Resin composition

Abstract

A resin composition of the present invention comprises a biodegradable polymer and a biodegradable nucleating agent and thus is biodegradable, and exhibits a high crystallization rate, which leads to excellent productivity during processing such as injection molding, extrusion molding, and sheet extrusion.

Description

Resin composition

[0001] Cross-citation with related application(s)

[0002] This application claims the benefit of priority based on Korean Patent Application No. 10-2024-0125901 filed September 13, 2024 and Korean Patent Application No. 10-2025-0130650 filed September 12, 2025, and all contents disclosed in the documents of said Korean patent applications are incorporated herein as part of this specification.

[0003] The present invention relates to a resin composition comprising a biodegradable polymer and a biodegradable nucleating agent, which is biodegradable and has excellent processability due to a high crystallization rate.

[0004]

[0005] Biodegradable polymers are polymers that decompose through the action of microorganisms when buried, and they are attracting attention as materials to replace petroleum-based plastic materials that do not decompose naturally.

[0006] However, biodegradable polymers such as polylactide have the disadvantage of poor processability due to their low degree of crystallinity; therefore, to improve this, a method is used in which a nucleating agent is added to promote crystallization.

[0007] Nucleating agents added to conventional biodegradable resins include inorganic materials such as talc and boron nitride, as well as petroleum-based nucleating agents. However, these nucleating agents are non-biodegradable, posing a problem of residue even after the biodegradable resin has decomposed; furthermore, petroleum-based nucleating agents have the disadvantage of generating microplastics, which causes environmental problems.

[0008]

[0009] The present invention aims to provide an eco-friendly resin composition that exhibits excellent processability due to a high crystallization rate and biodegradability.

[0010]

[0011] According to one embodiment of the present invention, a resin composition comprising a biodegradable polymer and a nucleating agent represented by the following chemical formula 1 is provided:

[0012] [Chemical Formula 1]

[0013] R-[A-(B)n] k

[0014] In the above chemical formula 1,

[0015] R is a trivalent or higher linker derived from a polyfunctional monomer, and

[0016] A is a direct linkage; or a linker derived from an ether, sulfide, ester, thioester, ketone, sulfoxide, sulfone, sulfonate ester, amine, amide, imine, imide, or urethane, and

[0017] B is a substituent represented by the following chemical formula 1-1 or chemical formula 1-2, and

[0018] [Chemical Formula 1-1]

[0019]

[0020] [Chemical Formula 1-2]

[0021]

[0022] * is the part connected to A, and

[0023] k is an integer greater than or equal to 3, and

[0024] n is an integer from 1 to 700.

[0025]

[0026] The resin composition of the present invention exhibits a fast crystallization rate, resulting in excellent processability, and since both the polymer and the nucleating agent are biodegradable, it can be usefully utilized as an eco-friendly material.

[0027]

[0028] Figure 1 is the result of the DSC isothermal crystallization experiment of Example 13.

[0029]

[0030] The terms used herein are merely for describing exemplary embodiments and are not intended to limit the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, terms such as “comprising,” “comprising,” or “having” are intended to indicate the presence of the implemented features, steps, components, or combinations thereof, and should be understood as not precluding the existence or addition of one or more other features, steps, components, or combinations thereof.

[0031]

[0032] The present invention is capable of various modifications and may take various forms, and specific embodiments are illustrated and described in detail below. However, this is not intended to limit the invention to the specific disclosed forms, and it should be understood that the invention includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the invention.

[0033]

[0034] In the present invention, “biodegradable resin” or “biodegradable polymer” refers to a polymer that is decomposed by microorganisms into natural byproducts such as water, carbon dioxide, nitrogen, biomass, and inorganic salts.

[0035]

[0036] In this specification, the term “substituted or unsubstituted” means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; aryl thiooxy group; alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; alkylaryl group; alkylamine group; aralkylamine group; heteroarylamine group; arylamine group; arylphosphine group; or heterocyclic groups comprising one or more of N, O, and S atoms, or that it is substituted or unsubstituted with two or more of the exemplified substituents connected. For example, “substituents connected with two or more substituents” may be a biphenyl group. That is, the biphenyl group can be an aryl group, or it can be interpreted as a substituent in which two phenyl groups are connected.

[0037]

[0038] In this specification, the number of carbon atoms in the carbonyl group is not particularly limited, but it is preferred to have 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

[0039]

[0040]

[0041] In the present specification, the oxygen of the ester group may be substituted with 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, it may be a compound of the following structural formula, but is not limited thereto.

[0042]

[0043]

[0044] In the present specification, the number of carbon atoms in the imide group is not particularly limited, but it is preferred to have 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

[0045]

[0046]

[0047] In this specification, the silyl groups specifically include, but are not limited to, trimethylsilyl groups, triethylsilyl groups, t-butyldimethylsilyl groups, vinyldimethylsilyl groups, propyldimethylsilyl groups, triphenylsilyl groups, diphenylsilyl groups, phenylsilyl groups, etc.

[0048]

[0049] In this specification, boron groups specifically include trimethylboron groups, triethylboron groups, t-butyldimethylboron groups, triphenylboron groups, phenylboron groups, etc., but are not limited thereto.

[0050]

[0051] In this specification, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

[0052]

[0053] In the present specification, the alkyl group may be a straight chain or a branched chain, and while the number of carbon atoms is not particularly limited, it 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 yet 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 4-methylhexyl, 5-methylhexyl, etc., but are not limited to these.

