JP2009291167A - Method for producing oligoalkylene carbonate and polyalkylene carbonate compounds - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an industrially excellent producing method of a low environmental burden, which swiftly obtains an oligoalkylene carbonate or polyalkylene carbonate compound in high yield by a simple operation in the presence of a small amount of hydrolase. <P>SOLUTION: The method for producing an oligoalkylene carbonate or polyalkylene carbonate compound by transesterification reaction between alkylenediol diacylate and carbonate compounds in the presence of a hydrolase (especially, lipase) is provided. In this method, owing to making the catalyst present stably without its deactivation, the new industrial production process (method) using a smaller amount of the enzyme than ever along with high reaction rate is found. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an oligoalkylene carbonate compound obtained by a reaction between an alkylene diol diacylate compound and a carbonate compound using a hydrolase, and a method for producing a polyalkylene carbonate compound.

  The oligoalkylene carbonate compound and polyalkylene carbonate compound produced by the method of the present invention are compounds useful as an excellent polymer functional material having biodegradability.

  Conventionally, an oligoalkylene carbonate compound and a polyalkylene carbonate compound are used as, for example, a base material for a sustained-release drug in the field of pharmaceuticals and cosmetics in addition to excellent biodegradability and high safety to living bodies. In addition, it is expected to be used in various fields as a polymer material such as functional and high performance organic materials.

As a method for obtaining an oligoalkylene carbonate compound or a polyalkylene carbonate compound, a method for producing a phosgene and a diol compound has been widely known for a long time. However, another production method has been desired to produce toxic phosgene while producing halogen compounds as a by-product as waste.
In recent years, a method of reacting an alkylene diol compound and a carbonate compound using an enzyme by a polymerization reaction using a hydrolase has also been reported (for example, Patent Document 1, Non-Patent Document 1, and Non-Patent Document). 2).
In many methods using these enzymes, the reaction is carried out using a large amount of enzyme. The reason is that it is generally known that in this enzyme reaction, the enzyme is easily deactivated by alcohol as a substrate or by-product alcohol compound. It has already been reported that lipase from anantarcica is inhibited by glycerol (see, for example, Patent Document 2). The document further states that secondary alcohols are preferably not included in the initial reaction mixture. Accordingly, in a polymerization reaction in which a poly (alkylene carbonate) compound is obtained from an alkylene diol compound and a carbonate compound, the raw material alkylene diol compound or the alcohol compound by-produced by the reaction becomes an enzyme denaturant. It is known that the activity is often lost and as a result, the reaction itself is stopped. Therefore, in order to sufficiently advance the reaction, it is necessary to appropriately add a large amount of enzyme to compensate for this inactivated component, but the use of such a large amount of chemicals and the method of producing waste are It was difficult to say that this was an industrially suitable production method.

JP 2000-80160 A JP-T-08-503850 Macromol. Chem. Phys. 201, 1632 (2000) Macromolecules, 40, 7934 (2007)

  An object of the present invention is to quickly obtain an oligoalkylene carbonate compound or a polyalkylene carbonate compound with good yield from an alkylene diol diacylate compound and a carbonate compound in the presence of a small amount of hydrolase by a simple operation. An object of the present invention is to provide a manufacturing method that can be industrially excellent and has a low environmental load.

As a result of intensive studies in order to solve the problems, the present inventors have found that, in the presence of a hydrolase (particularly lipase), an oligoalkylene carbonate obtained by an ester exchange reaction between an alkylene diol diacylate compound and a carbonate compound, or In the production method for obtaining a polyalkylene carbonate compound, the present invention finds a novel industrial production process that uses a smaller amount of enzyme and has a higher reaction rate than the conventional method by stably presenting the catalyst without deactivating it. It came.

That is, the subject of the present invention is the following formula (I) in the presence of a hydrolase;

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and may have a substituent. R ² represents from 1 to C atoms. 20 linear, branched or cyclic alkylene groups, or aromatic ring-containing or heterocyclic ring-containing alkylene groups, which may have a substituent)
An alkylene diol diacylate compound represented by the following formula (II);

(Wherein R ³ and R ⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, or an aryl group, and has a substituent. Is also good.)
Or formula (III);

(In the formula, R ⁶ represents a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an aromatic ring-containing or heterocyclic ring-containing alkylene group, and may have a substituent. R ⁵ and R ⁷ each independently represents an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group, and may have a substituent. Further, R ⁵ and R ⁷ may be combined to form a ring.)
And a dicarbonate compound represented by the following formula (IV):

(In the formula, R ² has the same meaning as described above, and X and Y may be the same or different from each other, and each is selected from R ¹ , OR ³ , or OR ^{4 as} defined above. N represents the degree of polymerization and represents an integer of 2 or more.)
Or formula (V);

(In the formula, X ′ and Y ′ may be the same or different from each other, and are each selected from R ¹ , OR ⁵ , or OR ^7. A and B are the same or different from each other. And one is selected from R ² and R ⁶ as defined above, and n ′ represents the degree of polymerization and represents an integer of 1 or more.)
It solves by the manufacturing method of oligoalkylene carbonate and polyalkylene carbonate compound shown by these.

According to the present invention, oligoalkylene carbonates of various combinations of alkylene groups and polyalkylenes can be produced from an alkylene diol diacylate compound and a carbonate compound in the presence of a hydrolase under mild conditions by a simple and industrially suitable method. The production of carbonate compounds became possible.
In addition, by using the alkylene diol diacylate compound according to the production method of the present invention, an alcohol compound that has a denaturing action on the enzyme is not by-produced during the reaction. The enzyme can be present stably. As a result, it became possible to carry out the polymerization reaction for a long time, and it was possible to obtain oligoalkylene carbonates and polyalkylene carbonate compounds having various degrees of polymerization.
Furthermore, the removal of the ester compound produced as a by-product in the present invention out of the reaction system is advantageous in that it has a lower boiling point than the alcohol compound produced as a by-product when a diol compound is used as a conventional raw material. Therefore, by removing the by-produced alcohol compound from the reaction system, it was found that the equilibrium of this reaction, which is a reversible reaction, moves in the direction of production of the target product, and the reaction proceeds quickly. It became possible to obtain oligoalkylene carbonate and polyalkylene carbonate compounds with a short reaction time and the use of a small amount of enzyme.

