3) is not particularly limited, and may be, for example, a batch type, a semi-batch type, or a continuous type. Further, the contact between the deacyloxylation reaction solution and water may be carried out in one step or in multiple steps. Further, when the deacyloxylation reaction solution is brought into contact with water, the distillate may be supplied with water, or the distillate may be supplied to the water in the container. The method may be a parallel flow type or a countercurrent type. Further, the flow of the distillate and the flow of water may be laminar flow or turbulent flow, respectively.

The separation device that can be used in the separation step (3) is not particularly limited as long as it can separate the target aqueous phase and the organic phase and can separate and obtain each of them, but for example, a stirring blade is provided. Complete mixing tank; static mixer (static mixer); non-stirring stepped extractor; stirring stepped extractor and the like. One type of separation device may be used alone, or the same type of separation device or two or more types of separation devices may be connected in series or in parallel.
A countercurrent multi-stage extractor may be used from the viewpoint of efficiently containing the water-soluble monocarboxylic acid in the aqueous phase with a small amount of water used. Further, in the present invention, the ratio of the mass concentration of the water-soluble monocarboxylic acid in the aqueous phase to the mass concentration of the water-soluble monocarboxylic acid in the organic phase after the separation operation (hereinafter, may be referred to as a partition coefficient) is sufficient. Because of its high price, a multi-stage mixer-settler in which a stationary tank is installed in a complete mixing tank or a static mixer is repeatedly connected in series can also be used. From the viewpoint that the aqueous phase having a desired water-soluble monocarboxylic acid concentration can be separately used in the esterification step (1) and the separation step (3), it is preferable to use a multi-stage mixer-settler as the separation device.

(Separation condition)
From the viewpoint of suppressing the oxidation of alkapoliene and water-soluble monocarboxylic acid, the distillate obtained in the water and deacyloxylation step (2) has oxygen gas removed by a method such as bubbling with an inert gas. Is preferable. All the operations in the separation step (3) are not particularly limited, but are preferably carried out in an inert gas atmosphere.
Needless to say, through a series of operations in the separation step (3), the temperature is carried out from above the freezing point of water to below the boiling temperature of water, but it is preferably 5 to 95 ° C. From the viewpoint of increasing the carboxylic acid concentration, 10 to 50 ° C. is more preferable, and 15 to 35 ° C. is further preferable.
Through the series of operations in the separation step (3), the pressure is not particularly limited, but it is convenient and preferable to carry out under atmospheric pressure, but it is also possible to carry out under atmospheric pressure by introducing an inert gas. it can. From the viewpoint of suppressing volatilization of water and water-soluble monocarboxylic acid and suppressing inflow of air from the outside, it is preferable to carry out at atmospheric pressure to 700 kPaA, and more preferably to carry out at 110 to 500 kPaA.
The contact time between the distillate obtained in the deacyloxylation step (2) and water is not particularly limited, but the separation and recovery rate of the water-soluble monocarboxylic acid into the aqueous phase is increased, and the water-soluble monocarboxylic acid is distributed. From the viewpoint of keeping the composition constant, 0.1 to 10 hours is preferable, and 0.2 to 5 hours is more preferable.

<Isolation step (4)>
The isolation step (4) is a step of isolating alkapoliene having a mixing ratio of the water-soluble monocarboxylic acid of 0.10% by mass or less from the organic phase separated and obtained in the separation step (3).
As a method for isolating alkapoliene, a known method for isolating an organic compound can be adopted, and although it is not particularly limited, a method for isolating by distillation is convenient and preferable. The method for isolating alkapoliene by distillation will be described in detail below.

Since the organic phase separated and obtained in the separation step (3) does not contain or hardly contains a water-soluble monocarboxylic acid, a high boiling point by-product is produced even if the organic phase is distilled. It is difficult to do so, and the yield of alkapoliene can be maintained high. Further, the mixing ratio of the water-soluble monocarboxylic acid in the obtained alkapolyene is also low, and tends to be 0.10% by mass or less. Before distillation, it is preferable to sufficiently remove the slightly mixed water-soluble monocarboxylic acid by washing with an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. , The amount of water-soluble monocarboxylic acid mixed in alkapoliene can be efficiently reduced, which leads to a reduction in the number of theoretical plates of the distillation column.
The distillation operation itself can be carried out with reference to, for example, the methods described in US Pat. No. 3,338,801 or JP-A-2016-216385.

In order to suppress the polymerization of alkapoliene during distillation, a polymerization inhibitor may be added to the organic phase before distillation. The polymerization inhibitor is not particularly limited, but for example, quinones such as hydroquinone and benzoquinone; 4-methoxyphenol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, and the like. Alkylphenol compounds such as 2-tert-butyl-4,6-dimethylphenol and p-tert-butylcatechol; amine compounds such as phenothiazine; and the like can be mentioned. As the polymerization inhibitor, one type may be used alone, or two or more types may be used in combination. Among these, 4-methoxyphenol or 2,4-di-tert-butylphenol is preferably used from the viewpoint of industrial availability.
When a polymerization inhibitor is used, the amount used is not particularly limited, but it may be 10 mol% or less with respect to alkapoliene in the organic phase, and an effect can be obtained even if it is 1 mol% or less. Even if the polymerization inhibitor is added in an amount of 10 mol% or more based on the alkapoliene in the organic phase, the effect tends to level off and cannot be said to be beneficial.

