Diol compound and polymer thereof, and method for producing the same

Abstract

To provide a novel diol compound that makes it possible to prepare a high-molecular-weight resin having a skeleton derived from 3HB even by chemical synthesis, and a resin (polymer) containing the diol compound as a polymerization component, and a method for producing them.SOLUTION: A diol compound is represented by the formula (1) (where R1 is a divalent group, m is 0 or 1). In the formula (1), R1 may be a residue of a diol selected from an aliphatic diol, an alicyclic diol, and an aromatic diol. In the formula (1), m may be 1.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel diol compound having a skeleton derived from 3-hydroxybutyric acid (also known as 3HB), a resin (polymer) containing this diol compound as a polymerization component, and a method for producing them. [Background technology]

[0002] From the perspective of environmental conservation and the realization of a sustainable society, efforts are being made to convert some or all of plastic raw materials into biomass, and the use of bio-based or biodegradable plastics is increasing. Plastic is an essential material in human life, but plastic released into the environment drifts on the ocean and is broken down and fragmented by ultraviolet rays and other factors, producing microplastics with diameters of 5 mm or less. Furthermore, there are concerns that these microplastics may cause endocrine disruption if ingested by birds, fish, and other living organisms.

[0003] In recent years, efforts have been made to impart biodegradability to garbage bags, for example, in order to solve the above-mentioned microplastic problem. Examples of biodegradable plastics include polylactic acid (PLA), polyhydroxyalkanoate (PHA), polybutylene succinate (PBS), and polycaprolactone (PCL). However, these biodegradable plastics have low biodegradability (or biogasification) under anaerobic conditions and low biodegradability in the ocean. Because these biodegradable plastics are highly dense and sink in the ocean, solving the microplastic problem requires the development of plastics that are highly biodegradable even under anaerobic conditions, such as in the ocean.

[0004] H. Yagi et al., Polymer Degradation and Stability, 110, (2014), 278-283 (Non-Patent Document 1) evaluated the biodegradability of various biodegradable polyesters under anaerobic conditions and disclosed that poly-3-hydroxybutyrate (PHB) exhibits higher biodegradability under anaerobic conditions than PLA, PCL, and PBS. However, poly-3-hydroxyalkanoates such as PHB, which are produced (biosynthesized) by microorganisms, lack the mechanical properties required for general-purpose plastic molded bodies and are also economically unviable, and therefore have not been widely used.

[0005] Meanwhile, Japanese Patent Laid-Open Publication No. 2017-025138 (Patent Document 1) discloses a biodegradable copolymer in which the proportion of 3-hydroxybutyric acid (3HB) units is 1 to 20 mol% relative to all constituent units, as a biodegradable plastic into which 3HB units have been introduced by chemical synthesis. Patent Document 1 describes that a biodegradable copolymer in which 3HB units have been randomly introduced has high biodegradability under aerobic and anaerobic conditions. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2017-025138 [Non-patent literature]

[0007] [Non-Patent Document 1] H.Yagi et al., Polymer Degradation and Stability, 110, (2014), 278-283(Table 1) Summary of the Invention [Problem to be solved by the invention]

[0008] In the examples of Patent Document 1, it is described that a copolyester containing 3HB units at a ratio of 4.6 or 8.7 mol % was prepared by adding monomers that form PBS, PBSA, etc., and (R)-3HB all at once and polymerizing them, and that the weight average molecular weight Mw was 5790 to 6820.

[0009] However, the biodegradable copolymer described in Patent Document 1 has low reactivity of the monomer 3HB, and is easily decomposed by intramolecular dehydration caused by heat or acid, making it difficult to increase the molecular weight and sometimes resulting in insufficient mechanical properties.

[0010] Therefore, an object of the present invention is to provide a novel diol compound that can be used to prepare a high molecular weight resin having a skeleton derived from 3HB, even by chemical synthesis, a resin (polymer) containing this diol compound as a polymerization component, and methods for producing these.

[0011] Another object of the present invention is to provide a novel diol compound that can prepare a resin having excellent mechanical properties and high moldability (or productivity) even though it has a skeleton derived from 3HB, a resin (polymer) containing this diol compound as a polymerization component, and methods for producing them.

[0012] Yet another object of the present invention is to provide a novel diol compound capable of preparing a resin having excellent mechanical properties and exhibiting biodegradability, a resin (polymer) containing this diol compound as a polymerization component, and methods for producing these. [Means for solving the problem]

[0013] 3-Hydroxyalkanoic acids (3HA) such as 3HB have a highly reactive carboxyl group and a less reactive secondary alcohol hydroxyl group. Therefore, when 3HA is used as a polymerization component (resin raw material or monomer) to synthesize a resin (polymer), not only is the polymerization reaction difficult to proceed due to the secondary alcohol, but intramolecular dehydration due to heating or acid is likely to occur between the hydrogen atom at the α-position of the carboxyl group and the hydroxyl group (secondary alcohol) at the β-position, leading to decomposition to unsaturated monocarboxylic acids such as crotonic acid. This makes it difficult to synthesize high-molecular-weight polymers containing 3HA units.

[0014] Therefore, the present inventors have conducted extensive research to achieve the above object, and have found that the carboxyl group of 3HB can be substituted with a specific diol (a group R 1 The present inventors have discovered that by using a diol compound having an ester bond (a 3HB skeleton-containing diol compound) obtained by reacting a diol compound having an ester bond with a derivative of a diol having a residue of (diol having a residue of) as a polymerization component, it is possible to chemically synthesize a high molecular weight resin despite containing a 3HB skeleton, and have completed the present invention.

[0015] That is, the diol compound of the present invention is represented by the following formula (1).

[0016] [ka]

[0017] (In the formula, R 1 represents a divalent group, and m represents 0 or 1).

[0018] In the formula (1), R 1 may be a residue of a diol selected from an aliphatic diol, an alicyclic diol, and an aromatic diol. Furthermore, m may be 1. In the formula (1), the structural unit derived from 3-hydroxybutyric acid may contain at least a structural unit in which the steric configuration of the asymmetric carbon atom is the R configuration. The diol compound may be a polymerization component of a biodegradable resin.

[0019] The present invention includes a method for producing a diol compound represented by the formula (1) above by reacting a compound represented by the following formula (2) with 3-hydroxybutyric acid.

[0020] [ka]

[0021] (In the formula, L 1 indicates a leaving group, and L 2 denotes a leaving group or hydroxyl group, and R 1 is the same as the above formula (1).

[0022] In the above method, the 3-hydroxybutyric acid may contain the R-form ((R)-3-hydroxybutyric acid).

[0023] The present invention also encompasses a thermoplastic resin containing a diol component as a polymerization component, wherein the diol component contains at least the diol compound represented by formula (1). In the thermoplastic resin, the proportion of the structural units derived from the diol compound represented by formula (1) may be about 10 to 100 mol % relative to all structural units derived from the diol component.

[0024] The polymerization components may further include at least one selected from a diisocyanate component and a dicarboxylic acid component. The diisocyanate component may include an aliphatic diisocyanate component, an alicyclic diisocyanate component, or an aromatic diisocyanate component, and the dicarboxylic acid component may include an acid halide or an acid anhydride of at least one dicarboxylic acid selected from an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, and an aromatic dicarboxylic acid. The weight-average molecular weight of the thermoplastic resin may be approximately 30,000 or more. The thermoplastic resin may be a biodegradable resin.

[0025] The present invention also encompasses a method for producing the thermoplastic resin by polymerizing a polymerization component containing at least the diol compound represented by formula (1). In this method, the polymerization temperature may be about 150°C or lower.

[0026] The present invention also encompasses a method for improving the biodegradability (or enzymatic decomposition properties) of a thermoplastic resin obtained by polymerizing a polymerization component containing at least the diol compound represented by the formula (1).

[0027] Furthermore, the present invention also includes a molded article containing the thermoplastic resin. The molded article may be in the form of a film. [Effects of the Invention]

[0028] By using the diol compound (also referred to as 3HB diol) of the present invention represented by formula (1) as a polymerization component, a resin having a 3HB-derived skeleton can be prepared with a high molecular weight, even by chemical synthesis. Moreover, such a high molecular weight resin can be prepared simply (easily or efficiently). Furthermore, even though the resin has a 3HB-derived skeleton, it has excellent mechanical properties and moldability (or productivity). Furthermore, the resin has excellent mechanical properties and can also exhibit biodegradability. The 3HB-derived skeleton is particularly useful because it is easily biodegradable under both aerobic and anaerobic conditions. [Brief explanation of the drawings]

[0029] [Figure 1] FIG. 1 is a 1H-NMR (nuclear magnetic resonance) spectrum of CHDM-Ts obtained in Example 1. [Figure 2] FIG. 2 is a 13C-NMR spectrum of CHDM-Ts obtained in Example 1. [Figure 3] FIG. 3 is a 1H-NMR spectrum of 3HB diol (1,4-bis(3-hydroxybutanoyloxymethyl)cyclohexane) obtained in Example 1 and represented by formula (1-1) described below. [Figure 4]FIG. 4 is a 13C-NMR spectrum of 3HB diol (1,4-bis(3-hydroxybutanoyloxymethyl)cyclohexane) obtained in Example 1 and represented by formula (1-1) described below. [Figure 5] FIG. 5 is a 1H-NMR spectrum of the polyester urethane obtained in Example 2. [Figure 6] FIG. 6 is a 13C-NMR spectrum of the polyester urethane obtained in Example 2. [Figure 7] FIG. 7 is a 1H-NMR spectrum of the 3HB diol [1,2-bis(3-hydroxybutanoyloxymethyl)ethane] obtained in Example 3 and represented by formula (1-2) described below. [Figure 8] FIG. 8 is a 13C-NMR spectrum of the 3HB diol [1,2-bis(3-hydroxybutanoyloxymethyl)ethane] obtained in Example 3 and represented by formula (1-2) described below. [Figure 9] FIG. 9 shows the FT-IR spectra of 3HB polyester urethane before and after the biodegradation test of Example 4 (the solid line indicates the results before the test, and the dashed line indicates the results after the test). [Figure 10] FIG. 10 shows the evaluation results of the biodegradation test of cyclohexanedimethanol (CHDM) in Comparative Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0030] [3HB skeleton-containing diol compound represented by formula (1)]

[0031] [ka]

[0032] (In the formula, R 1 represents a divalent group, and m represents 0 or 1).

