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

Abstract

Provided in the present invention are: a 3-hydroxypropionate (co)polymer composition comprising a 3-hydroxypropionate (co)polymer and an isocyanate compound; 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; and methods for preparing a 3-hydroxypropionate (co)polymer and a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer.

Description

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

[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.

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

[0003] When using β-propiolactone, multiple synthetic steps using ethylene oxide are required, so there is a disadvantage in terms of economic feasibility compared to when using 3-hydroxypropionic acid, and there is the problem of 0% bio-content.

[0004] Meanwhile, in the case of polymerization using the synthesis of 3-hydroxypropionic acid, several steps such as freeze-drying, ultrasonication, and solvent elution are required to obtain poly(3-hydroxypropionic acid), and a large amount of solvent must be used at this time. To solve this problem, there have been attempts to polycondense 3-hydroxypropionic acid, but there are limitations in obtaining high-molecular-weight poly(3-hydroxypropionic acid) due to the byproduct in the form of cyclic oligomers. There have been attempts to increase the molecular weight by ROP of low-molecular-weight cyclic oligomers, but there are difficulties in separation and purification. Therefore, a method for producing high-molecular-weight poly(3-hydroxypropionic acid) from 3-hydroxypropionic acid is required.

[0005] Furthermore, polylactic acid (PLA) is a plant-derived resin derived from plants such as corn. It is biodegradable and has excellent tensile strength and elasticity, making it an environmentally friendly material that has been attracting attention. However, compared to conventional petroleum-based resins, its impact and heat resistance are inferior, limiting its application. Furthermore, its poor elongation to break (elongation to break) characteristics make it brittle, limiting its use as a general-purpose resin.

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

[0007] However, in the case of biodegradable materials, a certain molecular weight or higher is generally required to have unique mechanical properties, and thus a high molecular weight poly(lactic acid-b-3-hydroxypropionic acid) copolymer is required to be manufactured. However, during the condensation polymerization process of 3-hydroxypropionic acid, a low molecular weight cyclic structure is created, so not only cannot a high molecular weight poly(3-hydroxypropionic acid) be manufactured, but also the manufacturing yield of poly(3-hydroxypropionic acid) is reduced. Therefore, a method for manufacturing a poly(lactic acid-b-3-hydroxypropionic acid) copolymer having both a high molecular weight and excellent mechanical properties is required.

[0008] The present invention provides a 3-hydroxypropionate (co)polymer composition and a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition having a high molecular weight and excellent tensile strength, Young's modulus, and elongation, and relates to a method for producing such a 3-hydroxypropionate (co)polymer and a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer.

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

[0010] According to another embodiment of the present invention, 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 is provided.

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

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

[0013] Hereinafter, 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 according to specific embodiments of the present invention will be described in more detail.

[0014] Furthermore, unless the steps constituting the manufacturing method described herein are explicitly stated to be sequential or consecutive, or there is another special order, the order of one step constituting a manufacturing method from another step is not limited to the order described in the specification. Accordingly, the order of the steps constituting the manufacturing method may be varied within a range readily understandable to those skilled in the art, and in such cases, any subsequent changes apparent to those skilled in the art are within the scope of the present invention.

[0015] Additionally, in this specification, the terms first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

[0016] Additionally, in this specification, (co)polymer means both a copolymer and a homopolymer.

[0017] In addition, unless otherwise stated herein, the weight average molecular weight of polymers, copolymers, etc. can be measured using gel permeation chromatography (GPC). Specifically, the (co)polymer is dissolved in chloroform to a concentration of 2 mg / ml, 20 μl is injected into GPC, and GPC analysis is performed at 40°C. At this time, chloroform is used as the mobile phase of GPC, and it is introduced at a flow rate of 1.0 mL / min, two Agilent Mixed-B columns are connected in series, and an RI Detector is used as the detector. The Mw value is derived using a calibration curve formed using a polystyrene standard sample. 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, the term "substituted or unsubstituted" in the present specification means a group that is substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a nitrile group; a nitro group; a hydroxy group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; a heteroarylamine group; an arylphosphine group; or a heterocyclic group containing at least one of N, O, and S atoms, or a substituted or unsubstituted group in which two or more substituents among the above-mentioned substituents are linked. For example, the "substituent linked by two or more substituents" may be a biphenyl group. That is, the biphenyl group can be an aryl group or can be interpreted as a substituent in which two phenyl groups are connected.

[0019] In this specification, the number of carbon atoms in the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

[0020]

[0021] In the present specification, the ester group may have the oxygen of the ester group replaced by a straight-chain, branched-chain 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.

[0022]

[0023] In this specification, the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

[0024]

[0025] In the present specification, the silyl group specifically includes, but is not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, etc.

[0026] In this specification, the boron group specifically includes, but is not limited to, a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, etc.

[0027] In this specification, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

[0028] In the present 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 number of carbon atoms of the alkyl group is 1 to 20. According to another embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another embodiment, the number of carbon atoms of the alkyl group is 1 to 6. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, 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, cyclohectylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, Examples include, but are not limited to, 4-methylhexyl and 5-methylhexyl.

[0029] In the present 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, stilbenyl, and styrenyl.

[0030] In the present 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. Specifically, examples thereof 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, cyclooctyl, and the like.

[0031] In the present 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.

[0032] In the present specification, the fluorenyl group may be substituted, and two substituents may combine with each other to form a spiro structure. When the fluorenyl group is substituted,

[0033]

[0034] It can be, but is not limited to, the following.

[0035] In the present specification, a heteroaryl group is a heterocyclic group that contains at least one of O, N, Si, and S as a heteroatom and has aromaticity, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heteroaryl groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, Examples include, but are not limited to, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, and dibenzofuranyl group.

[0036] In this specification, the aryl group among the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is the same as the examples of the aryl group described above. In this specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the examples of the alkyl group described above. In this specification, the heteroaryl among the heteroarylamine may be applied to the description of the heterocyclic group described above. In this specification, the alkenyl group among the aralkenyl group is the same as the examples of the alkenyl group described above. In this specification, the description of the aryl group described above may be applied to the arylene except that it is a divalent group. In this specification, the description of the heterocyclic group described above may be applied to the heteroarylene except that it is a divalent group. In this specification, the description of the aryl group or the cycloalkyl group described above may be applied to the hydrocarbon ring except that it is not a monovalent group but is formed by combining two substituents. In the present specification, the description of the heterocyclic group described above may be applied, except that the heterocyclic group is not monovalent and is formed by combining two substituents.