Further, the purity of alkapoliene can be further increased by adding a solvent to the organic phase and then distilling.
Examples of such a solvent include saturated aliphatic hydrocarbons such as butane, isobutane, n-pentane, isopentane, 2,2,4-trimethylpentane, hexane, n-heptane, isoheptane, n-octane, isooctane, nonane and decane. Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, methylcycloheptane; dimethyl ether, methyl ethyl ether, diethyl ether, ethyl-n-propyl ether, din-propyl ether, n- Acyclic monoethers such as butyl methyl ether, tert-butyl methyl ether, din-butyl ether, din-octyl ether, ethylphenyl ether, diphenyl ether; 1,2-dimethoxyethane, 1,2-diethoxyethane, 1, 2-Diisopropoxyetane, 1,2-dibutoxyethane, 1,2-diphenoxyethane, 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2-diphenoxypropane, 1,3- Acyclic diethers such as dimethoxypropane, 1,3-diethoxypropane, 1,3-diisopropoxypropane, 1,3-dibutoxypropane, 1,3-diphenoxypropane, cyclopentylmethyl ethers; tetrahydrofuran, tetrahydropyran, Cyclic ethers such as 1,4-dioxane and 2-methyl tetrahydrofuran; and the like. The solvent can be used as long as it is a solvent that does not mix with the alkapolyene fraction, or a solvent that does not affect the polymerization for use even if it is mixed. One type of solvent may be used alone, or two or more types may be used in combination, but it is preferable to use one type alone from the viewpoint of simplifying the solvent recovery operation.
When a solvent is used, the amount used is not particularly limited, but from the viewpoint of effectively increasing the purity of alkapolyene, it is preferably 50% by mass or less with respect to the content of alkapoliene in the organic phase. From the viewpoint of increasing the volumetric efficiency, it is more preferably 25% by mass or less.
In addition, when a nitrile compound such as water or acetonitrile is added to the organic phase, the effect of further increasing the purity of alkapoliene can be obtained.

(Isolator-Distillation device)
The type of distillation operation in the isolation step (4) is not particularly limited, and may be, for example, a batch type, a semi-batch type, or a continuous type. Examples of the distillation apparatus include a shelf ridge and a filling tower. One type of distillation apparatus may be used alone, or the same type of distillation apparatus or two or more types of distillation apparatus may be connected in series or in parallel.
The distillation apparatus also includes a reflux condenser for condensing the distilled gas component and a stationary tank for receiving the condensed solution. From the viewpoint of promoting the distillation of alkapoliene, an exhaust pump for reducing the pressure in the reactor may be attached to a reflux condenser or a stationary tank.
Due to the high purity of alkapoliene in the organic phase to be subjected to distillation, alkapoliene can be sufficiently separated and purified by using one distillation column such as a filling column or a shelf column alone. The number of theoretical plates of the distillation column is preferably 2 to 100, more preferably 4 to 50. The reflux ratio is preferably 1 to 100, more preferably 5 to 50. With such a distillation column, high-purity alkapoliene can be obtained with a high distillation yield while suppressing polymerization.

(Distillation conditions)
From the viewpoint of suppressing the oxidation of alkapoliene to be obtained, it is preferable that the organic phase to be distilled has oxygen gas removed by a method such as bubbling with an inert gas.
From the viewpoint of suppressing polymerization due to retention of alkapoliene in the distillation column, it is preferable to quickly discharge alkapoliene to the outside of the distillation column. Since the discharge of alkapoliene can be promoted by increasing the amount of gas distilled from the distillation column introduced into the reflux condenser, even if the inert gas is aerated from the bottom of the distillation column to the reflux condenser or a stationary tank. Good.
Alkapoliene, for example 1,3,7-octatriene, has a boiling point of 125 ° C. at atmospheric pressure, and can be distilled even if the liquid temperature is lower than 150 ° C. when passing through an inert gas, but the inert gas. From the viewpoint of reducing the amount of gas used and improving the distillation yield, it is preferable to distill at less than atmospheric pressure. The distillation temperature is preferably 50 to 130 ° C, more preferably 70 to 120 ° C. The distillation pressure is preferably 5 to 100 kPaA, more preferably 10 to 80 kPaA. Under these distillation conditions, the polymerization of alkapoliene can be suppressed while the amount of the inert gas used is small, and the distillation yield of the target alkapolyene is 90 mol% or more, further 94 mol% or more. Can be done.

<Recovery and reuse process (5)>
In the recovery and reuse step (5), first, a water-soluble monocarboxylic acid is extracted from the aqueous phase separated and obtained in the separation step (3) with an allyl alcohol compound substituted with an alkenyl group. Then, at least one part of the mixed solution (X) containing the allyl alcohol compound substituted with the alkenyl group thus obtained and the water-soluble monocarboxylic acid (preferably 50% by mass or more of the mixed solution (X), more preferably 65. The allyl alcohol compound in which the alkenyl group in the esterification step (1) is substituted in an amount of mass% or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably substantially 100% by mass). This step is used as a source of the water-soluble monocarboxylic acid.
In the method for producing an alkapoliene of the present invention, the present recovery and reuse step (5) can be carried out when the esterification step (1) is carried out by any of a batch type, a semi-batch type or a continuous type. It is possible, and in particular, when the esterification step (1) is carried out continuously, it is not necessary to store the aqueous phase or the mixed solution (X) separated and obtained in the separation step (3). Industrially preferred.

In the present invention, the water-soluble monocarboxylic acid produced as a by-product in the deacyloxylation step (2) can be reused for the production of alkapoliene by the present recovery and reuse step (5), so that the alkapoliene can be reused while suppressing the production cost. It is advantageous in that it can be manufactured industrially. Further, although the mixed solution (X) used for reuse in the present recovery and reuse step (5) tends to contain 25% by mass or less of water, the content thereof is the separation step (3). Since the amount is significantly smaller than that of the aqueous phase separated and obtained in the above-mentioned separation step (3), the aqueous phase separated and obtained in the above-mentioned separation step (3) is esterified rather than being used as a source of the water-soluble monocarboxylic acid in the above-mentioned esterification step (1). The step (1) can be carried out efficiently. From this viewpoint, the content of water in the mixed solution (X) is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 13% by mass or less. The lower limit of the content of water in the mixture (X) is not particularly limited, but tends to be 3% by mass or more, and in some cases, 5% by mass or more or 8% by mass or more.
Alkapoliene may be mixed in the mixed solution (X), but the content thereof usually tends to be 3% by mass or less, and is often 1% by mass or less.
If necessary, the aqueous phase separated and obtained in the separation step (3) may be concentrated by a distillation means such as simple distillation or vacuum distillation, and then contacted with an allyl alcohol compound substituted with an alkenyl group.