The present invention provides a hydrolase, an alkylene diol diacylate compound represented by formula (I) (compound (I)), and a carbonate compound represented by formula (II) in the presence or absence of an organic solvent. Compound (II)) is mixed to obtain an oligoalkylene carbonate or a polyalkylene carbonate compound represented by formula (IV) having an alkylene group; R ² , reaction formula [1];

(In the formula, R ¹ to R ⁴ , X, Y, and n are as defined above. Z is selected from R ³ or R ^{4 as} defined above.)
Alternatively, an alkylene diol dicarbonate compound (compound (III)) represented by the formula (III) is used instead of the compound (II), and a reaction similar to the reaction formula [1] is performed to obtain an alkylene group; R ² and Reaction formula [2] for obtaining an oligoalkylene carbonate or polyalkylene carbonate compound represented by formula (V) having R ⁶ ;

(Wherein R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , A, B, X ′, Y ′, and n ′ are as defined above. W is the same as defined above. One selected from ⁵ or R ⁷ )
It is carried out by two polymerization reactions shown by the following.
Moreover, the said polymerization reaction of this invention is performed with the following two operation methods.

(Method 1: One-pot synthesis method) Method 1 is carried out by the following two steps.
First step: For example, compound (II) is not removed while mixing with a hydrolase, compound (I), compound (II) or compound (III) by stirring or the like in the presence or absence of an organic solvent. The target compound of formula (IV) or formula (V) is removed while removing the ester compound (compound (VI)) represented by formula (VI) produced by the reaction under reduced pressure and / or heating conditions. The reaction solution containing the oligoalkylene carbonate or polyalkylene carbonate compound represented by (1) is obtained.
Second step: Subsequently, the ester compound represented by the formula (VI) generated by the reaction is removed from the reaction solution obtained in the first step under a reduced pressure and / or higher heating conditions than in the first step. A polymerization reaction is performed to synthesize the target oligoalkylene carbonate compound or polyalkylene carbonate.

(Method 2; Step Synthesis Method) Method 2 is performed by the following two steps.
First step: The same reaction conditions and reaction operations as those in Method 1 and First Step are performed, and after completion of the reaction, the objective oligoalkylene carbonate compound or polyalkylene carbonate is isolated and obtained.
Second step: In the presence or absence of an organic solvent, a hydrolase, the polyalkylene carbonate compound or oligoalkylene carbonate compound obtained in the first step, compound (II) or compound (III) are mixed, The polymerization reaction is performed under the same reaction conditions as in Method 1 and the second step, and the oligoalkylene carbonate compound or polyalkylene carbonate having a higher degree of polymerization is synthesized.

In the reaction of the present invention, the starting alkylene diol diacylate compound (compound (I)) is represented by the formula (I) in the above reaction formula.
In the formula (I), R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and may have a substituent.

In formula (I), the alkyl group in R ¹ represents a linear alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, and is a linear alkyl group Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the branched alkyl group include an isopropyl group, An isobutyl group, an amyl group, etc. are mentioned. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. These groups include various isomers.

The alkyl group in R ¹ may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom); an alkoxyl group having 1 to 4 carbon atoms such as methoxyl group, ethoxyl group, propoxyl group and butoxyl group (various isomers). Amino group; dialkylamino group (including various isomers) such as dimethylamino group, diethylamino group, dipropylamino group; cyano group; nitro group, etc., preferably fluorine atom, chlorine atom, An amino group and a dialkylamino group. One or more of these substituents may be present relative to the alkyl group.
Specific examples of the alkyl group having a substituent include 3-methylcyclobutyl group, 3-ethylcyclopentyl group, 1-fluorocyclopropyl group, 2-chlorocyclopropyl group, 3-fluorocyclobutyl group, 2-chlorocyclo Butyl group, 2-methoxycyclopropyl group, 3-aminocyclopentyl group, 4-dimethylaminocyclohexyl group, 2-chlorocyclohexyl group, 2,2-dichlorocyclohexyl group, 2-cyanocyclohexyl group, trifluoromethyl group, trichloromethyl Group, 2-trifluoroethyl group and the like.

In formula (I), examples of the aralkyl group in R ¹ include those having 1 to 6 carbon atoms such as benzyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, phenethyl group, phenylpropyl group, and phenylbutyl group. Examples thereof include an aralkyl group having 7 to 20 carbon atoms in which a phenyl group, a naphthyl group, an anthryl group, or a phenanthryl group is substituted on the alkyl group.

The aralkyl group in R ¹ may have a substituent on the aryl group or on the alkyl chain. Examples of the substituent include alkyl groups having 1 to 4 carbon atoms (including various isomers) such as methyl group, ethyl group, propyl group, and butyl group; halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine) Atoms); alkoxyl groups having 1 to 4 carbon atoms such as methoxyl group, ethoxyl group, propoxyl group and butoxyl group (including various isomers); alkylene dioxy groups having 1 to 4 carbon atoms such as methylenedioxy group Groups, phenyl groups, biphenyl groups, naphthyl groups, and nitro groups. In addition, you may have 1 or more types of these substituents with respect to the said aralkyl group.
Specific examples of the aralkyl group include 2-methylbenzyl group, 3,4-dimethylbenzyl group, 2-fluorobenzyl group, 3-chlorobenzyl group, 3,4-dichlorobenzyl group, 4-bromobenzyl group, 4- Iodobenzyl group, 4-methoxybenzyl group, 3,4-dimethoxybenzyl group, 4-isopropoxybenzyl group, 3,4-methylenedioxybenzyl group, 2-nitrobenzyl group, 2- (4-fluorophenyl) propyl Group, 1- (3-methylnaphthyl) methyl group, 2- (1,3-dimethylnaphthyl) methyl group and the like.

R ¹ is preferably a linear alkyl group having 1 to 4 carbon atoms, an isopropyl group, an isobutyl group, a cyclic alkyl group having 3 to 6 carbon atoms, a 3-methylcyclobutyl group, or 1-fluoro. Cyclopropyl group, 2-chlorocyclobutyl group, trifluoromethyl group, trifluoromethyl group, and 2-trifluoroethyl group, benzyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-phenethyl group, 2 An aralkyl group in which an aryl group is substituted on an alkyl group having 1 to 4 carbon atoms such as a phenethyl group, a 3-phenylpropyl group, or a 3-phenylbutyl group, and more preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group Group, cyclopropyl group, trifluoromethyl group, trifluoromethyl group, 2-trifluoroethyl group, benzyl group, 2 -Methylbenzyl group, 2-fluorobenzyl group, 3-chlorobenzyl group, 3,4-dichlorobenzyl group, 4-methoxybenzyl group, 3,4-dimethoxybenzyl group, 3,4-methylenedioxybenzyl group, 2 A nitrobenzyl group, a 1- (3-methylnaphthyl) methyl group, and a 2- (1,3-dimethylnaphthyl) methyl group.