[0037] Also, in this specification, means a bond that connects to another substituent.

[0038]

[0039] According to one embodiment of the invention, a 3-hydroxypropionate (co)polymer composition comprising a 3-hydroxypropionate (co)polymer and an isocyanate compound is provided.

[0040] The present inventors have completed the invention by confirming that a 3-hydroxypropionate (co)polymer composition comprising 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.

[0041] The above 3-hydroxypropionate (co)polymer composition may be manufactured by the 3-hydroxypropionate (co)polymer manufacturing method described below, but is not limited thereto.

[0042] The 3-hydroxypropionate (co)polymer included in the above composition is a 3-hydroxypropionate (co)polymer in which 3-hydroxypropionic acid is (co)polymerized, and the isocyanate included in the above composition may be a starting material that reacts with the 3-hydroxypropionate (co)polymer. In addition, the 3-hydroxypropionate (co)polymer is a (co)polymer in which the 3-hydroxypropionate (co)polymer in which 3-hydroxypropionic acid is (co)polymerized reacts with an isocyanate, and the isocyanate included in the above composition may be a residue remaining after reaction with the (co)polymer.

[0043] The above isocyanate is not particularly limited as long as it is a compound containing one or more isocyanate groups, but may be, for example, at least one 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.

[0044] In addition, the isocyanate may be used 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 for the 3-hydroxypropionate (co)polymer. If the content of isocyanate is too low for the 3-hydroxypropionate (co)polymer, the molecular weight improvement effect due to the isocyanate reaction may not appear, and if the content of isocyanate is too high, the uniformity, quality, and processability of the product manufactured with the final copolymer may deteriorate due to the formation of a crosslinking structure.

[0045]

[0046] In the 3-hydroxypropionate (co)polymer composition according to the above embodiment, the 3-hydroxypropionate (co)polymer may be a first 3-hydroxypropionate copolymer in which 3-hydroxypropionic acid and a diol are copolymerized.

[0047] The diol copolymerized with the above 3-hydroxypropionic acid is not limited thereto, but is preferably a diol containing hydroxy groups at both terminals, and may be, for example, at least one 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. In addition, in order to improve the yield of the above 3-hydroxypropionate copolymer and to recover a high molecular weight copolymer, it is preferable to use 1,4-butanediol.

[0048] For 100 parts by weight of the 3-hydroxypropionic acid, the content of the diol may be 0.05 parts by weight or more and 5.00 parts by weight or less, 0.10 parts by weight or more and 4.50 parts by weight or less, 0.30 parts by weight or more and 4.00 parts by weight or less, 0.50 parts by weight or more and 3.50 parts by weight or less, 1.00 parts by weight or more and 3.40 parts by weight or less, 1.50 parts by weight or more and 3.30 parts by weight or less, or 2.00 parts by weight or more and 3.00 parts by weight or less. If the content of the diol is too low for the 3-hydroxypropionic acid, even if isocyanate is reacted in a later step, the effect of increasing the molecular weight of the copolymer may not appear, and if the content of the diol is too high, the molecular weight of the copolymer may appear low.

[0049]

[0050] The first 3-hydroxypropionate copolymer produced by copolymerizing the above 3-hydroxypropionic acid and diol can have both terminals substituted with hydroxyl groups, and thus a high molecular weight copolymer can be produced through subsequent reaction with isocyanate.

[0051] The above first 3-hydroxypropionate copolymer can be represented by the following chemical formula 1.

[0052] [Chemical Formula 1]

[0053]

[0054] In the above chemical formula 1,

[0055] R1 is substituted or unsubstituted C 1-20 Alkylene; substituted or unsubstituted C 6-60 Arylene; or C containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S 2-60 It is a heteroarylene,

[0056] n and m are each independently integers from 5 to 1000.

[0057] For example, the above R1 is 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, etc.

[0058] For example, the above n and m can each independently be an integer from 10 to 900, from 50 to 800, from 100 to 700, or from 150 to 600.

[0059] In addition, the first 3-hydroxypropionate copolymer may have a weight average molecular weight of 2,000 or more and 100,000 or less, 5,000 or more and 80,000 or less, 8,000 or more and 60,000 or less, 10,000 or more and 40,000 or less, 15,000 or more and 35,000 or less, 15,000 or more and 30,000 or less, 15,000 or more and 25,000 or less, or 15,000 or more and 20,000 or less.

[0060] In addition, the first 3-hydroxypropionate copolymer may have a number average molecular weight of 2,000 or more and 15,000 or less, 5,000 or more and 13,000 or less, 7,000 or more and 11,000 or less, or 8,000 or more and 10,000 or less.

[0061] Additionally, the first 3-hydroxypropionate copolymer may have a polydispersity index (PDI) of 1.0 or more and 3.5 or less, 1.2 or more and 3.0 or less, 1.4 or more and 2.5 or less, or 1.6 or more and 2.0 or less.

[0062]

[0063] Additionally, the 3-hydroxypropionate (co)polymer may 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.

[0064] The hydroxyl groups at both ends 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 due to this chain extension reaction, the molecular weight of the second 3-hydroxypropionate copolymer is greatly improved, and the problem of the molecular weight of the polymer being reduced due to the generation of byproducts in the form of cyclic oligomers can be prevented. In addition, the second 3-hydroxypropionate copolymer can have a higher weight average molecular weight and number average molecular weight than the first 3-hydroxypropionate copolymer.

[0065] The above second 3-hydroxypropionate copolymer may include a repeating unit represented by the following chemical formula 2.

[0066] [Chemical Formula 2]

[0067]

[0068] In the above chemical formula 2,

[0069] 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 heteroarylene having 2 to 60 carbon atoms containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O, S, and Si.

[0070] For example, the R2 may be a substituted or unsubstituted ethyl ester alkylene having 1 to 20 carbon atoms, an arylene having 6 to 20 carbon atoms, or a heteroarylene having 2 to 20 carbon atoms containing at least one heteroatom selected from the group consisting of N, O, S, and Si. In addition, the R2 is 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 pentylene, ethyl ester substituted hexylene, 1,2-phenylene, It may be 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, 2,4'-ethylenediphenylene.