[0054]

[0055] In the present specification, the alkenyl group may be a straight chain or a branched chain, 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 of the alkenyl group is 2 to 20. According to another embodiment, the number of carbon atoms of the alkenyl group is 2 to 10. According to yet another embodiment, the number of carbon atoms of the alkenyl group is 2 to 6. Specific examples include 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 group, styrenyl group, etc., but are not limited to these.

[0056]

[0057] In the present specification, the cycloalkyl group is not particularly limited, but it is preferable that it has 3 to 60 carbon atoms, and according to one embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 30. According to another embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specifically, 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, etc. are used, but are not limited thereto.

[0058]

[0059] 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 number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20. As a monocyclic aryl group, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. As a polycyclic aryl group, the aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.

[0060]

[0061] In this specification, the fluorenyl group may be substituted, and two substituents may combine to form a spiro structure. When the fluorenyl group is substituted, It can be the back. However, it is not limited to this.

[0062]

[0063] In the present specification, the heteroaryl group comprises one or more of O, N, Si, and S as heteroatoms and is an aromatic heteroaryl group, and while the number of carbon atoms is not particularly limited, it is preferred to have 2 to 60 carbon atoms. Examples of heteroaryl groups include thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, triazole, pyridyl, bipyridyl, pyrimidyl, triazine, acryl, pyridazine, pyrazinyl, quinolinyl, quinazolin, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinoline, indole, carbazole, benzoxazole, benzimidazole, benzothiazole, benzocarbazole, benzothiophen, dibenzothiophen, benzofuranyl, phenanthroline, thiazolyl, isooxazolyl, and oxadiazole. There are thiadiazolyl groups, benzothiazolyl groups, phenothiazinyl groups, and dibenzofuranyl groups, but are not limited to these.

[0064]

[0065] In this specification, the aryl group among the aralkyl group, ar alkenyl group, alkylaryl group, and arylamine group is the same as the examples of aryl groups described above. In this specification, the alkyl group among the aralkyl group, alkylaryl group, and alkylamine group is the same as the examples of alkyl groups described above. In this specification, the description regarding the heterocyclic group described above may be applied to the heteroaryl group among the heteroaryl amine. In this specification, the alkenyl group among the ar alkenyl group is the same as the examples of alkenyl groups described above. In this specification, the description regarding the aryl group described above may be applied to the arylene except that it is a divalent group. In this specification, the description regarding the heterocyclic group described above may be applied to the heteroarylene except that it is a divalent group. In this specification, the description regarding the aryl group or cycloalkyl group described above may be applied to the hydrocarbon ring except that it is not a monovalent group and is formed by the combination of two substituents. In this specification, the description of the aforementioned heterocyclic ring may apply except that the heterocyclic ring is not monovalent and is formed by the combination of two substituents.

[0066]

[0067] The resin composition of the present invention comprises a biodegradable polymer and a nucleating agent represented by the following chemical formula 1:

[0068] [Chemical Formula 1]

[0069] R-[A-(B)n] k

[0070] In the above chemical formula 1,

[0071] R is a trivalent or higher functional group derived from a polyfunctional monomer, and

[0072] A is a direct linkage; or a linker derived from an ether, sulfide, ester, thioester, ketone, sulfoxide, sulfone, sulfonate ester, amine, amide, imine, imide, or urethane, and

[0073] B is a substituent represented by the following chemical formula 1-1 or chemical formula 1-2, and

[0074] [Chemical Formula 1-1]

[0075]

[0076] [Chemical Formula 1-2]

[0077]

[0078] * is the part connected to A, and

[0079] k is an integer greater than or equal to 3, and

[0080] n is an integer from 1 to 700.

[0081]

[0082] The types of the above biodegradable polymers are not particularly limited, but may be one or more selected from the group consisting of, for example, polylactide (PLA); poly(butylene adipate-co-terephthalate) (PBAT); polybutylene succinate (PBS); polyhydroxyalkanoates (PHA) such as poly(3-hydroxypropionate) (P3HP) and poly(3-hydroxybutyrate) (PHB); polylactate-co-3-hydroxypropionate (PLH); poly(3-hydroxypropionate)-b-polycaprolactone-b-polylactide (P3HP-b-PCL-b-PLA); and poly(3-hydroxypropionate)-b-(polycaprolactone-r-lactide) (P3HP-b-(PCL-r-LA)).

[0083]

[0084] Preferably, the biodegradable polymer may be polylactide.

[0085]

[0086] In one embodiment, the PLA may have a weight-average molecular weight (Mw) of 150,000 g / mol or more, or 180,000 g / mol or more, or 200,000 g / mol or more, and 300,000 g / mol or less, or 260,000 g / mol or less.

[0087]

[0088] In one embodiment, the PBAT may have a weight-average molecular weight of 70,000 g / mol or more, 86,000 g / mol or more, or 92,000 g / mol or more, and 10,000 g / mol or less, or 98,000 g / mol or less, or 95,000 g / mol or less. In addition, the PBAT may have a polydispersity index (PDI) of 2.3 or more, or 2.4 or more, and 2.6 or less.

[0089]

[0090] In one embodiment, the PBS may have a weight-average molecular weight of 70,000 g / mol or more, or 80,000 g / mol or more, or 84,000 g / mol or more, and 95,000 g / mol or less, or 87,000 g / mol. Additionally, the PBS may have a polydispersity index (PDI) of 1.6 or more, or 1.8 or more, and 2.0 or less, or 1.9 or less.

