Copolymer and method for preparing copolymer

Abstract

The present invention relates to: a copolymer having eco-friendliness, biodegradability, excellent mechanical properties, and excellent adhesiveness at low temperatures; and a method for preparing the copolymer.

Description

Copolymers and methods for producing copolymers

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority to Republic of Korea Patent Application No. 10-2023-0104461, dated August 9, 2023, and Republic of Korea Patent Application No. 10-2024-0105624, dated August 7, 2024, the entire contents of which are incorporated herein by reference.

[0003] The present invention relates to a copolymer and a method for producing a copolymer.

[0004]

[0005] Polylactic acid (PLA) is a type of aliphatic polyester that is attracting attention as an eco-friendly material that is biodegradable and has excellent tensile strength and elasticity.

[0006]

[0007] Unlike conventional petroleum-based resins like polystyrene, polyvinyl chloride, and polyethylene, these plastics can help prevent the depletion of petroleum resources and reduce carbon dioxide emissions, potentially reducing environmental pollution, a drawback of petroleum-based plastic products. Consequently, as environmental pollution caused by waste plastics becomes a growing social issue, efforts are being made to expand their application to products previously used with conventional plastics (petroleum-based resins), such as food packaging and containers and electronic device cases.

[0008]

[0009] However, compared to conventional petroleum-based resins, polylactic acid has poor elongation to break characteristics and brittleness, which limits its processability, and thus has limitations as a general-purpose resin.

[0010] Accordingly, research is needed on copolymers that maintain the mechanical properties of polylactic acid while improving elongation properties.

[0011]

[0012] The present invention provides a copolymer and a method for producing the copolymer having excellent mechanical properties, excellent adhesiveness at low temperatures, along with environmental friendliness and biodegradability.

[0013] According to one embodiment of the present invention, a copolymer is provided, which includes a repeating unit represented by the following chemical formula 1, a repeating unit represented by the following chemical formula 2, and a repeating unit represented by the following chemical formula 3, and includes 20 mol or more and 200 mol or less of the repeating unit represented by the above chemical formula 2 with respect to 1 mol of the repeating unit represented by the above chemical formula 1.

[0014] [Chemical Formula 1]

[0015]

[0016] [Chemical Formula 2]

[0017]

[0018] [Chemical Formula 3]

[0019]

[0020] In the above chemical formula 1, L1 is a substituted or unsubstituted alkylene group having 4 or more carbon atoms, n is an integer of 5 or more, in the above chemical formula 2, L2 is a substituted or unsubstituted alkylene group having 2 or more carbon atoms, and in the above chemical formula 3, L3 is a substituted or unsubstituted alkylene group having 1 or more carbon atoms or an arylene group having 1 or more carbon atoms.

[0021]

[0022] According to another embodiment of the present invention, a method for producing a copolymer is provided, comprising the steps of: preparing a prepolymer by ring-opening polymerizing a monomer represented by the following chemical formula 7 in the presence of a compound represented by the following chemical formula 6; and preparing a copolymer by reacting the prepolymer with a monomer represented by the following chemical formula 8; wherein 20 mol or more and 200 mol or less of the compound represented by the above chemical formula 7 are added per 1 mol of the compound represented by the above chemical formula 6.

[0023] [Chemical Formula 6]

[0024]

[0025] In the above chemical formula 6, L1 is a substituted or unsubstituted alkylene group having 4 or more carbon atoms, n is an integer of 5 or more,

[0026] [Chemical Formula 7]

[0027]

[0028] In the above chemical formula 7, L2 is a substituted or unsubstituted alkylene group having 2 or more carbon atoms,

[0029] [Chemical Formula 8]

[0030]

[0031] In the above chemical formula 8, L3 is a substituted or unsubstituted alkylene group having 1 or more carbon atoms or an arylene group having 1 or more carbon atoms.

[0032]

[0033] Unless otherwise specified throughout this specification, the terms “include” or “comprising” refer to the inclusion of a component (or component) without limitation, and cannot be construed as excluding the addition of other components (or components).

[0034] In the present invention, terms such as first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

[0035] 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.

[0036] In addition, unless otherwise stated herein, the weight average molecular weight can be measured using gel permeation chromatography (GPC). Specifically, the prepolymer or copolymer 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.

[0037] In this specification, copolymer is used to mean a copolymer including random copolymers, block copolymers, graft copolymers, etc.

[0038] In this specification, the term “block” means a polymer in which two or more repeating units are connected, and the term “block copolymer” means a copolymer in which two or more types of blocks are each connected by one or more direct bonds or linkages.

[0039]

[0040] In the present specification, an alkyl group is a monovalent functional group derived from an alkane, which may be straight or branched, and the number of carbon atoms in the straight-chain alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the number of carbon atoms in the branched-chain alkyl group is 3 to 20. 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, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, Examples thereof include, but are not limited to, 5-methylhexyl, 2,6-dimethylheptan-4-yl, etc. The alkyl group may be substituted or unsubstituted.

[0041] In this specification, a haloalkyl group means a functional group in which a halogen group is substituted on the above-described alkyl group, and examples of the halogen group include fluorine, chlorine, bromine, or iodine. The haloalkyl group may be substituted or unsubstituted.

[0042] In the present specification, the aryl group is a monovalent functional group derived from arene, and may be a monocyclic aryl group or a polycyclic aryl group. The monocyclic aryl group may include, but is not limited to, a phenyl group, a biphenyl group, a terphenyl group, etc. The polycyclic aryl group may include, but is not limited to, a naphthyl group, anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, etc. The aryl group may be substituted or unsubstituted.

[0043] In this specification, an alkylene group is a divalent functional group derived from an alkane, and the description of the alkyl group described above can be applied to these groups, except that they are divalent functional groups.

[0044] In the present specification, an arylene group is a divalent functional group derived from arene, and the description of the above-mentioned aryl group may be applied to these except that they are divalent functional groups. For example, they may be a phenylene group, a biphenylene group, a terphenylene group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, etc. The arylene group may be substituted or unsubstituted.

[0045] In this specification, , or means a bond that connects to another substituent.

[0046] In this specification, a direct bond or single bond means that no atoms or atomic groups exist at that position, and are connected by a bond line.

[0047] In this specification, the term "substitution" means that another functional group is bonded instead of a hydrogen atom in a compound, and the position of substitution is not limited as long as it is a position where a hydrogen atom is substituted, i.e., a position where a substituent can be substituted, and when two or more are substituted, the two or more substituents may be the same or different from each other.

