3-hydroxypropionate (co)polymer composition, poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition, method for producing 3-hydroxypropionate (co)polymer, and method for producing poly(lactic acid-b-3-hydroxypropionic acid) block copolymer

Abstract

The present invention provides a 3-hydroxypropionate (co)polymer composition containing a 3-hydroxypropionate (co)polymer and an isocyanate compound, a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition containing a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer and an isocyanate compound, and methods for producing a 3-hydroxypropionate (co)polymer and a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer.

Description

[Technical Field]

[0001] The present invention relates to a 3-hydroxypropionate (co)polymer composition, a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition, a method for producing a 3-hydroxypropionate (co)polymer, and a method for producing a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer. [Background technology]

[0002] Poly(3-hydroxypropionic acid) has biodegradable properties, and due to these environmentally friendly properties, research into its use has been actively conducted recently. There are two main methods for producing poly(3-hydroxypropionic acid): one is a petrochemical-based method that uses β-propiolactone (PL) for polymerization, and the other is a method that uses bio-based 3-hydroxypropionic acid (3HP).

[0003] When using β-propiolactone, several synthesis steps using ethylene oxide are required, which is economically disadvantageous compared to using 3-hydroxypropionic acid, and there is also the problem that the bio content is 0%.

[0004] On the other hand, when polymerizing 3-hydroxypropionic acid, obtaining poly(3-hydroxypropionic acid) requires various steps, such as freeze-drying, ultrasonication, and solvent elution, which requires the use of large amounts of solvent. To address this issue, attempts have been made to polycondense 3-hydroxypropionic acid, but the production of high-molecular-weight poly(3-hydroxypropionic acid) is limited by the generation of cyclic oligomers as by-products. Attempts have been made to increase the molecular weight by ROP of low-molecular-weight cyclic oligomers, but separation and purification are difficult. Therefore, a method for producing high-molecular-weight poly(3-hydroxypropionic acid) from 3-hydroxypropionic acid is needed.

[0005] Polylactic acid (PLA) is a plant-derived resin obtained from plants such as corn. It is biodegradable and has attracted attention as an environmentally friendly material with excellent tensile strength and elastic modulus. However, compared to existing petroleum-based resins, it has poor impact resistance and heat resistance, limiting its range of applications. Furthermore, its poor elongation to break and brittleness limit its use as a general-purpose resin.

[0006] To overcome these drawbacks, research is being conducted on copolymers containing other repeating units to polylactic acid, and in particular, 3-hydroxypropionic acid has been attracting attention as a comonomer for improving elongation. In particular, poly(lactic acid-b-3-hydroxypropionic acid) block copolymers have been attracting attention, and these copolymers have the effect of improving elongation properties while maintaining the inherent properties of polylactic acid.

[0007] However, biodegradable materials generally require the production of high-molecular-weight poly(lactic acid-b-3-hydroxypropionic acid) copolymers with specific mechanical properties and a certain molecular weight or higher. However, during the condensation polymerization of 3-hydroxypropionic acid, low-molecular-weight cyclic structures are generated, which not only makes it impossible to produce high-molecular-weight poly(3-hydroxypropionic acid) but also reduces the production yield of poly(3-hydroxypropionic acid). Therefore, there is a need for a method for producing poly(lactic acid-b-3-hydroxypropionic acid) copolymers with excellent mechanical properties while maintaining a high molecular weight. Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention provides a 3-hydroxypropionate (co)polymer composition and a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition that have excellent tensile strength, Young's modulus, elongation, etc., despite their high molecular weights, and relates to methods for producing such 3-hydroxypropionate (co)polymers and poly(lactic acid-b-3-hydroxypropionic acid) block copolymers. [Means for solving the problem]

[0009] According to one embodiment of the present invention, there is provided a 3-hydroxypropionate (co)polymer composition comprising a 3-hydroxypropionate (co)polymer and an isocyanate compound.

[0010] According to another embodiment of the present invention, there is provided a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition comprising a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer and an isocyanate compound.

[0011] According to yet another embodiment of the present invention, there is provided a method for producing a 3-hydroxypropionate (co)polymer, comprising: (co)polymerizing 3-hydroxypropionic acid to produce a 3-hydroxypropionate (co)polymer in a reactor; and adding an isocyanate compound to the reactor to react with the 3-hydroxypropionate (co)polymer.

[0012] According to yet another embodiment of the present invention, there is provided a method for producing a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer, the method including the steps of (co)polymerizing 3-hydroxypropionic acid to produce a 3-hydroxypropionate (co)polymer in a reactor; adding an isocyanate compound to the reactor to react with the 3-hydroxypropionate (co)polymer; and ring-opening polymerizing a lactide monomer with the 3-hydroxypropionate (co)polymer to produce a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer.

[0013] The following provides a more detailed description of specific embodiments of the invention, including 3-hydroxypropionate (co)polymer compositions, poly(lactic acid-b-3-hydroxypropionic acid) block copolymer compositions, methods for producing 3-hydroxypropionate (co)polymers, and methods for producing poly(lactic acid-b-3-hydroxypropionic acid) block copolymers.

[0014] Furthermore, unless expressly stated as sequential or continuous, or unless otherwise specifically stated, the steps constituting the manufacturing method described herein should not be construed as being limited to the order in which one step and another step constituting a manufacturing method are described in the specification. Therefore, the order of the steps constituting the manufacturing method may be changed within a range that can be easily understood by a person skilled in the art, and in this case, any accompanying changes that are obvious to a person skilled in the art are included within the scope of the present invention.

[0015] Furthermore, in this specification, the terms first and second are used to describe various components, and the terms are used only to distinguish one component from another.

[0016] Furthermore, in this specification, the term "(co)polymer" is meant to include both copolymers and homopolymers.

[0017] Unless otherwise specified herein, the weight-average molecular weight of a polymer, copolymer, or the like can be measured using gel permeation chromatography (GPC). Specifically, the (co)polymer is dissolved in chloroform to a concentration of 2 mg / mL, and 20 μL is injected into the GPC. GPC analysis is performed at 40°C. Chloroform is used as the mobile phase for GPC at a flow rate of 1.0 mL / min. Two Agilent Mixed-B columns are used in series, and an RI detector is used as the detector. The Mw value is derived using a calibration curve generated using polystyrene standard test strips. Nine weight-average molecular weights of polystyrene standard specimens were used: 2,000 g / mol, 10,000 g / mol, 30,000 g / mol, 70,000 g / mol, 200,000 g / mol, 700,000 g / mol, 2,000,000 g / mol, 4,000,000 g / mol, and 10,000,000 g / mol.

[0018] In addition, as used herein, the term "substituted or unsubstituted" refers to a group substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, halogen, nitrile, nitro, hydroxy, carbonyl, ester, imide, amino, phosphine oxide, alkoxy, aryloxy, alkylthioxy, arylthioxy, alkylsulfoxy, arylsulfoxy, silyl, boron, alkyl, cycloalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylaryl, alkylamine, aralkylamine, heteroarylamine, arylamine, arylphosphine, or heterocyclic groups containing one or more N, O, and S atoms, or a group substituted or unsubstituted with two or more of the above-listed substituents linked together. For example, a "substituent linked to two or more substituents" may be a biphenyl group. In other words, a biphenyl group may be an aryl group or may be interpreted as a substituent linked to two phenyl groups.

[0019] In this specification, the number of carbon atoms in the carbonyl group is not particularly limited, but it is preferably 1 to 40. Specifically, the carbonyl group may have a structure as shown below, but is not limited thereto. [ka]

[0020] In this specification, the oxygen of the ester group may be substituted with a linear, branched, or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a compound having the following structural formula, but is not limited thereto. [ka]

[0021] In this specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably 1 to 25. Specifically, the imide group may have a compound with the following structure, but is not limited thereto. [ka]

[0022] In this specification, specific examples of silyl groups include, but are not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, and phenylsilyl groups.