[0071] In addition, in the above 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 can be represented by the following chemical formula 2-1.

[0072] [Chemical Formula 2-1]

[0073]

[0074] In the above chemical formula 2-1,

[0075] R3 is substituted or unsubstituted C 1-20 Alkylene; substituted or unsubstituted C 6-60Arylene; or C containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S 2-60 It may be a heteroarylene.

[0076] For example, the above R3 is 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, etc.

[0077] Additionally, q and r can each independently be an integer from 5 to 1000, for example, q and r can each independently be an integer from 10 to 900, 50 to 800, 100 to 700, or 150 to 600.

[0078] [Chemical Formula 2-2]

[0079]

[0080] In the above chemical formula 2-2, p may be an integer from 5 to 1000, for example, p may be an integer from 10 to 900, 50 to 800, 100 to 700, or 150 to 600.

[0081]

[0082] The terminal group of the above second 3-hydroxypropionate copolymer can be selected from the terminal groups represented by the following chemical formulas 3 to 5.

[0083] [Chemical Formula 3]

[0084]

[0085] [Chemical Formula 4]

[0086]

[0087] [Chemical Formula 5]

[0088]

[0089] In the above chemical formula 4,

[0090] R3 is substituted or unsubstituted C 1-20 Alkylene; substituted or unsubstituted C 6-60 Arylene; or C containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S 2-60 It may be a heteroarylene, and the R3 is 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, etc.

[0091] Additionally, in the above chemical formulas 3 to 5, * may be a point connected to the main chain or terminal group of the copolymer, respectively.

[0092] In addition, 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 the acid value range as described above, the second 3-hydroxypropionate copolymer can exhibit excellent characteristics such as high molecular weight, tensile strength, Young's modulus, and elongation, and the acid value can be measured by titrating a 0.02 N potassium methoxide solution as a titration solution.

[0093]

[0094] In addition, 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.

[0095] Additionally, 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.

[0096] Additionally, 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.

[0097]

[0098] The 3-hydroxypropionate (co)polymer composition according to the above embodiment may further comprise an oxazoline compound. Accordingly, the composition may comprise a 3-hydroxypropionate (co)polymer, an isocyanate, and an oxazoline.

[0099] The above oxazoline may be a starting material reacted with a 3-hydroxypropionate (co)polymer or a residue remaining after reacting with a 3-hydroxypropionate (co)polymer.

[0100] The above oxazoline compound is not particularly limited as long as it is a compound containing one or more oxazoline groups, but may be, for example, at least one selected from the group consisting of 1,3-phenylene bisoxazoline (2,2'-(1,3-phenylene)bis(2-oxazoline)), 1,4-phenylene bisoxazoline (2,2'-(1,4-phenylene)bis(2-oxazoline)), and 2,6-pyridylene bisoxazoline (2,2'-(2,6-pyridylene)-bis(2-oxazoline)).

[0101] In addition, the oxazoline compound may be introduced 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, based on 100 parts by weight of the 3-hydroxypropionate (co)polymer. If the introduction amount of the oxazoline compound is too small compared to the 3-hydroxypropionate (co)polymer, the molecular weight of the (co)polymer may not increase, and if the introduction amount of the oxazoline compound is too large compared to the (co)polymer, by-products may be generated or a crosslinked structure may be formed.

[0102] In addition, the weight ratio of the oxazoline compound and 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 is too high with respect to the oxazoline compound, crosslinking may occur first before the molecular weight of the (co)polymer increases, making it difficult to produce a high-molecular-weight (co)polymer, and if the content of the isocyanate compound is too low with respect to the oxazoline compound, it may be difficult to produce a high-molecular-weight (co)polymer.

[0103] The above 3-hydroxypropionate (co)polymer may be a (co)polymer reacted with an isocyanate and an oxazoline compound, and the oxyzoline compound may react with a functional group at the end of a repeating unit of poly(3-hydroxypropionic acid) to link two peptide bonds (-CONH-), and the above isocyanate compound may react with a functional group at the end of a repeating unit of poly(3-hydroxypropionic acid) to link two peptide bonds.

[0104] For example, the 3-hydroxypropionate (co)polymer may include a repeating unit represented by the following chemical formula 6.

[0105] [Chemical Formula 6]

[0106]

[0107] In the above chemical formula 6,

[0108] 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 heteroarylene having 2 to 60 carbon atoms containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O, S, and Si.

[0109] For example, the R2 may be a substituted or unsubstituted ethyl ester alkylene having 1 to 20 carbon atoms, an arylene having 6 to 20 carbon atoms, or a heteroarylene having 2 to 20 carbon atoms containing at least one heteroatom selected from the group consisting of N, O, S, and Si. In addition, the R2 is 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 pentylene, ethyl ester substituted hexylene, 1,2-phenylene, It may be 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, 2,4'-ethylenediphenylene.

[0110] In addition, in the above 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 can be represented by the following chemical formula 6-1.

[0111] [Chemical Formula 6-1]

[0112]

[0113] In the above chemical formula 6-1,

[0114] 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 containing at least one heteroatom selected from the group consisting of N, O, S, and Si.

[0115] For example, the R4 may be a substituted or unsubstituted ethyl ester alkylene having 1 to 20 carbon atoms, an arylene having 6 to 20 carbon atoms, or a heteroarylene having 2 to 20 carbon atoms containing at least one heteroatom selected from the group consisting of N, O, S, and Si. In addition, the R2 is 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 pentylene, ethyl ester substituted hexylene, 1,2-phenylene, It may be 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, 2,4'-ethylenediphenylene.

[0116] Additionally, a and b can each independently be integers from 10 to 5,000, for example, integers from 100 to 4,000, 300 to 3,000, and 500 to 1,000.

[0117] [Chemical Formula 6-2]

[0118]

[0119] In the above chemical formula 6-2,

[0120] R5 is substituted or unsubstituted C 1-20 Alkylene; substituted or unsubstituted C 6-60 Arylene; or C containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S 2-60 It may be a heteroarylene.

[0121] For example, the above R5 is 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, etc.

[0122] Additionally, d and e can each independently be an integer from 5 to 1000, for example, d and e can each independently be an integer from 10 to 900, 50 to 800, 100 to 700, or 150 to 600.