The content of the allyl alcohol compound substituted with the alkenyl group in the mixed solution (X) is not particularly limited, but from the viewpoint of ease of operation control of the esterification step (1), the mixed solution ( It is preferably 0.5 to 3.5 mol, more preferably 0.8 to 2.5 mol, and 1.2 to 2.2 mol with respect to 1 mol of the water-soluble monocarboxylic acid in X). It is more preferably mol.
The content of the allyl alcohol compound substituted with the alkenyl group in the mixed solution (X) is not particularly limited in the above range, but is in contact with the aqueous phase separated and obtained in the separation step (3). The amount of the allyl alcohol compound substituted with the alkenyl group to be subjected to is preferably 50 to 350 parts by mass, more preferably 80 to 300 parts by mass, and 100 to 250 parts by mass with respect to 100 parts by mass of the aqueous phase. It is more preferably 100 to 200 parts by mass, and most preferably 100 to 200 parts by mass.

In the operation of extracting the water-soluble monocarboxylic acid from the aqueous phase separated and obtained in the separation step (3) with the allyl alcohol compound in which the alkenyl group is substituted, the water-soluble monocarboxylic acid may remain in the aqueous phase. The aqueous phase in which the water-soluble monocarboxylic acid remains may be mixed with water to be brought into contact with the deacyloxylation reaction solution in the [i] separation step (3), or [ii] the water-soluble monocarboxylic acid may be used. After the acid and water are separated by a known method to isolate the water-soluble monocarboxylic acid, the isolated water-soluble monocarboxylic acid may be stored, if necessary, or the esterification step (1). It may be reused as a raw material of, [iii] after concentration, it may be recovered and reused as a raw material of the esterification step (1), [iv] it may be discarded, and [v] the above. It may be used for other purposes other than.

The contact between the aqueous phase separated and obtained in the separation step (3) and the allyl alcohol compound substituted with the alkenyl group may be carried out in one step or in multiple steps. Further, a method of supplying the allyl alcohol compound substituted with an alkenyl group to the aqueous phase in the container, a method of supplying the aqueous phase to the allyl alcohol compound substituted with an alkenyl group in the container, or a contact method may be used. May be a parallel flow type or a countercurrent type. Further, the flow of the aqueous phase and the flow of the allyl alcohol compound substituted with the alkenyl group may be laminar flow or turbulent flow, respectively.

After contacting the aqueous phase separated and obtained in the separation step (3) with the allyl alcohol compound substituted with the alkenyl group, the aqueous phase and the allyl alcohol compound substituted with the alkenyl group are preferably stirred and then allowed to stand. It is divided into an organic phase containing (the organic phase corresponds to the mixed solution (X)). As described above, the organic phase (mixed solution (X)) contains a water-soluble monocarboxylic acid. The aqueous phase and the organic phase are separated by a separation device or the like, and at least one part of the organic phase (mixed solution (X)) is used as a source of raw materials for the esterification step (1).
The separation device that can be used here is not particularly limited as long as it is a device that can separate and acquire the aqueous phase and the organic phase, but for example, a complete mixing tank equipped with a stirring blade; a static mixer. (Static type mixer); Non-stirring type step type extractor; Stirring type step type extractor and the like. One type of separation device may be used alone, or the same type of separation device or two or more types of separation devices may be connected in series or in parallel.
Further, in the present invention, from the viewpoint that the mixed solution (X) having a desired mass concentration of the water-soluble monocarboxylic acid can be separately used in the esterification step (1) and the separation step (3), the separation apparatus can be used. As a result, it is preferable to use a multi-stage mixer.

Needless to say, through a series of operations in the contact between the aqueous phase separated and obtained in the separation step (3) and the allyl alcohol compound substituted with the alkenyl group and the separation into the aqueous phase and the organic phase, the temperature is water from above the freezing point of water. Although it is carried out at the boiling temperature of 5 to 95 ° C., 10 to 50 ° C. is more preferable, and 15 to 35 ° C. is more preferable from the viewpoint of increasing the partition coefficient and increasing the concentration of the water-soluble monocarboxylic acid in the organic phase. More preferred.
Through the series of operations in the separation, the pressure is not particularly limited, but it is convenient and preferable to carry out under atmospheric pressure, but it can also be carried out under atmospheric pressure by introducing an inert gas. From the viewpoint of suppressing the volatilization of water, the allyl alcohol compound substituted with the alkenyl group, and the water-soluble monocarboxylic acid, and suppressing the inflow of the atmosphere from the outside, it is preferable to carry out at atmospheric pressure to 700 kPaA, at 110 to 500 kPaA. It is more preferable to carry out.
The contact time between the aqueous phase separated and obtained in the separation step (3) and the allyl alcohol compound (organic phase) substituted with the alkenyl group is not particularly limited, but the extraction rate of the water-soluble monocarboxylic acid into the organic phase is increased. From the viewpoint, 0.1 to 10 hours is preferable, and 0.2 to 5 hours is more preferable.