[0023] In this specification, specific examples of the boron group include, but are not limited to, a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group.

[0024] In this specification, examples of halogen groups include fluorine, chlorine, bromine or iodine.

[0025] In this specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Exemplary alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 4-methylhexyl, 5-methylhexyl, and the like.

[0026] In this specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the number of carbon atoms in the alkenyl group is 2 to 20. According to another embodiment, the number of carbon atoms in the alkenyl group is 2 to 10. According to another embodiment, the number of carbon atoms in the alkenyl group is 2 to 6. Specific examples include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, a stilbenyl group, and a styrenyl group.

[0027] In this specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctyl.

[0028] In this specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The monocyclic aryl group may be, but is not limited to, a phenyl group, a biphenyl group, a terphenyl group, etc. The polycyclic aryl group may be, but is not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, etc.

[0029] In this specification, the fluorenyl group may be substituted, and two of the substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted, [ka] However, the present invention is not limited to this.

[0030] In this specification, the heteroaryl group is a heterocyclic group containing one or more heteroelements selected from O, N, Si, and S and having aromaticity. The number of carbon atoms is not particularly limited, but those having 2 to 60 carbon atoms are preferred. Examples of heteroaryl groups include, but are not limited to, thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, triazole, pyridyl, bipyridyl, pyrimidyl, triazine, acridyl, pyridazine, pyrazinyl, quinolinyl, quinazoline, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinoline, indole, carbazole, benzoxazole, benzimidazole, benzothiazole, benzocarbazole, benzothiophene, dibenzothiophene, benzofuranyl, phenanthroline, thiazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, and dibenzofuranyl groups.

[0031] Herein, the aryl groups in the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group are as exemplified above for the aryl group. Herein, the alkyl groups in the aralkyl group, alkylaryl group, and alkylamine group are as exemplified above for the alkyl group. Herein, the heteroaryl in the heteroarylamine is as exemplified above for the heterocyclic group. Herein, the alkenyl group in the aralkenyl group is as exemplified above for the alkenyl group. Herein, the arylene is as exemplified above for the aryl group, except that it is a divalent group. Herein, the heteroarylene is as exemplified above for the heterocyclic group, except that it is a divalent group. Herein, the hydrocarbon ring is not a monovalent group, but is formed by the bonding of two substituents, and the explanation for the aryl group or cycloalkyl group above is applicable. Herein, the heterocycle is not a monovalent group, but is formed by the bonding of two substituents, and the explanation for the heterocyclic group above is applicable.

[0032] In addition, in this specification, [ka] denotes a bond that is connected to another substituent.

[0033] According to one embodiment of the invention, there is provided a 3-hydroxypropionate (co)polymer composition comprising a 3-hydroxypropionate (co)polymer and an isocyanate compound.

[0034] The present inventors have confirmed that a 3-hydroxypropionate (co)polymer composition containing a 3-hydroxypropionate (co)polymer and an isocyanate compound has excellent mechanical properties such as tensile strength and elongation, despite having a high molecular weight, and have completed the present invention.

[0035] The 3-hydroxypropionate (co)polymer composition may be one produced by a method for producing a 3-hydroxypropionate (co)polymer, which will be described later, but is not limited thereto.

[0036] The 3-hydroxypropionate (co)polymer contained in the composition may be a 3-hydroxypropionate (co)polymer obtained by (co)polymerizing 3-hydroxypropionic acid, and the isocyanate contained in the composition may be a starting material that reacts with the 3-hydroxypropionate (co)polymer. Alternatively, the 3-hydroxypropionate (co)polymer may be a (co)polymer obtained by reacting a 3-hydroxypropionate (co)polymer obtained by (co)polymerizing 3-hydroxypropionic acid with an isocyanate, and the isocyanate contained in the composition may be a residue remaining after the reaction with the (co)polymer.

[0037] The isocyanate is not particularly limited as long as it is a compound containing one or more isocyanate groups, and may be, for example, one or more selected from the group consisting of hexamethylene diisocyanate, L-lysine ethyl ester diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, and toluene diisocyanate.

[0038] Furthermore, the isocyanate may be present in an amount of 0.1 to 10.0 parts by weight, 0.3 to 9.0 parts by weight, 0.5 to 8.0 parts by weight, 0.8 to 7.0 parts by weight, 1.0 to 5.0 parts by weight, or 1.5 to 4.0 parts by weight relative to the 3-hydroxypropionate (co)polymer. If the isocyanate content relative to the 3-hydroxypropionate (co)polymer is too low, the effect of increasing molecular weight through the isocyanate reaction may not be achieved. If the isocyanate content is too high, crosslinking may occur, resulting in a decrease in the uniformity and processability of the final product made from the copolymer.

[0039] In the 3-hydroxypropionate (co)polymer composition according to the embodiment, the 3-hydroxypropionate (co)polymer may be a first 3-hydroxypropionate copolymer in which 3-hydroxypropionic acid and a diol are copolymerized.

[0040] The diol copolymerized with the 3-hydroxypropionic acid is preferably, but not limited to, a diol having hydroxy groups at both ends, such as one or more selected from the group consisting of 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol, ethylene glycol, diethylene glycol, neopentyl glycol, and isosorbide. Furthermore, in order to improve the yield of the 3-hydroxypropionate copolymer and recover a high molecular weight copolymer, it is preferable to use 1,4-butanediol.

[0041] The amount of the diol relative to 100 parts by weight of the 3-hydroxypropionic acid may be 0.05 to 5.00 parts by weight, 0.10 to 4.50 parts by weight, 0.30 to 4.00 parts by weight, 0.50 to 3.50 parts by weight, 1.00 to 3.40 parts by weight, 1.50 to 3.30 parts by weight, or 2.00 to 3.00 parts by weight. If the amount of diol relative to the 3-hydroxypropionic acid is too low, the effect of increasing the molecular weight of the copolymer may not be achieved even if an isocyanate is reacted in a later stage, and if the amount of diol is too high, the molecular weight of the copolymer may actually be reduced.

[0042] The first 3-hydroxypropionate copolymer produced by copolymerizing 3-hydroxypropionic acid and a diol may have both ends substituted with hydroxy groups, which allows a high molecular weight copolymer to be produced by subsequent reaction with an isocyanate. The first 3-hydroxypropionate copolymer may be represented by the following Formula 1: [ka] In the above Chemical Formula 1, R1 is a substituted or unsubstituted C 1-20 Alkylene; substituted or unsubstituted C 6-60 arylene; or C containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S 2-60 heteroarylene, and n and m are each independently an integer of 5 to 1,000.

[0043] For example, R1 may be a substituted or unsubstituted C 2-10 alkylene; or substituted or unsubstituted C 6-20 It may be arylene. More preferably, R1 may be ethylene, propylene, butylene, pentylene, hexylene, heptylene, phenylene, or the like.

[0044] For example, the n and m may each independently be an integer of 10 to 900, 50 to 800, 100 to 700, or 150 to 600.

[0045] The first 3-hydroxypropionate copolymer may have a weight average molecular weight of 2,000 to 100,000, 5,000 to 80,000, 8,000 to 60,000, 10,000 to 40,000, 15,000 to 35,000, 15,000 to 30,000, 15,000 to 25,000, or 15,000 to 20,000.

[0046] The first 3-hydroxypropionate copolymer may have a number average molecular weight of 2,000 to 15,000, 5,000 to 13,000, 7,000 to 11,000, or 8,000 to 10,000.

[0047] Furthermore, the first 3-hydroxypropionate copolymer may have a polydispersity index (PDI) of 1.0 to 3.5, 1.2 to 3.0, 1.4 to 2.5, or 1.6 to 2.0.