[0091]

[0092] In one embodiment, the P3HP may have a weight-average molecular weight of 49,000 g / mol or more, or 60,000 g / mol or more, or 70,000 g / mol or more, and 80,000 g / mol or less, or 79,000 g / mol or less. Additionally, the P3HP may have a polydispersity index (PDI) of 1.7 or more, or 1.9 or more, and 2.3 or less, or 2.1 or less.

[0093]

[0094] In one embodiment, the PLH may preferably be used such that the content of poly(3-hydroxypropionate) is 5 wt% or more, or 10 wt% or more, or 15 wt% or more, or 25 wt% or more, and 40 wt% or less, 35 wt% or less, or 30 wt% or less. The PLH may be used such that the weight-average molecular weight is 25,000 g / mol or more, or 30,000 g / mol or more, and 140,000 g / mol or less, or 130,000 g / mol or less.

[0095]

[0096] More specifically, when the content of poly(3-hydroxypropionate) of PLH is 10 to 15 weight%, a weight-average molecular weight of 93,000 g / mol to 130,000 g / mol and a polydispersity index (PDI) of 2.3 to 2.5 can be used.

[0097]

[0098] In addition, when the content of poly(3-hydroxypropionate) of PLH is 25 to 30 weight%, a weight-average molecular weight of 30,000 g / mol to 40,000 g / mol and a polydispersity index (PDI) of 2.0 to 2.2 may be used.

[0099]

[0100] In one embodiment, the P3HP-b-PCL-b-PLA may have a weight-average molecular weight of 30,000 g / mol or more, or 40,000 g / mol or more, or 50,000 g / mol or more, and 150,000 g / mol or less, or 130,000 g / mol or less, or 120,000 g / mol or less. Additionally, the P3HP-b-PCL-b-PLA may have a polydispersity index (PDI) of 2.7 or more, or 2.7 or more and 10.0 or less, or 9.0 or less. In addition, the above P3HP-b-PCL-b-PLA may have a (weight sum of P3HP block and PCL block):(weight of PLA block) ratio of 5:95 to 30:80 or 10:90 to 20:80, and the weight ratio of P3HP block to PCL block may be 1:0.5 to 1:2 or 1:0.5 to 1:1. For example, the weight ratio of P3HP block to PCL block to PLA block may be 5:5:90 to 10:10:80.

[0101]

[0102] In one embodiment, the P3HP-b-(PCL-r-LA) may have a weight-average molecular weight of 70,000 g / mol or more, or 80,000 g / mol or more, or 90,000 g / mol or more, and 150,000 g / mol or less, or 130,000 g / mol or less, or 110,000 g / mol or less. Additionally, the P3HP-b-(PCL-r-LA) may have a polydispersity index (PDI) of 2.3 or more, or 2.5 or more, and 15 or less, or 13 or less. In addition, the above P3HP-b-(PCL-r-LA) may have a weight ratio of P3HP block to PCL-r-LA block of 5:95 to 30:70 or 10:90 to 20:80, and the weight ratio of caprolactone-derived repeating unit to lactide-derived repeating unit of PCL-r-LA block may be 5:95 to 30:70 or 10:90 to 20:80.

[0103]

[0104] The nucleating agent represented by the above chemical formula 1 exhibits biodegradability and plays a role in improving processability by increasing the crystallization rate of biodegradable polymers.

[0105]

[0106] Specifically, the resin composition comprising the above-mentioned biodegradable polymer and the nucleating agent represented by Chemical Formula 1 exhibits a semi-crystallization time that is 20% or more, 40% or more, 44% or more, 50% or more, 55% or more, or 60% or more faster compared to the biodegradable polymer itself that does not contain the nucleating agent. This rate of increase (%) in semi-crystallization time can be calculated using the formula (t0-t1) / t0*100, where t0 is the semi-crystallization time of the biodegradable polymer and t1 is the semi-crystallization time of the resin composition. The upper limit of the rate of increase in semi-crystallization time is not limited, but, for example, it may be 95% or less, or 90% or less.

[0107]

[0108] Accordingly, a resin composition containing a nucleating agent represented by the above chemical formula 1 can improve productivity by exhibiting a shortened cycle time in processing steps such as injection molding, extrusion molding, and sheet extrusion.

[0109]

[0110] The nucleating agent represented by Chemical Formula 1 above is a branched poly(3-hydroxypropionic acid) copolymer, which is a polymer of polyfunctional monomers having three or more functional groups. That is, in Chemical Formula 1 above, R can be defined as a branched structure, and for example, the branched structure is (where n1 to n3 are each independently integers from 1 to 700) or (Here, n1 to n4 are each independently integers from 1 to 700) may have a structure such as, but is not limited thereto.

[0111]

[0112] In the above chemical formula 1, preferably, k is an integer of 3 or more, or 4 or more, and 10 or less, 9 or less, or 8 or less.

[0113]

[0114] Preferably, the R is a substituted or unsubstituted C 1-60 Alkyl, substituted, or unsubstituted C 3-60 Cycloalkyl, substituted or unsubstituted C 6-60 aryl or substituted or unsubstituted C containing one or more of N, O, and S 2-60 It is a linker of trivalent or higher, or tetravalent or higher, derived from a heteroaryl, and at least one of the carbon atoms of the alkyl, cycloalkyl, aryl, and heteroaryl is substituted or unsubstituted with at least one heteroatom selected from the group consisting of N, O, and S or a carbonyl.