[0123] d and e are each independently an integer from 5 to 1000,

[0124] [Chemical Formula 6-3]

[0125]

[0126] In the above chemical formula 6-3,

[0127] c can be an integer from 5 to 1000, for example, n and m can each independently be an integer from 10 to 900, 50 to 800, 100 to 700, or 150 to 600.

[0128]

[0129] The 3-hydroxypropionate (co)polymer containing a repeating unit represented by the above chemical formula 6 may have terminal groups of the following 7 to 9.

[0130] [Chemical Formula 7]

[0131]

[0132] [Chemical Formula 8]

[0133]

[0134] [Chemical Formula 9]

[0135]

[0136] In the above chemical formula 8,

[0137] 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 containing at least one heteroatom selected from the group consisting of N, O, S, and Si.

[0138] Additionally, in the above chemical formulas 7 to 9, * may be a point connected to the main chain or terminal group of the copolymer, respectively.

[0139] In addition, the 3-hydroxypropionate (co)polymer including the repeating unit represented by the above 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 the acid value range as described above, the 3-hydroxypropionate (co)polymer can exhibit excellent characteristics such as high molecular weight, tensile strength, Young's modulus, and elongation, and the acid value can be measured by titrating a 0.02 N potassium methoxide solution as a titration solution.

[0140]

[0141] According to another embodiment of the invention, 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 is provided.

[0142] The above poly(lactic acid-b-3-hydroxypropionic acid) composition may be manufactured by the poly(lactic acid-b-3-hydroxypropionic acid) manufacturing method described below, but is not limited thereto.

[0143] The above poly(lactic acid-b-3-hydroxypropionic acid) block copolymer may be a block copolymer in which a first 3-hydroxypropionate copolymer in which 3-hydroxypropionic acid and a diol are copolymerized isocyanate reacted with a second 3-hydroxypropionate copolymer, and lactide is ring-opened and polymerized. In addition, the isocyanate in the composition may be a residue remaining after reacting with the first 3-hydroxypropionate copolymer.

[0144] In addition, the poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition may further include an oxazoline compound. Accordingly, the poly(lactic acid-b-3-hydroxypropionic acid) block copolymer may be a block copolymer in which lactide is ring-opened and polymerized into a 3-hydroxypropionate (co)polymer in which a 3-hydroxypropionate polymer, an isocyanate, and an oxazoline compound are reacted.

[0145] The above poly(lactic acid-b-3-hydroxypropionic acid) block copolymer may have a weight average molecular weight of 120,000 or more, and more specifically, may be 120,000 or more and 800,000 or less, 150,000 or more and 500,000 or less, 200,000 or more and 400,000 or less, or 220,000 or more and 300,000 or less. If the weight average molecular weight of the above poly(lactic acid-b-3-hydroxypropionic acid) block copolymer is too low, the overall mechanical properties may be significantly deteriorated.

[0146] The above poly(lactic acid-b-3-hydroxypropionic acid) block copolymer may have a number average molecular weight of 100,000 or more, and more specifically, 100,000 or more and 700,000 or less, 120,000 or more and 500,000 or less, 150,000 or more and 400,000 or less, or 200,000 or more and 300,000 or less.

[0147] 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.

[0148] The above 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, 600% or more and 1000% or less.

[0149]

[0150] According to another embodiment of the present invention, there is provided a method comprising the steps of: (co)polymerizing 3-hydroxypropionic acid to produce a 3-hydroxypropionate (co)polymer in a reactor; and

[0151] A method for producing a 3-hydroxypropionate (co)polymer is provided, comprising a step of introducing an isocyanate compound into the above reactor and reacting it with the 3-hydroxypropionate (co)polymer.

[0152] The above (co)polymerization can be carried out under a sulfonic acid catalyst. The sulfonic acid catalyst is not particularly limited as long as it contains at least one sulfonic group, but may be, for example, p-toluenesulfonic acid, m-xylene-4-sulfonic acid, 2-mesitylenesulfonic acid, or p-xylene-2-sulfonic acid. The catalyst can be used in an amount of 0.01 to 0.5 mol% relative to 3-hydroxypropionic acid.

[0153] The step of (co)polymerizing the above 3-hydroxypropionic acid to produce a 3-hydroxypropionate (co)polymer in a reactor may be a step of copolymerizing the above 3-hydroxypropionate and a diol to produce a first 3-hydroxypropionate copolymer.

[0154] The process for producing the above first 3-hydroxypropionate copolymer may include a step (step 1) of producing an oligomer by copolymerizing 3-hydroxypropionic acid and a diol, and a step (step 2) of producing a 3-hydroxypropionic acid copolymer by polymerizing the oligomer.

[0155] The polymerization reaction of the above step 1 may be a melt polymerization reaction, and melt polymerization means that the reactants 3-hydroxypropionic acid and diol and the product oligomer remain in a liquid state. In addition, the polymerization reaction of the above step 1 may be carried out at a temperature of 50°C or more and 150°C or less and a pressure of 1 torr or more and 200 torr or less. For example, the reaction temperature of the above step 1 may be 60°C or more, 70°C or more, 80°C or more, 85°C or more, or 90°C or more, and 140°C or less, 130°C or less, 120°C or less, or 110°C or less. In addition, the step 1 may be performed under a pressure of 2 torr or more, 5 torr or more, 10 torr or more, or 15 torr or more, and 150 torr or less, 130 torr or less, 110 torr or less, or 100 torr or less. In addition, the reaction time of the step 1 may be appropriately considered in consideration of the molecular weight, yield, etc. of the produced oligomer, and is preferably performed for 1 to 10 hours, 1.5 to 8 hours, or 2 to 5 hours.

[0156] The polymerization reaction of the above step 2 may also be a melt polymerization reaction, and may be carried out at a temperature of 70°C or more and 150°C or less. The reaction temperature of the above step 2 may be 75°C or more, 80°C or more, 85°C or more, 90°C or more, or 95°C or more, and 140°C or less, 130°C or less, 120°C or less, or 110°C or less. In addition, the pressure of the step 2 may be 2 torr or more, 5 torr or more, 10 torr or more, or 15 torr or more, and 150 torr or less, 130 torr or less, 110 torr or less, or 100 torr or less. The reaction time of the above step 2 can be appropriately considered in consideration of the molecular weight, yield, etc. of the polymer produced, and can preferably be performed for 1 hour to 60 hours, 5 hours to 50 hours, 10 hours to 40 hours, or 15 hours to 30 hours.