[0048] The 3-hydroxypropionate (co)polymer may also be a second 3-hydroxypropionate copolymer in which a first 3-hydroxypropionate copolymer in which 3-hydroxypropionic acid and a diol are copolymerized is reacted with an isocyanate.

[0049] The terminal hydroxy groups of the first 3-hydroxypropionate copolymer can undergo a urethane bond reaction with the isocyanate group of the isocyanate to produce a second 3-hydroxypropionate copolymer, and this chain extension reaction significantly increases the molecular weight of the second 3-hydroxypropionate copolymer, preventing problems such as the generation of cyclic oligomer-type by-products and a decrease in the molecular weight of the polymer. In addition, the second 3-hydroxypropionate copolymer may have a higher weight average molecular weight and number average molecular weight than the first 3-hydroxypropionate copolymer.

[0050] The second 3-hydroxypropionate copolymer may include a repeating unit represented by the following Chemical Formula 2: [ka] In the above Chemical Formula 2, R2 may be a single bond; a substituted or unsubstituted alkylene having 1 to 60 carbon atoms; a substituted or unsubstituted alkenylene having 1 to 60 carbon atoms; a substituted or unsubstituted arylene having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene having 2 to 60 carbon atoms and containing one or more heteroatoms selected from the group consisting of N, O, S, and Si.

[0051] For example, R2 may be an ethyl ester-substituted or unsubstituted alkylene having 1 to 20 carbon atoms, an arylene having 6 to 20 carbon atoms, or a heteroarylene having 2 to 20 carbon atoms and containing one or more heteroatoms selected from the group consisting of N, O, S, and Si. Furthermore, R2 may be methylene, ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,3-butylene, 1,2-butylene, 1,5-pentylene, 1,4-pentylene, 1,3-pentylene, 1,2-pentylene, 1,6-hexylene, 1,5-hexylene, 1,4-hexylene, 1,3-hexylene, 1,2-hexylene, 1,7-heptylene, 1,6-heptylene, 1,5-heptylene, 1,4-heptylene, 1,3-heptylene, 1,2-heptylene, ethyl ester-substituted ethylene, ethyl ester-substituted propylene, ethyl ester-substituted butylene, ethyl ester-substituted ethyl ester-substituted pentylene, ethyl ester-substituted hexylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,5-naphthalene, 1,6-naphthalene, 1,7-naphthalene, 1,8-naphthalene, toluene, 2,3-pyridylene, 2,4-pyridylene, 2,5-pyridylene, 2,6-pyridylene, 4,4'-methylenediphenylene, 3,3'-methylenediphenylene, 2,2'-methylenediphenylene, 2,4'-methylenediphenylene, 4,4'-ethylenediphenylene, 3,3'-ethylenediphenylene, 2,2'-ethylenediphenylene, and 2,4'-ethylenediphenylene.

[0052] In addition, in the chemical formula 2, X and Y are each independently represented by the following chemical formula 2-1 or the following chemical formula 2-2, but at least one of them may be represented by the following chemical formula 2-1. [ka] In the above chemical formula 2-1, R3 is a substituted or unsubstituted C 1-20 Alkylene; substituted or unsubstituted C 6-60arylene; or C containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S 2-60 It may be heteroarylene.

[0053] For example, R3 may be a substituted or unsubstituted C 2-10 alkylene; or substituted or unsubstituted C 6-20 It may be arylene. More preferably, R1 may be ethylene, propylene, butylene, pentylene, hexylene, heptylene, phenylene, or the like.

[0054] Furthermore, q and r may each independently be an integer of 5 to 1000, and for example, q and r may each independently be an integer of 10 to 900, 50 to 800, 100 to 700, or 150 to 600. [ka]

[0055] In the chemical formula 2-2, p may be an integer of 5 to 1000, and for example, p may be an integer of 10 to 900, 50 to 800, 100 to 700, or 150 to 600.

[0056] The end groups of the second 3-hydroxypropionate copolymer may be selected from the end groups represented by the following Chemical Formulas 3 to 5. [ka]

[0057] In the above Chemical Formula 4, R3 is a substituted or unsubstituted C 1-20 Alkylene; substituted or unsubstituted C 6-60 arylene; or C containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S 2-60 heteroarylene, wherein R3 is a substituted or unsubstituted C2-10 alkylene; or substituted or unsubstituted C 6-20 It may be arylene. More preferably, R1 may be ethylene, propylene, butylene, pentylene, hexylene, heptylene, phenylene, or the like.

[0058] In addition, in the chemical formulae 3 to 5, * may be a point at which the copolymer is linked to the main chain or terminal group, respectively.

[0059] Furthermore, the second 3-hydroxypropionate copolymer may have an acid value of 100 meq / kg or less, 95 meq / kg or less, 90 meq / kg or less, 85 meq / kg or less, 80 meq / kg or less, 75 meq / kg or less, 1 meq / kg or more and 70 meq / kg or less, 2 meq / kg or more and 65 meq / kg or less, 3 meq / kg or more and 60 meq / kg or less, 4 meq / kg or more and 55 meq / kg or less, 5 meq / kg or more and 50 meq / kg or less, 7 meq / kg or more and 45 meq / kg or less, 8 meq / kg or more and 40 meq / kg or less, 10 meq / kg or more and 35 meq / kg or less, or 15 meq / kg or more and 30 meq / kg or less. Within this acid value range, the second 3-hydroxypropionate copolymer can exhibit excellent characteristics such as tensile strength, Young's modulus, and elongation while having a high molecular weight, and the acid value can be measured by titration using a 0.02N potassium methoxide solution as the titrant.

[0060] The second 3-hydroxypropionate copolymer may have a weight average molecular weight of 40,000 or more, 41,000 or more and 400,000 or less, 42,000 or more and 380,000 or less, or 43,000 or more and 350,000 or less.

[0061] Furthermore, the second 3-hydroxypropionate copolymer may have a number average molecular weight of 15,000 or more, 16,000 or more and 200,000 or less, or 17,000 or more and 150,000 or less.

[0062] The second 3-hydroxypropionate copolymer may have a polydispersity index (PDI) of 1.5 or more and 7.0 or less, 2.0 or more and 6.5 or less, 2.3 or more and 6.0 or less, or 2.5 or more and 5.5 or less.

[0063] The 3-hydroxypropionate (co)polymer composition according to one embodiment may further include an oxazoline compound, such that the composition may include a 3-hydroxypropionate (co)polymer, an isocyanate, and an oxazoline.

[0064] The oxazoline may be the starting material reacted with the 3-hydroxypropionate (co)polymer or may be a residue remaining after reaction with the 3-hydroxypropionate (co)polymer.

[0065] The oxazoline compound is not particularly limited as long as it is a compound containing one or more oxazoline groups, and may be, for example, one or more selected from the group consisting of 1,3-phenylenebisoxazoline (2,2'-(1,3-phenylene)bis(2-oxazoline)), 1,4-phenylenebisoxazoline (2,2'-(1,4-phenylene)bis(2-oxazoline)), and 2,6-pyridylenebisoxazoline (2,2'-(2,6-pyridylene)-bis(2-oxazoline)).

[0066] The oxazoline compound may be added in an amount of 0.001 to 5,000 parts by weight, 0.005 to 4,000 parts by weight, 0.010 to 3,000 parts by weight, or 0.050 to 2,500 parts by weight, relative to 100 parts by weight of the 3-hydroxypropionate (co)polymer. If the amount of the oxazoline compound added is too small compared to the 3-hydroxypropionate (co)polymer, the molecular weight of the (co)polymer may not increase, whereas if the amount of the oxazoline compound added is too large compared to the (co)polymer, by-products may be produced or a crosslinked structure may be formed.