In the alkylene diol diacylate compound represented by the formula (I) in the reaction formula of the present invention, R ² may have a substituent and is a linear or branched chain having 1 to 20 carbon atoms. Or a cyclic alkylene group, an aromatic ring-containing or heterocyclic ring-containing alkylene group;
Examples of the alkylene group in R ² include a saturated linear alkylene group such as a methylene group, an ethylene group, a hexamethylene group, and a dodecamethylene group; for example, a 2-butene group (formula ( VII)), 2-butyne group (formula (VIII)), 2,4-hexadiene group (formula (IX)) and other linear alkylene groups having an unsaturated bond, 2-methyl-1,3-propylene group (Formula (X)), 2,2-dimethyl-1,3-propylene group, 2-methyl-2-ethyl-1,3-propylene group (formula (XI)), 2-cyclopropyl-1,3-propylene group A saturated branched alkylene group such as a propylene group (formula (XII)), 2-cyclopentyl-1,3-propylene group; a 2-methyl-1,4-butyl-2-ene group (formula (XIII)), etc. Branched alkylene having an unsaturated bond Group, and a saturated cyclic alkylene group such as cyclobutylene group, cyclohexamethylene group (formula (XIV)); 1,4-cyclohex-2-ene group (formula (XV)), 1,4-cyclohe A cyclic alkylene group having an unsaturated bond such as oxa-2,5-diene group is shown.
In the alkylene group containing an unsaturated bond, the unsaturated bond can be formed with a carbon atom other than the terminal end of the bond. In the case of branched and cyclic alkylene groups, various isomers are included.

(The wavy line in the formula indicates a binding site with an oxygen atom. Formula (XIV) indicates that the position of the bond is not limited.)

Examples of the aromatic group or heterocyclic ring-containing alkylene group in R ² include a 1,4-bis (alkylene) phenyl group (formula (XVI)) and 1,1′-bis (alkylene) as also shown in the following formula: ) An alkylene group containing an aromatic ring such as a biphenyl group or 2,6-bis (alkylene) naphthyl group (formula (XVII)); 2,5-bis (alkylene) pyridyl group (formula (XVIII)), 1,4 -An alkylene group containing an aromatic heterocycle such as a bis (alkylene) thiophenyl group (formula (XIX)); 1,4-bis (alkylene) piperidyl group formula (XX)), 2,3-bis (alkylene) And an alkylene group containing an alicyclic heterocycle such as (epoxy group) or (formula (XXI)). In the formulas (XVI) to (XXI), L and M are each selected from a linear, branched or cyclic alkylene group containing a saturated or unsaturated bond as defined above. , M represents the number of L or M, and each represents an integer of 0 or 1 to 3, in which the total number of carbon atoms as an aromatic ring-containing or heterocyclic ring-containing alkylene group does not exceed 20. . In the aromatic ring-containing or heterocyclic ring-containing alkylene group, the aromatic ring, the heterocyclic ring, and the unsaturated bond in L and M of formula (XVI) to formula (XXI) should be formed with carbon atoms other than the bond terminal portion. In the case of branched and cyclic alkylene groups, various isomers are included.

(The wavy line in the formula represents a bonding site with an oxygen atom. L and M are each selected from a linear, branched, or cyclic saturated or unsaturated alkylene group, and l, m Represents the number of substituents L or M, and represents an integer of 0 or 1 to 3, respectively.
Among these alkylene diol diacylate compounds, those not commercially available are synthesized separately, for example, by obtaining the corresponding diol compound and acylating. Further, among the corresponding diol compounds that are not commercially available, for example, the corresponding dialdehyde compound, dicarboxylic acid compound or dicarboxylic acid ester compound is obtained and hydride reduced, or the corresponding alkylene halide compound is obtained. Separately synthesized and prepared by obtaining and hydrolyzing.

In formula (I), the alkylene group in R ² may have a substituent. Examples of the substituent include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom); alkoxyl groups having 1 to 4 carbon atoms such as methoxyl group, ethoxyl group, propoxyl group, butoxyl group (various isomers). Amino group; dialkylamino group having 1 to 3 carbon atoms such as dimethylamino group, diethylamino group, dipropylamino group (including various isomers); cyano group, nitro group, phenyl group , A naphthyl group, a biphenyl group, a vinyl group, an allyl group, a propargyl group, and the like, but the total number of carbon atoms does not exceed 20. Preferably they are a fluorine atom, a chlorine atom, an amino group, a dimethylamino group, and a diethylamino group.

  Specific examples of the alkylene group having a substituent include 2-methylpentylene group, 2-fluoropentylene group, 3-chloropentylene group, 3-methoxypentylene group, 3-aminopentylene group, 2-dimethyl. Aminopentylene group, 3-chlorohexylene group, 3,4-dichlorohexylene group, and 3-cyanohexylene group, 2-cyano-2-butene group, 2-fluoro-2-butene group, 1,4 -Bis (methylene) tetrafluorophenyl group, 1,4-bis (ethylene) -2-nitro-thiophenyl group and the like.

R ² is preferably a linear, branched or cyclic alkylene group having a saturated or unsaturated bond having 2 to 12 carbon atoms, and an aromatic or heterocyclic ring containing 4 to 20 carbon atoms. An alkylene group, more preferably a linear, branched or cyclic alkylene group having a saturated or unsaturated bond having 2 to 12 carbon atoms.

In the reaction of the present invention, the carbonate compound (compound (II)) as a raw material is represented by the formula (II) in the above reaction formula. In the formula (II), in the formula, R ³ and R ⁴ may be the same or different from each other, and each represents an alkyl group, an aralkyl group, or an aryl group having the same meaning as R ^1, and has a substituent. Also good.

In formula (II), the alkyl group and aralkyl group which may have a substituent in R ³ and R ⁴ have the same meanings as the alkyl group and aralkyl group described in R ¹ .
Aryl group in R ^3, R ⁴ are, for example, a phenyl group, a naphthyl group, an aromatic hydrocarbon group having 6 to 14 carbon atoms, such as anthryl and phenanthryl groups.
R ³ and R ⁴ are preferably straight chain having 1 to 4 carbon atoms and branched or cyclic alkyl group having 3 or 4 carbon atoms, phenyl group, naphthyl group, and benzyl group, and more preferably R ³ and R ⁴ are the same, and are a methyl group, an ethyl group, a phenyl group, and a benzyl group.

In the reaction of the present invention, the carbonate compound (compound (III)) is represented by the formula (III) in the above reaction formula. In the formula (III), R ⁶ represents a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, and an aromatic ring-containing or heterocyclic ring-containing alkylene group, and has a substituent. Also good.
The linear, branched or cyclic alkylene group of R ⁶ and the aromatic ring-containing or heterocyclic ring-containing alkylene group have the same meanings as described in R ² above.
R ⁶ is preferably a linear, branched or cyclic alkylene group having a saturated or unsaturated bond having 2 to 12 carbon atoms, and an aromatic ring-containing or heterocyclic ring having 4 to 20 carbon atoms. An alkylene group, more preferably a linear, branched or cyclic alkylene group having a saturated or unsaturated bond having 2 to 12 carbon atoms.