[0157] Meanwhile, since step 2 is performed subsequent to step 1, the catalyst added in each step 1 can also participate in the reaction in step 2. In addition, steps 1 and 2 can be performed sequentially.

[0158] The above first 3-hydroxypropionate copolymer may contain 0.05 parts by weight or more and 5.00 parts by weight or less, 0.10 parts by weight or more and 4.50 parts by weight or less, 0.30 parts by weight or more and 4.00 parts by weight or less, 0.50 parts by weight or more and 3.50 parts by weight or less, 1.00 parts by weight or more and 3.40 parts by weight or less, 1.50 parts by weight or more and 3.30 parts by weight or less, or 2.00 parts by weight or more and 3.00 parts by weight or less of the diol, based on 100 parts by weight of the 3-hydroxypropionic acid. If the content of the diol is too low with respect to the 3-hydroxypropionic acid, even if isocyanate is reacted in a later step, the effect of increasing the molecular weight of the copolymer may not appear, and if the content of the diol is too high, the molecular weight of the copolymer may appear low.

[0159]

[0160] The step of introducing an isocyanate compound into the reactor and reacting it with the 3-hydroxypropionate (co)polymer may include a step of reacting the first 3-hydroxypropionate copolymer with an isocyanate to produce a second 3-hydroxypropionate copolymer.

[0161] Meanwhile, the timing of the reaction between the first 3-hydroxypropionate copolymer and the isocyanate is not particularly limited, but in order to produce the high molecular weight copolymer, it is preferable to react at the polymerization terminal of the first 3-hydroxypropionate copolymer. For example, the isocyanate may be introduced into the reactor and reacted at a time when the polymerization reaction has progressed by 70% or more, 80% or more, 85% or more, 90% or more, 95% or more, and up to 100%. The timing of the reaction, that is, the time when the polymerization reaction has progressed by 70% or more, can be derived from the conversion rate of 3-hydroxypropionic acid into the 3-hydroxypropionic acid copolymer. In addition, the conversion rate into the copolymer can be measured or confirmed using an ampere meter or a nuclear magnetic resonance (NMR) device.

[0162] In addition, for the first 3-hydroxypropionate copolymer, the isocyanate may be used in an amount of 0.1 parts by weight or more to 10.0 parts by weight or less, 0.3 parts by weight or more to 9.0 parts by weight or less, 0.5 parts by weight or more to 8.0 parts by weight or less, 0.8 parts by weight or more to 7.0 parts by weight or less, 1.0 parts by weight or more to 5.0 parts by weight or less, or 1.5 parts by weight or more to 4.0 parts by weight or less. If the content of the isocyanate is too low for the 3-hydroxypropionic acid, the molecular weight improvement effect due to the isocyanate reaction may not appear, and if the content of the isocyanate is too high, the uniformity, quality, and processability of the product manufactured with the final copolymer may deteriorate due to the formation of a crosslinking structure.

[0163] The reaction with the above isocyanate can be carried out at a temperature of 80°C or more and 180°C or less for a time of 5 minutes or more and 300 minutes or less. For example, the reaction with the above isocyanate can be carried out at a temperature of 90°C or more and 170°C or less, 100°C or more and 160°C or less, 110°C or more and 150°C or less, 120°C or more and 140°C or less, for a time of 10 minutes or more and 280 minutes or less, 20 minutes or more and 260 minutes or less, 40 minutes or more and 240 minutes or less, 60 minutes or more and 220 minutes or less, or 90 minutes or more and 200 minutes or less.

[0164]

[0165] The step of introducing an isocyanate compound into the reactor and reacting it with the 3-hydroxypropionate (co)polymer may further include introducing an oxazoline compound into the reactor and reacting it with the 3-hydroxypropionate (co)polymer.

[0166] As the oxazoline compound and the isocyanate compound are introduced into the reactor, the functional groups at the terminals of the 3-hydroxypropionate (co)polymer can react with the oxazoline compound and the isocyanate compound. As a result, the terminals of the 3-hydroxypropionate (co)polymer can be capped with the oxazoline compound and the isocyanate compound. In addition, by capping the terminals of the 3-hydroxypropionate (co)polymer with the oxazoline compound and the isocyanate compound, the problem of the molecular weight of the polymer being lowered due to the generation of byproducts in the form of cyclic oligomers, etc., can be prevented, thereby producing a poly(3-hydroxypropionic acid) having a high molecular weight and excellent mechanical properties such as tensile strength and elongation.

[0167] Meanwhile, the timing of introducing the oxazoline compound and the isocyanate compound into the reactor is not particularly limited, but in order to produce the high molecular weight 3-hydroxypropionate (co)polymer, it is preferable to introduce them at the end of the polymerization reaction of the 3-hydroxypropionate (co)polymer. For example, the oxazoline compound and the isocyanate compound may be introduced at a time when the polymerization reaction has progressed by 70% or more, 80% or more, 85% or more, 90% or more, 95% or more and 100% or less. The timing of introducing the oxazoline compound and the isocyanate compound, i.e., the time when the polymerization reaction has progressed by 70% or more, can be derived from the conversion rate of 3-hydroxypropionic acid into the 3-hydroxypropionate (co)polymer. Additionally, the conversion rate to the above 3-hydroxypropionate (co)polymer can be measured or confirmed using an ampere meter or nuclear magnetic resonance (NMR) device.

[0168] In addition, the step of introducing an oxazoline compound and an isocyanate compound into the reactor may include introducing the isocyanate compound after introducing the oxazoline compound into the reactor. For example, the isocyanate compound may be introduced after introducing the oxazoline compound into the reactor and stirring for 30 minutes to 6 hours, 1 hour to 5 hours, or 2 hours to 4 hours.

[0169]

[0170] In addition, the oxazoline compound may be introduced 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, based on 100 parts by weight of the 3-hydroxypropionate (co)polymer. If the introduction amount of the oxazoline compound is too small compared to the 3-hydroxypropionate (co)polymer, the molecular weight of the 3-hydroxypropionate (co)polymer may not increase, and if the introduction amount of the oxazoline compound is too large compared to the 3-hydroxypropionate (co)polymer, by-products may be generated or a crosslinked structure may be formed.