[0048] The term "substituted or unsubstituted" as used herein means a group which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group; a nitro group; a hydroxy group; a carbonyl group; an ester group; an imide group; an amide group; a primary amino group; a carboxyl group; a sulfonic acid group; a sulfonamide 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 alkoxysilylalkyl group; an arylphosphine group; or a heterocyclic group containing one or more of N, O, and S atoms, or a substituted or unsubstituted group in which two or more of the above-mentioned substituents are linked. For example, a "substituent having two or more substituents connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, or may be interpreted as a substituent having two phenyl groups connected.

[0049]

[0050] Hereinafter, a copolymer and a method for producing the copolymer according to a specific embodiment of the invention will be described in more detail.

[0051]

[0052] According to one embodiment of the invention, a copolymer is provided, which includes a repeating unit represented by the chemical formula 1, a repeating unit represented by the chemical formula 2, and a repeating unit represented by the chemical formula 3, and includes 20 mol or more and 200 mol or less of the repeating unit represented by the chemical formula 2 per 1 mol of the repeating unit represented by the chemical formula 1.

[0053] The present inventors have completed the present invention by finding that the copolymer of the above embodiment simultaneously includes a repeating unit represented by the above chemical formula 1, a repeating unit represented by the above chemical formula 2, and a repeating unit represented by the above chemical formula 3, thereby simultaneously realizing excellent mechanical properties and elongation, and realizing excellent adhesiveness at low temperatures.

[0054] Specifically, since the copolymer of the above embodiment simultaneously includes a repeating unit represented by the above chemical formula 1, a repeating unit represented by the above chemical formula 2, and a repeating unit represented by the above chemical formula 3, a polymer film having excellent physical properties can be manufactured by having excellent mechanical properties and biodegradability derived from the repeating unit represented by the above chemical formula 2, and at the same time, flexibility and processability are improved due to the repeating unit represented by the above chemical formula 1. In addition, since the polymer film manufactured from the copolymer of the above embodiment exhibits cohesion derived from the molecular structure represented by the above chemical formula 1, it can be implemented as a heat-sealing film having excellent adhesive strength.

[0055]

[0056] Specifically, the copolymer of the above embodiment may include a repeating unit represented by the following chemical formula 1, a repeating unit represented by the following chemical formula 2, and a repeating unit represented by the following chemical formula 3.

[0057] [Chemical Formula 1]

[0058]

[0059] [Chemical Formula 2]

[0060]

[0061] [Chemical Formula 3]

[0062]

[0063] In the above chemical formula 1, L1 is a substituted or unsubstituted alkylene group having 3 or fewer carbon atoms, n is an integer of 5 or more, in the above chemical formula 2, L2 is a substituted or unsubstituted alkylene group having 2 or more carbon atoms, and in the above chemical formula 3, L3 is a substituted or unsubstituted alkylene group having 1 or more carbon atoms or an arylene group having 1 or more carbon atoms.

[0064]

[0065] Since conventional copolymers do not contain the repeating unit represented by the above chemical formula 1, there was a problem in that processability was limited due to the high melting point and high crystallinity, making conventional polymer processing methods such as thermoforming and film processing impossible. Since the copolymer of the above embodiment contains the repeating unit represented by the above chemical formula 1, it has excellent low-temperature properties and stability against hydrolysis, and can realize excellent elongation due to the low glass transition temperature.

[0066] The above copolymer may include a random copolymer, a block copolymer, a graft copolymer, etc. For example, the above copolymer may be a block copolymer.

[0067] A copolymer according to one embodiment of the present invention comprises a first block including a repeating unit represented by the chemical formula 1, and a second block including a repeating unit represented by the chemical formula 2, and since the first block and the second block are directly bonded, ester bonded, amide bonded, urethane bonded, or carbonate bonded, the copolymer can compensate for the disadvantage of low elongation properties of a biodegradable resin containing only polylactic acid. In addition, these copolymers have excellent biodegradability while compensating for the mechanical properties of each homopolymer.

[0068] That is, in the copolymer of the above embodiment, the repeating unit represented by the chemical formula 1, the repeating unit represented by the chemical formula 2, and the repeating unit represented by the chemical formula 3 may be connected by a direct bond, an ester bond, an amide bond, a urethane bond, a urea bond, or a carbonate bond.

[0069]

[0070] In the above chemical formula 1, L1 may be an alkylene group having 3 or fewer carbon atoms, and the alkylene group may be substituted or unsubstituted.

[0071] Additionally, in the above chemical formula 1, n may be an integer greater than or equal to 5 and less than or equal to 5000.

[0072] Specifically, in the above chemical formula 1, n may be an integer of 5 or more, 10 or more, or 5000 or less, 4000 or less, 3000 or less, 2000 or less, 1500 or less, 1000 or less, 500 or less, 100 or less, 50 or less, or 30 or less, and may be 5 or more and 5000 or less, 5 or more and 4000 or less, 5 or more and 3000 or less, 5 or more and 2000 or less, 5 or more and 1500 or less, 5 or more and 1000 or less, 5 or more and 500 or less, 5 or more and 100 or less, 5 or more and 50 or less, 5 or more and 30 or less, 10 or more and 5000 or less, 10 or more and 4000 or less, 10 or more and 3000 or less, 10 or more and 2000 or less, 10 or more and 1500 or less, 10 or more It can be an integer less than or equal to 1000, greater than or equal to 10 and less than or equal to 500, greater than or equal to 10 and less than or equal to 100, greater than or equal to 10 and less than or equal to 50, or greater than or equal to 10 and less than or equal to 30.

[0073]

[0074] In the above chemical formula 1, n may mean the number of repetitions within the repeating unit represented by the above chemical formula 1, and since n in the above chemical formula 1 is an integer of 5 or more, sufficient elongation can be secured compared to the case where n is less than 5.

[0075] The repeating unit represented by the above chemical formula 1 may be a repeating unit derived from a compound represented by the following chemical formula 6.

[0076] [Chemical Formula 6]

[0077]

[0078] In the above chemical formula 6, L1 is an alkylene group having 3 or fewer carbon atoms, and n is an integer of 5 or more.

[0079] Specifically, in the above chemical formula 6, L1 is an alkylene group having 3 or fewer carbon atoms, and the alkylene group may be substituted or unsubstituted.

[0080] Additionally, in the above chemical formula 6, n may be an integer greater than or equal to 5 and less than or equal to 5000.