(Impurities that alkapoliene can contain)
By the way, according to the investigation by the present inventors, it has been found that the alkapoliene obtained by the conventional production method may contain at least one impurity selected from the group consisting of peroxides and their decomposition products. .. The alkapoliene obtained by the production method of the present invention has a low content of at least one impurity selected from the group consisting of peroxides and decomposition products thereof. Specifically, the total content of impurities in the alkapoliene obtained by the production method of the present invention can be 0.30 mmol / kg or less, 0.15 mmol / kg or less, and 0. It can be 10 mmol / kg or less (provided that one of the peroxide and its decomposition products is 0 mmol / kg).

For example, when the alkapoliene is 1,3,7-octatriene, the peroxides include 5-hydroperoxy-1,3,7-octatriene and 6-hydroperoxy-1,3,7-octatriene. And so on. Examples of the decomposition product of the peroxide include compounds that can be produced by decomposing 5-hydroperoxy-1,3,7-octatriene or 6-hydroperoxy-1,3,7-octatriene. Specifically, 5-hydroxy-1,3,7-octatriene, 6-hydroxy-1,3,7-octatriene and the like can be mentioned. These are compounds that can be produced by oxygen oxidation of 1,3,7-octatriene. Among these, peroxides and their decomposition products include, in particular, 5-hydroperoxy-1,3,7-octatriene, 6-hydroperoxy-1,3,7-octatriene, 5-hydroxy-1, 3,7-Octatriene and 6-hydroxy-1,3,7-octatriene are important compounds. If such impurities are contained, it may have an adverse effect depending on the use of alkapoliene. Therefore, it is preferable that the content of the impurities is small. For example, when an alkapolyene such as 1,3,7-octatriene is subjected to a polymerization reaction, the above-mentioned impurities may have an adverse effect such as inhibiting the polymerization reaction.
Here, the total content of the above impurities in the alkapoliene is a value obtained by titrating iodine (I ₂ ) generated by allowing potassium iodide to act on the alkapoliene with sodium thiosulfate.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, the chemical solution used was one in which the dissolved gas was replaced with an inert gas and the antioxidant and water were removed.
As 2,7-octadien-1-ol, those manufactured by Kuraray Co., Ltd. were used.

The following abbreviations described in each of the examples described below refer to the following compounds.
ODA: 2,7-Octadiene-1-ol MICK: Methyl isopropylketone ODAAc: 1-acetoxy-2,7-octadien IODAAc: 3-acetoxy-1,7-octadien

The analysis method and calculation method used in each example will be described in detail below.
<[1] Analysis of components contained in the esterification reaction solution A, A', the esterification distillate A, A', or the deacyloxylation reaction solution A>
The components contained in the esterification reaction solutions A and A', the esterification distillate A and A', and the deacyloxylation reaction solution A obtained in each example were analyzed according to the following methods.
To 0.50 g of esterification reaction solution A, A', esterification distillate A, A', or deacyloxylation reaction solution A, 0.50 g of triethylene glycol dimethyl ether and 0.20 g of diethylene glycol dimethyl ether are added and mixed. Obtained liquid. Using the mixed solution, the following gas chromatography measurement conditions I were applied to the esterification reaction solutions A and A'and the esterification distillates A and A', and the following gas chromatography measurement conditions were applied to the deacyloxylation reaction solution A. It was analyzed by gas chromatography according to II, and the concentration of each component was calculated from the area ratio with respect to the internal standard substance diethylene glycol dimethyl ether according to the following formula 1.
In the analysis of the esterification reaction solutions A and A'and the esterification distillates A and A', MIPC was used for the holding time of about 2.2 minutes, acetic acid was used for the holding time of about 5.0 minutes, and the holding time was about 7.5. Peaks of ODAAc can be observed at about 8.3 minutes and ODA at about 10.3 minutes, diethylene glycol dimethyl ether at about 3.7 minutes, and triethylene glycol dimethyl ether at about 11.9 minutes.
In the analysis of the deacyloxylation reaction solution A, total octatriene was used for the holding time of about 2.3 to 3.0 minutes, IODAac was used for the holding time of about 10.7 minutes, acetic acid was used for the holding time of about 11.7 minutes, and the holding time was about 11.7 minutes. Peaks of ODAAc can be observed at about 16.7 minutes and 17.5 minutes, diethylene glycol dimethyl ether at a retention time of about 6.9 minutes, and triethylene glycol dimethyl ether at a retention time of about 20.6 minutes.
The water content was measured with a Karl Fischer titer under the measurement conditions described below.

(Gas Chromatography Measurement Condition I)
Equipment: GC-2025 manufactured by Shimadzu Corporation
Column: DB-Wax manufactured by Agilent Technologies, Inc. (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm)
Carrier gas: Helium (100 kPaG) was circulated at a flow rate of 0.91 mL / min.
Sample injection volume: 0.1 μL of the drug solution was injected at a split ratio of 20/1.
Detector: Hydrogen flame ionization detector (FID)
Detector temperature: 250 ° C
Vaporization chamber temperature: 250 ° C
Temperature rise conditions: The temperature was maintained at 120 ° C. for 8 minutes, the temperature was raised to 220 ° C. at 10 ° C./min, and the temperature was maintained for 3 minutes.
It should be noted that G of the above kPaG indicates that it is a gauge pressure, and the same applies hereinafter.

(Gas Chromatography Measurement Condition II)
Equipment: GC-2025 manufactured by Shimadzu Corporation
Column: DB-Wax manufactured by Agilent Technologies, Inc. (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm)
Carrier gas: Helium (100 kPaG) was circulated at a flow rate of 1.04 mL / min.
Sample injection volume: 0.1 μL of the drug solution was injected at a split ratio of 50/1.
Detector: FID
Detector temperature: 250 ° C
Vaporization chamber temperature: 250 ° C
Heating conditions: The temperature was maintained at 90 ° C. for 13 minutes, the temperature was raised to 220 ° C. at 10 ° C./min, and the temperature was maintained for 3 minutes.