[0171] Additionally, 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, per 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 occur slowly, resulting in poor mechanical properties such as tensile properties. 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 polymer with a high molecular weight.

[0172]

[0173] According to another embodiment of the present invention, there is provided a step of producing a 3-hydroxypropionate (co)polymer by (co)polymerizing 3-hydroxypropionic acid in a reactor;

[0174] A step of introducing an isocyanate compound into the reactor and reacting it with the 3-hydroxypropionate (co)polymer; and

[0175] A method for producing a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer is provided, comprising the step of producing a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer by ring-opening polymerizing a lactide monomer into the above 3-hydroxypropionate (co)polymer.

[0176] The step of (co)polymerizing the above 3-hydroxypropionic acid to produce a 3-hydroxypropionate (co)polymer in a reactor; and the step of introducing an isocyanate compound into the reactor and reacting it with the 3-hydroxypropionate (co)polymer are as described above in the method for producing a 3-hydroxypropionate (co)polymer according to another embodiment.

[0177] For example, the step of (co)polymerizing the above 3-hydroxypropionic acid to produce a 3-hydroxypropionate (co)polymer in a reactor may be a step of copolymerizing the above 3-hydroxypropionate and a diol to produce a first 3-hydroxypropionate copolymer.

[0178] Additionally, an oxazoline compound can be further added to the reactor and reacted with the 3-hydroxypropionate (co)polymer.

[0179] The step of ring-opening polymerizing a lactide monomer into the above 3-hydroxypropionate (co)polymer to produce a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer can be performed in the presence of a lactide ring-opening catalyst.

[0180] The above polymerization may be carried out under the presence of one or more catalysts selected from the group consisting of an organometallic complex catalyst and an organic catalyst. For example, the organometallic complex catalyst may be a catalyst represented by the following chemical formula 10.

[0181] [Chemical Formula 10]

[0182] MA 1 p A 2 2-p

[0183] In the above chemical formula 10,

[0184] M is Al, Mg, Zn, Ca, Sn, Fe, Y, Sm, Lu, Ti or Zr,

[0185] p is an integer from 0 to 2,

[0186] A 1 and A 2 Each can independently be an alkoxy or carboxyl group.

[0187] More specifically, the catalyst may be tin(II) 2-ethylhexanoate (Sn(Oct)2; hereinafter also referred to as Tin Octoate).

[0188] Meanwhile, the organic catalyst may be used without limitation in its composition as long as it is generally used in the production of polylactide resin by ring-opening polymerization of lactide monomers. For example, the organic catalyst may be at least one 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 creatine.

[0189] The content of the catalyst may be 0.0001 to 10 mol%, 0.005 to 8 mol%, 0.05 to 5 mol%, or 0.09 to 3 mol% with respect to 100 mol% of the lactide monomer. If the content of the catalyst is too high with respect to 100 mol% of the lactide monomer, the polymerization activity may not be sufficient, and if the content of the catalyst is too high, the amount of residual catalyst in the manufactured block copolymer may increase, which may result in decomposition of the copolymer due to depolymerization such as transesterification reaction or reduction in molecular weight. In addition, the ring-opening polymerization may be performed at a temperature of 150 to 200°C, 160 to 190°C, or 170 to 180°C, and may be performed for 5 minutes to 24 hours, 30 minutes to 20 hours, 1 hour to 15 hours, or 2 hours to 10 hours.

[0190] In the above block copolymer, the weight ratio of the lactide and 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 3-hydroxypropionate (co)polymer is contained too little with respect to the lactide, brittleness may increase, and if the 3-hydroxypropionate (co)polymer is contained too much with respect to the lactide, the molecular weight may decrease, thereby deteriorating processability and heat stability.

[0191] 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 having a high molecular weight and excellent tensile strength, Young's modulus, and elongation, and can provide a method for producing such a 3-hydroxypropionate (co)polymer and a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer.

[0192] Hereinafter, embodiments of the present invention will be described in more detail in the following examples. However, the following examples are merely illustrative of embodiments of the present invention, and the content of the present invention is not limited by the following examples.

[0193]

[0194] Example 1

[0195] 60 g of 3-hydroxypropionic acid and 0.42 g (1 mol%) of 1,4-butanediol were added to an oil bath and reacted at 90°C and 100 Torr for 2 hours. Afterwards, 176 mg of a p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath, the pressure was reduced to 20 torr, and the reaction was carried out for 2 hours. A polymer was prepared by polymerizing at 1 torr or less for 24 hours. After the reaction was completed, the reactant was dissolved in chloroform at a ratio of 10 g / 50 mL and extracted with 500 mL of methanol to obtain a polymer, which was then vacuum dried for 12 hours.

[0196] Afterwards, 20 g of the polymer was placed in an oil bath under a nitrogen atmosphere, and 0.19 ml of hexamethylene diisocyanate was placed therein, followed by stirring and reaction at 140°C for 180 minutes to produce a 3-hydroxypropionate polymer.

[0197]

[0198] Example 2

[0199] A 3-hydroxypropionate polymer was prepared 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.

[0200]

[0201] Example 3

[0202] A 3-hydroxypropionate polymer was prepared 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.

[0203]

[0204] Example 4

[0205] A 3-hydroxypropionate polymer was prepared in the same manner as in Example 1, except that instead of stirring and reacting for 180 minutes after adding 0.19 ml of hexamethylene diisocyanate, stirring and reacting for 90 minutes after adding 0.39 ml of hexamethylene diisocyanate was performed.

[0206]

[0207] Example 5

[0208] A 3-hydroxypropionate polymer was prepared in the same manner as in Example 1, except that instead of stirring and reacting for 180 minutes after adding 0.19 ml of hexamethylene diisocyanate, stirring and reacting for 90 minutes after adding 0.42 ml of hexamethylene diisocyanate was performed.

[0209]

[0210] Example 6

[0211] 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, adding 0.48 ml of hexamethylene diisocyanate and stirring and reacting at a temperature of 120°C for 120 minutes was performed.