[0081] Specifically, in the above chemical formula 6, n may be an integer of 5 or more, 10 or more, or 5000 or less, 4000 or less, 3000 or less, 2000 or less, 1500 or less, 1000 or less, 500 or less, 100 or less, 50 or less, or 30 or less, and may be 5 or more and 5000 or less, 5 or more and 4000 or less, 5 or more and 3000 or less, 5 or more and 2000 or less, 5 or more and 1500 or less, 5 or more and 1000 or less, 5 or more and 500 or less, 5 or more and 100 or less, 5 or more and 50 or less, 5 or more and 30 or less, 10 or more and 5000 or less, 10 or more and 4000 or less, 10 or more and 3000 or less, 10 or more and 2000 or less, 10 or more and 1500 or less, 10 or more It can be an integer less than or equal to 1000, greater than or equal to 10 and less than or equal to 500, greater than or equal to 10 and less than or equal to 100, greater than or equal to 10 and less than or equal to 50, or greater than or equal to 10 and less than or equal to 30.

[0082]

[0083] Specifically, the repeating unit represented by the above chemical formula 1 may include a repeating unit represented by the following chemical formula 1-1.

[0084] [Chemical Formula 1-1]

[0085]

[0086] In the above chemical formula 1-1, R1 to R6 are each independently hydrogen or an alkyl group, and n is an integer of 5 or more.

[0087] Specifically, in the above chemical formula 1-1, n may be an integer of 5 or more, 10 or more, or 5000 or less, 4000 or less, 3000 or less, 2000 or less, 1500 or less, 1000 or less, 500 or less, 100 or less, 50 or less, or 30 or less, and may be 5 or more and 5000 or less, 5 or more and 4000 or less, 5 or more and 3000 or less, 5 or more and 2000 or less, 5 or more and 1500 or less, 5 or more and 1000 or less, 5 or more and 500 or less, 5 or more and 100 or less, 5 or more and 50 or less, 5 or more and 30 or less, 10 or more and 5000 or less, 10 or more and 4000 or less, 10 or more and 3000 or less, 10 or more and 2000 or less, 10 or more and 1500 or less, 10 or more It can be an integer less than or equal to 1000, greater than or equal to 10 and less than or equal to 500, greater than or equal to 10 and less than or equal to 100, greater than or equal to 10 and less than or equal to 50, or greater than or equal to 10 and less than or equal to 30.

[0088]

[0089] Since the copolymer of the above embodiment includes a repeating unit represented by the above chemical formula 1-1, it has excellent low-temperature properties and stability against hydrolysis, and is also capable of high-temperature thermoforming such as polymer processing thermoforming and film processing, thereby realizing excellent processability. In addition, due to the low glass transition temperature, crystallinity is reduced, thereby realizing excellent elongation and excellent processability.

[0090]

[0091] Meanwhile, the copolymer of the above embodiment may include a repeating unit represented by the following chemical formula 2.

[0092] [Chemical Formula 2]

[0093]

[0094] In the above chemical formula 2, L2 is an alkylene group having 2 or more carbon atoms.

[0095] Since the above copolymer includes a repeating unit represented by the above chemical formula 2, processability can be improved, the biodegradability rate can be controlled, and analysis of the material can be facilitated.

[0096]

[0097] The repeating unit represented by the above chemical formula 2 may be a repeating unit derived from a compound represented by the following chemical formula 7.

[0098] [Chemical Formula 7]

[0099]

[0100] In the above chemical formula 7, L2 is an alkylene group having 2 or more carbon atoms.

[0101] A copolymer including a repeating unit represented by the above chemical formula 2 can be produced by ring-opening polymerization of a compound represented by the above chemical formula 6 and a compound represented by the above chemical formula 7.

[0102] Specifically, the repeating unit represented by the above chemical formula 2 may include a repeating unit represented by the following chemical formula 2-1.

[0103] [Chemical Formula 2-1]

[0104] .

[0105] The repeating unit represented by the above chemical formula 2-1 may be a repeating unit derived from a lactide monomer.

[0106]

[0107] The above copolymer may include a repeating unit represented by the following chemical formula 10.

[0108] [Chemical Formula 10]

[0109]

[0110] In the above chemical formula 10, P is an integer greater than or equal to 2.

[0111]

[0112] Including a repeating unit represented by the above chemical formula 10, where p is an integer greater than or equal to 2, may mean that the copolymer of the above embodiment includes a third block comprising a repeating unit represented by the above chemical formula 2.

[0113]

[0114] In addition, the copolymer may include a structure in which repeating units represented by the following chemical formula 10 are bonded to both terminals of the functional group of the following chemical formula 11.

[0115] [Chemical Formula 10]

[0116]

[0117] In the above chemical formula 10, p is an integer greater than or equal to 2,

[0118] [Chemical Formula 11]

[0119]

[0120] In the above chemical formula 11, n is an integer greater than or equal to 5.

[0121] More specifically, the copolymer may include a repeating unit represented by the following chemical formula 10-1.

[0122] [Chemical Formula 10-1]

[0123] .

[0124]

[0125]

[0126] The copolymer of the above embodiment may include a repeating unit represented by the following chemical formula 3.

[0127] [Chemical Formula 3]

[0128]

[0129] In the above chemical formula 3, L3 is a substituted or unsubstituted alkylene group having 1 or more carbon atoms or an arylene group having 1 or more carbon atoms. Specifically, in the above chemical formula 3, L3 may be a substituted or unsubstituted alkylene group having 5 or more carbon atoms or an arylene group having 5 or more carbon atoms, an alkylene group having 6 or more carbon atoms or an arylene group having 6 or more carbon atoms.

[0130]

[0131] The copolymer of the above embodiment may include a repeating unit represented by the following chemical formula 4.

[0132] [Chemical Formula 4]

[0133]

[0134] In the above chemical formula 4, q is an integer of 2 or more, L4 is a substituted or unsubstituted alkylene group having 2 or more carbon atoms, and L5 is a substituted or unsubstituted alkylene group having 1 or more carbon atoms or an arylene group having 1 or more carbon atoms.

[0135]

[0136] The repeating unit represented by the above chemical formula 4 may be a repeating unit in which the repeating unit represented by the above chemical formula 2 and the repeating unit represented by the above chemical formula 3 are directly connected by bond.

[0137] As described below, the copolymer of the above embodiment is prepared by reacting a prepolymer prepared by ring-opening polymerization of a monomer represented by the above chemical formula 7 in the presence of a compound represented by the above chemical formula 6 with a monomer represented by the above chemical formula 8, and thus may include a repeating unit represented by the above chemical formula 4.

[0138] Specifically, in the above chemical formula 4, L5 may be a substituted or unsubstituted alkylene group having 5 or more carbon atoms, an arylene group having 5 or more carbon atoms, an alkylene group having 6 or more carbon atoms, or an arylene group having 6 or more carbon atoms.