[0033] In the formula (1), R 1The divalent group represented by the formula (I) may be a residue of a diol, and examples thereof include residues of diols selected from aliphatic diols, alicyclic diols, and aromatic diols.

[0034] In this specification and claims, the term "residue of a diol" refers to a divalent group obtained by removing two hydroxyl groups (OH) from the chemical structure of a diol. 1 is expressed by the formula (3) HO-R 1 It means a residue of a diol represented by —OH.

[0035] Examples of the aliphatic diol include alkylene glycol and polyalkylene glycol.

[0036] Examples of alkylene glycols (or alkanediols) include linear or branched C alkylene glycols such as ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, tetramethylene glycol (or 1,4-butanediol), 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, and 1,10-decanediol. 2-20 Alkylene glycol (e.g., linear or branched C 2-16 alkylene glycols, etc.

[0037] Examples of polyalkylene glycols (or polyalkanediols) include di- or deca-linear or branched C alkylene glycols such as diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol. 2-20 Alkylene glycol (e.g., di- or deca-straight or branched C 2-16 alkylene glycols, etc.), and preferably di- or hexa-straight or branched chain C 2-12 Alkylene glycols (e.g., di- or hexa-straight or branched C 2-8 alkylene glycols, etc.), more preferably di- or tetra-linear or branched C2-6 Alkylene glycol (e.g., di- or tetra-linear or branched C 2-4 alkylene glycols, etc.

[0038] Examples of alicyclic diols include cycloalkanediols (e.g., C cyclohexanediol, etc.) 3-12 Cycloalkanediols, preferably C 4-10 Cycloalkanediols, more preferably C 5-8 cycloalkanediols, etc.); bis(hydroxyalkyl)cycloalkanes [e.g., bis(hydroxy C) such as cyclohexanedimethanol] 1-6 Alkyl)C 3-12 Cycloalkanes, etc.]; hydrogenated biphenols or bisphenols (e.g., hydrogenated bisphenol A, etc.); alkylene oxide (or corresponding alkylene carbonate, haloalkanol) adducts thereof [e.g., C 2-4 C alkylene oxide adducts, preferably ethylene oxide adducts, propylene oxide adducts, etc. 2-3 alkylene oxide adducts, etc.], and hydrogenated products corresponding to the aromatic diols described below.

[0039] Examples of aromatic diols include dihydroxyarenes (e.g., dihydroxy C such as hydroquinone and resorcinol). 6-14 arenes, preferably dihydroxy C 6-10 arenes, etc.); bis(hydroxyalkyl)arenes [e.g., bis(hydroxy C 1-6 Alkyl)C 6-14 arenes, preferably bis(hydroxy C 1-4 Alkyl)C 6-10 arenes, etc.]; biphenols (e.g., p,p'-biphenol, etc.); bisphenols (e.g., bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G, bisphenol S, etc.); their alkylene oxide (or corresponding alkylene carbonate, haloalkanol) adducts [e.g., C2-4 C alkylene oxide adducts, preferably ethylene oxide adducts, propylene oxide adducts, etc. 2-3 alkylene oxide adducts, etc.].

[0040] These R 1 Among the diol residues represented by the formula (I), from the viewpoint of biodegradability, etc., aliphatic diol residues or alicyclic diol residues are preferred, and aliphatic diol residues are particularly preferred. Preferred aliphatic diol residues include linear or branched C 2-12 Alkylene glycol (e.g., linear or branched C 2-8 alkylene glycols), more preferably linear or branched C 2-6 Alkylene glycol (e.g., linear or branched C 2-4 alkylene glycol, etc.), and particularly preferably a linear or branched C 2-3 Examples include residues of alkylene glycols.

[0041] In addition, from the viewpoint of handling (or productivity) and heat resistance, a residue of an alicyclic diol is preferred. A preferred residue of an alicyclic diol is a residue of a bis(hydroxyalkyl)cycloalkane, more preferably a residue of a bis(hydroxy C 1-4 Alkyl)C 4-10 Residues of cycloalkanes [e.g., bis(hydroxy C 1-3 Alkyl)C 5-8 residues of cycloalkanes], particularly preferably bis(hydroxy C) such as benzenedimethanol 1-2 Alkyl)C 5-8 Examples include residues of cycloalkanes.

[0042] In the formula (1), m is 0 (i.e., 3HB and R 1 a dimer formed with the diol corresponding to R) or 1 (i.e., two 3HB and R 1and a corresponding diol), m is preferably 1, since a skeleton derived from 3HB (or 3HB unit) can be efficiently introduced into the resin.

[0043] In this specification and claims, the term "structural unit derived from 3-hydroxybutyric acid" or "3HB unit" refers to a unit (or divalent group) represented by the following formula, in which a hydrogen atom is removed from the hydroxyl group of 3HB and a hydroxyl group is removed from the carboxyl group.

[0044] [ka]

[0045] The configuration of the 3HB unit in formula (1) (the configuration at the asymmetric carbon atom) may be either the R-configuration (R-form) or the S-configuration (S-form), but from the viewpoint of biodegradability, it is preferable to have at least one 3HB unit in the R-configuration (R-form). In particular, when m is 1, the configurations of the two 3HB units may be the same or different, but from the viewpoint of biodegradability, it is preferable that both are in the R-configuration.

[0046] Representative diol compounds represented by the formula (1) include, for example, compounds in which m is 1 and R 1 is a residue of an aliphatic diol, specifically, a bis(3-hydroxybutanoyloxy)alkane [e.g., bis(3-hydroxybutanoyloxy) C such as 1,2-bis(3-hydroxybutanoyloxy)ethane] 2-6 Alkanes, preferably bis(3-hydroxybutanoyloxy)C 2-4 alkane, etc.]; m is 1, and R 1 is a residue of an alicyclic diol, specifically, bis(3-hydroxybutanoyloxyalkyl)cycloalkanes [e.g., bis(3-hydroxybutanoyloxy) C such as 1,4-bis(3-hydroxybutanoyloxymethyl)cyclohexane] 1-4 Alkyl)C 5-10Cycloalkanes, preferably bis(3-hydroxybutanoyloxy)C 1-3 Alkyl)C 5-8 Cycloalkanes, etc.

[0047] (Method for producing diol compound represented by formula (1)) The method for producing the 3HB skeleton-containing diol compound represented by the formula (1) is not particularly limited as long as it includes at least the following reaction step (ii), and for example, it can be produced by the following reaction steps (i) to (ii).

[0048] [ka]

[0049] (In the formula, L 1 indicates a leaving group, and L 2 denotes a leaving group or hydroxyl group, and R 1 and m are the same as described above, including preferred embodiments).

[0050] (i) Preparation of a compound represented by formula (2) The compound represented by the formula (2) can be prepared by converting at least one hydroxyl group of the diol represented by the formula (3) into a leaving group.

[0051] Representative examples of the diol represented by the formula (3) include the diol represented by the formula (3) 1 Examples of the diol include the aliphatic diols, alicyclic diols, and aromatic diols exemplified in the above section, and preferred examples include aliphatic diols such as ethylene glycol and alicyclic diols such as cyclohexanedimethanol.

[0052] L 1 , L 2 Examples of the leaving group represented by the formula [-O-SO2-R 2 ](where R 2represents a hydrocarbon group, a fluorohydrocarbon group, or a fluorine atom.), a halogen atom (e.g., a chlorine atom, a bromine atom, an iodine atom, preferably a bromine atom, etc.), etc. Among these leaving groups, the group [—O—SO—R 2 and halogen atoms such as bromine atoms are preferred.

[0053] The group [-O-SO2-R 2 ], R 2 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, a cycloalkyl group, an aryl group, and a group in which two or more of these groups are combined. Examples of the alkyl group include C groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. 1-6 Examples of the cycloalkyl group include a C alkyl group such as a cyclopentyl group and a cyclohexyl group. 5-10 Examples of the aryl group include a C aryl group such as a phenyl group and a naphthyl group. 6-12 Examples of groups formed by combining two or more of these include alkylaryl groups (e.g., mono- or tri-C groups such as tolyl and xylyl groups). 1-6 Alkyl C 6-10 aryl groups, aralkyl groups (e.g., benzyl groups, phenethyl groups, etc.) 6-10 Aryl C 1-6 alkyl groups, etc.

[0054] The group [-O-SO2-R 2 ], R 2 The fluorohydrocarbon group represented by the formula (I) may be a group in which at least one hydrogen atom of a hydrocarbon group is substituted with a fluorine atom, and in particular, a perfluorohydrocarbon group in which all hydrogen atoms are substituted with fluorine atoms is preferred. Therefore, examples of the fluorohydrocarbon group include the above-mentioned R 2 and groups in which at least one (preferably all) hydrogen atoms of a hydrocarbon group represented by the following formula are substituted with a fluorine atom. Specific examples of the fluorinated hydrocarbon group include fluorinated alkyl groups (e.g., C groups such as trifluoromethyl group and nonafluorobutyl group).1-6 perfluoroalkyl groups, etc.

[0055] Preferred R 2 As examples, alkyl groups (C such as methyl groups) 1-4 alkyl groups, aryl groups (phenyl groups, etc.) 6-10 aryl groups, etc.), alkylaryl groups (mono- or tri-C 1-4 Alkyl C 6-10 aryl groups, etc.), perfluoroalkyl groups (trifluoromethyl groups, nonafluorobutyl groups, etc.) 1-6 perfluoroalkyl groups, and fluorine atoms, and more preferably alkylaryl groups (particularly C groups such as p-methylphenyl group (p-tolyl group)). 1-4 Alkyl C 6-10 aryl groups, etc.).

[0056] In addition, L 2 is a leaving group, L 1 and L 2 The types of leaving groups represented by may be different from each other, but are preferably the same.