[0212]

[0213] Example 7

[0214] A 100 ml Schlenk flask containing 100 ml of a 60% 3-hydroxypropionic acid aqueous solution was placed in an oil bath, and approximately 60% of the moisture in the 3-hydroxypropionic acid was removed at 90° C. and 100 Torr for 2 hours. Then, 0.2112 parts by weight of a p-toluenesulfonic acid (p-TSA) catalyst based on 100 parts by weight of 3-hydroxypropionic acid was placed in the reaction flask, and a melt polycondensation reaction was performed at 90° C. and 1 Torr for 24 hours. After the reaction was completed, the reactant was dissolved in chloroform at a ratio of 10 g / 50 mL and extracted with 500 mL of methanol to obtain poly(3-hydroxypropionic acid).

[0215] Afterwards, 10 g of the poly(3-hydroxypropionic acid) was added to a 100 ml Schlenk flask and dried at 40°C for 12 hours. Afterwards, 0.234 g of 1,3-phenylene bisoxazoline was added and stirred at 160°C for 2 hours. Afterwards, 0.053 g of hexamethylene diisocyanate was added and stirred at 100°C for 90 minutes.

[0216]

[0217] Example 8

[0218] Poly(3-hydroxypropionic acid) was prepared 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.

[0219]

[0220] Example 9

[0221] Poly(3-hydroxypropionic acid) was prepared 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.

[0222]

[0223] Example 10

[0224] Poly(3-hydroxypropionic acid) was prepared 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.

[0225]

[0226] Comparative Example 1

[0227] 60 g of 3-hydroxypropionic acid was added to an oil bath and reacted at 90°C and 100 Torr for 2 hours. Afterwards, 176 mg of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath, the pressure was reduced to 20 torr and the reaction was carried out for 2 hours. A polymer was produced by polymerizing at 1 torr or less for 24 hours. After the reaction was completed, the reactant was dissolved in chloroform at a ratio of 10 g / 50 mL and extracted with 500 mL of methanol to obtain a polymer, which was then vacuum dried for 12 hours.

[0228] Afterwards, 20 g of the polymer was placed in an oil bath under a nitrogen atmosphere, and 0.12 ml of hexamethylene diisocyanate was placed therein, followed by stirring and reaction at 140°C for 180 minutes to produce a 3-hydroxypropionate polymer.

[0229]

[0230] Comparative Example 2

[0231] A 3-hydroxypropionate polymer was prepared 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.

[0232]

[0233] Comparative Example 3

[0234] 3-Hydroxypropionic acid (3475 g) was added to an oil bath and reacted at 90 ℃ and 100 Torr for 2 hours. Afterwards, 14.7 g of p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath, the pressure was reduced to 20 torr, and the reaction was carried out for 2 hours. Then, a polymerization reaction was carried out at 1 torr or less for 24 hours to produce a 3-hydroxypropionic acid polymer. After the reaction was completed, the reactant was dissolved in chloroform at a ratio of 10 g / 50 mL and extracted with 500 mL of methanol to obtain a polymer, which was then vacuum dried for 12 hours to recover the 3-hydroxypropionic acid polymer.

[0235]

[0236] Comparative Example 4

[0237] 3475 g of 3-hydroxypropionic acid and 34.8 g of 1,4-butanediol were added to an oil bath and reacted at 90 ℃ and 100 Torr for 2 hours. Afterwards, 14.7 g of a p-toluenesulfonic acid (p-TSA) catalyst was added to the oil bath, the pressure was reduced to 20 torr, the reaction was performed for 2 hours, and the polymerization reaction was performed at 1 torr or less for 24 hours to produce a polymer. After the reaction was completed, the reactant was dissolved in chloroform at a ratio of 10 g / 50 mL and extracted with 500 mL of methanol to obtain a polymer, which was then vacuum dried for 12 hours to recover the polymer.

[0238]

[0239] Comparative Example 5

[0240] Poly(3-hydroxypropionic acid) was prepared in the same manner as in Example 1, except that 0.234 g of 1,3-phenylene bisoxazoline and 0.053 g of hexamethylene diisocyanate were not used.

[0241]

[0242] Comparative Example 6

[0243] Poly(3-hydroxypropionic acid) was prepared in the same manner as in Example 7, except that 0.053 g of hexamethylene diisocyanate was not used.

[0244]

[0245] Experimental example

[0246] The physical properties of the polymers manufactured in the above examples and comparative examples were evaluated using the following method, and the results are shown in Table 1 below.

[0247]

[0248] 1. Molecular weight measurement

[0249] For the polymers of the above examples and comparative examples, the weight average molecular weight (Mw), number average molecular weight (Mn), maximum peak molecular weight (Mp), and polydispersity index (PDI) were measured by gel permeation chromatography (GPC, Waters Alliance e2695).

[0250] - Solvent: chloroform (eluent)

[0251] - Flow rate: 1.0 ml / min

[0252] - Column temperature: 35 ℃

[0253] - Standard: Polystyrene

[0254]

[0255] 2. Measurement of tensile strength, Young's modulus, and elongation

[0256] The polymers of the above examples and comparative examples were used to produce dogbone film specimens according to ASTM D 882 standards at 90°C using a hot press (Limotem QM900S), and the thickness thereof was controlled as described in Table 1 below. In addition, the tensile strength, Young's modulus, and elongation were measured for the specimens using a universal testing machine (Zwick).

[0257]

[0258] Number average molecular weight (Mn) Weight average molecular weight (Mw) Molecular weight of maximum peak (Mp) Polydispersity index (PDI) Tensile strength (yield point, MPa) Tensile strength (break point, MPa) Young's modulus (Gpa) Elongation (%) Thickness (㎛) Example 117, 291, 43, 225, 620 2.5022-0.812170 Example 221, 819, 62, 350, 33, 476 2.9016-0.911870 Example 322, 778, 63, 368, 37, 980 2.8023-0.881770 Example 438, 871, 144, 7 8456,5353.7230-1.191070 Example 544,204225,51062,4295.1041-0.968270 Example 626,26474,53139,8222.8418-1.164770 Example 726,00099,000-3.8130411.0964770 Example 830,00090,000 -3.0027380.9767870Example 930,000116,000-3.8726470.89664120Example 1030,000107,000-3.5727380.96622120Comparative Example 114,52427,78126,0631.9127-1.0170Comparative Example 220,16034,32832,41 71.7014-0.9370Comparative Example 313,69124,04123,5771.7614-1.0470Comparative Example 49,98319,64616,7061.9710-0.8770Comparative Example 515,00024,000-1.60-140.986060Comparative Example 624,00062,000-2.5828111.037070

[0259] Referring to Table 1 above, it was confirmed that Examples 1 to 10 had higher molecular weights and better tensile strength and elongation than Comparative Examples 1 to 6.