[0139]

[0140] More specifically, the copolymer of the above embodiment may include a repeating unit represented by the following chemical formula 5.

[0141] [Chemical Formula 5]

[0142]

[0143] In the above chemical formula 5, L6 and L8 are each independently a substituted or unsubstituted alkylene group having 2 or more carbon atoms, L7 is a substituted or unsubstituted alkylene group having 3 or less carbon atoms, L9 is a substituted or unsubstituted alkylene group having 1 or more carbon atoms or an arylene group having 1 or more carbon atoms, n1 is an integer of 5 or more, q1 is an integer of 2 or more, and q2 is an integer of 2 or more.

[0144]

[0145] The repeating unit represented by the above chemical formula 5 may be a repeating unit in which the repeating unit represented by the above chemical formula 1, the repeating unit represented by the above chemical formula 2, and the repeating unit represented by the above chemical formula 3 are directly connected by bonds.

[0146] As described below, the copolymer of the above embodiment is prepared by reacting a prepolymer prepared by ring-opening polymerization of a monomer represented by the above chemical formula 7 in the presence of a compound represented by the above chemical formula 6 with a monomer represented by the above chemical formula 8, and thus may include a repeating unit represented by the above chemical formula 5.

[0147] Specifically, in the above chemical formula 9, L9 may be a substituted or unsubstituted alkylene group having 5 or more carbon atoms, an arylene group having 5 or more carbon atoms, an alkylene group having 6 or more carbon atoms, or an arylene group having 6 or more carbon atoms.

[0148] Additionally, in the above chemical formula 5, n1 may be an integer greater than or equal to 5 and less than or equal to 5000.

[0149] Specifically, in the above chemical formula 5, n1 may be an integer of 5 or more, 10 or more, or 5000 or less, 4000 or less, 3000 or less, 2000 or less, 1500 or less, 1000 or less, 500 or less, 100 or less, 50 or less, or 30 or less, and may be 5 or more and 5000 or less, 5 or more and 4000 or less, 5 or more and 3000 or less, 5 or more and 2000 or less, 5 or more and 1500 or less, 5 or more and 1000 or less, 5 or more and 500 or less, 5 or more and 100 or less, 5 or more and 50 or less, 5 or more and 30 or less, 10 or more and 5000 or less, 10 or more and 4000 or less, 10 or more and 3000 or less, 10 or more and 2000 or less, 10 or more and 1500 or less, 10 or more It can be an integer less than or equal to 1000, greater than or equal to 10 and less than or equal to 500, greater than or equal to 10 and less than or equal to 100, greater than or equal to 10 and less than or equal to 50, or greater than or equal to 10 and less than or equal to 30.

[0150]

[0151] Since the copolymer of the above embodiment includes a repeating unit represented by the above chemical formula 5, it can simultaneously implement excellent mechanical properties and elongation, and can implement excellent adhesiveness at low temperatures.

[0152]

[0153] The copolymer of the above embodiment may include repeating units represented by the above chemical formula 1 in an amount of 5 wt% or more and 95 wt% or less of the total repeating units.

[0154] Specifically, the copolymer of the above embodiment contains the repeating unit represented by the above chemical formula 1 in an amount of 5 wt% or more, 10 wt% or more, 15 wt% or more, 18 wt% or more, 95 wt% or less, 90 wt% or less, 80 wt% or less, 70 wt% or less, 65 wt% or less, 5 wt% or more and 95 wt% or less, 5 wt% or more and 90 wt% or less, 5 wt% or more and 80 wt% or less, 5 wt% or more and 70 wt% or less, 5 wt% or more and 65 wt% or less, 10 wt% or more and 95 wt% or less, 10 wt% or more and 90 wt% or less, 10 wt% or more and 80 wt% or less, 10 wt% or more and 70 wt% or less, 10 wt% or more and 65 wt% or less, 15 wt% or more and 95 wt% or less, 15 wt% or more and 90 wt% or less, 15 It may contain from 80 wt% to 80 wt%, from 15 wt% to 70 wt%, from 15 wt% to 65 wt%, from 18 wt% to 95 wt%, from 18 wt% to 90 wt%, from 18 wt% to 80 wt%, from 18 wt% to 70 wt%, from 18 wt% to 65 wt%.

[0155] Since the copolymer of the above embodiment includes the repeating unit represented by the above chemical formula 1 in an amount of 5 wt% or more and 95 wt% or less based on the total repeating unit, excellent mechanical properties are maintained while elongation is improved, so that excellent mechanical properties and elongation can be implemented simultaneously.

[0156]

[0157] If the copolymer contains less than 5 wt% of the repeating unit represented by the above chemical formula 1 based on the total repeating units, the elongation may be poor and the processability may be limited, and if the copolymer contains more than 95 wt% of the repeating unit represented by the above chemical formula 1 based on the total repeating units, the mechanical properties may be deteriorated.

[0158]

[0159] Meanwhile, the copolymer may contain 20 mol or more and 200 mol or less of the repeating unit represented by the chemical formula 2 per 1 mol of the repeating unit represented by the chemical formula 1.

[0160] More specifically, the copolymer may contain 20 mol or more, 25 mol or more, 200 mol or less, 160 mol or less, 20 mol or more and 200 mol or less, 20 mol or more and 160 mol or less, 25 mol or more and 200 mol or less, 25 mol or more and 160 mol or less of the repeating unit represented by the above chemical formula 2, per 1 mol of the repeating unit represented by the above chemical formula 1.

[0161] Since the above copolymer contains 20 moles or more of the repeating unit represented by the above chemical formula 2 per mole of the repeating unit represented by the above chemical formula 1, excellent mechanical properties can be realized.

[0162] When the copolymer contains less than 20 moles of the repeating unit represented by the chemical formula 2 per mole of the repeating unit represented by the chemical formula 1, the mechanical properties of the copolymer produced may be deteriorated.

[0163]

[0164] In addition, the copolymer may contain 1.0 mol or less of the repeating unit represented by the chemical formula 3 per 1 mol of the repeating unit represented by the chemical formula 2.

[0165] More specifically, the copolymer may contain 0.1 mol or more, 0.5 mol or more, and 1.0 mol or less, 0.1 mol or more and 1.0 mol or less, or 0.5 mol or more and 1.0 mol or less of the repeating unit represented by the chemical formula 3, per 1 mol of the repeating unit represented by the chemical formula 1.

[0166] Since the above copolymer contains 1.0 mol or less of the repeating unit represented by the above chemical formula 3 per 1 mol of the repeating unit represented by the above chemical formula 1, excellent mechanical properties can be realized.