[0067] Furthermore, the weight ratio of the oxazoline compound to the isocyanate compound may be 1:0.0001 to 1:10, 1:0.0010 to 1:8, 1:0.0020 to 1:6, 1:0.0050 to 1:5, 1:0.0100 to 1:4, 1:0.0500 to 1:3, or 1:0.1000 to 1:2. If the content of the isocyanate compound relative to the oxazoline compound is excessively high, crosslinking may occur before the molecular weight of the (co)polymer increases, making it difficult to produce a high molecular weight (co)polymer. Conversely, if the content of the isocyanate compound relative to the oxazoline compound is excessively low, making it difficult to produce a high molecular weight (co)polymer.

[0068] The 3-hydroxypropionate (co)polymer may be a (co)polymer obtained by reacting an isocyanate with an oxazoline compound, and the oxazoline compound can react with the terminal functional groups of the repeating units of poly(3-hydroxypropionic acid) to link them with two peptide bonds (-CONH-), and the isocyanate compound can react with the terminal functional groups of the repeating units of poly(3-hydroxypropionic acid) to link them with two peptide bonds.

[0069] For example, the 3-hydroxypropionate (co)polymer may include a repeating unit represented by the following chemical formula 6: [ka]

[0070] In the above Chemical Formula 6, R2 may be a single bond; a substituted or unsubstituted alkylene having 1 to 60 carbon atoms; a substituted or unsubstituted alkenylene having 1 to 60 carbon atoms; a substituted or unsubstituted arylene having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene having 2 to 60 carbon atoms and containing one or more heteroatoms selected from the group consisting of N, O, S, and Si.

[0071] For example, R2 may be an ethyl ester-substituted or unsubstituted alkylene having 1 to 20 carbon atoms, an arylene having 6 to 20 carbon atoms, or a heteroarylene having 2 to 20 carbon atoms and containing one or more heteroatoms selected from the group consisting of N, O, S, and Si. Furthermore, R2 may be methylene, ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,3-butylene, 1,2-butylene, 1,5-pentylene, 1,4-pentylene, 1,3-pentylene, 1,2-pentylene, 1,6-hexylene, 1,5-hexylene, 1,4-hexylene, 1,3-hexylene, 1,2-hexylene, 1,7-heptylene, 1,6-heptylene, 1,5-heptylene, 1,4-heptylene, 1,3-heptylene, 1,2-heptylene, ethyl ester-substituted ethylene, ethyl ester-substituted propylene, ethyl ester-substituted butylene, ethyl ester-substituted and ethyl ester-substituted pentylene, ethyl ester-substituted hexylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,5-naphthalene, 1,6-naphthalene, 1,7-naphthalene, 1,8-naphthalene, toluene, 2,3-pyridylene, 2,4-pyridylene, 2,5-pyridylene, 2,6-pyridylene, 4,4'-methylenediphenylene, 3,3'-methylenediphenylene, 2,2'-methylenediphenylene, 2,4'-methylenediphenylene, 4,4'-ethylenediphenylene, 3,3'-ethylenediphenylene, 2,2'-ethylenediphenylene, and 2,4'-ethylenediphenylene.

[0072] Furthermore, in Chemical Formula 2, A and B are each independently represented by the following Chemical Formula 6-1, the following Chemical Formula 6-2, or the following Chemical Formula 6-3, but at least one of them may be represented by the following Chemical Formula 6-1. [ka] In the above chemical formula 6-1, R4 may be a single bond; a substituted or unsubstituted alkylene having 1 to 60 carbon atoms; a substituted or unsubstituted alkenylene having 1 to 60 carbon atoms; a substituted or unsubstituted arylene having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene having 2 to 60 carbon atoms and containing one or more heteroatoms selected from the group consisting of N, O, S, and Si.

[0073] For example, R4 may be an ethyl ester-substituted or unsubstituted alkylene having 1 to 20 carbon atoms, an arylene having 6 to 20 carbon atoms, or a heteroarylene having 2 to 20 carbon atoms and containing one or more heteroatoms selected from the group consisting of N, O, S, and Si. Furthermore, R2 may be methylene, ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,3-butylene, 1,2-butylene, 1,5-pentylene, 1,4-pentylene, 1,3-pentylene, 1,2-pentylene, 1,6-hexylene, 1,5-hexylene, 1,4-hexylene, 1,3-hexylene, 1,2-hexylene, 1,7-heptylene, 1,6-heptylene, 1,5-heptylene, 1,4-heptylene, 1,3-heptylene, 1,2-heptylene, ethyl ester-substituted ethylene, ethyl ester-substituted propylene, ethyl ester-substituted butylene, ethyl ester-substituted and ethyl ester-substituted pentylene, ethyl ester-substituted hexylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,5-naphthalene, 1,6-naphthalene, 1,7-naphthalene, 1,8-naphthalene, toluene, 2,3-pyridylene, 2,4-pyridylene, 2,5-pyridylene, 2,6-pyridylene, 4,4'-methylenediphenylene, 3,3'-methylenediphenylene, 2,2'-methylenediphenylene, 2,4'-methylenediphenylene, 4,4'-ethylenediphenylene, 3,3'-ethylenediphenylene, 2,2'-ethylenediphenylene, and 2,4'-ethylenediphenylene.

[0074] Furthermore, a and b may each independently be an integer of 10 to 5,000, for example, an integer of 100 to 4,000, 300 to 3,000, or 500 to 1,000. [ka] In the above chemical formula 6-2, R5 is a substituted or unsubstituted C 1-20 Alkylene; substituted or unsubstituted C 6-60 arylene; or C containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S 2-60 It may be heteroarylene.

[0075] For example, R5 may be a substituted or unsubstituted C 2-10 alkylene; or substituted or unsubstituted C 6-20 It may be arylene. More preferably, R1 may be ethylene, propylene, butylene, pentylene, hexylene, heptylene, phenylene, or the like.

[0076] Furthermore, d and e may each independently be an integer of 5 to 1000, and for example, d and e may each independently be an integer of 10 to 900, 50 to 800, 100 to 700, or 150 to 600.

[0077] d and e each independently represent an integer of 5 to 1000; [ka] In the above chemical formula 6-3, c may be an integer of 5 to 1000, and for example, n and m may each independently be an integer of 10 to 900, 50 to 800, 100 to 700, or 150 to 600.

[0078] The 3-hydroxypropionate (co)polymer containing the repeating unit represented by the chemical formula 6 may have terminal groups 7 to 9 shown below. [ka]

[0079] In the above Chemical Formula 8, R4 may be a single bond; a substituted or unsubstituted alkylene having 1 to 60 carbon atoms; a substituted or unsubstituted alkenylene having 1 to 60 carbon atoms; a substituted or unsubstituted arylene having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene having 2 to 60 carbon atoms and containing one or more heteroatoms selected from the group consisting of N, O, S, and Si.

[0080] In addition, in the chemical formulae 7 to 9, * may be a point at which the copolymer is linked to the main chain or terminal group, respectively.

[0081] Furthermore, the 3-hydroxypropionate (co)polymer containing the repeating unit represented by Chemical Formula 6 may have an acid value of 20 meq / kg or less, 0.1 meq / kg or more and 18 meq / kg or less, 0.2 meq / kg or more and 17 meq / kg or less, 0.3 meq / kg or more and 15 meq / kg or less, 0.4 meq / kg or more and 13 meq / kg or less, 0.5 meq / kg or more and 11 meq / kg or less, 0.7 meq / kg or more and 10 meq / kg or less, 0.8 meq / kg or more and 9 meq / kg or less, 1.0 meq / kg or more and 8 meq / kg or less, or 1.5 meq / kg or more and 5 meq / kg or less. Within this acid value range, 3-hydroxypropionate (co)polymers can exhibit excellent characteristics such as tensile strength, Young's modulus, and elongation, despite their high molecular weight. The acid value can be measured by titration using 0.02N potassium methoxide solution as the titrant.