[0115]

[0116] In one embodiment, R is a tetravalent, pentavalent, or hexavalent linker derived from a polyfunctional monomer, and k may be 4, 5, or 6 depending on R.

[0117]

[0118] The nucleating agent represented by the above chemical formula 1 is a polymer in which 3-hydroxypropionic acid is condensed polymerized with a polyfunctional monomer, or β-propiolactone is ring-opened polymerized with a polyfunctional monomer.

[0119]

[0120] The above-mentioned polyfunctional monomers include glycerol, pentaerythritol, 3-arm-poly(ethylene glycol) (number of ethylene glycol repeating units in each arm: 2 to 15), 4-arm-poly(ethylene glycol) (number of ethylene glycol repeating units in each arm: 2 to 10), di(trimethylolpropane), tripentaerythritol, xylitol, sorbitol, inositol, cholic acid, β-cyclodextrin, tetrahydroxyperylene, 2,2'-bis(hydroxymethyl)butyric acid (BHB), pyridinetetraamine (PTA), diethyltriaminepentaacetic acid, melamine, propane-1,2,3-triamine, tetraacetylenepentaamine, benzene-1,3,5-triamine, toluene-2,4,6-triisocyanate, One or more selected from the group consisting of 2-isocyanatoethyl-2,6-diisocyanatocaproate, triphenylphetan-4,4,4-triisocyanate, trimethylolpropane, triethanolamine, triglycidyl, and s-triazine-1,3,5-triethanol ether may be used.

[0121]

[0122]

[0123] In one embodiment, the polyfunctional monomer may be one or more selected from the group consisting of pentaerythritol, 4-arm-poly(ethylene glycol) (2 to 10 repeating units of ethylene glycol in each arm), tripentaerythritol, xylitol, sorbitol, and inositol.

[0124]

[0125] In one embodiment, the polyfunctional monomer may be pentaerythritol.

[0126]

[0127] The nucleating agent may be a condensation polymerized form of 0.1 mol% to 20 mol% of a polyfunctional monomer with respect to the content of 3-hydroxypropionic acid or β-propiolactone, respectively, and preferably, the content of the polyfunctional monomer may be 0.1 mol% to 15 mol%, 0.5 mol% to 10 mol%, or 1 mol% to 8 mol%, or 0.1 mol% or more, 0.5 mol% or more, or 1.0 mol% or more, or 15 mol% or less, 10 mol% or less, or 8 mol% or less.

[0128]

[0129] Meanwhile, the nucleating agent represented by the above chemical formula 1 may have additionally polymerized comonomers at the terminal functional groups contained within it.

[0130]

[0131] The above terminal functional group is derived from the polyfunctional monomer, 3-hydroxypropionic acid, β-propiolactone, used in the preparation of the branched poly(3-hydroxypropionic acid) polymer represented by Chemical Formula 1, and refers to a terminal functional group (e.g., -OH, -COOH) capable of further polymerization reaction.

[0132]

[0133] In addition, the type of comonomer copolymerized above is not particularly limited as long as it is a monomer capable of reacting with the aforementioned terminal functional group, and, for example, may be an ester-based comonomer. Specifically, glycolate, lactic acid, hydroxybutyrate, hydroxyvalerate, hydroxypentanoate, hydroxyotanoate, lactone-based compounds, etc. may be used, but are not limited thereto.

[0134]

[0135] The above nucleating agent may have a weight-average molecular weight (Mw, g / mol) of 1,000 or more, 1,500 or more, 1,900 or more, 2,000 or more, or 2,500 or more, and 100,000 or less, 80,000 or less, 50,000 or less, 40,000 or less, 35,000 or less, or 20,000 or less.

[0136]

[0137] The nucleating agent may have a number average molecular weight (Mn, g / mol) of 500 or more, 700 or more, 1,000 or more, 1,200 or more, 1,800 or more, or 2,000 or more, and 50,000 or less, 30,000 or less, 20,000 or less, 10,000 or less, 9,500 or less, or 8,000 or less.

[0138]

[0139] The nucleating agent may have a polydispersity index (PDI) of 1.0 to 13.0, or may be 1.1 or higher, 1.2 or higher, or 1.3 or higher, or 14.0 or lower, 13.5 or lower, 12.0 or lower, 11.0 or lower, or 10.0 or lower.

[0140]

[0141] The measurement methods for the weight-average molecular weight, number-average molecular weight, and polydispersity index described above will be explained in detail in the experimental examples section below.

[0142]

[0143] The nucleating agent represented by the above chemical formula 1 can be prepared according to a manufacturing method comprising the step of polymerizing, for example, 3-hydroxypropionic acid or β-propiolactone with the polyfunctional monomer described above.

[0144]

[0145] When a nucleating agent represented by the above chemical formula 1 is prepared by condensation polymerization with 3-hydroxypropionic acid and a polyfunctional monomer, the polyfunctional monomer may be included in an amount of 0.1 mol% to 20 mol% relative to the content of the 3-hydroxypropionic acid. When polymerized within the above content range, it is suitable for forming a desired branched structure with an appropriate cross-linked structure in excellent yield. If the polyfunctional monomer is less than 0.1 mol%, it is difficult to form the desired cross-linked structure, and if it exceeds 20 mol%, cross-linking occurs in the form of a relatively low molecular weight oligomer, making it difficult to obtain a high molecular weight polymer, and there is a problem of reduced process efficiency due to a longer reaction time. Preferably, the content of the polyfunctional monomer may be 0.1 mol% to 15 mol%, 0.5 mol% to 10 mol%, or 1 mol% to 8 mol%, or 0.1 mol% or more, 0.5 mol% or more, or 1.0 mol% or more, or 15 mol% or less, 10 mol% or less, or 8 mol% or less. In this case, a polymer can be formed without the aforementioned problems.