[0167] When the copolymer contains more than 1.0 mol of the repeating unit represented by the chemical formula 3 per 1 mol of the repeating unit represented by the chemical formula 1, the mechanical properties of the copolymer produced may be deteriorated.

[0168]

[0169] The above copolymer may have a weight average molecular weight (Mw) of 10,000 g / mol or more and 500,000 g / mol or less as measured using gel permeation chromatography (GPC).

[0170] Specifically, the copolymer may have a weight average molecular weight (Mw) measured using gel permeation chromatography (GPC) of 10,000 g / mol or more, 15,000 g / mol or more, 20,000 g / mol or more, 30,000 g / mol or more, 50,000 g / mol or more, 70,000 g / mol or more, 100,000 g / mol or more, 500,000 g / mol or less, 400,000 g / mol or less, 300,000 g / mol or less, 200,000 g / mol or less, and 10,000 g / mol or more and 500,000 g / mol or less, 15,000 g / mol or more and 500,000 g / mol or less, 20,000 g / mol or more. 500,000 g / mol or less, 30,000 g / mol or more but 500,000 g / mol or less, 50,000 g / mol or more but 500,000 g / mol or less, 70,000 g / mol or more but 500,000 g / mol or less, 100,000 g / mol or more but 500,000 g / mol or less, 10,000 g / mol or more but 400,000 g / mol or less, 15,000 g / mol or more but 400,000 g / mol or less, 20,000 g / mol or more but 400,000 g / mol or less, 30,000 g / mol or more but 400,000 g / mol or less, 50,000 g / mol or more but 400,000 g / mol or less, 70,000 g / mol or more 400,000 g / mol or less, 100,000 g / mol or more but 400,000 g / mol or less, 10,000 g / mol or more but 300,000 g / mol or less, 15,000 g / mol or more but 300,000 g / mol or less, 20,000 g / mol or more but 300,000 g / mol or less, 30,000 g / mol or more but 300,000 g / mol or less, 50,000 g / mol or more but 300,000 g / mol or less, 70,000 g / mol or more but 300,000 g / mol or less, 100,000 g / mol or more but 300,000 g / mol or less, 10,000 g / mol or more but 200,000 g / mol or less, 15,000 g / mol or more but 200,000 g / mol or less, 20,000 g / mol or more but 200,000 g / mol or less, 30,000 g / mol or more but 200,000 g / mol or less, 50,000 g / mol or more but 200,000 g / mol or less, 70,000 g / mol or more but 200,000 g / mol or less, 100,000 g / mol or more but 200,000 g / mol or less.

[0171] Meanwhile, the copolymer of the above embodiment may have a tensile elongation of 400% or more.

[0172] Specifically, the copolymer of the above embodiment may have a tensile elongation of 400% or more, 450% or more, 500% or more, 10000% or less, 5000% or less, 1500% or less, 1200% or less, 400% or more but 10000% or less, 400% or more but 5000% or less, 400% or more but 1500% or less, 400% or more but 1200% or less, 450% or more but 10000% or less, 450% or more but 5000% or less, 450% or more but 1500% or less, 450% or more but 1200% or less, 500% or more but 10000% or less, 500% or more but 5000% or less, 500% or more but 1500% or less, 500% or more but 1200% or less.

[0173] The method for measuring the above tensile elongation is not particularly limited, but can be measured according to ASTM D638, for example, and more specifically, after manufacturing an ASTM D536 V Type specimen at 190 ℃ to 200 ℃ using a hot-press device, it can be measured using a UTM device at 10 mm / s and 60 kg / f load.

[0174]

[0175] Additionally, the copolymer of the above embodiment may have a tensile strength of 10 Mpa or more and 50 Mpa or less.

[0176] Specifically, the copolymer of the above embodiment may have a tensile strength of 10 Mpa or more, 15 Mpa or more, 50 Mpa or less, 40 Mpa or less, 10 Mpa or more and 50 Mpa or less, 10 Mpa or more and 40 Mpa or less, 15 Mpa or more and 50 Mpa or less, 15 Mpa or more and 40 Mpa or less.

[0177] The method for measuring the above tensile strength is not particularly limited, but for example, it can be measured according to ASTM D638, and more specifically, after manufacturing an ASTM D536 V Type specimen at 190 ℃ to 200 ℃ using a hot-press device, it can be measured using a UTM device at 10 mm / s and 60 kg / f load.

[0178]

[0179] The copolymer of the above embodiment may be a biodegradable copolymer exhibiting biodegradability.

[0180] In this specification, a biodegradable resin or biodegradable (co)polymer means a resin or (co)polymer that undergoes natural decomposition when exposed to the outside, and specifically, may mean a resin or (co)polymer that undergoes decomposition by 20% or more by weight relative to the weight of the initial resin or (co)polymer when exposed to the outside environment at room temperature (10°C to 30°C) for 30 days or more.

[0181] That is, the copolymer of the above embodiment can undergo natural decomposition upon external exposure, and specifically, can undergo decomposition of 20 wt% or more upon exposure to an external environment at room temperature (10°C to 30°C) for 30 days or more.

[0182] The method for measuring the biodegradability is not particularly limited, but for example, after setting the moisture content in aerobic compost to a level of 40% or more and 70% or less at room temperature (10°C to 30°C), mixing the compost and resin or (co)polymer in a weight ratio of 10:1, and calculating the ratio of the mass decomposed into water and CO2 based on the initial mass of the sample over time can be measured.

[0183]

[0184] According to another embodiment of the invention, a method for producing a copolymer may be provided, comprising the steps of: preparing a prepolymer by ring-opening polymerizing a monomer represented by the following chemical formula 7 in the presence of a compound represented by the following chemical formula 6; and preparing a copolymer by reacting the prepolymer with a monomer represented by the following chemical formula 8; wherein 20 mol or more and 200 mol or less of the compound represented by the above chemical formula 7 are added per 1 mol of the compound represented by the above chemical formula 6.

[0185] [Chemical Formula 6]

[0186]

[0187] In the above chemical formula 6, L1 is a substituted or unsubstituted alkylene group having 3 or fewer carbon atoms, n is an integer of 5 or more,

[0188] [Chemical Formula 7]

[0189]

[0190] In the above chemical formula 7, L2 is a substituted or unsubstituted alkylene group having 2 or more carbon atoms,

[0191] [Chemical Formula 8]

[0192]

[0193] In the above chemical formula 8, L3 is a substituted or unsubstituted alkylene group having 1 or more carbon atoms or an arylene group having 1 or more carbon atoms.