In formula (III), R ⁵ and R ⁷ each independently represent an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group, and having a substituent. May be. Furthermore, R ⁵ and R ⁷ may be bonded to each other to form a cyclic carbonate compound.
The alkyl group, aralkyl group, and aryl group of R ⁵ and R ^{7 have} the same meanings as described in R ³ and R ⁴ above. Moreover, as a cyclic carbonate compound, diethylene carbonate etc. are mentioned, for example.
R ⁵ and R ⁷ are preferably straight chain having 1 to 4 carbon atoms and branched or cyclic alkyl group having 3 or 4 carbon atoms, phenyl group, naphthyl group, benzyl group, and diethylene. Carbonate, more preferably, R ³ and R ⁴ are the same and are a methyl group, an ethyl group, a phenyl group, and a benzyl group.

In the production method of the present invention, an ester compound (compound (VI) or compound (VI ′)) represented by formula (VI) or formula (VI ′) is formed after the reaction. In reaction formula [1] or reaction formula [2], R ² in formula (VI) or formula (VI ′) has the same meaning as described above. Z is selected from R ³ or R ⁴ as defined above, and W is selected from R ⁵ or R ^{7 as} defined above.

In the present invention, the desired oligoalkylene carbonate compound or polyalkylene carbonate compound is represented by the formula (IV) and formula (V), respectively, in the above reaction formula.
In the formula (IV), the end groups X and Y may be the same or different from each other, and in the formula (V) each selected from R ¹ , OR ³ , or OR ^{4 as} defined above, A And B have the same meanings as R ² and R ⁶ , and the end groups X ′ and Y ′ may be the same or different from each other, and each of R ¹ , OR ⁵ , and OR ⁷ has the same meaning as described above. To be elected. n represents a polymerization degree and represents an integer of 2 or more.
Here, the terminal groups; X, Y, X ′, and Y ′ depend on the feed ratio of the raw materials and the reaction conditions, but in many cases, the acyl group having R ¹ , or OR ³ , OR ⁴ , OR ⁵ or a carbonate group having oR ^7.

  In the reaction of the present invention, if a small amount of water is present during the reaction, for example, by adding it, etc., the polymerization reaction and hydrolysis of the present invention proceed at the same time. From the reaction formula [1], an oligoalkylene carbonate compound or a polyalkylene carbonate compound represented by the following formula (XXII):

(Wherein R ² has the same meaning as described above, and X ″ is selected from R ¹ , OR ³ , OR ⁴ or O—R ² —OH as defined above. N ′ represents the degree of polymerization. Represents an integer of 1 or more.)
From the reaction formula [2], an oligoalkylene carbonate compound or a polyalkylene carbonate compound represented by the following formula (XXIII):

Wherein Y ″ is selected from R ¹ , OR ⁵ , OR ⁷ , O—R ² —OH, or O—R ⁶ —OH. A, B, and G are the same as or different from each other. And one selected from each of R ² and R ⁶ as defined above. N ′ represents the degree of polymerization and represents an integer of 1 or more.)
As above, compound (XXII) or compound (XXII) having a hydroxyl group at the terminal can be produced.
In addition, these compounds may be produced by moisture contained in the reagent or catalyst, or a trace amount of moisture mixed from outside the system.

  The amount of compound (II) and compound (III) to be used is preferably 1.0 to 10 mol, more preferably 1.05 to 5 mol, particularly preferably 1.1 to 1 mol, relative to 1 mol of compound (I). 3 moles.

  Examples of the hydrolase used in the present invention include protease, esterase, lipase, etc., but preferably isolated from pig liver-derived esterase (PLE), pig liver-derived lipase (PPL), yeast or bacteria. Lipases of possible microorganisms, more preferably lipases originating from Burkholderia cepacia (Pseudomonas cepacia), such as Amano PS (manufactured by Amano Enzyme), Candida ann Lipases originating from Candida antarctica (for example, Novozym 435 (manufactured by Novozyme), etc.), lipases originating from Rhizomucor Miehei (eg, Lipozyme RM IM (manufactured by Novozyme), etc.), Lipase TL originated from Thermomyces lanuginosus, Mucole Miehei (Muc) or Miehei) lipase (Lipase MM), particularly preferably lipase originating from Candida antarctica. In addition, these hydrolase can use a commercial item as it is as a natural form or an immobilized enzyme, and may use it individually or in mixture of 2 or more types.

The hydrolase may be used in a natural form or commercially available as an immobilized enzyme after chemical treatment or physical treatment.
As the chemical treatment or physical treatment method, for example, a hydrolase is dissolved in a buffer solution (an organic solvent may be present if necessary), and this is directly or stirred and then freeze-dried. And the like. The freeze-drying here is, for example, J.I. Am. Chem. Soc. 122 (8), 1565-1571 (2000), the aqueous solution or water-containing substance is rapidly frozen at a temperature below the freezing point, reduced to below the water vapor pressure of the frozen material, and sublimated to remove water. It is a method of drying a substance. Note that catalytic treatment (reactivity, selectivity, etc.) can be improved by the treatment.

  The amount of the hydrolase used is preferably 0.1 to 1000 mg, more preferably 1 to 200 mg, and particularly preferably 10 to 100 mg with respect to 1 g of compound (I).

The reaction of the present invention can be carried out in an organic solvent or without solvent.
The organic solvent used in the reaction of the present invention is not particularly limited as long as it does not deactivate the enzyme, but it is desirable to use a dehydrated solvent.
Examples of the organic solvent used in the reaction of the present invention include aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane and cycloheptane; benzene, toluene and Aromatic hydrocarbons such as xylene; ethers such as diethyl ether, t-butyl methyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran and 1,4-dioxane; ketones such as acetone and methyl ethyl ketone; acetonitrile, propionitrile And at least one selected from nitriles such as n-hexane, n-heptane, cyclopentane, cyclohexane, toluene, diisopropyl ether, t-butyl methyl ether, cyclopentyl methyl ether. Ether or tetrahydrofuran, more preferably n-hexane, cyclohexane, toluene, diisopropyl ether, t-butyl methyl ether, cyclopentyl methyl ether, and acetonitrile, particularly preferably cyclohexane, toluene, t-butyl methyl ether. In addition, you may use these organic solvents individually or in mixture of 2 or more types.

  The amount of the organic solvent to be used is preferably 2 to 200 mL, more preferably 5 to 50 mL, and particularly preferably 2 to 20 mL with respect to 1 g of compound (I).

  The reaction of the present invention is carried out by the two methods shown in Method 1 and Method 2 described above. In any method, it is desirable to carry out in a range that does not inactivate according to the characteristics of each enzyme used. The pH of the reaction solution is not particularly limited, but is preferably a pH value of 5 to 9, more preferably a pH value of 6 to 8.5, and particularly preferably a pH value of 6.5 to 8.