[0146]

[0147] In addition, when the nucleating agent represented by Chemical Formula 1 is prepared by ring-opening polymerization with β-propiolactone and a polyfunctional monomer, the polyfunctional monomer may be included in an amount of 0.1 mol% to 20 mol% relative to the β-propiolactone content. When polymerized within the above content range, it is suitable for forming a desired branched structure with an appropriate cross-linking structure in excellent yield. If the polyfunctional monomer is less than 0.1 mol%, it is difficult to form the desired cross-linking structure, and if it exceeds 20 mol%, cross-linking occurs in the form of a relatively low molecular weight oligomer, making it difficult to obtain a high molecular weight polymer, and there is a problem of reduced process efficiency due to a longer reaction time. Preferably, the content of the polyfunctional monomer may be 0.1 mol% to 15 mol%, 0.5 mol% to 10 mol%, or 1 mol% to 8 mol%, or 0.1 mol% or more, 0.5 mol% or more, or 1.0 mol% or more, or 15 mol% or less, 10 mol% or less, or 8 mol% or less. In this case, a polymer can be formed without the aforementioned problems.

[0148]

[0149] The above polymerization can be carried out in the presence of a sulfonic acid-based catalyst and a tin-based catalyst. The catalyst promotes the polymerization of 3-hydroxypropionic acid and β-propiolactone, respectively, while simultaneously having the effect of inhibiting the formation of cyclic oligomers during the polymerization process.

[0150]

[0151] Preferably, the sulfonic acid-based catalyst is p-toluenesulfonic acid, m-xylene-4-sulfonic acid, 2-mesylenesulfonic acid, or p-xylene-2-sulfonic acid. Also preferably, the tin-based catalyst is SnCl2 or Sn(oct)2.

[0152]

[0153] Preferably, the sulfonic acid-based catalyst is used in an amount of 0.001 mol% to 1 mol% relative to 3-hydroxypropionic acid and β-propiolactone, respectively. Within the above range, polymerization can be promoted while simultaneously suppressing the formation of cyclic oligomers. Preferably, the content of the sulfonic acid-based catalyst may be 0.01 mol% to 0.8 mol%, or 0.02 mol% to 0.5 mol%, or 0.01 mol% or more, or 0.02 mol% or more, or 0.8 mol% or less, or 0.5 mol% or less.

[0154]

[0155] Preferably, the tin-based catalyst is used in an amount of 0.00025 mol% to 1 mol% relative to 3-hydroxypropionic acid and β-propiolactone, respectively. Within the above range, polymerization can be promoted while simultaneously suppressing the formation of cyclic oligomers. Preferably, the tin-based catalyst may be 0.001 mol% to 0.8 mol%, 0.005 to 0.5 mol%, or 0.01 to 0.3 mol%, or 0.001 mol% or more, 0.005 mol% or more, or 0.01 mol% or more, or 0.8 mol% or less, 0.5 mol% or less, or 0.3 mol% or less.

[0156]

[0157] The above polymerization is carried out by performing the reaction at 80°C to 100°C and 8 mbar to 12 mbar for 110 to 130 minutes, and then 10 -2 The reaction can be carried out for 4 to 26 hours under vacuum conditions of torr. When melt polymerization is performed under the above conditions, the generation of by-products can be suppressed.

[0158]

[0159] More specifically, an oligomerization reaction is performed at 80°C to 100°C and 8 mbar to 12 mbar for 110 to 130 minutes, and then 10 -2The reaction can be carried out for 4 to 26 hours under vacuum conditions of torr to form a polymer of Formula 1.

[0160]

[0161] The subsequent polymerization described above can be carried out at the same temperature as the oligomerization reaction, or at a temperature raised to 100°C to 120°C.

[0162]

[0163] Preferably, the reaction is carried out for about 120±5 minutes at about 90±3℃ and about 10±1 mbar, and then the temperature is raised to the same temperature or about 110±3℃ to about 10 -2 The reaction can be carried out under vacuum conditions of torr. For reference, the reaction after oligomerization can be appropriately controlled depending on the content range of the polyfunctional monomer used. If an excess amount of polyfunctional monomer is used, the reaction time may be prolonged, leading to chain transfer as a side reaction and gelation, so the reaction can be appropriately controlled and carried out within about 24 hours.

[0164]

[0165] Meanwhile, the above 3-hydroxypropionic acid, β-propiolactone, and polyfunctional monomer may each be pretreated at 30°C to 100°C and 30 mbar to 150 mbar, respectively, before polymerization, if necessary. Through the above pretreatment step, moisture present in the 3-hydroxypropionic acid and polyfunctional monomer can be removed.

[0166]

[0167] The nucleating agent represented by Chemical Formula 1 above may be included in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the biodegradable polymer, or 0.5 parts by weight or more, or 1 part by weight or more and 10 parts by weight or less, or 8 parts by weight or less, or 5 parts by weight or less. When the content of the nucleating agent satisfies the above range, the resin composition can have uniform physical properties and significantly improve the crystallization rate of the biodegradable polymer, thereby improving processability.