[0057] The method for converting the hydroxyl group into a leaving group is not particularly limited, and a conventional method may be selected depending on the type of leaving group and the diol represented by formula (3). For example, 1 , L 2 When the leaving group represented by the formula (I) is a halogen atom, a halogenating agent corresponding to the halogen atom (for example, a hydrogen halide such as hydrogen chloride, hydrogen bromide, or hydrogen iodide, a thionyl halide such as thionyl chloride, a phosphorus trihalide such as phosphorus trichloride or phosphorus tribromide, or a zinc halide such as zinc chloride) may be reacted with a diol represented by the formula (3); 1 , L 2 The leaving group represented by the formula [-O-SO2-R 2 ], when a sulfonylating agent [e.g., a compound of formula X 1 -SO2-R 2 (In the formula, X 1 indicates a halogen atom, and R 2is the same as above, including preferred embodiments.) a compound represented by formula R 2 -SO2-O-SO2-R 2 (In the formula, R 2 are the same as above, including preferred embodiments.) with a diol represented by formula (3). Usually, when the diol represented by formula (3) is an aliphatic diol, the former method of reacting with a halogenating agent is often used, but commercially available products can also be used. Furthermore, when the diol represented by formula (3) is an alicyclic diol, the latter method of reacting with a sulfonylating agent is often used.

[0058] Among the sulfonylating agents, those of formula X 1 -SO2-R 2 Preferred is a compound represented by formula X 1 -SO2-R 2 In the compound represented by the formula: 1 Examples of the atom include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferred.

[0059] Representative formula X 1 -SO2-R 2 Examples of the compound represented by the formula (I) include the above-mentioned preferred compounds represented by the formula (I), such as p-toluenesulfonyl chloride (or tosyl chloride) and methylsulfonyl chloride (or mesyl chloride). 2 and sulfonyl chlorides corresponding to the following:

[0060] The proportion of the sulfonylating agent used may be selected from the range of, for example, about 0.1 to 10 moles (for example, 1 to 5 moles) per mole of the diol represented by formula (3). 2 When L in formula (2) is a leaving group, it may be preferably about 2 to 4 moles, more preferably about 2.5 to 3.5 moles. 2 When is a hydroxyl group, the proportion of the sulfonylating agent may be small, for example, about 0.5 to 1 mole per mole of the diol represented by formula (3).

[0061] The reaction between the diol represented by formula (3) and the sulfonylating agent is usually carried out in the presence of a base. Examples of the base include organic bases such as amines; inorganic bases such as metal hydroxides (e.g., alkali metal hydroxides such as sodium hydroxide and potassium hydroxide), metal carbonates, and metal hydrogencarbonates (e.g., alkali metal carbonates such as sodium carbonate and potassium carbonate). These bases can be used alone or in combination. Among these bases, organic bases such as amines are preferred.

[0062] Examples of amines include trialkylamines (e.g., trimethylamine, triethylamine, etc.) 1-6 alkylamines), N,N,N'N'-tetraalkylalkanediamines (e.g., N,N,N'N'-tetraC alkylamines such as N,N,N'N'-tetramethyl-1,6-hexanediamine, 1-6 Alkyl C 2-12 alkanediamines), heterocyclic tertiary amines (pyridine, etc.), and other tertiary amines.

[0063] These amines can be used alone or in combination of two or more. Among these amines, trialkylamines such as triethylamine and N,N,N'N'-tetraalkylalkanediamines such as N,N,N'N'-tetramethyl-1,6-hexanediamine are preferred.

[0064] The proportion of the amines used may be, for example, about 2 to 10 moles, preferably about 2.5 to 5 moles, and more preferably about 3 to 3.5 moles, per mole of the diol represented by the formula (3).

[0065] The reaction of the diol represented by formula (3) with the sulfonylating agent may be carried out in the presence of a solvent. Examples of the solvent include nitriles (e.g., acetonitrile), hydrocarbons (e.g., aromatic hydrocarbons such as toluene), and halogenated hydrocarbons (e.g., dichloromethane). These solvents can be used alone or in combination. Among these solvents, nitriles such as acetonitrile are preferred.

[0066] The proportion of the solvent is not particularly limited, and may be, for example, about 100 to 1000 parts by mass relative to 100 parts by mass of the total amount of the diol represented by the formula (3), the sulfonylating agent, and the base.

[0067] In the reaction of the diol represented by formula (3) with the sulfonylating agent, the reaction temperature may be, for example, −30° C. to 30° C., preferably −20° C. to 10° C., and more preferably −5° C. to 5° C., and the reaction may usually be carried out under ice-cooling. The reaction time may be, for example, 1 to 48 hours, and preferably about 12 to 36 hours.

[0068] The reaction of the diol represented by formula (3) with the sulfonylating agent can usually be carried out in an inert atmosphere (e.g., nitrogen gas; a rare gas such as argon gas, etc.) with stirring, and may be carried out under normal pressure, elevated pressure, or reduced pressure.

[0069] The reaction of the diol represented by formula (3) with the sulfonylating agent may be carried out by slowly adding the sulfonylating agent (and, if necessary, the solvent) dropwise to a mixture of the diol represented by formula (3) and the base (and, if necessary, the solvent) while keeping the mixture at a low temperature (for example, ice-cooling) and slowly adding the sulfonylating agent (and, if necessary, the solvent) thereto (for example, over about 0.5 to 3 hours).

[0070] After completion of the reaction, the reaction product may be separated and purified by a conventional method, for example, a separation and purification means such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, reprecipitation, centrifugation, column chromatography, or a combination of these.

[0071] (ii) Preparation of the compound represented by formula (1) The compound represented by the formula (1) can be prepared by reacting the compound represented by the formula (2) with 3HB. 2 When is a leaving group, compounds of formula (1) in which m is 1 (trimers) can be prepared, and L 2 When is a hydroxyl group, a compound (dimer) of formula (1) in which m is 0 can be prepared.

[0072] Examples of the compound represented by formula (2) include sulfonyl compounds of the diol represented by formula (3) (e.g., tosylate, mesylate, triflate, etc.) which do not contain the leaving group [—O—SO—R 2 ]), halides, etc., and specific examples of the sulfonyl compounds include sulfonyl compounds of alicyclic diols such as 1,4-bis(p-toluenesulfonyloxymethyl)cyclohexane, etc.; and specific examples of the halides include halides of aliphatic diols such as 1,2-dibromoethane, etc.

[0073] The 3HB used in the reaction may be an optical isomer (R or S) or a racemate, but from the viewpoint of biodegradability, it preferably contains at least the R isomer ((R)-3-hydroxybutyric acid). The proportion of the R isomer in 3HB, i.e., the optical purity (or optical isomer excess), is, for example, about 50% ee or more (e.g., 80% ee or more), preferably 90% ee or more (e.g., 95 to 100% ee), and more preferably 98 to 100% ee (e.g., 99 to 100% ee, particularly essentially 100% ee). If the optical purity is too low, there is a risk of significant deterioration in mechanical properties and biodegradability.

[0074] The proportion of 3HB used may be selected from the range of, for example, about 1 to 10 moles, and preferably about 2 to 3 moles, per mole of the compound represented by the formula (2).

[0075] The reaction of the compound represented by formula (2) with 3HB may usually be carried out in the presence of a base. Examples of the base include the bases exemplified in the section (i) Preparation of the Compound Represented by Formula (2) above. These bases can be used alone or in combination of two or more. Among these bases, inorganic bases are preferred, more preferably metal carbonates or metal hydrogencarbonates (e.g., alkali metal carbonates such as sodium carbonate and potassium carbonate), and even more preferably alkali metal carbonates such as potassium carbonate.

[0076] The ratio of the base to 1 mole of 3HB is, for example, 1 to 2 moles, preferably 1 to 1.2 moles. It may be about 1 / 2.

[0077] The reaction of the compound represented by formula (2) with 3HB may be carried out in the presence of a solvent. Examples of the solvent include amides (e.g., N,N-diC amides such as N,N-dimethylformamide, N,N-diethylformamide, and N,N-dimethylacetamide). 1-4 Alkyl C 1-3 NCs such as acylamides and N-methyl-2-pyrrolidone 1-4 Alkyl-2-pyrrolidone, etc. The solvents can be used alone or in combination of two or more. The proportion of the solvent may be, for example, about 100 to 1000 parts by mass per 100 parts by mass of the total amount of the compound represented by formula (2), 3HB, and base.

[0078] In the reaction of the compound represented by the formula (2) with 3HB, the reaction conditions are 1 , L 2 It may be selected appropriately depending on the type of L 1 , L 2 is the group [-O-SO2-R 2 In the case of the above, the reaction temperature may be, for example, 0 to 100°C, preferably 30 to 70°C, and more preferably 40 to 60°C, and the reaction may usually be carried out under ice cooling, and the reaction time may be, for example, 1 to 96 hours, and preferably about 24 to 72 hours. 1 , L 2When is a halogen atom, the reaction temperature may be, for example, 30 to 130°C, preferably 60 to 100°C, and more preferably 70 to 90°C, and the reaction time may be, for example, 1 to 48 hours, and preferably about 12 to 24 hours.

[0079] The reaction of the compound represented by formula (2) with 3HB can usually be carried out in an inert atmosphere (e.g., nitrogen gas; a rare gas such as argon gas, etc.) with stirring, and may be carried out under normal pressure, elevated pressure, or reduced pressure.

[0080] After completion of the reaction, the reaction product may be separated and purified by a conventional method, for example, a separation and purification means such as neutralization, washing, dehydration, filtration, adsorption, concentration, extraction, crystallization, reprecipitation, centrifugation, column chromatography, or a combination of these.

[0081] [Thermoplastic resin] The diol compound represented by the formula (1) can be effectively used as a polymerization component (monomer) for forming a thermoplastic resin having a 3HB skeleton (or 3HB unit). By using the diol compound represented by the formula (1) as a polymerization component, decomposition of 3HB can be effectively suppressed and a high molecular weight can be achieved.

[0082] The thermoplastic resin may contain, as a polymerization component, a diol component containing at least the diol compound represented by the formula (1), and may be, for example, a step-growth polymerization (polycondensation or polyaddition) thermoplastic resin such as a polyurethane resin (or a thermoplastic polyurethane resin) (e.g., a polyester urethane resin), a polyester resin (a polyester resin, a polyester carbonate resin), or a polyether resin, with a polyurethane resin or a polyester resin being preferred.