[0082] According to another embodiment of the invention, there is provided a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition comprising a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer and an isocyanate compound.

[0083] The poly(lactic acid-b-3-hydroxypropionic acid) composition may be one produced by the method for producing poly(lactic acid-b-3-hydroxypropionic acid) described below, but is not limited thereto.

[0084] The poly(lactic acid-b-3-hydroxypropionic acid) block copolymer may be a block copolymer obtained by ring-opening polymerization of lactide to a second 3-hydroxypropionate copolymer obtained by reacting a first 3-hydroxypropionate copolymer, in which 3-hydroxypropionic acid and a diol are copolymerized, with an isocyanate. In the composition, the isocyanate may be a residue remaining after the reaction with the first 3-hydroxypropionate copolymer.

[0085] The poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition may further contain an oxazoline compound, and thus the poly(lactic acid-b-3-hydroxypropionic acid) block copolymer may be a block copolymer obtained by ring-opening polymerization of lactide with a 3-hydroxypropionate (co)polymer obtained by reacting a 3-hydroxypropionate polymer, an isocyanate, and an oxazoline compound.

[0086] The poly(lactic acid-b-3-hydroxypropionic acid) block copolymer may have a weight-average molecular weight of 120,000 or more, more specifically, 120,000 to 800,000, 150,000 to 500,000, 200,000 to 400,000, or 220,000 to 300,000. If the weight-average molecular weight of the poly(lactic acid-b-3-hydroxypropionic acid) block copolymer is too small, the overall mechanical properties may be significantly reduced.

[0087] The poly(lactic acid-b-3-hydroxypropionic acid) block copolymer may have a number average molecular weight of 100,000 or more, more specifically, 100,000 to 700,000, 120,000 to 500,000, 150,000 to 400,000, or 200,000 to 300,000.

[0088] The poly(lactic acid-b-3-hydroxypropionic acid) block copolymer may have a polydispersity index of 2.0 or more and 10.0 or less, more specifically, 2.5 or more, 3.0 or more, or 3.5 or more, and 8.0 or less, or 6.0 or less, or 5.0 or less.

[0089] The poly(lactic acid-b-3-hydroxypropionic acid) block copolymer may have an elongation of 200% or more, 300% or more, 400% or more, 500% or more, or 600% or more to 1000% or less.

[0090] According to yet another embodiment of the present invention, a method for producing a 3-hydroxypropionate (co)polymer by (co)polymerizing 3-hydroxypropionic acid in a reactor is provided. The method for producing 3-hydroxypropionate (co)polymer includes the step of adding an isocyanate compound to the reactor and reacting it with the 3-hydroxypropionate (co)polymer.

[0091] The (co)polymerization may be carried out in the presence of a sulfonic acid catalyst. The sulfonic acid catalyst is not particularly limited as long as it contains one or more sulfonic groups, and may be, for example, p-toluenesulfonic acid, m-xylene-4-sulfonic acid, 2-mesitylenesulfonic acid, or p-xylene-2-sulfonic acid. The catalyst may be used in an amount of 0.01 to 0.5 mol % relative to the 3-hydroxypropionic acid.

[0092] The step of (co)polymerizing 3-hydroxypropionic acid to prepare a 3-hydroxypropionate (co)polymer in a reactor may be a step of copolymerizing 3-hydroxypropionate and a diol to prepare a first 3-hydroxypropionate copolymer.

[0093] The process for producing the first 3-hydroxypropionate copolymer can include copolymerizing 3-hydroxypropionic acid and a diol to produce an oligomer (Step 1), and polymerizing the oligomer to produce a 3-hydroxypropionic acid copolymer (Step 2).

[0094] The polymerization reaction in Step 1 may be a melt polymerization reaction, where the reactants, 3-hydroxypropionic acid and diol, and the product, oligomer, maintain a liquid state. The polymerization reaction in Step 1 may be carried out at a temperature of 50°C to 150°C and a pressure of 1 to 200 torr. For example, the reaction temperature in Step 1 may be 60°C to 70°C, 80°C to 85°C, or 90°C or higher, and 140°C to 130°C, 120°C to 110°C or lower. Step 1 may be carried out under a pressure of 2 torr to 150 torr, 130 torr to 110 torr, or 100 torr or lower. Furthermore, the reaction time of step 1 can be appropriately determined in consideration of the molecular weight, yield, etc. of the oligomer produced, and is preferably 1 to 10 hours, 1.5 to 8 hours, or 2 to 5 hours.

[0095] The polymerization reaction in step 2 may also be a melt polymerization reaction and may be carried out at a temperature of 70°C or higher and 150°C or lower. The reaction temperature in step 2 may be 75°C or higher, 80°C or higher, 85°C or higher, 90°C or higher, or 95°C or higher, and 140°C or lower, 130°C or lower, 120°C or lower, or 110°C or lower. The pressure in step 2 may be 2 torr or higher, 5 torr or higher, 10 torr or higher, or 15 torr or higher, and 150 torr or lower, 130 torr or lower, 110 torr or lower, or 100 torr or lower. The reaction time in step 2 may be appropriately determined in consideration of the molecular weight and yield of the polymer produced, and is preferably 1 hour to 60 hours, 5 hours to 50 hours, 10 hours to 40 hours, or 15 hours to 30 hours.

[0096] Meanwhile, since step 2 is performed following step 1, the catalyst added in step 1 can also participate in the reaction in step 2. Steps 1 and 2 may also be performed consecutively.

[0097] The first 3-hydroxypropionate copolymer may contain the diol in an amount of 0.05 to 5.00 parts by weight, 0.10 to 4.50 parts by weight, 0.30 to 4.00 parts by weight, 0.50 to 3.50 parts by weight, 1.00 to 3.40 parts by weight, 1.50 to 3.30 parts by weight, or 2.00 to 3.00 parts by weight, per 100 parts by weight of the 3-hydroxypropionic acid. If the diol content is too low relative to the 3-hydroxypropionic acid, the effect of increasing the molecular weight of the copolymer may not be achieved even if an isocyanate is reacted in a later stage. If the diol content is too high, the molecular weight of the copolymer may actually be reduced.

[0098] The step of adding an isocyanate compound to the reactor to react with the 3-hydroxypropionate (co)polymer may include reacting the first 3-hydroxypropionate copolymer with an isocyanate to produce a second 3-hydroxypropionate copolymer.

[0099] The reaction time point between the first 3-hydroxypropionate copolymer and the isocyanate is not particularly limited. However, to produce the high molecular weight copolymer, it is preferable to react the isocyanate with the polymerization terminal of the first 3-hydroxypropionate copolymer. For example, the isocyanate can be added to the reactor and reacted when the polymerization reaction has progressed to 70% or more, 80% or more, 85% or more, 90% or more, or 95% or more but not more than 100%. The reaction time point, i.e., when the polymerization reaction has progressed to 70% or more, can be determined from the conversion rate of 3-hydroxypropionic acid to 3-hydroxypropionic acid copolymer. The conversion rate to the copolymer can be measured or confirmed using an ampere meter or nuclear magnetic resonance (NMR) device.

[0100] The isocyanate may be present in an amount of 0.1 to 10.0 parts by weight, 0.3 to 9.0 parts by weight, 0.5 to 8.0 parts by weight, 0.8 to 7.0 parts by weight, 1.0 to 5.0 parts by weight, or 1.5 to 4.0 parts by weight relative to the first 3-hydroxypropionate copolymer. If the isocyanate content is too low relative to the 3-hydroxypropionic acid, the molecular weight increasing effect due to the isocyanate reaction may not be achieved. If the isocyanate content is too high, crosslinking may occur, resulting in a decrease in the uniformity and processability of the final product made from the copolymer.