Further, this reaction is a reversible reaction, and the reaction proceeds rapidly by moving the chemical equilibrium to the product side. In addition, an ester compound (compound (VI) or compound (VI ′)) having a lower boiling point than that of alcohol produced as a by-product in the conventional method is produced as a by-product.
Therefore, in the method of the present invention, it is preferable to carry out the reaction while performing an operation for removing the ester compound.
For example, as such a method, in the reaction formula [1], R ¹ is selected from a methyl group, an ethyl group, or a propyl group, and R ³ and R ⁴ are each selected from a methyl group, an ethyl group, a propyl group, and a butyl group. In this case, the ester compound (compound (VI)) produced by the reaction has a lower boiling point than the starting carbonate compound (compound (II)). Therefore, the ester compound (compound (VI)) can be selectively removed from the reaction system by appropriately adjusting the reaction temperature and / or the degree of reduced pressure during the reaction. As a result, since the equilibrium of the reaction moves to the production system, this reaction can proceed quickly, and a polycarbonate compound represented by the higher molecular weight formula (IV) can be obtained in a shorter reaction time. Can do. The removed ester compound (compound (VI)) can be used again as a reaction solvent.

The reaction temperature of the present invention is 0 to 130 ° C, more preferably 10 to 90 ° C, particularly preferably 40 to 70 ° C.
The reaction in the first step and the second step of the method of the present invention is preferably carried out with respect to the compound (I), compound (II) or compound (III) as the starting material, preferably an ester compound (compound (VI ) Or compound (VI ′)) is a reaction temperature in consideration of pressure conditions, and more preferably, the compound (VI) or compound (VI ′) is completely removed at the end of the reaction. The reaction temperature is adjusted appropriately.

The reaction pressure in method 1 and method 2 of the present invention is not particularly limited, and can be performed under normal pressure or reduced pressure.
The reaction in the first step and the second step of the method of the present invention is preferably carried out with respect to the compound (I), compound (II) or compound (III) as the starting material, preferably an ester compound (compound (VI ) Or compound (VI ′)) can be selectively removed, and the reaction pressure is 0.13 kPa or more and less than 101.3 kPa (1 mmHg or more and less than 760 mmHg) in consideration of temperature conditions, and more preferably at the end of the reaction. The reaction is carried out while appropriately adjusting the reaction temperature such that the compound (VI) or the compound (VI ′) is completely removed.

  The method of the present invention can be carried out while analyzing the solution during the reaction using, for example, gel permeation chromatography (GPC). Therefore, by analyzing the reaction appropriately and performing, for example, adjusting the reaction time, reaction temperature, etc., a polyalkylene carbonate compound having a desired molecular weight (degree of polymerization) can also be obtained as the desired product. Moreover, the oligoalkylene carbonate compound whose molecular weight is 1000 or less can also be obtained by the same operation.

  The oligoalkylene carbonate compound or polyalkylene carbonate compound represented by formula (IV) or formula (V) obtained by the reaction of the present invention is dissolved in, for example, the reaction product obtained after the second step. In order to allow the reaction, an appropriate amount of an organic solvent having the same meaning as the organic solvent used in the reaction is added (or if dissolved in the used organic solvent, as it is), and then the enzyme or immobilized enzyme is filtered. After separation, the obtained filtrate can be obtained by removing the organic solvent under reduced pressure.

  The production apparatus of the present invention is not particularly limited, and can be performed by a general production apparatus such as a reaction vessel or a heating (cooling) apparatus. Furthermore, in order to remove the ester compounds (compound (VI) and compound (VI ′)) from the reaction vessel, it is preferable to provide, for example, a distillation apparatus, a distillate recovery apparatus, etc., and an apparatus capable of adjusting the reaction pressure. It is more preferable to use the provided manufacturing apparatus. Moreover, compound (VI) and / or compound (VI ') can be used again for reaction among the distillate collect | recovered by the collection | recovery apparatus.

  The obtained oligoalkylene carbonate compound and polyalkylene carbonate compound (compound (IV) or compound (V)) are obtained by a general method such as crystallization, recrystallization, liquid separation, extraction, and column chromatography. Further purification is also possible.

  Since the oligoalkylene carbonate compound and the polyalkylene carbonate compound (compound (IV) or compound (V)) obtained by the method of the present invention have a weight average molecular weight of 1,000 or more and a dispersity of 3.0 or less, It is easy to mold as a polymer material. Moreover, it is a chemically safer product in that it does not contain a halogen compound as compared with the conventional method using phosgene. Moreover, since it has a biodegradable element, it is also a polymer material with little environmental load.

Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto. In addition to the IR, NMR spectrum analysis, etc., the obtained target product was obtained by using gel permeation chromatography (GPC; column used; TSK gel G2000H _XL (manufactured by TOSOH) and GPC KF-804L (manufactured by Shodex)). The molecular weight was measured.

Example 1 (Synthesis of polyhexamethylene carbonate)
In a glass reaction vessel equipped with a Dean-Stark distillation device, a pressure adjustment device, a temperature adjustment device, a thermometer, a dropping device and a stirring measure, 50.00 g (0.25 mol) of 1,6-hexanediol diacetate and dimethyl carbonate 22 2.27 g (0.25 mol) was mixed, and 2.50 g of lipase derived from Candida antarctica (Novozym 435 (trade name); manufactured by Novozyme) was added while maintaining the temperature at 30 ° C. The reaction was allowed to stir for 6 hours. Next, 22.27 g (0.25 mol) of dimethyl carbonate was added to the resulting mixture, and the mixture was allowed to react with stirring at 50 ° C. for 48 hours. Then, the reaction was carried out by stirring at 70 ° C. for 32 hours (the pH at this time was measured with a pH meter, indicating pH = 8.5).
After completion of the reaction, 200 mL of acetonitrile was added to the obtained reaction solution, and after filtration, the solvent was removed from the obtained filtrate by concentration under reduced pressure. As a result, 33.71 g of the target polyhexamethylene carbonate was obtained as a white solid.
The physical property values of the obtained polyhexamethylene carbonate were as follows.