(Measurement condition of water content)
Equipment: Karl Fischer Moisture Analyzer manufactured by Mitsubishi Chemical Analytech Co., Ltd., CA-200 type (desktop coulometric moisture meter)
Anode solution: Aquamicron AKX manufactured by Mitsubishi Chemical Corporation
Cathode solution: Aquamicron CXU manufactured by Mitsubishi Chemical Corporation
Sample injection amount: 1 g of the drug solution was injected.

<[2] Purity of 1,3,7-octatorien>
The purity of 1,3,7-octatriene was analyzed by gas chromatography according to the following gas chromatography measurement condition III, and the percentage of the peak area of 1,3,7-octatorien to the peak area of all octatriene was determined. This value was taken as the purity of 1,3,7-octatriene.
The peaks of all octatrienes can be observed at the retention time of about 5.0 to 14.0 minutes, and the peaks of 1,3,7-octatorien can be observed at the retention times of about 9.2 minutes and 9.4 minutes.
(Gas Chromatography Measurement Condition III)
Equipment: GC-2010Plus manufactured by Shimadzu Corporation
Column: Rxi-5ms manufactured by Restek Corporation (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm)
Carrier gas: Helium (100 kPaG) was circulated at a flow rate of 1.33 mL / min.
Sample injection volume: 0.1 μL of the drug solution was injected at a split ratio of 100/1.
Detector: FID
Detector temperature: 280 ° C
Vaporization chamber temperature: 280 ° C
Heating conditions: The temperature was maintained at 40 ° C. for 10 minutes, the temperature was raised to 250 ° C. at 20 ° C./min, and the temperature was maintained for 5 minutes.

<[3] Analysis of components contained in organic phase A, distillation raw material A, distillation purified product A, and recovery liquid A>
The organic phase A obtained in the separation step (3A) described later, the distillation raw material A obtained by washing the organic phase A with an aqueous sodium hydroxide solution in the isolation step (4A) described later, and the distillation raw material A distilled. The distilled purified product A and the recovered liquid A obtained in the recovery and reuse step (5A) described later were analyzed by gas chromatography according to the gas chromatography measurement conditions II and III. The purity of 1,3,7-octatriene was determined as described in [2] above, and the composition of the contained components was determined as described in [1] above.

<[4] Analysis of components contained in aqueous phase A>
The aqueous phase A obtained in the separation step (3A) described later was analyzed by gas chromatography according to the gas chromatography measurement condition I. The composition of the contained components was determined as described in [1] above.

<[5] Esterification rate in the esterification step (1A)>
The esterification rate in the esterification step (1A) described later was calculated according to the following formula 2.

<[6] Acetic acid recovery rate in esterification step (1A)>
In the esterification step (1A) described later, it was investigated how much acetic acid not used in the reaction could be recovered. From the content of acetic acid in the esterification distillates A and A'in the esterification step (1A), the recovery rate of acetic acid was determined according to the following formula 3.
The number of moles of unreacted acetic acid in the following formula 3 corresponds to the number of moles of acetic acid used in the esterification step (1A) minus the number of moles of ODAAc produced.

<[7] Recovery rate of organic solvent in esterification step (1A)>
In order to investigate how much the organic solvent could be recovered in the esterification step (1A), the recovery rate of the organic solvent was determined according to the following formula 4.

<[8] Deacyloxylation rate in the deacyloxylation step (2A)>
The deacyloxylation rate in the deacyloxylation step (2A) was calculated according to the following formula 5.

<[9] Usage rate of water used for separation and recovery of acetic acid in the separation step (3A)>
The usage rate of the water used for the separation and recovery of acetic acid (hereinafter, may be referred to as separated water) in the separation step (3A) was calculated according to the following formula 6.

<[10] Separation and recovery rate of all octatrienes in the separation step (3A)>
The separation recovery rate of all octatrienes in the separation step (3A) was calculated according to the following formula 7.

<[11] Separation and recovery rate of acetic acid in the separation step (3A)>
The separation and recovery rate of acetic acid in the separation step (3A) was calculated according to the following formula 8.

<[12] Separation and recovery of total octatriene after washing with aqueous sodium hydroxide solution in isolation step (4A)>
In the isolation step (4A), the separation and recovery rate of all octatrienes was calculated according to the following formula 9 for the organic phase after washing with an aqueous sodium hydroxide solution.

<[13] Distillation yield of total octatriene in isolation step (4A)>
The distillation yield of all octatrienes in the isolation step (4A) was calculated according to the following formula 10.

<[14] Separation and recovery rate of acetic acid in the recovery and reuse step (5A)>
The recovery rate of acetic acid by ODA in the recovery and reuse step (5A) was calculated according to the following formula 11.

[Example 1]
(Esterification step (1A))

After replacing the inside of a 2 L glass reactor equipped with a thermometer, an electric heater, an electromagnetic induction stirrer, a chemical charging port, a gas inlet, and a Dean-Stark apparatus having a reflux condenser with argon, the reaction The vessel was charged with 542.60 g (4.300 mol) of ODA, 516.60 g (8.603 mol) of acetic acid and 309.20 g (3.590 mol) of MIPC.
After replacing the inside of the system with argon, argon was passed at 6 L / hr (ntp; normal temperature pressure) while adjusting to atmospheric pressure, and the mixture was heated at 100 rpm for 30 minutes until the liquid temperature reached 122 ° C. .. The reaction was carried out for 36 hours by controlling the temperature so that the liquid temperature was 122 ± 5 ° C., with the time when the desired liquid temperature was reached as 0 hour. Then, the internal liquid was cooled to 30 ° C. to terminate the reaction. During the reaction, water and MILPC were distilled off using a Dean-Stark apparatus, and a total of 77.10 g (4.283 mol) of water was removed from the reactor.
Next, the pressure inside the system was reduced to 12.5 kPaA, and then the internal liquid was heated to 65 ° C. Then, acetic acid, MIPC and the like were distilled off over 10 hours while raising the liquid temperature so that the distillation temperature became 50 ± 10 ° C.
716.17 g of the solution remaining in the reactor (hereinafter, this may be referred to as "esterification reaction solution A") and the distilled solution (hereinafter, this may be referred to as "esterification distillate A"). ) 546.98 g was obtained.
The components contained in the esterification reaction solution A and the esterification distillate A analyzed according to the above analysis method are as shown in Table 1 below. Table 1 also shows the esterification rate, the acetic acid recovery rate, and the organic solvent recovery rate obtained according to the above calculation method.