[0101] The reaction with the isocyanate may be carried out at a temperature of 80° C. to 180° C. for a time period of 5 to 300 minutes. For example, the reaction with the isocyanate may be carried out at a temperature of 90° C. to 170° C., 100° C. to 160° C., 110° C. to 150° C., or 120° C. to 140° C. for a time period of 10 to 280 minutes, 20 to 260 minutes, 40 to 240 minutes, 60 to 220 minutes, or 90 to 200 minutes.

[0102] The step of adding an isocyanate compound to the reactor and reacting it with the 3-hydroxypropionate (co)polymer may further include adding an oxazoline compound to the reactor and reacting it with the 3-hydroxypropionate (co)polymer.

[0103] By adding an oxazoline compound and an isocyanate compound to the reactor, the functional groups at the terminals of the 3-hydroxypropionate (co)polymer can react with the oxazoline compound and the isocyanate compound. This allows the terminals of the 3-hydroxypropionate (co)polymer to be capped with the oxazoline compound and the isocyanate compound. Furthermore, by capping the terminals of the 3-hydroxypropionate (co)polymer with the oxazoline compound and the isocyanate compound, problems such as the generation of cyclic oligomer-type by-products and a decrease in the molecular weight of the polymer can be prevented, and poly(3-hydroxypropionic acid) with excellent mechanical properties such as tensile strength and elongation, despite its high molecular weight, can be produced.

[0104] Meanwhile, the timing of adding the oxazoline compound and the isocyanate compound to the reactor is not particularly limited. However, in order to produce the high molecular weight 3-hydroxypropionate (co)polymer, it is preferable to add them at the end of the polymerization reaction of the 3-hydroxypropionate (co)polymer. For example, the oxazoline compound and the isocyanate compound can be added when the polymerization reaction has progressed to 70% or more, 80% or more, 85% or more, 90% or more, or 95% to 100%. The timing of adding the oxazoline compound and the isocyanate compound, i.e., when the polymerization reaction has progressed to 70% or more, can be derived from the conversion rate of 3-hydroxypropionic acid to 3-hydroxypropionate (co)polymer. The conversion rate to 3-hydroxypropionate (co)polymer can be measured or confirmed using an ampere meter or nuclear magnetic resonance (NMR) device.

[0105] In addition, the step of adding the oxazoline compound and the isocyanate compound to the reactor may include adding the oxazoline compound to the reactor and then adding the isocyanate compound. For example, the oxazoline compound may be added to the reactor and stirred for 30 minutes to 6 hours, 1 hour to 5 hours, or 2 hours to 4 hours, and then the isocyanate compound may be added.

[0106] Furthermore, the oxazoline compound may be added in an amount of 0.001 to 5,000 parts by weight, 0.005 to 4,000 parts by weight, 0.010 to 3,000 parts by weight, or 0.050 to 2,500 parts by weight, relative to 100 parts by weight of the 3-hydroxypropionate (co)polymer. If the amount of the oxazoline compound added is too small compared to the amount of the 3-hydroxypropionate (co)polymer, the molecular weight of the 3-hydroxypropionate (co)polymer may not increase, whereas if the amount of the oxazoline compound added is too large compared to the amount of the 3-hydroxypropionate (co)polymer, by-products may be produced or a crosslinked structure may be formed.

[0107] The isocyanate compound may be added in an amount of 0.001 to 5,000 parts by weight, 0.005 to 4,500 parts by weight, 0.010 to 4,000 parts by weight, 0.050 to 3,500 parts by weight, 0.100 to 3,400 parts by weight, 0.200 to 3,300 parts by weight, or 0.300 to 3,200 parts by weight, relative to 100 parts by weight of the 3-hydroxypropionate (co)polymer. If the amount of the isocyanate compound added is too small compared to the 3-hydroxypropionate (co)polymer, crystallization of the polymer may be delayed, resulting in deterioration of mechanical properties such as tensile strength. If the amount of the isocyanate compound added is too large compared to the 3-hydroxypropionate (co)polymer, crosslinking may occur before the molecular weight of the polymer increases, making it difficult to produce a high molecular weight polymer.

[0108] According to yet another embodiment of the present invention, a method for producing a 3-hydroxypropionate (co)polymer by (co)polymerizing 3-hydroxypropionic acid in a reactor is provided. adding an isocyanate compound to the reactor to react with the 3-hydroxypropionate (co)polymer; and The present invention provides a method for producing a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer, which comprises the step of ring-opening polymerizing a lactide monomer with the 3-hydroxypropionate (copolymer) to produce a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer.

[0109] The step of (co)polymerizing 3-hydroxypropionic acid to prepare a 3-hydroxypropionate (co)polymer in a reactor; and the step of adding an isocyanate compound to the reactor and reacting it with the 3-hydroxypropionate (co)polymer are the same as those described above in the method for preparing a 3-hydroxypropionate (co)polymer according to yet another embodiment.

[0110] For example, the step of (co)polymerizing 3-hydroxypropionic acid to prepare a 3-hydroxypropionate (co)polymer in a reactor may be a step of copolymerizing 3-hydroxypropionate and a diol to prepare a first 3-hydroxypropionate copolymer.

[0111] Additionally, an oxazoline compound can be further added to the reactor to react with the 3-hydroxypropionate (co)polymer.

[0112] The step of ring-opening polymerizing the 3-hydroxypropionate (co)polymer with lactide monomer to prepare poly(lactic acid-b-3-hydroxypropionic acid) block copolymer can be carried out in the presence of a lactide ring-opening catalyst.

[0113] The ring-opening polymerization may be carried out in the presence of one or more catalysts selected from the group consisting of organometallic complex catalysts and organic catalysts. For example, the organometallic complex catalyst may be a catalyst represented by the following chemical formula 10:

[0114] [Chemical formula 10] MA 1 p A 2 2-p In the above Chemical Formula 10, M is Al, Mg, Zn, Ca, Sn, Fe, Y, Sm, Lu, Ti or Zr; p is an integer from 0 to 2, A 1 and A 2 may each independently be an alkoxy or carboxyl group.

[0115] More specifically, the catalyst may be tin(II) 2-ethylhexanoate (Sn(Oct)2; hereinafter, also referred to as Tin Octoate).

[0116] Meanwhile, the organic catalyst may be any organic catalyst commonly used in the production of polylactide resins by ring-opening polymerization of lactide monomers, regardless of its structure. For example, the organic catalyst may be one or more selected from the group consisting of 1,5,7-triazobicyclo-[4,4,0]dec-5-ene (TBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 4-dimethylaminopyridine (DMAP), 4-(1-pyrrolidinyl)pyridine (PPY), imidazole, triazolium, thiourea, tertiary amine, and creatinine.

[0117] The catalyst content may be 0.0001 to 10 mol%, 0.005 to 8 mol%, 0.05 to 5 mol%, or 0.09 to 3 mol% relative to 100 mol% of the lactide monomer. If the catalyst content relative to 100 mol% of the lactide monomer is too low, the polymerization activity may be insufficient. If the catalyst content is too high, the amount of residual catalyst in the produced block copolymer may increase, resulting in copolymer decomposition or molecular weight reduction due to depolymerization such as transesterification. The ring-opening polymerization may be carried out at a temperature of 150 to 200°C, 160 to 190°C, or 170 to 180°C for 5 minutes to 24 hours, 30 minutes to 20 hours, 1 hour to 15 hours, or 2 hours to 10 hours.