IR (KBr, cm ⁻¹ ); 1741.5 (carbonate; C═O).
¹ H-NMR (CDCl ₃ , δ (ppm)); 1.41-1.42 (4H, m), 1.67-1.70 (4H, m), 4.12-4.14 (4H, m).
¹³ C-NMR (CDCl ₃ , δ (ppm)); 25.4, 28.5, 67.7, 155.3.
Elemental analysis; calculated value (C ₇ H ₁₂ O ₃ ) _n : C, 58.31%; H, 8.37%
Found: C, 58.07%; H, 8.27%
Melting point: 57-58 ° C
GPC (polystyrene standard: eluent tetrahydrofuran)
Number average molecular weight: 5142
Weight average molecular weight: 10471
Dispersity: 2.04

Example 2 (Synthesis of polyhexamethylene carbonate)
In a glass reaction vessel equipped with a Dean-Stark distillation device, a pressure adjustment device, a temperature adjustment device, a thermometer, a dropping device and a stirring measure, 150.00 g (0.74 mol) of 1,6-hexanediol diacetate and dimethyl carbonate 133 .62 g (0.25 mol) was mixed, and 7.50 g of lipase derived from Candida antarctica (Novozym 435 (trade name); manufactured by Novozyme) was added while maintaining the temperature at 50 ° C. The reaction was stirred for 48 hours. Next, at the same temperature, the internal pressure of the reaction system was reduced to 10 kPa (75 mmHg) over 4 hours. (When the pH at this time was measured with a pH test paper, the color was in the range of pH = 6 to 7).
After 20 hours, a part of the system was sampled, acetonitrile was added, and after filtration, the solvent was removed from the obtained filtrate by concentration under reduced pressure to obtain the desired polyhexamethylene carbonate as a white solid.
The physical property values of the obtained polyhexamethylene carbonate were as follows.

IR (KBr, cm ⁻¹ ); 1741.2 (carbonate; C═O).
¹ H-NMR (CDCl ₃ , δ (ppm)); 1.39-1.45 (4H, m), 1.66-1.72 (4H, m), 4.10-4.15 (4H, m).
¹³ C-NMR (CDCl ₃ , δ (ppm)); 25.4, 28.6, 67.8, 155.4.
GPC (polystyrene standard: eluent tetrahydrofuran)
Number average molecular weight: 3194
Weight average molecular weight: 7723
Dispersity: 2.42

Example 3 (Synthesis of polybutylene carbonate)
In a glass reaction vessel equipped with a pressure adjusting device, a temperature adjusting device, a thermometer, a dropping device and a stirring measure, 2.00 g (11.5 mmol) of 1,4-butanediol diacetate and 3.10 g of dimethyl carbonate (34.34). 4 mmol) was mixed, and 100 mg of Candida antarctica-derived lipase (Novozym 435 (trade name); manufactured by Novozyme) was added while stirring at 50 ° C., followed by stirring at the same temperature for 45 hours. It was. Next, the internal pressure of the reaction system was reduced to 10 kPa (75 mmHg), and the reaction was carried out by stirring at the same temperature for 24 hours.
After completion of the reaction, 10 mL of tetrahydrofuran was added to the obtained reaction solution, and after filtration, the solvent was removed from the obtained filtrate by concentration under reduced pressure. As a result, 2.06 g of the target polybutylene carbonate was obtained as a white solid.
The physical property values of the resulting polybutylene carbonate were as follows.

IR (liquid film, cm ⁻¹ ); 1744.0 (carbonate; C═O).
_{^{1 H-NMR (CDCl 3,}} δ (ppm)); 1.73-1.87 (4H, m), 4.15-4.18 (4H, m).
¹³ C-NMR (CDCl ₃ , δ (ppm)); (25.1, 25.2), (67.3, 67, 4), (155.2, 155.3, 155.4).
GPC (polystyrene standard: eluent tetrahydrofuran)
Number average molecular weight: 1700
Weight average molecular weight: 2671
Dispersity: 1.57

Example 4 (Synthesis of polypropylene carbonate)
1,3-propanediol diacetate 500 mg (3.1 mmol) and dimethyl carbonate 1125 mg (12.5 mmol) are mixed in a glass reaction vessel equipped with a pressure adjusting device, a temperature adjusting device, a thermometer, a dropping device and a stirring device. Then, while maintaining the temperature at 30 ° C., 25 mg of Candida antarctica-derived lipase (Novozym 435 (trade name); manufactured by Novozyme) was added, and the mixture was stirred for 72 hours at the same temperature. The reaction mixture was filtered, and the obtained filtrate was concentrated under reduced pressure to obtain 200 mg of an oily substance. Next, 10 mg of Candida antarctica-derived lipase (Novozym 435 (trade name); manufactured by Novozyme) was added while maintaining the oily substance at 50 ° C., and the pressure inside the reaction system was reduced to 10 kPa (75 mmHg). Then, the reaction was carried out by stirring at the same temperature for 14 hours. After completion of the reaction, 2 mL of tetrahydrofuran was added to the resulting reaction solution, and after filtration, the solvent was removed from the obtained filtrate by concentration under reduced pressure. As a result, 200 mg of the target polypropylene carbonate was obtained as a white solid.
The physical property values of the obtained polypropylene carbonate were as follows.

GPC (polystyrene standard: eluent tetrahydrofuran)
Number average molecular weight: 1462
Weight average molecular weight: 2746
Dispersity: 1.88

Example 5 (Synthesis of polyethylene carbonate)
In a glass reaction vessel equipped with a pressure adjusting device, a temperature adjusting device, a thermometer, a dropping device and a stirring measure, 820 mg (5.6 mmol) of 1,2-ethanediol diacetate and 1,2-bis (methoxycarbonyloxy) Ethane (1000 mg, 5.6 mmol) was mixed and lipase 41 mg (Novozym 435 (trade name) manufactured by Novozyme) from Candida antarctica was added while maintaining the temperature at 30 ° C. for 3 hours at the same temperature. The reaction was stirred. Next, the internal pressure of the reaction system was reduced to 0.1 kPa (1 mmHg), and the reaction was carried out by stirring at 70 ° C. for 6 hours. After completion of the reaction, 5 mL of tetrahydrofuran was added to the resulting reaction solution, and after filtration, the solvent was removed from the obtained filtrate by concentration under reduced pressure. As a result, 877 mg of the target product, polyethylene carbonate, was obtained as a white solid.
The physical property values of the obtained polyethylene carbonate were as follows.