[0083] Therefore, the polymerization components forming the thermoplastic resin usually contain other polymerization components different from the diol component, such as a diisocyanate component, a dicarboxylic acid component, and a carbonate bond-forming component (e.g., phosgenes such as phosgene, phosgene polymers (diphosgene, triphosgene, etc.); carbonate diesters such as diphenyl carbonate). These other polymerization components can be used alone or in combination of two or more. Among these other polymerization components, diisocyanate components and dicarboxylic acid components are preferred in terms of reactivity and productivity. Below, the diisocyanate component and dicarboxylic acid component, which can be the main polymerization components forming the thermoplastic resin in addition to the diol component, are described in detail.

[0084] (Diol component) The diol component contains at least a diol compound represented by the formula (1) (also referred to as a first diol component), and the first diol component may be formed from a specific diol compound represented by the formula (1) alone or in combination of two or more. Preferred diol compounds as the first diol component are the same as those in the preferred embodiment described above for the formula (1).

[0085] When two or more diol compounds represented by the formula (1) are combined, for example, 1 Two or more diol compounds differing in the type of m or the steric configuration of the 3HB unit may be combined, or a compound in which m is 0 (dimer) and a compound in which m is 1 (trimer) may be combined (for example, in the production of a specific diol compound represented by the formula (1), when a mixture of the dimer and trimer is obtained, both may be used as polymerization components without being purified into either one).

[0086] The diol component may or may not contain a second diol component different from the first diol component, as necessary, taking into consideration the balance between the mechanical properties and other physical properties of the resulting resin and biodegradability. Representative examples of the second diol component include an aliphatic diol component, an alicyclic diol component, and an aromatic diol component. Specific examples of the second diol component include the R 1 Examples of the diol compounds include the same diol compounds corresponding to the aliphatic diols, alicyclic diols and aromatic diols exemplified in the above section.

[0087] These second diol components can be used alone or in combination of two or more. Among these second diol components, aliphatic diol components such as alkylene glycol are preferred, and linear or branched C 2-12 Alkylene glycol (e.g., linear or branched C 2-8 Alkylene glycols, etc.), especially linear or branched C 2-6 Alkylene glycol (e.g., linear or branched C 2-4 alkylene glycols), especially linear or branched C 2-3 Alkylene glycols and the like are preferred.

[0088] In the thermoplastic resin, the proportion of the structural units derived from the diol component (also referred to as diol units) may be selected from a range of, for example, about 1 to 70 mol% (e.g., 10 to 60 mol%), preferably about 30 to 55 mol% (e.g., 40 to 53 mol%), more preferably about 45 to 52 mol%, and usually about 50 mol%, relative to all structural units derived from the polymerization components of the thermoplastic resin.

[0089] Furthermore, in the thermoplastic resin, the proportion of the structural units derived from the first diol component (also referred to as first diol units) relative to the total diol units may be selected from a range of, for example, about 1 mol% or more (10 to 100 mol%), preferably 30 mol% or more (50 to 100 mol%), more preferably 60 mol% or more (70 to 100 mol%), even more preferably 80 mol% or more (90 to 100 mol%), and particularly preferably 95 mol% or more, or substantially 100 mol%. If the amount of the first diol units is too small, the biodegradability of the resin may be reduced.

[0090] The first diol units may be formed solely from structural units derived from a dimer in which m is 0 in formula (1), but from the viewpoint of efficiently introducing 3HB units, it is preferable that they contain at least structural units derived from a trimer in which m is 1. Therefore, the proportion of the structural units derived from the trimer relative to the total first diol units may be selected, for example, from a range of about 1 to 100 mol% (e.g., 10 to 99 mol%), preferably 30 to 100 mol% (e.g., 50 to 95 mol%), more preferably 60 to 100 mol% (e.g., 70 to 90 mol%), even more preferably 80 to 100 mol% (e.g., 90 to 100 mol%), and particularly preferably 95 to 100 mol% (substantially 100 mol%).

[0091] The proportion of 3HB units in the thermoplastic resin that have an R configuration (R-isomer) (or (R)-3HB units) relative to the total number of 3HB units may be selected from a range of, for example, about 1 to 100 mol % (e.g., 10 to 99 mol %), preferably 30 to 100 mol % (e.g., 50 to 95 mol %), more preferably 70 to 100 mol % (e.g., 90 to 100 mol %), even more preferably 95 to 100 mol % (e.g., 98 to 100 mol %), and particularly 99 to 100 mol % (e.g., 99.5 to 100 mol %, and particularly essentially 100 mol %). If the proportion of (R)-3HB units is too low, mechanical properties and biodegradability may be significantly reduced.

[0092] When a first diol component and a second diol component are combined, the ratio of the first diol units to the structural units (second diol units) derived from the second diol component (particularly an aliphatic diol component such as alkylene glycol) can be adjusted taking into account the mechanical properties, biodegradability, and other properties of the resin, and may be selected, for example, from a range of about 1 / 99 to 99 / 1 (former / latter molar ratio), or preferably about 1 / 99 to 10 / 90 from the viewpoint of imparting biodegradability without significantly impairing physical properties such as mechanical properties. If the amount of the first diol units is too small, the biodegradability of the resin may be reduced, and if the amount of the second diol units is too small, the mechanical properties and other properties of the resin may not be sufficiently improved.

[0093] In this specification and claims, a "diol unit" (including a "first diol unit") or a "structural unit derived from a diol component" means a unit (or a divalent group) obtained by removing hydrogen atoms from two hydroxyl groups of the corresponding diol component, and a "diol component" (including compounds exemplified as diol components) may be used synonymously with the corresponding "diol unit."

[0094] (Diisocyanate component) When the polymerization component contains a diisocyanate component, it can be combined with a first diol component (a diol compound having an ester bond represented by the formula (1)) to form a polyurethane resin (such as a polyester urethane resin).

[0095] The diisocyanate component may be a diisocyanate compound having two isocyanate groups as polymerizable groups in its chemical structure, or a derivative thereof, and examples thereof include an aliphatic diisocyanate component, an alicyclic diisocyanate component, an aromatic aliphatic diisocyanate component, an aromatic diisocyanate component, and a bifunctional urethane prepolymer.

[0096] In this specification and claims, the term "diisocyanate component" is used to mean not only diisocyanate compounds but also their derivatives. Examples of diisocyanate compound derivatives include multimers such as dimers (dimers or uretdione) and trimers (trimers or isocyanurates), and modified products such as biurets, allophanates, and carbodiimides.

[0097] Examples of the aliphatic diisocyanate component include linear or branched C diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and trimethylhexamethylene diisocyanate (TMDI). 2-16 Alkanediisocyanates and derivatives thereof are included.

[0098] Examples of alicyclic diisocyanate components include 1,4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), 4,4'-methylenebis(cyclohexyl isocyanate), hydrogenated xylylene diisocyanate (hydrogenated XDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), norbornane diisocyanate, and derivatives thereof.

[0099] Examples of the araliphatic diisocyanate component include xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and derivatives thereof.

[0100] Examples of the aromatic diisocyanate component include phenylene diisocyanate, tolylene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (MDI), toluidine diisocyanate (TODI), diphenyl ether diisocyanate, and derivatives thereof.

[0101] Examples of bifunctional urethane prepolymers include urethane prepolymers that are produced by reacting the above-mentioned diisocyanate component with a diol component (such as the second diol component) and have two free isocyanate groups.

[0102] These diisocyanate components can be used alone or in combination of two or more. Among these diisocyanate components, aliphatic diisocyanate components such as HDI are preferred from the viewpoints of handleability (moldability or productivity) and biodegradability.

[0103] In the thermoplastic resin, the proportion of the structural units derived from the diisocyanate component (also referred to as diisocyanate units) may be selected from a range of, for example, about 0 to 70 mol % (e.g., 10 to 60 mol %) relative to the total structural units derived from the polymerization components of the thermoplastic resin, preferably about 30 to 55 mol % (e.g., 40 to 53 mol %), more preferably about 45 to 52 mol %, and usually about 50 mol %.

[0104] Furthermore, in the thermoplastic resin, the proportion of structural units derived from an aliphatic diisocyanate component (also referred to as aliphatic diisocyanate units) relative to the total diisocyanate units may be selected from a range of, for example, about 1 mol% or more (e.g., 10 to 100 mol%), preferably 30 mol% or more (e.g., 50 to 100 mol%), more preferably 60 mol% or more (e.g., 70 to 100 mol%), even more preferably 80 mol% or more (e.g., 90 to 100 mol%), and particularly 95 mol% or more, or substantially 100 mol%. If the aliphatic diisocyanate units are too few (if other diisocyanate units such as aromatic diisocyanate units are too many), the biodegradability of the resin may be reduced.

[0105] In this specification and claims, the terms "diisocyanate unit" (including "aliphatic diisocyanate unit") or "structural unit derived from a diisocyanate component" refer to a unit (or divalent group) in which two isocyanate groups [-N=C=O] of the corresponding diisocyanate component are incorporated into a resin, i.e., the group [-NH-C(=O)-].

[0106] (Dicarboxylic acid component) When the polymerization component contains a dicarboxylic acid component, it can be combined with a first diol component or the like to form a polyester resin or the like.

[0107] The dicarboxylic acid component may be a dicarboxylic acid compound having two carboxyl groups as polymerizable groups in its chemical structure or an ester-forming derivative thereof, and examples thereof include an aliphatic dicarboxylic acid component, an alicyclic dicarboxylic acid component, and an aromatic dicarboxylic acid component.

[0108] In the present specification and claims, the term "dicarboxylic acid component" refers to a dicarboxylic acid and its ester-forming derivatives. Examples of the ester-forming derivatives include alkyl esters, acid halides, and acid anhydrides. Examples of the alkyl esters include lower alkyl esters, such as C alkyl esters, methyl esters, ethyl esters, and t-butyl esters. 1-4 Alkyl esters, etc. The ester-forming derivatives may be monoesters (half esters) or diesters.

[0109] Examples of the aliphatic dicarboxylic acid component include alkanedicarboxylic acids, specifically, C carboxylic acids such as succinic acid, adipic acid, sebacic acid, and decanedicarboxylic acid. 2-12 Alkane dicarboxylic acids, etc.; unsaturated aliphatic dicarboxylic acids, specifically C such as maleic acid, fumaric acid, and itaconic acid 2-10 Alkene-dicarboxylic acids; and ester-forming derivatives thereof.