[0194]

[0195] Specifically, in the above chemical formula 6, L1 may be an alkylene group having 3 or fewer carbon atoms, and the alkylene group may be substituted or unsubstituted.

[0196] Additionally, in the above chemical formula 6, n may be an integer greater than or equal to 5 and less than or equal to 5000.

[0197] Specifically, in the above chemical formula 6, n may be an integer of 5 or more, 10 or more, or 5000 or less, 4000 or less, 3000 or less, 2000 or less, 1500 or less, 1000 or less, 500 or less, 100 or less, 50 or less, or 30 or less, and may be 5 or more and 5000 or less, 5 or more and 4000 or less, 5 or more and 3000 or less, 5 or more and 2000 or less, 5 or more and 1500 or less, 5 or more and 1000 or less, 5 or more and 500 or less, 5 or more and 100 or less, 5 or more and 50 or less, 5 or more and 30 or less, 10 or more and 5000 or less, 10 or more and 4000 or less, 10 or more and 3000 or less, 10 or more and 2000 or less, 10 or more and 1500 or less, 10 or more It can be an integer less than or equal to 1000, greater than or equal to 10 and less than or equal to 500, greater than or equal to 10 and less than or equal to 100, greater than or equal to 10 and less than or equal to 50, or greater than or equal to 10 and less than or equal to 30.

[0198]

[0199] Specifically, the compound represented by the above chemical formula 6 may include a compound represented by the following chemical formula 6-1.

[0200] [Chemical Formula 6-1]

[0201]

[0202] In the above chemical formula 6-1, R1 to R6 are each independently hydrogen or an alkyl group, and n is an integer of 5 or more.

[0203]

[0204] The repeating unit derived from the compound represented by the above chemical formula 6 may be a repeating unit represented by the above chemical formula 1.

[0205] Specifically, the copolymer of the above embodiment may include repeating units derived from the compound represented by the above chemical formula 6 in an amount of 5 wt% or more and 95 wt% or less based on the total repeating units.

[0206] Specifically, the copolymer of the above embodiment contains the repeating unit represented by the above chemical formula 1 in an amount of 5 wt% or more, 10 wt% or more, 15 wt% or more, 18 wt% or more, 95 wt% or less, 90 wt% or less, 80 wt% or less, 70 wt% or less, 65 wt% or less, 5 wt% or more and 95 wt% or less, 5 wt% or more and 90 wt% or less, 5 wt% or more and 80 wt% or less, 5 wt% or more and 70 wt% or less, 5 wt% or more and 65 wt% or less, 10 wt% or more and 95 wt% or less, 10 wt% or more and 90 wt% or less, 10 wt% or more and 80 wt% or less, 10 wt% or more and 70 wt% or less, 10 wt% or more and 65 wt% or less, 15 wt% or more and 95 wt% or less, 15 wt% or more and 90 wt% or less, 15 It may contain from 80 wt% to 80 wt%, from 15 wt% to 70 wt%, from 15 wt% to 65 wt%, from 18 wt% to 95 wt%, from 18 wt% to 90 wt%, from 18 wt% to 80 wt%, from 18 wt% to 70 wt%, from 18 wt% to 65 wt%.

[0207]

[0208] Since the copolymer manufactured according to the method for manufacturing the copolymer of the above embodiment contains repeating units derived from the compound represented by the above chemical formula 6 in an amount of 5 wt% or more and 95 wt% or less based on the total repeating units, excellent mechanical properties and elongation can be simultaneously implemented.

[0209]

[0210] If the copolymer contains less than 5 wt% of the repeating unit represented by the above chemical formula 1 based on the total repeating units, the elongation may be poor and the processability may be limited, and if the copolymer contains more than 95 wt% of the repeating unit represented by the above chemical formula 1 based on the total repeating units, the mechanical properties may be deteriorated.

[0211] The molar content of the repeating unit derived from the compound represented by the above chemical formula 6 can be implemented by controlling the ratio of each monomer used in the copolymer of the above embodiment.

[0212]

[0213] The compound represented by the above chemical formula 6 may have a weight average molecular weight (Mw) of 500 g / mol to 10,000 g / mol as measured using gel permeation chromatography (GPC).

[0214] Specifically, the compound represented by the above chemical formula 6 may have a weight average molecular weight (Mw) measured using gel permeation chromatography (GPC) of 500 g / mol or more, 700 g / mol or more, 800 g / mol or more, 1000 g / mol or more, 10,000 g / mol or less, 5000 g / mol or less, 2000 g / mol or less, or 1500 g / mol or less, and may be 500 g / mol or more and 10,000 g / mol or less, 700 g / mol or more and 10,000 g / mol or less, 800 g / mol or more and 10,000 g / mol or less, 1000 g / mol or more and 10,000 g / mol or less, 500 g / mol or more and 5,000 g / mol or less, 700 g / mol or more and 5,000 g / mol or less, It may be 800 g / mol or more but less than 5,000 g / mol, 1000 g / mol or more but less than 5,000 g / mol, 500 g / mol or more but less than 2,000 g / mol, 700 g / mol or more but less than 2,000 g / mol, 800 g / mol or more but less than 2,000 g / mol, 1000 g / mol or more but less than 2,000 g / mol, 500 g / mol or more but less than 1500 g / mol, 700 g / mol or more but less than 1500 g / mol, 800 g / mol or more but less than 1500 g / mol, 1000 g / mol or more but less than 1500 g / mol.

[0215] In the presence of the compound represented by the above chemical formula 6, the step of producing a prepolymer by ring-opening polymerization of the monomer represented by the above chemical formula 7 can be carried out as bulk polymerization that substantially does not use a solvent. In this case, substantially not using a solvent can include a case where a small amount of solvent is used to dissolve the catalyst, for example, a solvent of less than 1 ml at most per 1 kg of the monomer used. Since the step of producing a copolymer by ring-opening polymerization of the monomer represented by the above chemical formula 7 in the presence of the compound represented by the above chemical formula 6 is carried out as bulk polymerization, it becomes possible to omit a process for removing the solvent after polymerization, and decomposition or loss of the resin in the solvent removal process can also be suppressed.

[0216]

[0217] Meanwhile, in the method for producing the copolymer, the compound represented by the chemical formula 7 may be added in an amount of 20 mol or more and 200 mol or less per 1 mol of the compound represented by the chemical formula 6.

[0218] More specifically, in the method for producing the copolymer, the compound represented by the chemical formula 7 may be included in an amount of 20 mol or more, 25 mol or more, 200 mol or less, 160 mol or less, 20 mol or more and 200 mol or less, 20 mol or more and 160 mol or less, 25 mol or more and 200 mol or less, or 25 mol or more and 160 mol or less, per 1 mol of the compound represented by the chemical formula 6.