(Deacyloxylation step (2A))

A 300 mL glass vacuum distillation unit equipped with a filling tower with an inner diameter of 25.4 mm and a height of 240 mm filled with McMahon packing, a receiver connected via a fractional distillation head reflux condenser, a magnetic rotor and a thermometer. Got ready.
After replacing the inside of the vacuum distillation apparatus with nitrogen, 90.00 g of the esterification reaction solution A (ODAAc mass is 88.17 g, 0.524 mol), 0.610 g of palladium acetate (2.72 mmol) and triphenylphosphine 2. 900 g (11.06 mmol) was charged.
The inside of the system was depressurized to 2.7 kPaA while stirring at 200 rpm, and the internal liquid was heated to 95 ° C. Subsequently, the esterification reaction solution A was supplied at 25.00 g / hr (24.49 g / hr, 0.146 mol / hr in terms of ODAAc), and at the same time, 24.50 g of the reaction solution obtained by the deacyloxylation reaction was supplied. Distilled at / hr. The fraction (initial fraction) up to 1 hour after the start of the supply and distillation was discarded. The temperature was controlled so that the liquid temperature was 95 ± 2 ° C., with the time point of initial distillation disposal being 0 hour, and the reaction was carried out for another 24 hours. During the reaction for 24 hours, 600.0 g of the esterification reaction solution A (587.82 g, 3.494 mol in terms of ODAAc) was supplied, while a fraction of 587.88 g (hereinafter referred to as "deacyloxylation reaction solution") was supplied. (Sometimes referred to as "A") was acquired.
The components contained in the deacyloxylation reaction solution A analyzed according to the above analysis method are as shown in Table 2 below. Table 2 also shows the deacyloxylation rate and the purity of 1,3,7-octatriene obtained according to the above calculation method.

(Separation step (3A))
After replacing the inside of a 1 L glass container equipped with a thermometer, a water bath, an electromagnetic induction stirrer, a chemical solution charging port and a gas inlet, with nitrogen, the deacylated oxidization reaction solution A587.88 g and water 176.36 g are added to the container. I prepared it.
Argon was passed at 6 L / hr (ntp) while adjusting the inside of the system to atmospheric pressure, and the mixture was heated at 100 rpm for 30 minutes until the liquid temperature reached 40 ° C. Then, the temperature was controlled so that the liquid temperature was 40 ± 2 ° C., and the mixture was stirred for 1 hour. Then, the internal liquid was allowed to stand at room temperature (20 to 25 ° C.) to separate the organic phase (sometimes referred to as organic phase A) and the aqueous phase (sometimes referred to as aqueous phase A). The usage rate of the separated water used for recovering acetic acid was 0.30 when calculated according to the above calculation method.
In this way, 397.22 g of organic phase A and 367.00 g of aqueous phase A were obtained. Table 3 below shows the components contained in the organic phase A and the aqueous phase A analyzed according to the analysis method. Table 3 also shows the separation and recovery rate of all octatriene, the purity of 1,3,7-octatriene, and the separation and recovery rate of acetic acid obtained according to the above calculation method.

(Isolation step (4A))
-Washing with alkaline aqueous solution-
200 g of a 10 mass% sodium hydroxide aqueous solution was brought into contact with 397.22 g of the organic phase A, and only the aqueous phase was discarded. 15 g of molecular sieves was added to the organic phase for dehydration to obtain 371.26 g of a raw material for distillation (hereinafter, this may be referred to as "distillation raw material A"). The distillation raw material A was analyzed according to the above analysis method. The mixing ratio of acetic acid was 0% by mass. The results are shown in Table 4.
Further, according to the above method, the separation recovery rate of all octatrienes and the purity of 1,3,7-octatriene were determined. The results are also shown in Table 4.

-Distillation-
A 1,000 mL glass vacuum distillation unit equipped with a filling tower with an inner diameter of 25.4 mm and a height of 240 mm filled with McMahon packing, a receiver connected via a fractional distillation head reflux condenser, a magnetic rotor and a thermometer. The distillation raw material A was distilled according to the following method.
First, the inside of the distillation apparatus was replaced with nitrogen, and 371.26 g of the distillation raw material A was charged. Then, the inside of the system is depressurized to 25 ± 2 kPaA while stirring at 100 rpm, and the mixture is heated until the internal liquid reaches 85 ± 2 ° C. and a fraction (hereinafter, this may be referred to as “distilled purified product A”) 357. .35 g was obtained. Distilled purified product A was analyzed according to the above analysis method. The results are shown in Table 4.
In addition, the distillation yield was determined according to the above method. The results are also shown in Table 4.