[0110] Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acids, specifically, C 1,4-cyclohexane dicarboxylic acids. 5-10 Cycloalkane dicarboxylic acids, etc.; bridged cyclic cycloalkane dicarboxylic acids, specifically, bi- or tricycloalkane dicarboxylic acids such as decalin dicarboxylic acid, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid, etc.; cycloalkene dicarboxylic acids, specifically, C such as cyclohexene dicarboxylic acid, etc. 5-10 Examples thereof include cycloalkene-dicarboxylic acids; bridged cyclic cycloalkene dicarboxylic acids, specifically bi- or tricycloalkene dicarboxylic acids such as norbornene dicarboxylic acid; and ester-forming derivatives thereof.

[0111] Examples of the aromatic dicarboxylic acid component include monocyclic aromatic dicarboxylic acids, polycyclic aromatic dicarboxylic acids, and ester-forming derivatives thereof. Examples of the monocyclic aromatic dicarboxylic acids include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid; alkyl benzene dicarboxylic acids, specifically, C alkyl benzene dicarboxylic acids such as 4-methylisophthalic acid; 1-4 alkyl-benzenedicarboxylic acids and the like.

[0112] Examples of polycyclic aromatic dicarboxylic acids include condensed polycyclic aromatic dicarboxylic acids, specifically condensed polycyclic C dicarboxylic acids such as naphthalenedicarboxylic acid, anthracenedicarboxylic acid, and phenanthrenedicarboxylic acid. 10-24 Arene-dicarboxylic acids, preferably fused polycyclic C 10-14 arene-dicarboxylic acids, etc.; biaryl dicarboxylic acids, specifically, bi-C such as 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and 3,3'-dicarboxy-1,1'-binaphthyl 6-10 Aryl-dicarboxylic acids, etc.; Bis(carboxyalkoxy)bis(C) 6-10 Aryl, specifically bis(carboxy C such as 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl 1-4 Alkoxy)BiC 6-10Aryl, etc.; Bis[(carboxyalkoxy)-C 6-10 aryl]alkanes, specifically bis[(carboxy C 1-4 Alkoxy)-C 6-10 Aryl]C 1-6 Alkanes, etc.; diarylalkanedicarboxylic acids, specifically, di-C such as 4,4'-diphenylmethanedicarboxylic acid 6-10 Aryl C 1-6 Alkane-dicarboxylic acids, etc.; diaryl ketone dicarboxylic acids, specifically, di(C) such as 4,4'-diphenyl ketone dicarboxylic acid 6-10 aryl) ketone-dicarboxylic acids; diaryl ether dicarboxylic acids, specifically, di(C) such as 4,4'-diphenyl ether dicarboxylic acid 6-10 aryl) ether-dicarboxylic acids; diarylsulfonedicarboxylic acids, specifically, di(C) such as 4,4'-diphenylsulfonedicarboxylic acid; 6-10 aryl) sulfone-dicarboxylic acids and the like.

[0113] Examples of the naphthalenedicarboxylic acid include 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid is the most common.

[0114] These dicarboxylic acid components can be used alone or in combination of two or more. Among these dicarboxylic acid components, aromatic dicarboxylic acid components such as monocyclic aromatic dicarboxylic acid components (e.g., benzenedicarboxylic acid) and condensed polycyclic aromatic dicarboxylic acid components (e.g., naphthalenedicarboxylic acid) are preferred from the viewpoint of mechanical properties, and C dicarboxylic acid components such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are also preferred. 6-10 Arene-dicarboxylic acid components (particularly benzenedicarboxylic acid components such as terephthalic acid) are preferred. From the viewpoint of biodegradability, aliphatic dicarboxylic acid components, for example, C 1000-12000 such as adipic acid, are preferred. 2-12Alkane-dicarboxylic acids are preferred.

[0115] In the thermoplastic resin, the proportion of the structural units derived from the dicarboxylic acid component (also referred to as dicarboxylic acid units) may be selected from a range of, for example, about 0 to 70 mol % (e.g., 10 to 60 mol %) relative to all structural units derived from the polymerization components of the thermoplastic resin, preferably about 30 to 55 mol % (e.g., 40 to 53 mol %), more preferably about 45 to 52 mol %, and usually about 50 mol %.

[0116] In this specification and claims, a "dicarboxylic acid unit" or a "structural unit derived from a dicarboxylic acid component" means a unit (or a divalent group) obtained by removing OH (hydroxyl group) from two carboxyl groups of the corresponding dicarboxylic acid.

[0117] (Method of manufacturing thermoplastic resin) The method for producing the thermoplastic resin is not particularly limited as long as it involves polymerization using the first diol component as a polymerization component, and a conventional method can be used by appropriately selecting the catalyst, reaction conditions, etc. depending on the type of thermoplastic resin (or polymerization component). The polymerization reaction may be carried out one or more times depending on the type of polymerization component. For example, the thermoplastic resin may be prepared by using the oligomer (or prepolymer) obtained in the first polymerization as a polymerization component in the second polymerization.

[0118] The reaction temperature (polymerization temperature) in each polymerization may be, from the viewpoint of effectively suppressing decomposition (such as thermal decomposition) of the 3HB units in the first diol component and achieving high molecular weight, for example, 150°C or lower (e.g., 30 to 150°C), preferably 120°C or lower (e.g., 50 to 120°C), more preferably 100°C or lower (e.g., 60 to 100°C), and particularly 90°C or lower (e.g., 70 to 90°C, preferably 75 to 85°C). Therefore, the polymerization components preferably have excellent reactivity with the first diol component (e.g., secondary alcohols of 3HB units) and can be easily polymerized even at relatively low temperatures, such as a diisocyanate component and an acid halide (e.g., acid chloride) or acid anhydride of a dicarboxylic acid.

[0119] (i) When the polymerization component contains a diisocyanate component When polymerizing polymerization components containing a diol component and a diisocyanate component, the ratio of the diol component to the diisocyanate component (or the ratio of the diol component to the diisocyanate component) used (or the ratio of the diol component to the diisocyanate component) may be adjusted in relation to the other polymerization components, and may be selected from a wide range, for example, from about 1 / 0.1 to 1 / 10 (e.g., 1 / 0.5 to 1 / 5) in the molar ratio of the former to the latter. Typically (especially when polymerizing polyurethane resins such as polyester urethane resins), the ratio may be about 1 / 0.8 to 1 / 1.2, preferably 1 / 0.9 to 1 / 1.1, and more preferably 1 / 1 to 1 / 1.1. It is preferable to use polymerization components such as the diol component that have been dried under reduced pressure for, for example, about 1 to 12 hours.

[0120] The reaction may be carried out in the presence of a catalyst, if necessary. Examples of the catalyst include organotin compounds, organozirconium compounds, organotitanium compounds, organometallic catalysts such as metal naphthenates, and tertiary amines or salts thereof.

[0121] Examples of organotin compounds include tin(II) alkanoates (or tin(II) bisalkanoates) such as tin(II) octoate (or tin(II) 2-ethylhexanoate); dialkyltin(IV) diacylates such as dibutyltin acetate and dibutyltin dilaurate (or dibutyltin(IV) dilaurate); and dialkyldialkoxytin(IV) compounds such as dibutyldimethoxytin(IV).

[0122] Examples of organic zirconium compounds include zirconium(IV) tetraalkoxides such as zirconium(IV) tetra-n-butoxide, zirconium(IV) tetraacetylacetonate, zirconium(IV) chelate complexes such as zirconium(IV) dibutoxybis(ethylacetoacetate), and the like.

[0123] Examples of organic titanium compounds include titanium(IV) tetraalkoxides such as titanium(IV) tetra-n-butoxide and titanium(IV) tetra-2-ethylhexyloxide, and titanium(IV) chelate complexes such as titanium(IV) tetraacetylacetonate.

[0124] Examples of metal naphthenates include copper naphthenate, zinc naphthenate, and cobalt naphthenate.

[0125] Tertiary amines include chain tertiary amines (or non-heterocyclic amines), heterocyclic amines, and the like.

[0126] Examples of the chain tertiary amine include trialkylamines such as triethylamine; cycloalkyl-dialkylamines such as cyclohexyldimethylamine; N-alkyl-dicycloalkylamines such as N-methyldicyclohexylamine; aralkyl-dialkylamines such as benzyldimethylamine; hydroxyalkyl-dialkylamines such as 2-hydroxyethyldimethylamine and 2-hydroxyethyldiethylamine; hydroxyalkoxyalkyl-dialkylamines such as 2-(2-hydroxyethoxy)ethyldimethylamine; and N,N,N,N-tetramethyl-1,4-butanediamine and N,N,N,N-tetramethyl-1,6-hexanediamine. N,N-bis[(dialkylamino)alkyl]amines such as N,N-bis[3-(dimethylamino)propyl]amine; N-alkyl-N,N-bis[(dialkylamino)alkyl]amines such as N,N,N',N'',N''-pentamethyldiethylenetriamine and N-methyl-N,N-bis[3-(dimethylamino)propyl]amine; bis(dialkylaminoalkyl)ethers such as bis(2-dimethylaminoethyl) ether; and N,N,N'-trialkyl-N'-(hydroxyalkyl)-bis(aminoalkyl)ethers such as N,N,N'-trimethyl-N'-(2-hydroxyethyl)-bis(2-aminoethyl) ether.

[0127] Examples of heterocyclic tertiary amines include pyridine, N,N-dimethylpiperazine, morpholines [e.g., N-alkylmorpholines (N-methylmorpholine, N-ethylmorpholine, etc.), bis(2-morpholinoethyl)ether, etc.], triethylenediamines [e.g., triethylenediamine (DABCO), hydroxymethyltriethylenediamine, etc.], and cyclic amidines [e.g., 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), 1,8-diaza-bicyclo[5.4.0]undecene-7(DBU)].

[0128] Tertiary amines (e.g., cyclic amidines) may be in the form of a salt, and examples thereof include organic acid salts such as carboxylates (formate, octylate, etc.) and sulfonates (p-toluenesulfonate, etc.), and phenol salts.

[0129] These catalysts can be used alone or in combination. Among these catalysts, organometallic catalysts (organotin compounds such as dibutyltin(IV) dilaurate) are often used.