[0168]

[0169] Meanwhile, the resin composition may include additional additives, such as antioxidants, as necessary, in addition to the biodegradable polymer and the nucleating agent represented by Chemical Formula 1. Examples of the antioxidants include the phosphorus-based antioxidant bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite (Songwon Industry, SONGNOX). ® 6260) may be used. When the above antioxidant is included, its content may be adjusted as needed, for example, at least 0.1 parts by weight or at least 0.2 parts by weight and at least 0.5 parts by weight or at least 0.4 parts by weight or at least 0.3 parts by weight per 100 parts by weight of the biodegradable polymer.

[0170]

[0171] 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.

[0172]

[0173] <Preparation Example and Comparative Preparation Example: Preparation of Nucleating Agent>

[0174] Preparation Example 1

[0175] 3-hydroxypropionic acid (3HP) and glycerol dissolved in water were placed in RBF and the moisture was dried at 90°C and 100 torr for 2 hours.

[0176] 70 g of dried 3-hydroxypropionic acid (3HP), 3.578 mg of glycerol (5 mol% relative to 3HP), and 295.6 mg of p-TSA (0.2 mol% relative to 3HP) as a catalyst were placed in a reactor, and an olimer solidification reaction was carried out at 90°C and 10 mbar for 2 hours. After polymerizing for 5 hours with the vacuum level adjusted to 0.1 torr, Sn(Oct)2 was added as a co-catalyst at 0.05 mol% relative to 3HP, and an additional polymerization reaction was carried out for 24 hours to produce a branched poly(3-hydroxypropionic acid) copolymer.

[0177]

[0178] Preparation Example 2

[0179] 87.31 g of 3HP, 1.32 g of pentaerythritol (PTEA) (1 mol%) relative to 3HP, and 184 mg of p-TSA (0.1 mol%) relative to 3HP were added to a 3-neck round flask to prepare the mixture.

[0180] A branched poly(3-hydroxypropionic acid) copolymer was prepared by setting the heating block to 90°C and the overhead stirrer to 300 rpm to stir while gradually reducing the pressure to 0.1 torr for 2 hours to remove moisture, and then carrying out condensation polymerization for 24 hours while maintaining the same pressure, temperature, and stirring speed.

[0181]

[0182] Preparation Example 3

[0183] 87.31 g of 3HP, 6.598 g of pentaerythritol (PTEA) (5 mol%) relative to 3HP, and 184 mg of p-TSA (0.1 mol%) as a catalyst were added to a 3-neck round flask.

[0184] A branched poly(3-hydroxypropionic acid) copolymer was prepared by setting the heating block to 90°C and the overhead stirrer to 300 rpm to stir while gradually reducing the pressure to 0.1 torr for 2 hours to remove moisture, and then carrying out condensation polymerization for 24 hours while maintaining the same pressure, temperature, and stirring speed.

[0185]

[0186] Preparation Example 4

[0187] 74.62 g of 3HP, 0.5112 g of glycerol (1 mol% relative to 3HP), and 211 mg of p-TSA (0.2 mol% relative to 3HP) as a catalyst were added to a 3-necked round flask to prepare the mixture.

[0188] A branched poly(3-hydroxypropionic acid) copolymer was prepared by setting the heating block to 90°C and the overhead stirrer to 300 rpm to stir while gradually reducing the pressure to 0.1 torr for 2 hours to remove moisture, and then carrying out condensation polymerization for 15 hours while maintaining the same pressure, temperature, and stirring speed.

[0189]

[0190] Comparative Manufacturing Example 1

[0191] 3-hydroxypropionic acid (3HP) dissolved in water was placed in RBF and the moisture was dried at 90°C and 100 torr for 2 hours.

[0192] 60 g of dried 3-hydroxypropionic acid (3HP) was placed in a reactor, and an olimer solidification reaction was carried out at 90°C and 10 mbar for 2 hours using 295.6 mg of p-TSA (0.2 mol% relative to 3HP) as a catalyst. After polymerization for 5 hours with the vacuum level adjusted to 0.1 torr, Sn(Oct)2 was added as a co-catalyst at 0.05 mol% relative to 3HP, and an additional polymerization reaction was carried out for 24 hours to produce a linear poly(3-hydroxypropionic acid) polymer.

[0193]

[0194] GPC (gel permeation chromatography) molecular weight evaluation

[0195] GPC analysis of the polymers of Preparation Examples 1 to 4 and Comparative Preparation Example 1 was performed using a Water e2695 model instrument and Agilent Plgel mixed c and b columns.

[0196] 20 µl of the sample was injected using chloroform as a solvent at a concentration of 4 mg / ml. The weight-average molecular weight, number-average molecular weight, and polydispersity index were measured using gel permeation chromatography (GPC, Tosoh ECO SEC Elite).

[0197] Solvent: chloroform (eluent)

[0198] Flow rate: 1.0 ml / min

[0199] Column temperature: 40℃

[0200] Standard: Polystyrene (corrected by a cubic function)

[0201]

[0202] MnMwPDI Manufacturing Example 12,525 3,377 8 13.38 Manufacturing Example 27,600 10,995 1.44 Manufacturing Example 32,26 32,955 1.3 Manufacturing Example 49,054 16,054 1.77 Comparative Manufacturing Example 116,197 33,663 2.08

[0203]

[0204] <Examples and Comparative Examples: Preparation of Resin Compositions>

[0205] Examples 1 to 30 and Comparative Examples 1 to 9

[0206] The resin compositions of each example and comparative example were prepared by mixing a biodegradable polymer and a nucleating agent with the compositions listed in Tables 2 and 3 below using a small extruder (Thermo Scientific Haake Mini CTW Mini Jet Combination) and a twin screw.