(Recovery and reuse process (5A))
-Recovery and reuse step (5A); Recovery of acetic acid The recovery liquid A obtained by extracting acetic acid from the aqueous phase obtained in the separation step (3A) by ODA was obtained as follows, and the recovery liquid A was esterified. It was used as a source of raw materials (ODA and acetic acid) in step (1A).
Specifically, after replacing the inside of a 1 L glass container provided with a thermometer, a water bath, an electromagnetic induction stirrer, a chemical liquid charging port and a gas introduction port with nitrogen, the aqueous phase A367.00 g and ODA542.60 g are added to the container. Was prepared.
Argon was passed at 6 L / hr (ntp) while adjusting the inside of the system to atmospheric pressure, and the mixture was heated at 100 rpm for 30 minutes until the liquid temperature reached 40 ° C. Then, the mixture was stirred for 1 hour while controlling the liquid temperature to 40 ± 2 ° C. Next, the internal liquid is cooled to room temperature (20 to 25 ° C.) and then allowed to stand, and the organic phase (recovery liquid A; corresponding to the above-mentioned mixed liquid (X)) and the aqueous phase are phase-separated. The recovered liquid A794.13 g was obtained.
The components contained in the recovered solution A analyzed according to the analysis method are shown in Table 5 below. Table 5 also shows the recovery rate of acetic acid obtained according to the above calculation method.

-Recovery and reuse step (5A); reuse in esterification step (1A) In the esterification step (1A), "ODA 542.60 g (4.300 mol), acetic acid 516.60 g (8.603 mol) and Instead of charging 309.20 g (3.590 mol) of MIPC, 794.13 g of the recovered liquid A74.13 g, 100.64 g of acetic acid, 16.45 g of MIPC and 546.98 g of the esterified distillate obtained above were charged. As a result, the composition of the charged chemical solution was 541.53 g (4.291 mol, 37.14% by mass) of ODA, 514.73 g (8.572 mol, 35.30% by mass) of acetic acid, and 304.12 g (3.531 mol, 20.86) of MIPC. Mass%), total octatriene was 3.216 g (0.030 mol, 0.22 mass%) and water was 94.60 g (6.49 mass%).
Then, the same operation as in the esterification step (1A) was carried out except that 171.30 g of water was removed from the reactor using a Dean-Stark apparatus during the reaction for 45 hours.
715.51 g of the solution remaining in the reactor (hereinafter, this may be referred to as "esterification reaction solution A'") and the distilled solution (hereinafter, this may be referred to as "esterification distillate A'"). There is) 536.24 g was obtained.
The components contained in the esterification reaction solution A'and the esterification distillate A'analyzed according to the above analysis method are as shown in Table 6 below. Table 6 also shows the esterification rate, the acetic acid recovery rate, and the organic solvent recovery rate obtained according to the above calculation method.

Subsequently, in the same operation as described above, 1,3,7-octatriene having a purity of 99.41% was obtained through a deacyloxylation step (2A), a separation step (3A) and an isolation step (4A).

According to Example 1, the deacyloxylation reaction solution was obtained through the esterification step (1A) and the deacyloxylation step (2A), and the reaction solution was separated in the separation step (3A). By contacting with water at No. 30, 89.73 mol% of acetic acid produced in the deacyloxylation reaction could be recovered in the aqueous phase. On the other hand, by washing the organic phase obtained in the separation step (3A) with an aqueous solution of sodium hydroxide and then performing simple distillation (isolation step (4A)), the formation of a high boiling point compound was not confirmed, and the purity was 99. 41% of 1,3,7-octatriene could be obtained with a distillation yield of 96.98 mol%.
Further, acetic acid was extracted from the aqueous phase recovered in the separation step (3A) by ODA, and the obtained recovery liquid A was used again in the esterification reaction step (1A) (recovery and reuse step (5A)). The same reaction results as when water was not contained in the raw material could be achieved, and the aqueous phase containing the acetic acid aqueous solution recovered in the separation step (3A) did not need to be discarded and could be effectively used in this reaction.

[Comparative Example 1] When total octatriene is distilled in the presence of acetic acid (distillation of an equimolar mixture of total octatriene and acetic acid)
As the total octatriene, 1,3,7-octatorien having a purity of 98.7% was used. 1202.85 g of a distillation raw material consisting of 773.49 g (7.15 mol, 64.30 mass%) of the total octatriene and 429.36 g (7.150 mol, 35.70 mass%) of acetic acid was prepared, and Sulzer Laboratory Packing EX was prepared. It was charged into a filled distillation apparatus (inner diameter 22.00 mm, height 1,200 mm, theoretical plate number 60). Distilled at a reflux ratio of 10 for 5 hours while heating so that the liquid temperature becomes 113 ± 2 ° C. under atmospheric pressure, and 35.50 g (0.328 mol, 43.49% by mass) of total octatriene and 46.13 g of acetic acid. 81.63 g of a fraction (distillation temperature 97 to 110 ° C.) composed of (1.292 mol, 56.51% by mass) was obtained. Subsequently, the reflux ratio was changed to 50 and distilled for 5 hours to obtain 10.00 g (0.092 mol, 42.78% by mass) of total octatriene and 13.38 g (0.223 mol, 57.22% by mass) of acetic acid. 23.38 g of a fraction (distillation temperature 97 to 110 ° C.) consisting of the above was obtained. A total fraction of 105.00 g consisting of 45.50 g (0.421 mol, 43.33 mass%) of total octatriene and 59.50 g (1.515 mol, 56.67 mass%) of acetic acid was obtained.
On the other hand, the undistilled matter remaining in the distillation apparatus was 656.63 g (6.070 mol, 59.81 mass%) of total octatriene and 369.86 g (6.159 mol, 33.69 mass%) of acetic acid, which are high boiling point compounds. It was 71.36 g (6.50% by mass). The amount of the high boiling point compound produced was 9.23% by mass based on 773.49 g of the total octatriene charged in the distillation operation.
In this way, when distillation is performed to separate acetic acid and total octatriene, not only the two cannot be completely separated, but also a high boiling point compound is produced, and the yield of total octatriene decreases. I found out.