[0130] The amount of the catalyst used may be, for example, about 0.00001 to 0.1 mol, preferably about 0.0001 to 0.01 mol, and more preferably about 0.0005 to 0.005 mol, per 1 mol of the diisocyanate component.

[0131] The reaction may be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it is inactive or non-reactive with diisocyanates, and examples thereof include ethers, ketones, esters, hydrocarbons, halogenated solvents, nitriles, amides, and sulfoxides.

[0132] Examples of ethers include dialkyl ethers such as diethyl ether and dipropyl ether; and cyclic ethers such as 1,4-dioxane and tetrahydrofuran.

[0133] Examples of ketones include acetone, methyl ethyl ketone (ethyl methyl ketone), dialkyl ketones such as diisopropyl ketone and isobutyl methyl ketone.

[0134] Examples of the esters include acetate esters such as methyl acetate, ethyl acetate, and butyl acetate.

[0135] Examples of hydrocarbons include aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene, xylene, and ethylbenzene.

[0136] Examples of halogen-based solvents include halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, trichloroethane, and tetrachloroethane.

[0137] The nitriles include acetonitrile.

[0138] Examples of amides include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone.

[0139] Examples of sulfoxides include dimethyl sulfoxide (DMSO).

[0140] These solvents can be used alone or in combination. Among these solvents, amides such as DMF are preferred. The solvent is preferably a dehydrated solvent.

[0141] The reaction may be carried out in air or in an inert gas atmosphere. Examples of inert gases include nitrogen gas and rare gases (argon gas, etc.). The reaction may be carried out under reduced pressure, but is usually carried out under elevated pressure or at normal pressure. The reaction temperature is preferably within the range of the polymerization temperature described above, and the reaction time may be, for example, 1 to 48 hours, preferably 12 to 36 hours.

[0142] After the reaction is completed, the product can be separated and purified by a conventional separation method such as filtration, concentration, drying, extraction, crystallization, recrystallization, reprecipitation, column chromatography, or a combination thereof.

[0143] (ii) When the polymerization component contains a dicarboxylic acid component When polymerizing a polymerization component containing a diol component and a dicarboxylic acid component, the polymer can be prepared by, for example, a melt polymerization method such as a transesterification method or a direct polymerization method, a solution polymerization method, an interfacial polymerization method, etc., and the solution polymerization method is preferred. The reaction may be carried out in the presence or absence of a solvent depending on the polymerization method.

[0144] The ratio (or charge ratio) of the diol component to the dicarboxylic acid component may be adjusted in relation to the other polymerization components. For example, the former / latter (molar ratio) may be selected from a wide range of about 1 / 0.1 to 1 / 10 (e.g., 1 / 0.5 to 1 / 5). Typically (especially when polymerizing polyester-based resins such as polyester resins), it may be about 1 / 0.8 to 1 / 1.2, preferably 1 / 0.9 to 1 / 1.1, and more preferably 1 / 1 to 1 / 1.1. However, this range is not necessarily required, and at least one component selected from each diol component and each dicarboxylic acid component may be used in excess of the expected introduction ratio. For example, when a diol component such as ethylene glycol that can be distilled from the reaction system is included in the polymerization components, it may be used in excess of the ratio (or introduction ratio) introduced into the polyester-based resin.

[0145] The reaction may be carried out in the presence of a catalyst. Conventional esterification catalysts, such as metal catalysts, can be used as the catalyst. Examples of metal catalysts include metal compounds containing alkali metals such as sodium; alkaline earth metals such as magnesium, calcium, and barium; transition metals such as titanium, manganese, and cobalt; metals in Group 12 of the periodic table such as zinc and cadmium; metals in Group 13 of the periodic table such as aluminum; metals in Group 14 of the periodic table such as germanium and lead; and metals in Group 15 of the periodic table such as antimony. Examples of metal compounds include alkoxides; organic acid salts such as acetates and propionates; inorganic acid salts such as borates and carbonates; metal oxides, and hydrates thereof. Representative metal compounds include germanium compounds such as germanium dioxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, and germanium-n-butoxide; antimony compounds such as antimony trioxide, antimony acetate, and antimony ethylene glycolate; titanium compounds such as tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate (titanium(IV) tetrabutoxide), titanium oxalate, and potassium titanium oxalate; manganese compounds such as manganese acetate tetrahydrate; and calcium compounds such as calcium acetate monohydrate.

[0146] These catalysts can be used alone or in combination of two or more. When using multiple catalysts, each catalyst can be added according to the progress of the reaction. Among these catalysts, manganese acetate tetrahydrate, calcium acetate monohydrate, germanium dioxide, titanium (IV) tetrabutoxide, etc. are preferred. The amount of catalyst used is, for example, 0.01 × 10 per mole of the dicarboxylic acid component. -4 ~100×10 -4 moles, preferably 0.1 x 10 -4 ~40×10 -4 It is a mole.

[0147] The reaction may be carried out in the presence of a stabilizer such as a heat stabilizer or an antioxidant, if necessary. Heat stabilizers are commonly used, and examples thereof include phosphorus compounds such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dibutyl phosphate (dibutyl phosphate), phosphorous acid, trimethyl phosphite, and triethyl phosphite. These heat stabilizers can be used alone or in combination. Among these heat stabilizers, dibutyl phosphate is commonly used. The amount of heat stabilizer used is, for example, 0.01 × 10 per mole of the dicarboxylic acid component. -4 ~100×10 -4 moles, preferably 0.1 x 10 -4 ~40×10 -4 It is a mole.

[0148] In addition, from the viewpoint of easily adjusting the polymerization temperature low and effectively suppressing decomposition of 3HB units, it is preferable to use an acid halide such as an acid chloride as the dicarboxylic acid component and react it with the diol component. When an acid halide is used as the dicarboxylic acid component, the reaction may be carried out in the presence of a base to trap the hydrogen halide produced in the reaction. Examples of the base include inorganic bases such as metal hydroxides (e.g., alkali metal hydroxides or alkaline earth metal hydroxides such as sodium hydroxide and calcium hydroxide) and metal carbonates (e.g., alkali metal carbonates or alkaline earth metal salts such as sodium carbonate and sodium bicarbonate); and organic bases such as amines (e.g., trialkylamines such as triethylamine, aromatic tertiary amines such as benzyldimethylamine, and heterocyclic tertiary amines such as pyridine). The base may be used alone or in combination. The amount of the base used may be, for example, 0.8 to 20 mol (e.g., 1 to 10 mol), preferably 1.2 to 5 mol, and more preferably about 1.5 to 3 mol per mol of the acid halide.

[0149] The reaction is usually carried out in an atmosphere of an inert gas, such as nitrogen gas, or a rare gas such as helium gas or argon gas. The reaction can also be carried out under reduced pressure, for example, at a pressure of 1×10 2 ~1×10 4The reaction can also be carried out at a pressure of about 100 Pa. Usually, the transesterification reaction is carried out in an inert gas atmosphere such as nitrogen gas, and the polycondensation reaction is carried out under reduced pressure. The reaction temperature is preferably in the range of the polymerization temperature described above, and the reaction time may be, for example, about 1 to 48 hours, and preferably about 12 to 36 hours.

[0150] After the reaction is completed, the product can be separated and purified by a conventional separation method such as filtration, concentration, drying, extraction, crystallization, recrystallization, reprecipitation, column chromatography, or a combination thereof.

[0151] (Characteristics and uses of thermoplastic resins) Although the thermoplastic resin has a skeleton (3HB unit) derived from 3HB, the molecular weight can be surprisingly increased significantly even when prepared by chemical synthesis, and therefore the resin has excellent mechanical properties and moldability (productivity).

[0152] The average molecular weight of the thermoplastic resin can be measured in polystyrene equivalent terms by gel permeation chromatography (GPC) or the like, and the weight average molecular weight Mw may be selected from a range of, for example, about 30,000 or more (e.g., 30,000 to 300,000), preferably about 50,000 or more (e.g., 80,000 to 200,000), more preferably about 100,000 or more (e.g., 110,000 to 180,000), and particularly about 120,000 or more (e.g., 130,000 to 150,000). The number average molecular weight Mn may be selected, for example, from a range of about 10,000 or more (e.g., 20,000 to 200,000), preferably about 30,000 or more (e.g., 40,000 to 100,000), more preferably about 50,000 or more (e.g., 55,000 to 80,000), and particularly about 60,000 or more (e.g., 60,000 to 65,000). The polydispersity Mw / Mn may be selected, for example, from a range of about 1 to 10 (e.g., 1.2 to 5), and preferably about 1.5 to 3 (e.g., 2 to 2.5).

[0153] If the average molecular weight, such as the weight average molecular weight Mw or the number average molecular weight Mn, is too low, the mechanical properties and moldability (productivity) tend to decrease, and it may become impossible to mold the polymer into a film or the like.

[0154] In this specification and claims, the weight average molecular weight Mw, the number average molecular weight Mn and the polydispersity Mw / Mn can be measured by the method described in the examples below.

[0155] Furthermore, the thermoplastic resin containing the first diol component represented by formula (1) as a polymerization component is likely to exhibit high biodegradability derived from the 3HB units under both aerobic and anaerobic conditions (particularly under anaerobic conditions), and therefore can also be used to prepare biodegradable resins. In other words, by using the first diol component represented by formula (1) as a polymerization component, the biodegradability of the resulting resin can be improved. Furthermore, it is possible to achieve both the aforementioned mechanical properties and moldability (or productivity) and biodegradability.

[0156] Therefore, molded articles containing at least the above-mentioned thermoplastic resins can be used for a variety of purposes by taking advantage of their excellent mechanical properties and moldability (or productivity), and can also be effectively used in disposable products, etc., because they are particularly biodegradable.

[0157] The molded article may contain a thermoplastic resin other than the thermoplastic resin (a thermoplastic resin that does not contain the diol compound represented by formula (1) as a polymerization component), conventional additives, etc. Examples of additives include fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, mold release agents, antistatic agents, dispersants, flow control agents, leveling agents, antifoaming agents, surface modifiers, hydrolysis inhibitors, carbon materials, stabilizers, and stress-reducing agents. Examples of stabilizers include antioxidants, ultraviolet absorbers, and heat stabilizers. Examples of stress-reducing agents include silicone oil, silicone rubber, various plastic powders, and various engineering plastic powders. These additives may be used alone or in combination.