[0219] By including 20 mol or more and 200 mol or less of the compound represented by the chemical formula 7 for 1 mol of the compound represented by the chemical formula 6, excellent mechanical properties can be realized.

[0220] In the method for producing the above copolymer, if the compound represented by the above chemical formula 7 is included in an amount of less than 20 moles per mole of the compound represented by the above chemical formula 6, the mechanical properties such as tensile strength of the produced copolymer may be reduced, or the melting point may be lowered, making it unsuitable for thermoforming and processing.

[0221]

[0222] Meanwhile, since the method for producing the copolymer involves a ring-opening polymerization reaction, it is carried out in the presence of a ring-opening catalyst. Preferably, the step of producing a prepolymer by ring-opening polymerizing the monomer represented by the above chemical formula 7 in the presence of the compound represented by the above chemical formula 6 may be carried out in the presence of a catalyst represented by the following chemical formula 9.

[0223] [Chemical Formula 6]

[0224] MA 1 q A 2 2-q

[0225] In the above chemical formula 6, M is Al, Mg, Zn, Ca, Sn, Fe, Y, Sm, Lu, Ti or Zr,

[0226] q is an integer from 0 to 2, and A 1 and A 2 are each independently an alkoxy or carboxyl group. For example, the catalyst represented by the above chemical formula 4 may be tin(II) 2-ethylhexanoate (Sn(Oct)2).

[0227]

[0228] In the step of producing a prepolymer by ring-opening polymerizing a monomer represented by the above chemical formula 7 in the presence of a compound represented by the above chemical formula 6, the catalyst represented by the above chemical formula 9 may be included in an amount of 0.001 part by weight or less based on 100 parts by weight of the total of the compound represented by the above chemical formula 6 and the monomer represented by the above chemical formula 7.

[0229] Specifically, in the step of producing a prepolymer by ring-opening polymerization of a monomer represented by the chemical formula 7 in the presence of a compound represented by the chemical formula 6, the catalyst represented by the chemical formula 9 is present in an amount of 0.0001 part by weight or more, 0.0002 part by weight or more, 0.0003 part by weight or more, 0.0004 part by weight or more, 0.001 part by weight or less, 0.0008 part by weight or less, 0.0005 part by weight or less, 0.0001 part by weight or more and 0.001 part by weight or less, 0.0002 part by weight or more and 0.001 part by weight or less, 0.0003 part by weight or more and 0.001 part by weight or less, 0.0004 part by weight or more and 0.001 part by weight or less, 0.0001 part by weight or more and 0.0008 part by weight or less, based on 100 parts by weight of the total of the compound represented by the chemical formula 6 and the monomer represented by the chemical formula 7. It may be included in the following amounts: 0.0002 parts by weight or more and 0.0008 parts by weight or less, 0.0003 parts by weight or more and 0.0008 parts by weight or less, 0.0004 parts by weight or more and 0.0008 parts by weight or less, 0.0001 parts by weight or more and 0.0005 parts by weight or less, 0.0002 parts by weight or more and 0.0005 parts by weight or less, 0.0003 parts by weight or more and 0.0005 parts by weight or less, 0.0004 parts by weight or more and 0.0005 parts by weight or less.

[0230] In the step of producing a prepolymer by ring-opening polymerizing a monomer represented by the above chemical formula 7 in the presence of a compound represented by the above chemical formula 6, the catalyst represented by the above chemical formula 9 is included in an amount of 0.001 parts by weight or less based on 100 parts by weight of the total of the compound represented by the above chemical formula 6 and the monomer represented by the above chemical formula 7, so that the impurity content in the produced copolymer is minimized, and an excellent tensile elongation of 400% or more can be realized.

[0231]

[0232] Preferably, the step of preparing a prepolymer by ring-opening polymerization of a monomer represented by the above formula 7 in the presence of a compound represented by the above formula 6 is performed at 150°C to 200°C. Preferably, the step of preparing a prepolymer by ring-opening polymerization of a monomer represented by the above formula 7 in the presence of a compound represented by the above formula 6 is performed for 5 minutes to 10 hours, more preferably for 10 minutes to 1 hour.

[0233]

[0234] According to one embodiment of the invention, a molded article molded from a resin composition comprising the copolymer may be provided. The resin composition comprising the copolymer may further include other additives that improve physical properties in addition to the copolymer.

[0235] The above molded article may include at least one molded article selected from the group consisting of injection molded articles, extrusion molded articles, inflation molded articles, fibers, nonwovens, foams, films, and sheets.

[0236] The use of the above molded product is not particularly limited, but for example, the above molded product may be an electronic material, a building material, a food packaging, a food container (such as a disposable cup or tray), an industrial product, an agricultural product (such as a mulching film), etc.

[0237]

[0238] According to the present invention, a copolymer and a method for producing the copolymer having excellent mechanical properties, excellent adhesiveness at low temperatures, and environmental friendliness and biodegradability can be provided.

[0239]

[0240] 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.

[0241]

[0242] <Examples and Comparative Examples>

[0243] Example 1

[0244] Poly(trimethylene ether) glycol (n= 46, number average molecular weight: 2700 g / mol) 20 g (0.007 mol) and lactide 80 g (0.56 mol) were added to a 500 mL Teflon-coated round flask, and the temperature was adjusted to room temperature.

[0245] After 80 mg of tin(II) 2-ethylhexanoate was added to the flask, the flask was placed in an oil bath, and the temperature was raised to 160°C under a nitrogen atmosphere, followed by ring-opening polymerization for 2 hours while stirring at 200 rpm. Afterwards, 1.24 g (0.007 mol) of hexamethylene diisocyanate was added to the flask, and the reaction was performed at 160°C for 1 hour to produce a copolymer. After the reaction was completed, the residual monomer was removed through a devolatilization step of the product to obtain a copolymer.

[0246]

[0247] The copolymer thus manufactured was dried under reduced pressure at 80°C for 6 hours under a vacuum of 1 torr, and then extruded into a sheet form at an extrusion temperature of 165°C using a single screw extruder with a diameter of 30 mm and a T die. This was electrostatically cast onto a drum cooled to 25°C to produce a polymer film.

[0248]

[0249] Example 2

[0250] A copolymer and a polymer film were prepared in the same manner as in Example 1, except that 40 g (0.015 mol) of poly(trimethylene ether) glycol (n= 46, number average molecular weight: 2700 g / mol) and 60 g (0.42 mol) of lactide were added.