[Reference Example 1] Follow-up test and investigation of the method described in Patent Document 3 (distillation after adding water to an equimolar mixture of total octatriene and acetic acid)
As the total octatriene, 1,3,7-octatorien having a purity of 98.7% was used. The total octatriene 530.08 g (4.900 mol, 50.34% by mass), acetic acid 294.25 g (4.900 mol, 27.94% by mass) and water 228.79 g (12.70 mol, 21.73% by mass). 1053.12 g of a distillation raw material made of the above material was prepared and charged into a distillation apparatus (inner diameter 22.00 mm, height 1,200 mm, theoretical plate number 60) filled with Sulzer Laboratory Packing EX. After the inside of the system is set to 50 ± 2 kPaA, the mixture is distilled at a reflux ratio of 3 for 10 hours while heating so that the liquid temperature becomes 78 ± 2 ° C. 671.86 g of a distillate (distillation temperature 71 ± 2 ° C.) was obtained. Here, the organic phase 513.86 g was 512.54 g (4.738 mol, 99.74 mass%) of total octatriene and 1.32 g (0.022 mol, 0.26 mass%) of acetic acid. The aqueous phase of 158.00 g was 14.90 g of acetic acid (0.248 mol, 9.43% by mass) and 143.10 g of water (7.943 mol, 90.57% by mass).
On the other hand, in the distillation apparatus, 278.03 g of acetic acid (4.630 mol, 72.92 mass%), 85.69 g of water (4.757 mol, 22.48 mass%), and 17.54 g of high boiling point compound (4.60 mass%). 381.26 g of a liquid consisting of (% by mass) remained. The amount of the high boiling point compound produced was 3.31% by mass based on 530.08 g of the total octatriene charged in the distillation operation.
In this way, by mixing water when separating acetic acid and all octatriene, it became easier to separate all octatriene and acetic acid, but acetic acid was slightly mixed in all octatriene, and 1, It can be said that there is room for further improvement in the purity of 3,7-octatriene. Further, although the amount was smaller than that of Comparative Example 1, the formation of a high boiling point compound was also confirmed, so that it can be said that there is room for improvement in the yield of 1,3,7-octatriene.

The present invention is useful as a method for producing an alkapolyene such as 1,3,7-octatriene. Alkapolienes such as 1,3,7-octatriene obtained by the present invention can be used as raw materials for adhesives and lubricants, and as raw materials for various functional materials (for example, lubricants and modifiers for various rubbers). It is useful as such.

Claims (11)

A method for producing an alkapolyene, which comprises the following steps (1) to (5).
(1) An esterification step in which an allyl alcohol compound substituted with an alkenyl group and a water-soluble monocarboxylic acid are reacted while distilling off by-produced water to obtain acyloxyalcopolyene.
(2) A deacyloxylation step of deacyloxylating the acyloxyalkapolyene obtained in the esterification step to obtain a distillate containing a mixture of the alkapoliene and a water-soluble monocarboxylic acid.
(3) Water is brought into contact with the distillate obtained in the deacyloxylation step to separate the distillate into two phases, an organic phase containing alkapolyene and an aqueous phase containing a water-soluble monocarboxylic acid, and then the above. A separation step of separating and acquiring the organic phase and the aqueous phase, respectively.
(4) A step of isolating an alkapolyene having a water-soluble monocarboxylic acid mixing ratio of 0.10% by mass or less from the organic phase separated and obtained in the separation step.
(5) A water-soluble monocarboxylic acid is extracted from the aqueous phase separated and obtained in the separation step with an alkenyl group-substituted allyl alcohol compound, and the alkenyl group-substituted allyl alcohol compound thus obtained and the water-soluble monocarboxylic acid are contained. A recovery and reuse step of using the mixed solution (X) to be used as a source of the allyl alcohol compound substituted with the alkenyl group and the water-soluble monocarboxylic acid in the esterification step. The method for producing an alkapoliene according to claim 1, wherein a high boiling point compound is produced as a by-product in the esterification step, and the acyloxyalkapolyene is subjected to a deacyloxylation step together with the high boiling point compound. The method for producing an alkapoliene according to claim 1 or 2, wherein in the esterification step, the conversion rate of the allyl alcohol compound substituted with the alkenyl group to acyloxyalcopolyene is 90 mol% or more. The method for producing an alkapolyene according to any one of claims 1 to 3, wherein the deacyloxylation step is carried out in the presence of a palladium compound and a tertiary phosphorus compound. The method for producing an alkapoliene according to any one of claims 1 to 4, wherein the conversion rate of the acyloxy alkapolyene to the alkapoliene to be subjected to the deacyloxylation step is 70 mol% or more. In the separation step, the content of the water-soluble monocarboxylic acid in the organic phase separated and obtained is 0 to 0.10 mol of the amount of the water-soluble monocarboxylic acid in the distillate obtained in the deacyloxylation step. The method for producing an alkapoliene according to any one of claims 1 to 5, which is%. Any of claims 1 to 6, wherein 40 mol% or more of the water-soluble monocarboxylic acid in the distillate obtained in the deacyloxylation step is contained in the mixed solution (X) used in the recovery and reuse step. The method for producing an alkapoliene according to item 1. The method for producing an alkapolyene according to any one of claims 1 to 7, wherein the purity of the alkapoliene isolated in the step (4) is 98.0% or more. The allyl alcohol compound substituted with the alkenyl group is at least one selected from the group consisting of 2,7-octadien-1-ol and 1,7-octadien-3-ol, and the alkapolyene is 1,. The method for producing an alkapoliene according to any one of claims 1 to 8, which is 3,7-octatriene. The method for producing an alkapolyene according to any one of claims 1 to 9, wherein the water-soluble monocarboxylic acid has 2 to 5 carbon atoms. The method for producing an alkapolyene according to any one of claims 1 to 10, wherein the water-soluble monocarboxylic acid is acetic acid or propionic acid.