[0158] The molded article can be produced by, for example, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, casting molding, or the like.

[0159] The shape of the molded body is not particularly limited, and examples thereof include one-dimensional structures such as linear, fibrous, and thread-like structures, two-dimensional structures such as film-like, sheet-like, and plate-like structures, and three-dimensional structures such as concave or convex lens-like, rod-like, hollow (tubular), container-like, and bag-like structures.

[0160] In particular, thermoplastic resins have excellent mechanical properties and moldability, so they can be easily formed into films, and even when thin, they have sufficient strength and are easy to handle. Therefore, the present invention also includes films (or sheets) formed from the above-mentioned thermoplastic resins.

[0161] The average thickness of such a film can be selected from the range of about 1 to 1000 μm depending on the application, and is, for example, about 1 to 200 μm, preferably about 5 to 150 μm, and more preferably about 10 to 120 μm (for example, about 80 to 120 μm).

[0162] Such a film can be produced by forming (or molding) the thermoplastic resin using a conventional film-forming method, such as a casting method (solvent casting method), a melt extrusion method, or a calendar method.

[0163] The film may be unstretched or stretched. The stretched film may be either a uniaxially stretched film or a biaxially stretched film. The stretching ratio in each direction in uniaxial or biaxial stretching is, for example, 1.1 to 10 times, preferably 1.2 to 8 times, and more preferably 1.5 to 6 times. In the case of biaxial stretching, the film may be uniformly stretched, for example, stretched 1.5 to 5 times in both the longitudinal and transverse directions, or may be unevenly stretched, for example, stretched 1.1 to 4 times in the longitudinal direction and 2 to 6 times in the transverse direction. In the case of uniaxial stretching, the film may be longitudinally stretched, for example, stretched 2.5 to 8 times in the longitudinal direction, or transversely stretched, for example, stretched 1.2 to 5 times in the transverse direction. The average thickness of the stretched film is, for example, 1 to 150 μm, preferably 3 to 120 μm, and more preferably 5 to 100 μm.

[0164] Such a stretched film can be obtained by stretching a film (or an unstretched film) after film formation. The stretching method is not particularly limited, and in the case of uniaxial stretching, either a wet stretching method or a dry stretching method may be used, and in the case of biaxial stretching, either a tenter method (flat method) or a tube method may be used, although the tenter method, which has excellent uniformity in stretched thickness, is preferred. [Example]

[0165] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Evaluation methods are described below.

[0166] [Evaluation method] (NMR) Using a nuclear magnetic resonance spectrometer (JASCO Corporation, "JNM-GSX270"), the sample was dissolved in CDCl3, 1 H-NMR spectrum (270 MHz) and 13 The C-NMR spectrum (67.5 MHz) was measured.

[0167] (GPC (gel permeation chromatography)) Using a GPC measurement device (JASCO Corporation, "GL-7400 Series"), the sample was dissolved in tetrahydrofuran (THF) and measured at a flow rate of 1 mL / min using RI detection, and the number-average molecular weight Mn, weight-average molecular weight Mw, and polydispersity Mw / Mn were calculated in terms of standard polystyrene.

[0168] (Biodegradation test) Biodegradability was evaluated under anaerobic conditions according to ISO 15985.

[0169] (FT-IR) A Fourier transform infrared spectrophotometer ("Nicolet iS5" manufactured by Thermo Fisher Scientific Co., Ltd.) was used to measure the ATR method (resolution 4 cm -1 The measurements were taken at 64 times.

[0170] [Example 1] (Tosylation of cyclohexanedimethanol)

[0171] [ka]

[0172] (wherein Ts represents a tosyl group (p-toluenesulfonyl group)).

[0173] Under an argon atmosphere, 3.51 g (24.3 mmol) of cyclohexanedimethanol (3-1), 7.39 g (73.0 mmol), 0.84 g (4.87 mmol) of N,N,N',N'-tetramethyl-1,6-hexanediamine, and 100 mL of acetonitrile were added to a flask and cooled on ice. A mixture of 13.92 g (73.0 mmol) of p-toluenesulfonyl chloride and 100 mL of acetonitrile was added dropwise over 1 hour, and the mixture was stirred under ice cooling for 1 hour and then at room temperature for 24 hours. 21.8 g (24.7 mmol) of N,N-dimethylethylenediamine was added, followed by 100 mL of water. The mixture was filtered, washed with 1 L of water, and dried under reduced pressure. Approximately 200 mL of a dichloromethane / methanol mixture (50 / 50, vol / vol) was added to the resulting reaction mixture and dissolved by heating. After cooling, the precipitate was filtered and dried under reduced pressure to obtain a white solid of 1,4-bis(p-toluenesulfonyloxymethyl)cyclohexane (CHDM-Ts: yield 9.89 g, isolated yield 89.9%) represented by the above formula (2-1).

[0174] The obtained CHDM-Ts 1 H-NMR spectrum and 13 The results of measuring the C-NMR spectrum are shown in FIGS. 1 and 2 and below.

[0175] 1 H-NMR(270MHz,CDCl3):δ=0.86-1.75(10H,-C H -C H 2-C H 2-C H -), 2.45(s,6H,C H 3-Ar-), 3.78-3.87(d,4H,-SO3-C H 2-CH-), 7.35 (d, 4H, Ar H ), 7.76(d,4H,Ar H ).

[0176] 13 C-NMR (67.5MHz, CDCl3): δ=21.74, 24.61(-CH- C H2- C H2-), 28.10( CH3-Ar-), 34.46, 37.01(-CH2- C H(CH2-)-CH2-), 127.73, 127.76, 129.71, 129.76, 132.87, 132.89, 144.58, 144.66 (ArC).

[0177] (Synthesis of 3HB diol)

[0178] [ka]

[0179] (wherein Ts represents a tosyl group (p-toluenesulfonyl group)).

[0180] Under an argon atmosphere, 9.20 g (20.3 mmol) of CHDM-Ts (2-1), 4.66 g (44.8 mmol) of (R)-3-hydroxybutyric acid ((R)-3HB, 99% ee or higher), and 150 mL of N,N-dimethylformamide (DMF) were dissolved in a flask. 6.18 g (44.8 mmol) of potassium carbonate was added and the mixture was stirred at 50 °C for 48 hours. 500 mL of water was added, and the mixture was extracted with 500 mL of hexane / ethyl acetate (3 / 1, vol / vol) three times, followed by washing with 500 mL of brine. After drying over magnesium sulfate, the solvent was evaporated and the residue was purified by column chromatography (hexane / ethyl acetate (volume ratio): 1 / 1 → 1 / 2) to obtain 3HB diol (1,4-bis(3-hydroxybutanoyloxymethyl)cyclohexane) (4.12 g, isolated yield: 44.8%) as a pale yellow oil.

[0181] The obtained 3HB diol represented by formula (1-1) 1 H-NMR spectrum and 13 The results of measuring the C-NMR spectrum are shown in FIGS. 3 and 4 and below.

[0182] 1 H-NMR(270MHz,CDCl3):δ=0.93-2.04(10H,-C H -C H 2-C H 2-CH -), 1.23(d,6H,C H 3-CH-), 2.51(d,4H,-C H 2-C(=O)-O-), 3.10(s,2H,-O H ), 4.00(d,4H,-CH-C H 2-O-), 4.10-4.30 (m, 2H, CH3-C H (-OH)-CH2-).

[0183] 13 C-NMR (67.5MHz, CDCl3): δ=22.48, 25.22(-CH- C H2- C H2-), 28.75( C H3-CH-), 34.32, 36.90(- C H-CH2-O-), 42.75(- C H2-C(=O)-O-), 60.33, 64.17(CH3- C H(-OH)-CH2-), 67.22, 69.40(-CH- C H2-O-).

[0184] Since the 3HB diol represented by formula (1-1) is an isomer mixture, 13 In the C-NMR spectrum, carbon was observed as two peaks (peaks corresponding to the two chemical shift values ​​listed above among the assignments).

[0185] [Example 2] (Polymerization of 3HB polyester urethane)

[0186] [ka]

[0187] 4.86 g (15.36 mmol) of the 3HB diol represented by formula (1-1) obtained in Example 1 was dried under reduced pressure at 60°C for 4 hours, after which 10.2 mg (0.016 mmol) of dibutyltin dilaurate was added and the atmosphere was replaced with argon. 15 mL of dehydrated DMF and 2.7269 g (16.21 mmol) of hexamethylene diisocyanate were added and stirred at 80°C for 24 hours to obtain a highly viscous, pale yellow solution. The resulting reaction solution was diluted with 20 mL of DMF, poured into 800 mL of water, filtered, and then dried under reduced pressure at 60°C for 6 hours. 100 mL of tetrahydrofuran was added, and the mixture was dissolved by heating. The mixture was then poured into 1 L of water and reprecipitated. After filtration, the mixture was dried under reduced pressure at 60°C for 8 hours to obtain the 3HB polyesterurethane shown in the lower part of the formula above as a white solid.

[0188] The obtained 3HB polyester urethane 1 H-NMR spectrum and 13 The results of measuring the C-NMR spectrum are shown in FIGS. 5 and 6 and below.

[0189] 1 H-NMR(270MHz,CDCl3):δ=0.91-1.89(18H,-NH-CH2-C H 2-C H 2-, -CH2-C H (-C H 2)-C H 2-), 1.30(d,6H,C H 3-CH-), 2.44-2.68(m, 4H, -CH-C H 2-C(=O)-O-), 3.07-3.16(m,4H,-NH-C H 2-CH2-CH2-), 3.85-3.98(d,4H,-CH-C H 2-O-), 4.60-5.00(br,2H,-N H -), 5.11-5.18(m,2H,CH3-C H -).

[0190] 13In the C-NMR spectrum, two peaks were observed: one representing the carbon derived from the ester bond (C=O at 170.31 ppm) and the other representing the carbon derived from the urethane bond (C=O at 155.54 ppm), confirming that the desired 3HB polyester urethane had been obtained.