[0207] In Tables 2 and 3 below, the nucleating agent content is expressed in parts by weight (wt%) per 100 parts by weight of the biodegradable polymer. If only a number is indicated in the 'Nucleating Agent Content' column of Tables 2 and 3, it means that the nucleating agent of Preparation Example 1 was used in that amount. If a nucleating agent other than Preparation Example 1 was used, the nucleating agent used is listed below the nucleating agent content value.

[0208] Each resin composition was prepared by the following method. Biodegradable polymers and nucleating agents were placed in an extruder, the discharge port was blocked, and the mixture was mixed at 60 rpm at a temperature of 90–190 ℃ (P3HP 90 ℃; PBS 130 ℃; PLA 190 ℃; PBAT 150 ℃; PLH 10% and PLH 30% 190 ℃). After mixing for 3 minutes, the mixture was extruded to obtain the resin composition.

[0209]

[0210] The biodegradable polymers used in the preparation of the resin compositions of each example and comparative example are as follows. The units of Mn and Mw below are g / mol.

[0211]

[0212] P3HP: 3-hydroxypropionic acid was placed in a reactor and dried at 50°C and 30 mbar for 5 hours to completely remove moisture. To the moisture-removed 3-hydroxypropionic acid (15 g), p-TSA (p-Toluenesulfonic acid) and 1,4-butanediol were added at 0.2 mol% and 1 mol%, respectively, relative to the 3-hydroxypropionic acid. The reaction was carried out for 2 hours while maintaining the temperature and pressure inside the reactor at 90°C and 10 mbar, respectively, to produce a 3-hydroxypropionic acid oligomer. Subsequently, the temperature and pressure inside the reactor were adjusted to 110°C and 0.3 mbar, respectively, and the reaction was carried out for 6 hours to produce poly(3-hydroxypropionate) (Mn 35311, Mw 75536, PDI 2.14).

[0213] P3HP-b-(PCL-r-LA): 16g of lactide, 2g of poly(3-hydroxypropionate), and 4g of caprolactone were placed in a reactor and polymerized for 90 minutes at 180℃ under nitrogen conditions to prepare.

[0214] P3HP-b-PCL-b-PLA: 16g of lactide and 2g of poly(3-hydroxypropionate) were placed in a reactor and polymerized for 20 minutes at 180°C under nitrogen, then 4g of caprolactone was added and polymerized for 20 minutes at 180°C under nitrogen to prepare.

[0215] PBS: Sigma-Aldrich (Mn 46809, Mw 84182, PDI 1.8)

[0216] PBAT: ANKOR Bioplastics, BG1070 (Mn 38660, Mw 97618, PDI 2.53)

[0217] PLH 10%: Poly(3-hydroxypropionate) was added at 10 wt% relative to lactide and ring-opening polymerization was performed at 180°C for 90 minutes under a nitrogen atmosphere (Mn 42721, Mw 101768, PDI 2.38).

[0218] PLH 30%: Poly(3-hydroxypropionate) was added to lactide at a ratio of 30 wt% and ring-opening polymerization was performed at 180°C for 90 minutes under a nitrogen atmosphere (Mn 29309, Mw 69265, PDI 2.36).

[0219] PLA: Totalenergies corbion, Luminy ® LX175 (Mn 124544, Mw 235402, PDI 1.89)

[0220]

[0221] Experimental Example 1: DSC (differential scanning calorimetry) non-isothermal crystallization experiment

[0222] Using the TA DSC250 model instrument, measurements were taken under the following conditions in a nitrogen gas flow state to determine the crystallization temperature (Tc, result of 1st cooling), glass transition temperature (Tg), cold crystallization temperature (Tcc, result of 2nd heating), enthalpy, and melting temperature (Tm).

[0223] 1) Increase temperature from 30℃ to 190℃ at 10℃ / min (1st heating) / Maintain temperature at 190℃ for 10 minutes

[0224] 2) Cool from 190℃ to -60℃ at 10℃ / min (1st cooling) / Maintain temperature at -60℃ for 10 minutes

[0225] 3) Increase temperature from -60℃ to 190℃ at 10℃ / min (2 nd heating)

[0226]

[0227] Experimental Example 2: DSC Isothermal Crystallization Experiment

[0228] The half crystallization time was determined by measuring under the following conditions in a nitrogen gas flow state using the TA DSC250 model instrument.

[0229] 1) Increase temperature from 30℃ to 190℃ at 10℃ / min (1st heating) / Maintain temperature at 190℃ for 10 minutes

[0230] 2) Depending on the biodegradable polymer included in the resin composition, cool to the temperature specified below and proceed with isotherm measurements for 100 minutes.

[0231]

[0232] P3HP-b-PCL-b-PLA: 80 ℃

[0233] P3HP-b-(PCL-r-LA): 80 ℃

[0234] P3HP: 40 ℃

[0235] PBS: 40 ℃

[0236] PBAT: 90 ℃

[0237] PLH 10%: 90 ℃

[0238] PLH 30%: 70 ℃

[0239] PLA: 110 ℃

[0240] Preparation Example 1: 30 ℃

[0241]

[0242]

[0243]

[0244] * ND: Unconfirmed

[0245]

[0246] Generally, if the crystallization rate of a resin composition is fast, the enthalpy of Tc is high, cold crystallization is minimal or absent, and the semi-crystallization time is short.