IR (liquid film, cm ⁻¹ ); 1747.5 (carbonate; C═O).
_{^{1 H-NMR (CDCl 3,}} δ (ppm)); 4.22-4.27 (2H, m), 4.36-4.38 (2H, m).
¹³ C-NMR (CDCl ₃ , δ (ppm)); (65.3, 65.4, 65.5, 65.6), (154.7, 154.8, 154.9, 155.0).
GPC (polystyrene standard: eluent tetrahydrofuran)
Number average molecular weight: 1451
Weight average molecular weight: 2723
Dispersity: 1.88

Example 6 (Synthesis of polypropylene carbonate)
In a glass reaction vessel equipped with a pressure adjusting device, a temperature adjusting device, a thermometer, a dropping device and a stirring measure, 417 mg (2.6 mmol) of 1,3-propanediol diacetate and 1,3-bis (methoxycarbonyloxy) Propane 500 mg (2.6 mmol) was mixed, and while maintaining the temperature at 50 ° C., 25 mg of Candida antarctica-derived lipase (Novozym 435 (trade name); manufactured by Novozyme) was added, and the internal pressure of the reaction system was adjusted. The pressure was reduced to 0.1 kPa (1 mmHg), and the reaction was stirred at 50 ° C. for 72 hours. GPC measurement was performed after completion of the reaction.
The physical property values of the obtained polypropylene carbonate were as follows.
GPC (polystyrene standard: eluent tetrahydrofuran)
Number average molecular weight: 1407
Weight average molecular weight: 2411
Dispersity: 1.71

Example 7 (Synthesis of copolymer: poly (propylene carbonate-co-butylene carbonate))
In a glass reaction vessel equipped with a pressure adjusting device, a temperature adjusting device, a thermometer, a dropping device, and a stirring measure, 1,3-propanediol diacetate 674 mg (4.2 mmol) and 1,4-bis (methoxycarbonyloxy) Butane 868 mg (2.6 mmol) was mixed, and while maintaining at 50 ° C., 38 mg of Candida antarctica-derived lipase (Novozym 435 (trade name); manufactured by Novozyme) was added, and the pressure in the reaction system was adjusted. The pressure was reduced to 30 kPa (225 mmHg), and the mixture was reacted by stirring at the same temperature for 6 hours. Next, the reaction system internal pressure was reduced to 9.5 kPa (71 mmHg), and the reaction was carried out by stirring at 70 ° C. for 8 hours. After completion of the reaction, 5 mL of tetrahydrofuran was added to the resulting reaction solution, and after filtration, the solvent was removed from the obtained filtrate by concentration under reduced pressure. As a result, the desired copolymer (poly (propylene carbonate-co-butylene carbonate)) was obtained. ) 863 mg was obtained as an oil.
The physical properties of the obtained copolymer (poly (propylene carbonate-co-butylene carbonate)) were as follows.

IR (liquid film, cm ⁻¹ ); 1744.7 (carbonate; C═O).
_{^{1 H-NMR (CDCl 3,}} δ (ppm)); 1.73-1.82 (m), 2.01-2.09 (m), 4.16-4.31 (m).
¹³ C-NMR (CDCl ₃ , δ (ppm)); (25.0, 25.1, 25.2, 25.4), (28.0, 28.0, 28.8, 28.9), (64.2, 64.3, 64.5, 64.6, 65.0), (67.3, 67.4, 67.5). (154.9, 155.0, 155.2, 155.4).
GPC (polystyrene standard: eluent tetrahydrofuran)
Number average molecular weight: 1824
Weight average molecular weight: 3134
Dispersity: 1.72

Example 8 (Synthesis of copolymer: poly (ethylene carbonate-co-hexamethylene carbonate))
In a glass reaction vessel equipped with a pressure adjusting device, a temperature adjusting device, a thermometer, a dropping device and a stirring measure, 681-mg (3.4 mmol) of 1,6-hexanediol diacetate and 1,2-bis (methoxycarbonyloxy) Mix ethane 600 mg (3.4 mmol), add Candida antarctica-derived lipase 34 mg (Novozym 435 (trade name); manufactured by Novozyme) while maintaining the temperature at 30 ° C. for 3 hours. The reaction was stirred. Next, the internal pressure of the reaction system was reduced to 0.1 kPa (1 mmHg), and the reaction was carried out by stirring at 70 ° C. for 6 hours. After completion of the reaction, 5 mL of tetrahydrofuran was added to the resulting reaction solution, and after filtration, the solvent was removed from the obtained filtrate by concentration under reduced pressure. As a result, the target copolymer (poly (ethylene carbonate-co-hexamethylene carbonate) was obtained. )) Obtained 524 mg as a white solid.
The physical properties of the obtained poly (ethylene carbonate-co-hexamethylene carbonate) were as follows.

IR (liquid film, cm ⁻¹ ); 1745.5 (carbonate; C═O).
¹ H-NMR (CDCl ₃ , δ (ppm)); 1.40-1.43 (m), 1.67-1.68 (m), 4.10-4.16 (m), 4.35 -4.53 (m).
¹³ C-NMR (CDCl ₃ , δ (ppm)); (25.3, 25.4), (28.5, 28.6), (65.1, 65.2, 65.5, 65.6) ), 155.0, 155.4.
GPC (polystyrene standard: eluent tetrahydrofuran)
Number average molecular weight: 4973
Weight average molecular weight: 8459
Dispersity: 1.70

Comparative Example 1 (Comparison of reaction rate of alcohol and ester to carbonate compound)
Initial reaction rate (V ₁ ) for synthesizing n-butyl methyl carbonate from n-butyl alcohol and dimethyl carbonate, and initial reaction rate (V ₂ ) for synthesizing n-butyl methyl carbonate from n-butyl acetate and dimethyl carbonate, Measurements were made under the same reaction conditions shown below, and the reaction rates were compared.
From a glass reaction vessel with an internal volume of 10 ml equipped with a stirrer, 1.00 g (13.5 mmol) of n-butyl alcohol, 5.68 ml (67.4 mmol) of dimethyl carbonate, and Candida antarctica Lipase 50.4 mg (Novozym 435 (trade name); manufactured by Novozyme) was mixed and allowed to react for 1 hour in a thermostatic bath at 30 ° C. with stirring. Likewise, 1.01 g (8.69 mmol) of n-butyl acetate, 3.63 ml (43.1 mmol) of dimethyl carbonate, and 50.5 mg of lipase derived from Candida antarctica (Novozym 435 (trade name)) And manufactured by Novozyme), and the mixture was reacted for 1 hour in a thermostatic bath at 30 ° C. with stirring. After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method). When n-butyl alcohol was used, 0.997 g of n-butyl alcohol remained (conversion rate: 0.3%). V ₁ = 0.0134 μmol / min · mg). When n-butyl acetate was used, 0.967 g of n-butyl acetate remained (conversion rate: 4.3%, V ₂ = 0.122 μmol / min · mg). The result was _V 2 _{/ V} 1 = 9.

From the above examples, the production method of the present invention is a method capable of synthesizing a polyalkylene carbonate compound having a good degree of polymerization without inactivating the hydrolase. Therefore, it is possible to reduce the amount of hydrolase used compared to the conventional method, and this is a production method with a low environmental load.

Further, conventionally, in the production of oligoalkylene carbonate compounds and polyalkylene carbonate compounds, the transesterification rate between an alkylene diol compound and a carbonate compound is significantly faster than the transesterification rate between an alkylene diacylate compound and a carbonate compound. From the results of Comparative Example 1, the results of Comparative Example 1 show that the results of the method of the present invention differ from this common sense, that is, the reaction rate of the transesterification reaction between the diacylate compound and the carbonate compound is faster. The manufacturing method is a more efficient method that can reduce the manufacturing time as compared with the conventional method.