[0191] GPC analysis of the resulting 3HB polyester urethane revealed that the number average molecular weight Mn was 63,000, the weight average molecular weight Mw was 142,000, and the polydispersity index Mw / Mn was 2.256, indicating that a high molecular weight polyester urethane had been obtained.

[0192] The resulting 3HB polyester urethane was pressed for 2 minutes at 120°C and 1 MPa using a press (AH-2003, manufactured by AS ONE Corporation), and then cooled at room temperature and 1 MPa to produce a film with an average thickness of 100 μm. The film had sufficient strength, was easy to prepare, and had high formability.

[0193] [Example 3] (Synthesis of 3HB diol)

[0194] [ka]

[0195] Under an argon atmosphere, 8.75 g (84.05 mmol) of (R)-3-hydroxybutyric acid ((R)-3HB, 99% ee or higher), 7.17 g (38.17 mmol) of 1,2-dibromoethane represented by formula (2-2) above, and 40 mL of DMF were added and stirred at room temperature. 11.62 g (84.07 mmol) of potassium carbonate was added and stirred, resulting in the evolution of CO2 and gelling after approximately 30 minutes. An additional 40 mL of DMF was added, and the mixture was heated and stirred at 80°C for 18 hours, yielding a white slurry. This white slurry was filtered through Celite, and the solvent was distilled off at 60°C and 0.2 kPa to yield a pale yellow oil. The resulting pale yellow oil was purified by column chromatography (CHCl3 / MeOH (volume ratio) = 75:1 → 10:1) to obtain 3HB diol (1,2-bis(3-hydroxybutanoyloxymethyl)ethane: yield 5.05 g, 56.5% yield) represented by the above formula (1-2) as a pale brown oil.

[0196] The obtained 3HB diol represented by formula (1-2) 1 H-NMR spectrum and 13 The results of measuring the C-NMR spectrum are shown in FIGS. 7 and 8 and below.

[0197] 1 H-NMR(270MHz,CDCl3):δ=1.23(d,6H,C H 3-CH-), 2.41-2.57 (dd, 4H, -C H 2-C(=O)-O-), 2.85-3.15(br,2H,-O H ), 4.16-4.27(m,2H,CH3-C H -), 4.33(t,4H,-OC H 2-).

[0198] 13 C-NMR(67.5MHz,CDCl3):δ=22.59( C H3-CH-), 42.91(- C H2-C(=O)-O-), 62.17(-O- C H2-), 64.19(CH3- C H-), 172.23(-CH2- C (=O)-O-).

[0199] In addition, in the 3HB diol represented by formula (1-2), no isomer mixture was confirmed.

[0200] [Comparative Example 1] (Polyurethane Polymerization and Its Biodegradability)

[0201] [ka]

[0202] 0.74 g of cyclohexanedimethanol (CHDM, vacuum dried at 60°C for 1.5 hours) and approximately 1 mg of tin ethylhexanoate were added to 5 mL of DMF and purged with nitrogen. 0.91 g of hexamethylene diisocyanate was added, heated to 80°C, and reacted for 7 hours. 10.0 mL of DMF was added to the resulting reaction solution, followed by 300.55 mL of distilled water. The precipitated white solid was filtered and dried at 60°C to obtain a polyurethane containing no 3HB units. The resulting polyurethane had an Mn of 5,500 and an Mw of 11,000.

[0203] This polyurethane not containing 3HB units was pressed for 2 minutes at 180°C and 1 MPa using a press ("AH-2003" manufactured by AS ONE Corporation), and then cooled at room temperature and 1 MPa to produce a film with an average thickness of 100 μm. A biodegradation test was conducted using the resulting polyurethane film, and it showed no tendency to biogasify even after 77 days, and its molecular weight remained almost unchanged (Mn=4900, Mw=9800).

[0204] [Example 4] (Biodegradability of 3HB polyester urethane) The 3HB polyester urethane obtained in Example 2 was pressed for 2 minutes at 180°C and 1 MPa using a press ("AH-2003" manufactured by AS ONE Corporation), and then cooled at room temperature and 1 MPa to produce a film with an average thickness of 100 μm. A biodegradation test was conducted using the resulting 3HB polyester urethane film, and after 77 days, approximately 5% was converted to biogas, and the Mn decreased from 63,000 to 880 and the Mw decreased from 142,000 to 2,200.

[0205] The FT-IR spectra of the 3HB polyesterurethane before and after the biodegradation test are shown in Figure 9. As is clear from Figure 9, when normalized by the peak top of the urethane bond, the absorption peak of the ester bond after the biodegradation test becomes relatively smaller, indicating that the ester bond between the 3HB unit and the CHDM unit has been selectively (or preferentially) cleaved.

[0206] Comparative Example 2 (Biodegradability of CHDM) The results of evaluating the biodegradability of the monomer CHDM are shown in Figure 10. As is clear from Figure 10, no tendency for biogasification was observed even after 35 days, indicating that CHDM is not biodegradable.

[0207] From these results, it is believed that CHDM remains even after the biodegradation test of the 3HB polyester urethane in Example 4, but because it is water-soluble, it is presumed to remain dissolved in the sludge after the test. The average molecular weight value after the biodegradation test in Example 4 (Mn = 880, Mw = 2200) does not reflect the effect of CHDM dissolved in the sludge, and therefore the actual value is likely to be even lower. [Industrial Applicability]

[0208] The diol compound of the present invention can be suitably used as a resin raw material (or polymerization component) [particularly as a resin raw material for biodegradable resins], and even when 3HB units are introduced into a resin by chemical synthesis, the molecular weight of the resin can be effectively increased, thereby improving the mechanical properties and moldability (or productivity).

[0209] Therefore, it can be used in various fields, such as abrasives (scrubbing agents such as toothpaste, facial cleansers, and body washes), paints, antistatic agents, inks, adhesives, pressure-sensitive adhesives, electrical and electronic materials (e.g., carrier transport agents, light-emitting bodies, and organic photoreceptors), electrical and electronic components or devices (e.g., optical lenses, optical films, optical disks, inkjet printers, digital paper, organic semiconductor lasers, and dye-sensitized solar cells), and mechanical parts or devices (e.g., automobiles, aerospace materials, and sensors). In particular, because of its high mechanical properties, it can be easily molded by extrusion molding, injection molding, and the like, and is suitable for use in various fields as molded parts (e.g., molded articles such as casings and housings, and tableware such as straws, cups, plates, chopsticks, spoons, and forks), containers (containers for food, daily necessities, electrical and electronic devices, and components), and packaging materials such as films, sheets, and bags (e.g., plastic shopping bags, Eco Bags (registered trademark), and garbage bags).

[0210] Furthermore, because it contains a skeleton derived from 3HB, it is biodegradable under aerobic and anaerobic conditions, making it suitable for use in disposable products such as tableware, containers, and bags, among other applications. This is useful for solving environmental issues such as microplastics, which have become increasingly important in recent years, and it can also be used in applications requiring biocompatibility and safety, such as in the medical field (e.g., medical devices, medical disposable products, etc.) and cosmetics.

Claims

1. The following formula (1) 【Chemical 1】 (In the formula, R １ is a linear or branched chain C ２－８ Alkylene glycol or bis(hydroxy C １－６ alkyl) C ３－１２ represents a divalent group obtained by removing two hydroxyl groups from the chemical structure of a cycloalkane, and m represents 0 or 1. A method for producing a diol compound having a structural unit derived from 3-hydroxybutyric acid represented by the formula: The following formula (2) 【Chemistry 2】 (In the formula, L １ represents a leaving group, and L ２ represents a leaving group or a hydroxyl group, and R １ is the same as the above formula (1). and 3-hydroxybutyric acid.

2. The method for producing a diol compound according to claim 1, wherein m is 1 in the formula (1).

3. 3. The method for producing a diol compound according to claim 1, wherein in the formula (1), the structural unit derived from 3-hydroxybutyric acid contains at least a structural unit in which the configuration of the asymmetric carbon atom is R-configuration.

4. The method for producing a diol compound according to any one of claims 1 to 3, wherein the diol compound is a polymerization component of a biodegradable resin.

5. The method for producing a diol compound according to any one of claims 1 to 4, wherein 3-hydroxybutyric acid contains an R-isomer.

6. A method for producing a thermoplastic resin containing a diol component as a polymerization component, the method comprising: a step of producing a diol compound by the production method according to any one of claims 1 to 5; and a step of polymerizing the obtained polymerization component containing at least the diol compound.

7. 7. The method for producing a thermoplastic resin according to claim 6, wherein the proportion of the constitutional units derived from the diol compound is 10 to 100 mol % based on the total constitutional units derived from the diol component.

8. 8. The method for producing a thermoplastic resin according to claim 6, wherein the polymerization components further comprise at least one selected from the group consisting of a diisocyanate component and a dicarboxylic acid component.

9. the diisocyanate component includes an aliphatic diisocyanate component, an alicyclic diisocyanate component, or an aromatic diisocyanate component; 9. The method for producing a thermoplastic resin according to claim 8, wherein the dicarboxylic acid component comprises an acid halide or an acid anhydride of at least one dicarboxylic acid selected from aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.

10. The method for producing a thermoplastic resin according to any one of claims 6 to 9, wherein the thermoplastic resin has a weight average molecular weight of 30,000 or more.

11. The method for producing a thermoplastic resin according to any one of claims 6 to 10, wherein the thermoplastic resin is a biodegradable resin.

12. The method for producing a thermoplastic resin according to any one of claims 6 to 11, wherein the polymerization is carried out at 150°C or less.

13. A method for producing a molded article containing a thermoplastic resin, the method comprising: producing a thermoplastic resin by the production method according to any one of claims 6 to 12; and molding the obtained thermoplastic resin.

14. The method for producing a molded article according to claim 13, wherein the molded article is in the form of a film.

15. The following formula (1) 【Chemistry 3】 (In the formula, R １ is a linear or branched chain C ２－８ Alkylene glycol or bis(hydroxy C １－６ alkyl) C ３－１２ represents a divalent group obtained by removing two hydroxyl groups from the chemical structure of a cycloalkane, and m represents 0 or 1. and a polymerization component including a diisocyanate component and a diol component including at least a diol compound having a structural unit derived from 3-hydroxybutyric acid represented by the formula (I), and improving the biodegradability under anaerobic conditions of the resulting thermoplastic resin.

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