[0247] Referring to Tables 2 and 3 above, it can be seen that the resin compositions of Examples 1 to 26 containing the nucleating agents of Preparation Examples 1 to 4 all have a confirmed Tc, and compared to their respective biodegradable polymers, the Tc enthalpy value is significantly higher, while the Tcc temperature and enthalpy values ​​are lower. In addition, it was confirmed that the semi-crystallization time of the resin compositions of the examples was significantly shorter compared to their respective biodegradable polymers. In particular, as shown in Fig. 1, the crystallization rate of Example 13 was so fast that it was impossible to separate the peaks using analytical equipment, making it impossible to measure the accurate semi-crystallization time. For the same reason, it was also impossible to measure the semi-crystallization time of Example 14.

[0248] Meanwhile, in the case of Comparative Example 9, which used a nucleating agent of Comparative Manufacturing Example 1 that does not satisfy the structure of Chemical Formula 1, it can be confirmed that the effect of improving the crystallization rate is significantly lower compared to Example 26, which used an equal amount of the nucleating agent of Manufacturing Example 1.

Claims

1. Biodegradable polymer; and A nucleating agent represented by the following chemical formula 1; comprising Resin composition: [Chemical Formula 1] R-[A-(B)n] k In the above chemical formula 1, R is a trivalent or higher linker derived from a polyfunctional monomer, and A is a direct linkage; or a linker derived from an ether, sulfide, ester, thioester, ketone, sulfoxide, sulfone, sulfonate ester, amine, amide, imine, imide, or urethane, and B is a substituent represented by the following chemical formula 1-1 or chemical formula 1-2, and [Chemical Formula 1-1] [Chemical Formula 1-2] * is the part connected to A, and k is an integer greater than or equal to 3, and n is an integer from 1 to 700.

2. In Paragraph 1, The above biodegradable polymer is one or more selected from the group consisting of polylactide; poly(butylene adipate-co-terephthalate); polybutylene succinate; polyhydroxyalkanoate; polylactate-co-3-hydroxypropionate; poly(3-hydroxypropionate)-b-polycaprolactone-b-polylactide; and poly(3-hydroxypropionate)-b-(polycaprolactone-r-lactide). Resin composition.

3. In Paragraph 1 or 2, The above biodegradable polymer is a polylactide having a weight-average molecular weight of 150,000 g / mol to 300,000 g / mol, Resin composition.

4. In any one of paragraphs 1 through 3, The above nucleating agent is included in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the biodegradable polymer, Resin composition.

5. In any one of paragraphs 1 through 4, R is C 1-60 Alkyl, C 3-60 Cycloalkyl, C 6-60 C containing aryl or one or more of N, O, and S 2-60 It is a linker of trivalent or higher derived from a heteroaryl, and At least one of the carbon atoms of the above alkyl, cycloalkyl, aryl, and heteroaryl is substituted or unsubstituted with at least one heteroatom selected from the group consisting of N, O, and S or a carbonyl, Resin composition.

6. In any one of paragraphs 1 through 4, R is a tetravalent or higher linker derived from a polyfunctional monomer, and k is an integer greater than or equal to 4, Resin composition.

7. In any one of paragraphs 1 through 6, The above nucleating agent is 3-hydroxypropionic acid condensed with a polyfunctional monomer, or β-propiolactone ring-opened with a polyfunctional monomer, Resin composition.

8. In any one of paragraphs 1 through 7, The above-mentioned polyfunctional monomer is glycerol, pentaerythritol, 3-arm-poly(ethylene glycol) (number of ethylene glycol repeating units in each arm: 2 to 15), 4-arm-poly(ethylene glycol) (number of ethylene glycol repeating units in each arm: 2 to 10), di(trimethylolpropane), tripentaerythritol, xylitol, sorbitol, inositol, cholic acid, β-cyclodextrin, tetrahydroxyperylene, 2,2'-bis(hydroxymethyl)butyric acid (BHB), pyridinetetraamine (PTA), diethyltriaminepentaacetic acid, melamine, propane-1,2,3-triamine, tetraacetylenepentaamine, benzene-1,3,5-triamine, toluene-2,4,6-triisocyanate, One or more selected from the group consisting of 2-isocyanatoethyl-2,6-diisocyanatocaproate, triphenylphetan-4,4,4-triisocyanate, trimethylolpropane, triethanolamine, triglycidyl, and s-triazine-1,3,5-triethanol ether, Resin composition.

9. In any one of paragraphs 1 through 7, The above polyfunctional monomer is one or more selected from the group consisting of pentaerythritol, 4-arm-poly(ethylene glycol) (2 to 10 ethylene glycol repeating units in each arm), tripentaerythritol, xylitol, sorbitol, and inositol. Resin composition.

10. In any one of paragraphs 1 through 9, The above nucleating agent has a weight-average molecular weight of 1,000 g / mol to 100,000 g / mol, Resin composition.

11. In any one of paragraphs 1 through 10, The above nucleating agent has a number average molecular weight of 500 g / mol to 50,000 g / mol, Resin composition.

12. In any one of paragraphs 1 through 11, The above nucleating agent has a polydispersity index of 1.0 to 14.0, Resin composition.

13. In any one of paragraphs 1 through 12, When the semi-crystallization time of the above biodegradable polymer is t0 and the semi-crystallization time of the above resin composition is t1, the semi-crystallization time increase rate expressed by the formula (t0-t1) / t0*100 is 20% or more, Resin composition.

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