[0118] In the block copolymer, the weight ratio of the lactide to the 3-hydroxypropionate (co)polymer may be 99:1 to 50:50, 98:2 to 55:45, 97:3 to 60:40, 96:4 to 70:30, or 95:5 to 80:20. If the amount of the 3-hydroxypropionate (co)polymer is too small relative to the lactide, brittleness increases, whereas if the amount of the 3-hydroxypropionate (co)polymer is too large relative to the lactide, the molecular weight decreases, which may result in reduced processability and heat resistance. [Effects of the Invention]

[0119] As described above, the present invention can provide a 3-hydroxypropionate (co)polymer composition and a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition that have excellent tensile strength, Young's modulus, elongation, etc., despite having a high molecular weight, and can also provide a method for producing such a 3-hydroxypropionate (co)polymer and a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer. DETAILED DESCRIPTION OF THE INVENTION

[0120] Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are merely illustrative of the present invention, and the present invention is not limited to these examples.

[0121] Example 1 60g of 3-hydroxypropionic acid and 0.42g (1 mol%) of 1,4-butanediol were added to an oil bath and reacted at 90°C and 100 torr for 2 hours. Then, 176mg of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath, and the reaction was carried out at a reduced pressure of 20 torr for 2 hours. The polymerization reaction was carried out at a pressure of less than 1 torr for 24 hours to produce a polymer. After the reaction was completed, the reactants were dissolved in chloroform at a ratio of 10g / 50mL and extracted with 500mL of methanol to obtain the polymer, which was then dried in vacuo for 12 hours.

[0122] Then, 20 g of the polymer was placed in an oil bath under a nitrogen atmosphere, and 0.19 ml of hexamethylene diisocyanate was added, followed by stirring and reaction at a temperature of 140° C. for 180 minutes to produce a 3-hydroxypropionate polymer.

[0123] Example 2 A 3-hydroxypropionate polymer was produced in the same manner as in Example 1, except that 0.26 ml of hexamethylene diisocyanate was used instead of 0.19 ml of hexamethylene diisocyanate.

[0124] Example 3 A 3-hydroxypropionate polymer was produced in the same manner as in Example 1, except that 0.34 ml of hexamethylene diisocyanate was used instead of 0.19 ml of hexamethylene diisocyanate.

[0125] Example 4 A 3-hydroxypropionate polymer was prepared in the same manner as in Example 1, except that 0.39 ml of hexamethylene diisocyanate was added and then stirred and reacted for 90 minutes, instead of adding 0.19 ml of hexamethylene diisocyanate and then stirring and reacting for 180 minutes.

[0126] Example 5 A 3-hydroxypropionate polymer was prepared in the same manner as in Example 1, except that 0.42 ml of hexamethylene diisocyanate was added and then stirred and reacted for 90 minutes, instead of adding 0.19 ml of hexamethylene diisocyanate and then stirring and reacting for 180 minutes.

[0127] Example 6 A 3-hydroxypropionate polymer was prepared in the same manner as in Example 1, except that, instead of adding 0.19 ml of hexamethylene diisocyanate and stirring and reacting at a temperature of 140°C for 180 minutes, 0.48 ml of hexamethylene diisocyanate was added and then stirred and reacted at a temperature of 120°C for 120 minutes.

[0128] Example 7 A 100mL Schlenk flask was placed in an oil bath and charged with 100mL of 60% aqueous 3-hydroxypropionic acid. Approximately 60% of the water in the 3-hydroxypropionic acid was removed at 90°C and 100 torr for 2 hours. Then, 0.2112 parts by weight of p-toluenesulfonic acid (p-TSA) catalyst per 100 parts by weight of 3-hydroxypropionic acid was added to the reaction flask, and a melt polycondensation reaction was carried out at 90°C and 1 torr for 24 hours. After the reaction was completed, the reactant was dissolved in chloroform at a ratio of 10g / 50mL and extracted with 500mL of methanol to obtain poly(3-hydroxypropionic acid).

[0129] Next, 10 g of the poly(3-hydroxypropionic acid) was added to a 100 ml Schlenk flask and dried at 40° C. for 12 hours. Next, 0.234 g of 1,3-phenylenebisoxazoline was added and stirred at 160° C. for 2 hours. Next, 0.053 g of hexamethylene diisocyanate was added and stirred at 100° C. for 90 minutes.

[0130] Example 8 Poly(3-hydroxypropionic acid) was produced in the same manner as in Example 7, except that 0.071 g of L-lysine ethyl ester diisocyanate was used instead of 0.053 g of hexamethylene diisocyanate.

[0131] Example 9 Poly(3-hydroxypropionic acid) was produced in the same manner as in Example 7, except that 0.142 g of L-lysine ethyl ester diisocyanate was used instead of 0.053 g of hexamethylene diisocyanate.

[0132] Example 10 Poly(3-hydroxypropionic acid) was produced in the same manner as in Example 7, except that 0.310 g of L-lysine ethyl ester diisocyanate was used instead of 0.053 g of hexamethylene diisocyanate.

[0133] Comparative Example 1 60g of 3-hydroxypropionic acid was added to an oil bath and reacted for 2 hours at 90°C and 100 torr. Then, 176mg of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath and reacted for 2 hours at a reduced pressure of 20 torr. The polymer was then polymerized for 24 hours at less than 1 torr. After the reaction was completed, the reactant was dissolved in chloroform at a ratio of 10g / 50mL and extracted with 500mL of methanol to obtain the polymer, which was then vacuum dried for 12 hours.

[0134] Then, 20 g of the polymer was placed in an oil bath under a nitrogen atmosphere, and 0.12 ml of hexamethylene diisocyanate was added, followed by stirring and reacting at a temperature of 140° C. for 180 minutes to produce a 3-hydroxypropionate polymer.

[0135] Comparative Example 2 A 3-hydroxypropionate polymer was produced in the same manner as in Comparative Example 1, except that 0.28 ml of hexamethylene diisocyanate was used instead of 0.12 ml of hexamethylene diisocyanate.

[0136] Comparative Example 3 3475g of 3-hydroxypropionic acid was added to an oil bath and reacted for 2 hours at 90°C and 100 torr. Then, 14.7g of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath and reacted for 2 hours at a reduced pressure of 20 torr. Polymerization was then carried out for 24 hours at less than 1 torr to produce 3-hydroxypropionic acid polymer. After the reaction was completed, the reactants were dissolved in chloroform at a ratio of 10g / 50mL and extracted with 500mL of methanol to obtain the polymer. The polymer was then vacuum dried for 12 hours to recover the 3-hydroxypropionic acid polymer.

[0137] Comparative Example 4 3475g of 3-hydroxypropionic acid and 34.8g of 1,4-butanediol were added to an oil bath and reacted at 90°C and 100 torr for 2 hours. Then, 14.7g of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath and reacted for 2 hours at a reduced pressure of 20 torr. Polymerization was carried out for 24 hours at less than 1 torr to produce a polymer. After the reaction was completed, the reactants were dissolved in chloroform at a ratio of 10g / 50mL and extracted with 500mL of methanol to obtain the polymer. The polymer was then vacuum dried for 12 hours to recover the polymer.

[0138] Comparative Example 5 Poly(3-hydroxypropionic acid) was produced in the same manner as in Example 1, except that 0.234 g of 1,3-phenylenebisoxazoline and 0.053 g of hexamethylene diisocyanate were not used.

[0139] Comparative Example 6 Poly(3-hydroxypropionic acid) was produced in the same manner as in Example 7, except that 0.053 g of hexamethylene diisocyanate was not used.

[0140] Experimental Example The physical properties of the polymers produced in the above examples and comparative examples were evaluated by the following methods, and the results are shown in Table 1 below.

[0141] 1. Molecular Weight Measurement The weight average molecular weight (Mw), number average molecular weight (Mn), maximum peak molecular weight (Mp), and polydispersity index (PDI) of the polymers of the examples and comparative examples were measured by gel permeation chromatography (GPC, Waters Alliance e2695). -Solvent: Chloroform (elution) -Flow rate: 1.0ml / min -Column temperature: 35℃ -Standard: Polystyrene

[0142] 2. Measurement of tensile strength, Young's modulus and elongation The polymers of the examples and comparative examples were used to prepare dogbone film specimens according to ASTM D882 standard at 90°C using a hot press (Limotem QM900S), and the thicknesses were controlled as shown in Table 1. The tensile strength, Young's modulus, and elongation of the specimens were measured using a universal testing machine (Zwick).