  The present invention relates to an oligoalkylene carbonate compound using an alkylene diol diacylate compound and a carbonate compound in the presence of a hydrolase, and a method for producing a polyalkylene carbonate compound. According to the present invention, the obtained oligoalkylene carbonate compound or polyalkylene carbonate compound is a useful compound as an excellent functional polymer material having biodegradability.

Claims (20)

A hydrolase, an alkylene diol diacylate compound represented by the following formula (I) in the presence or absence of an organic solvent;

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and may have a substituent. R ² represents from 1 to C atoms. 20 linear, branched or cyclic alkylene groups, or aromatic ring-containing or heterocyclic ring-containing alkylene groups, which may have a substituent)
And a carbonate compound represented by the following formula (II):

(Wherein R ³ and R ⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, or an aryl group, and has a substituent. Is also good.)
And the following formula (IV):

(In the formula, R ² has the same meaning as described above, and X and Y may be the same or different from each other, and each is selected from R ¹ , OR ³ , or OR ^{4 as} defined above. N represents the degree of polymerization and represents an integer of 2 or more.)
The manufacturing method of the oligo alkylene carbonate compound shown by these, and a polyalkylene carbonate compound. A hydrolase, an alkylene diol diacylate compound represented by the formula (I) according to claim 1 and a carbonate compound represented by the formula (III) in the presence or absence of an organic solvent;

(In the formula, R ⁶ represents a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an aromatic ring-containing or heterocyclic ring-containing alkylene group, and may have a substituent. R ⁵ and R ⁷ each independently represents an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group, and may have a substituent. R ⁵ and R ⁷ may form a ring together.)
And the following formula (V):

(In the formula, X ′ and Y ′ may be the same or different from each other, and are each selected from R ¹ , OR ⁵ , or OR ^7. A and B are the same or different from each other. And one is selected from R ² and R ⁶ as defined above, and n ′ represents the degree of polymerization and represents an integer of 1 or more.)
The manufacturing method of the oligo alkylene carbonate compound shown by these, and a polyalkylene carbonate compound. Formula (VI) resulting from the reaction;

(In the formula, R ¹ is as defined above. Z is selected from R ³ or R ^{4 as} defined above.)
Or formula (VI ′);

(In the formula, R ¹ is as defined above. W is selected from R ⁵ or R ^{7 as} defined above.)
A process for producing an oligoalkylene carbonate compound represented by the formula (IV) or the formula (V) according to claim 1 or 2, and a polyalkylene carbonate compound, wherein the ester compound represented by formula (IV) is removed.   The oligoalkylene carbonate compound or polyalkylene carbonate compound according to formula (IV) or formula (V), characterized in that it has a weight average molecular weight of 500 to 100,000 obtained by the method according to claim 1. .   The oligoalkylene carbonate compound or polyalkylene carbonate compound according to formula (IV) or formula (V), characterized in that it has a number average molecular weight of 500 to 100,000 obtained by the method according to claim 1. .   The oligoalkylene carbonate compound or polyalkylene carbonate compound according to formula (IV) or formula (V), characterized by having a molecular weight distribution of 3.0 or less, obtained by the method according to claim 1. .   The method for producing an oligoalkylene carbonate compound and a polyalkylene carbonate compound according to claim 1, wherein the hydrolase is protease, esterase or lipase.   The method for producing an oligoalkylene carbonate compound and a polyalkylene carbonate compound according to claim 1, wherein the hydrolase is lipase.   The method for producing an oligoalkylene carbonate compound and a polyalkylene carbonate compound according to claim 8, wherein the lipase is a lipase originating from Candida antarctica. The method for producing an oligoalkylene carbonate and a polyalkylene carbonate compound according to claim 1, wherein R ¹ is a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group. R ² is a linear, branched or cyclic alkylene group having a saturated or unsaturated bond having 2 to 12 carbon atoms, and an aromatic ring-containing or heterocyclic ring-containing alkylene group having 6 to 20 carbon atoms. A method for producing an oligoalkylene carbonate compound and a polyalkylene carbonate compound according to claim 1. The oligo according to claims 1 to ^3, wherein R ³ and R ⁴ are the same, a straight-chain having 1 to 4 carbon atoms, and a branched or cyclic alkyl group having 3 or 4 carbon atoms. A method for producing an alkylene carbonate compound and a polyalkylene carbonate compound.   The method for producing an oligoalkylene carbonate compound and a polyalkylene carbonate compound according to claim 1, wherein the reaction is carried out in an organic solvent.   The oligo according to claims 1 to 3, wherein the organic solvent is at least one organic solvent selected from the group consisting of nitriles, ethers, ketones, esters, aliphatic hydrocarbons and aromatic hydrocarbons. A method for producing an alkylene carbonate compound and a polyalkylene carbonate compound.   The oligoalkylene carbonate compound according to claim 3, wherein the compound (VI) or the compound (VI ') is distilled off at a reaction pressure of 0.13 kPa or more and less than 101.3 kPa. A method for producing an alkylene carbonate compound.   The method for producing an oligoalkylene carbonate compound and a polyalkylene carbonate compound according to claims 1 to 3, wherein the reaction is carried out at a pH of 5 to 9.   The reaction solution is subjected to a reaction while being analyzed by gel permeation chromatography (GPC) to obtain a polyalkylene carbonate compound having a desired molecular weight (degree of polymerization) or an oligoalkylene carbonate compound having a molecular weight of 1000 or less; The method for producing an oligoalkylene carbonate and a polyalkylene carbonate compound according to claim 1.   4. The method for producing an oligoalkylene carbonate compound and a polyalkylene carbonate compound according to claim 1, wherein a trace amount of water is present during the reaction. The oligoalkylene carbonate compound or polyalkylene carbonate compound represented by the following formula (XXII) obtained by the presence of a trace amount of water during the reaction according to the method of claim 1.

(Wherein R ² has the same meaning as described above, and X ″ is selected from R ¹ , OR ³ , OR ⁴ or O—R ² —OH as defined above. N ′ represents the degree of polymerization. Represents an integer of 1 or more.) The oligoalkylene carbonate compound or polyalkylene carbonate compound represented by the following formula (XXIII), which is obtained in the method of claim 2 in the presence of a small amount of water during the reaction.

Wherein Y ″ is selected from R ¹ , OR ⁵ , OR ⁷ , O—R ² —OH, or O—R ⁶ —OH. A, B, and G are the same as or different from each other. And one selected from each of R ² and R ⁶ as defined above. N ′ represents the degree of polymerization and represents an integer of 1 or more.)