Claims

A 3-hydroxypropionate (co)polymer composition comprising a 1.3-hydroxypropionate (co)polymer and an isocyanate compound.

2. In paragraph 1, A 3-hydroxypropionate (co)polymer composition comprising 0.1 part by weight or more and 10.0 parts by weight or less of the isocyanate compound in the 3-hydroxypropionate (co)polymer.

3. In paragraph 1, A 3-hydroxypropionate (co)polymer composition, wherein the above 3-hydroxypropionate (co)polymer is a first 3-hydroxypropionate copolymer in which 3-hydroxypropionic acid and a diol are copolymerized.

4. In paragraph 3, A 3-hydroxypropionate (co)polymer composition wherein the first 3-hydroxypropionate copolymer is substituted at both terminals with hydroxy groups.

5. In paragraph 1, The above 3-hydroxypropionate (co)polymer is a 3-hydroxypropionate (co)polymer composition, wherein a first 3-hydroxypropionate copolymer in which 3-hydroxypropionic acid and a diol are copolymerized is a second 3-hydroxypropionate copolymer in which isocyanate is reacted.

6. In paragraph 5, The second 3-hydroxypropionate copolymer is a 3-hydroxypropionate (co)polymer composition comprising a repeating unit represented by the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, R2 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 containing at least one heteroatom 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 is represented by the following chemical formula 2-1, [Chemical Formula 2-1] In the above chemical formula 2-1, R3 is substituted or unsubstituted C 1-20 Alkylene; substituted or unsubstituted C 6-60 Arylene; or C containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S 2-60 It is a heteroarylene, q and r are each independently an integer from 5 to 1000, [Chemical Formula 2-2] In the above chemical formula 2-2, p is an integer between 5 and 1000.

7. In paragraph 1, A 3-hydroxypropionate (co)polymer composition further comprising an oxazoline compound.

8. In paragraph 7, A 3-hydroxypropionate (co)polymer composition, wherein the weight ratio of the oxazoline compound and the isocyanate compound is 1:0.0001 to 1:

10.

9. In paragraph 7, The above 3-hydroxypropionate (co)polymer is a 3-hydroxypropionate (co)polymer composition comprising a repeating unit represented by the following chemical formula 6: [Chemical Formula 6] R2 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 containing at least one heteroatom 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, [Chemical Formula 6-1] In the above chemical formula 6-1, R4 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 heteroarylene having 2 to 60 carbon atoms containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O, S and Si, a and b are each independently an integer from 10 to 5,000, [Chemical Formula 6-2] In the above chemical formula 6-2, R5 is substituted or unsubstituted C 1-20 Alkylene; substituted or unsubstituted C 6-60 Arylene; or C containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S 2-60 It is a heteroarylene, d and e are each independently an integer from 5 to 1000, [Chemical Formula 6-3] In the above chemical formula 6-3, c is an integer between 5 and 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. In paragraph 10, The above poly(lactic acid-b-3-hydroxypropionic acid) block copolymer is a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition, which is a block copolymer in which a first 3-hydroxypropionate copolymer in which 3-hydroxypropionic acid and a diol are copolymerized and a second 3-hydroxypropionate copolymer in which lactide is ring-opened and polymerized is reacted with an isocyanate.

12. In paragraph 10, A poly(lactic acid-b-3-hydroxypropionic acid) block copolymer composition further comprising an oxazoline compound. A step of producing a 3-hydroxypropionate (co)polymer by (co)polymerizing 13.3-hydroxypropionic acid in a reactor; and A method for producing a 3-hydroxypropionate (co)polymer, comprising the step of introducing an isocyanate compound into the reactor and reacting it with the 3-hydroxypropionate (co)polymer.

14. In paragraph 13, A method for producing a 3-hydroxypropionate (co)polymer, wherein the above (co)polymerization is carried out in the presence of a sulfonic acid catalyst.

15. In paragraph 13, A method for producing a 3-hydroxypropionate (co)polymer, wherein the reaction with the above isocyanate is carried out at a temperature of 80°C or more and 180°C or less for a time of 5 minutes or more and 300 minutes or less.

16. In paragraph 13, The step of producing a 3-hydroxypropionate (co)polymer by (co)polymerizing the above 3-hydroxypropionic acid in a reactor is as follows: A method for producing a 3-hydroxypropionate (co)polymer, which is a step of producing a first 3-hydroxypropionate copolymer by copolymerizing the above 3-hydroxypropionate and diol.

17. In paragraph 16, A method for producing a 3-hydroxypropionate (co)polymer, wherein the first 3-hydroxypropionate copolymer comprises 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. In paragraph 13, A method for producing a 3-hydroxypropionate (co)polymer, wherein an oxazoline compound is further added to the above reactor and reacted with the 3-hydroxypropionate (co)polymer.

19. In paragraph 18, A method for producing a 3-hydroxypropionate (co)polymer, wherein the above oxazoline compound and 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. In paragraph 18, A method for producing a 3-hydroxypropionate (co)polymer, wherein the isocyanate compound is added to the reactor after the oxazoline compound is added. A step of producing a 3-hydroxypropionate (co)polymer by (co)polymerizing 21.3-hydroxypropionic acid in a reactor; A step of introducing an isocyanate compound into the reactor and reacting it with the 3-hydroxypropionate (co)polymer; and A method for producing a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer, comprising the step of producing a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer by ring-opening polymerizing a lactide monomer into the above 3-hydroxypropionate (co)polymer.

22. In paragraph 21, The step of producing a 3-hydroxypropionate (co)polymer by (co)polymerizing the above 3-hydroxypropionic acid in a reactor is as follows: A method for producing a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer, which is a step of producing a first 3-hydroxypropionate copolymer by copolymerizing the above 3-hydroxypropionate and diol.

23. In paragraph 21, A method for producing a poly(lactic acid-b-3-hydroxypropionic acid) block copolymer, wherein an oxazoline compound is further added to the above reactor and reacted with the 3-hydroxypropionate (co)polymer.

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