[0143] [Table 1]

[0144] Referring to Table 1, it was confirmed that Examples 1 to 10 had higher molecular weights than Comparative Examples 1 to 6, and were also superior in tensile strength and elongation.

Claims

1. A 3-hydroxypropionate (co)polymer composition comprising a 3-hydroxypropionate (co)polymer and an isocyanate compound.

2. The 3-hydroxypropionate (co)polymer composition according to claim 1, wherein the isocyanate compound is contained in an amount of 0.1 part by weight or more and 10.0 parts by weight or less relative to the 3-hydroxypropionate (co)polymer.

3. The 3-hydroxypropionate (co)polymer composition according to claim 1, wherein the 3-hydroxypropionate (co)polymer is a first 3-hydroxypropionate copolymer in which 3-hydroxypropionic acid and a diol are copolymerized.

4. The 3-hydroxypropionate (co)polymer composition according to claim 3, wherein the first 3-hydroxypropionate copolymer is substituted at both ends with hydroxy groups.

5. The 3-hydroxypropionate (co)polymer composition according to claim 1, wherein the 3-hydroxypropionate (co)polymer is a second 3-hydroxypropionate copolymer obtained by reacting a first 3-hydroxypropionate copolymer in which 3-hydroxypropionic acid and a diol are copolymerized with an isocyanate.

6. The 3-hydroxypropionate (co)polymer composition of claim 5, wherein the second 3-hydroxypropionate copolymer comprises a repeating unit represented by the following Chemical Formula 2: 【Chemistry 1】 In the above Chemical Formula 2, R ２ is a single bond; a substituted or unsubstituted alkylene having 1 to 60 carbon atoms; a substituted or unsubstituted alkenylene having 1 to 60 carbon atoms; a substituted or unsubstituted arylene having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene having 2 to 60 carbon atoms and containing one or more heteroatoms selected from the group consisting of N, O, S and Si, X and Y are each independently represented by the following chemical formula 2-1 or the following chemical formula 2-2, but at least one of them is represented by the following chemical formula 2-1: 【Chemistry 2】 In the above chemical formula 2-1, R ３ is a substituted or unsubstituted C １－２０ Alkylene; substituted or unsubstituted C ６－６０ arylene; or C containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S ２－６０ is heteroarylene, q and r each independently represent an integer of 5 to 1000; 【Transformation 3】 In the above chemical formula 2-2, p is an integer from 5 to 1000.

7. The 3-hydroxypropionate (co)polymer composition of claim 1, further comprising an oxazoline compound.

8. 8. The 3-hydroxypropionate (co)polymer composition according to claim 7, wherein the weight ratio of said oxazoline compound and said isocyanate compound is 1:0.0001 to 1:

10.

9. The 3-hydroxypropionate (co)polymer composition according to claim 7, wherein the 3-hydroxypropionate (co)polymer comprises a repeating unit represented by the following chemical formula 6: 【Chemistry 4】 R ２ is a single bond; a substituted or unsubstituted alkylene having 1 to 60 carbon atoms; a substituted or unsubstituted alkenylene having 1 to 60 carbon atoms; a substituted or unsubstituted arylene having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene having 2 to 60 carbon atoms and containing one or more heteroatoms selected from the group consisting of N, O, S and Si, A and B are each independently represented by the following chemical formula 6-1, the following chemical formula 6-2, or the following chemical formula 6-3, but at least one is represented by the following chemical formula 6-1: 【Transformation 5】 In the above chemical formula 6-1, R ４ is a single bond; a substituted or unsubstituted alkylene having 1 to 60 carbon atoms; a substituted or unsubstituted alkenylene having 1 to 60 carbon atoms; a substituted or unsubstituted arylene having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene having 2 to 60 carbon atoms and containing one or more heteroatoms selected from the group consisting of N, O, S and Si, a and b are each independently an integer from 10 to 5,000; 【Transformation 6】 In the above chemical formula 6-2, R ５ is a substituted or unsubstituted C １－２０ Alkylene; substituted or unsubstituted C ６－６０ arylene; or C containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S ２－６０ is heteroarylene, d and e each independently represent an integer from 5 to 1000; 【Transformation 7】 In the above chemical formula 6-3, c is an integer from 5 to 1000.

10. A poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition comprising a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer and an isocyanate compound.

11. The poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition according to claim 10, wherein the poly(lactic acid-b-3-hydroxypropionic acid) block copolymer is a block copolymer obtained by reacting a first 3-hydroxypropionate copolymer, in which 3-hydroxypropionic acid and a diol are copolymerized, with an isocyanate to form a second 3-hydroxypropionate copolymer, and then ring-opening polymerizing lactide to the second 3-hydroxypropionate copolymer.

12. The poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition of claim 10, further comprising an oxazoline compound.

13. (co)polymerizing 3-hydroxypropionic acid to produce 3-hydroxypropionate (co)polymer in a reactor; and a step of adding an isocyanate compound to the reactor and reacting the isocyanate compound with the 3-hydroxypropionate (co)polymer.

14. The method for producing a 3-hydroxypropionate (co)polymer according to claim 13, wherein the (co)polymerization is carried out in the presence of a sulfonic acid catalyst.

15. The method for producing a 3-hydroxypropionate (co)polymer according to claim 13, wherein the reaction with the isocyanate is carried out at a temperature of 80°C or higher and 180°C or lower for a time of 5 minutes or higher and 300 minutes or lower.

16. The step of (co)polymerizing 3-hydroxypropionic acid to prepare 3-hydroxypropionate (co)polymer in a reactor includes: The method for preparing a 3-hydroxypropionate (co)polymer according to claim 13, wherein the step of copolymerizing the 3-hydroxypropionate and the diol to prepare a first 3-hydroxypropionate copolymer.

17. The method for producing a 3-hydroxypropionate (co)polymer according to claim 16, wherein the first 3-hydroxypropionate copolymer contains 0.05 parts by weight or more and 5.00 parts by weight or less of the diol per 100 parts by weight of the 3-hydroxypropionic acid.

18. The method for producing 3-hydroxypropionate (co)polymer according to claim 13, wherein an oxazoline compound is further added to the reactor to react with the 3-hydroxypropionate (co)polymer.

19. The method for producing a 3-hydroxypropionate (co)polymer according to claim 18, wherein the oxazoline compound and the isocyanate compound are each independently added in an amount of 0.001 parts by weight or more and 5,000 parts by weight or less per 100 parts by weight of poly(3-hydroxypropionic acid).

20. The method for producing a 3-hydroxypropionate (co)polymer according to claim 18, wherein the oxazoline compound is first charged into the reactor, and then the isocyanate compound is charged into the reactor.

21. (co)polymerizing 3-hydroxypropionic acid to produce a 3-hydroxypropionate (co)polymer in a reactor; adding an isocyanate compound to the reactor to react with the 3-hydroxypropionate (co)polymer; and and ring-opening polymerization of the 3-hydroxypropionate (co)polymer with lactide monomer to produce a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer.

22. The step of (co)polymerizing 3-hydroxypropionic acid to prepare 3-hydroxypropionate (co)polymer in a reactor includes: The method for producing a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer according to claim 21, wherein the step of copolymerizing the 3-hydroxypropionate and the diol produces a first 3-hydroxypropionate copolymer.

23. The method for producing a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer according to claim 21, wherein an oxazoline compound is further added to the reactor to react with the 3-hydroxypropionate (co)polymer.

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