[0251]

[0252] Comparative Example 1

[0253] In Example 1, a copolymer and a polymer film were prepared in the same manner as in Example 1, except that 0.67 g (0.007 mol) of 1,4-butanediol and 80 g (0.56 mol) of lactide were added without adding poly(trimethylene ether) glycol.

[0254]

[0255] Comparative Example 2

[0256] 100 g (0.037 mol) of poly(trimethylene ether) glycol (n=46, number average molecular weight: 2700 g / mol) was added to a 500 mL Teflon-coated round flask, and the temperature was adjusted to room temperature. 3.10 g (0.018 mol) of hexamethylene diisocyanate was added to the flask, and the flask was placed in an oil bath, heated to 120°C under a nitrogen atmosphere, and stirred at 200 rpm for 2 hours to produce a prepolymer.

[0257] 20.6 g of the above prepolymer and 80 g (0.56 mol) of lactide were added to a 500 mL Teflon-coated round flask and reacted at 160°C for 2 hours to produce a copolymer. After the reaction was completed, the residual monomer was removed through a devolatilization step of the product to obtain a copolymer.

[0258]

[0259] A polymer film was manufactured using the manufactured copolymer in the same manner as in Example 1.

[0260]

[0261] Comparative Example 3

[0262] A copolymer and a polymer film were prepared in the same manner as in Example 1, except that 52 g (0.0193 mol) of poly(trimethylene ether) glycol (n= 46, number average molecular weight: 2700 g / mol) and 48 g (0.33 mol) of lactide were added.

[0263]

[0264] evaluation

[0265] (1) GPC (Gel Permeation Chromatography) analysis

[0266] The number average molecular weight (Mn) of the copolymers of the above examples and comparative examples was measured using gel permeation chromatography (GPC, Waters E2640).

[0267]

[0268] Specifically, the copolymers of the above examples and comparative examples were each dissolved in chloroform to a concentration of 2 mg / ml, and 20 μl was injected into GPC. Chloroform was used as the mobile phase of GPC, and the flow rate was 1.0 mL / min, and the analysis was performed at 40°C. Two Agilent Mixed-B columns were connected in series. An RI Detector was used as the detector. The Mw value was derived using a calibration curve formed using polystyrene (PS) standard samples. 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.

[0269]

[0270] (3) Property evaluation

[0271] The tensile strength, Young's modulus, and tensile elongation of the copolymers of the examples and comparative examples were measured.

[0272]

[0273] Specifically, the test was conducted according to ASTM D638, and after manufacturing ASTM D536 V Type specimens at 140 ℃ to 200 ℃ using a hot-press machine (Limotem QM900S), measurements were made using a UTM machine (Universal Testing Machine) at 10 mm / s and 60 kg / f load.

[0274]

[0275] (4) Glass transition temperature (Tg, ℃) and melting point (Tm, ℃)

[0276] Using a differential scanning calorimeter (TA Instruments), the copolymers of the examples and comparative examples were melted and rapidly cooled, and then heated at 10°C / min to measure the temperature. The mid value of the baseline and each tangent near the endothermic curve was set as Tg, and the maximum temperature of the melting endothermic peak of the crystal was set as Tm.

[0277]

[0278] Number average molecular weight (g / mol) Tensile strength (MPa) Young's modulus (GPa) Tensile elongation (%) Glass transition temperature (Tg, ℃) Melting point (Tm, ℃) Example 1 118,000 36.6 0.7 25 10 24 147 Example 2 109,000 16.8 0.03 1200-21 124 Comparative example 191,400 57.21 90 450 158 Comparative example 273,300 42.7 0.7 1360 30 154 Comparative example 373,600 7.9 0.00 9 14 40-4067

[0279] According to Table 1 above, the copolymer of the example exhibited a tensile elongation of 510% or more, confirming that the elongation was secured and that physical properties could be measured through thermoforming and processing. On the other hand, the copolymer of Comparative Examples 1 and 2 exhibited a tensile elongation of 360% or less, confirming that it exhibited a poor tensile elongation compared to the example.

[0280] In addition, the copolymer of Comparative Example 3 showed poor tensile strength with a tensile strength of 7.9 MPa, and it was confirmed that the melting point was low at 67 ℃, making it unsuitable for thermoforming and processing.

[0281]

[0282]

[0283] (5) Adhesion

[0284] The polymer films manufactured in the above examples and comparative examples were cut into pieces of 20 mm in length and 15 mm in width, and then the middle portions were bonded using a sealer at a temperature of 80 to 130 °C with a sealing time of 0.3 to 1 second to create specimens. The specimens were evaluated for adhesive strength (gf / 15 mm) using a UTM according to the ASTM D1876-01 standard. In addition, the phenomenon observed during peeling was evaluated according to the following criteria.

[0285] The comparison group corresponds to the adhesive strength measured under the same conditions for linear low density polyethylene (LLDPE) film, which is conventionally used for low-temperature bonding.

[0286] ◎: Adhesive, and delamination does not occur at the adhesive area when peeled off.

[0287] Δ: Bonded, but delamination occurred at the bonded area.

[0288] ×: Not bonded.

[0289]

[0290] Bonding temperature (℃) Bonding time (s) Bonding strength Bonding strength (gf / 15mm) Example 1600.3Δ2800.3◎191800.5◎527801◎7611001◎7771301◎881 Example 2801◎7031001◎7171301◎820 Comparative example 1801X-1001X-1301X-Comparative example 2801X-1001X-1301X-Comparative example 3 Low melting point, so evaluation is not possible Comparative group 800.3X-801Δ68

[0291] According to Table 2 above, it was confirmed that the polymer film of the example exhibited excellent adhesive strength even when sealed for less than 1 second at a low temperature of 80°C, thereby realizing excellent low-temperature adhesive strength. On the other hand, it was confirmed that the polymer films of the comparative example and the comparative group exhibited poor adhesive strength and adhesive strength compared to the example at low to high temperatures.

[0292] In particular, it was confirmed that the polymer film of Comparative Example 3 had a low melting point and was therefore unsuitable for thermoforming and processing.

[0293]

[0294] (6) Biodegradability measurement

[0295] The biodegradability of the copolymer of cellulose, a standard material, and the example was measured under the industrial composting conditions of ISO14855-1.

[0296]

[0297] Specifically, it was conducted under industrial composting conditions (58℃, aerobic compost conditions, setting the moisture content in the compost to 50%, mixing the compost and the measured polymer at a weight ratio of 10:1 and measuring the CO2 generated), and degradation (%) means the value calculated by decomposing the mass into water and CO2 based on the initial mass of the sample. In addition, for comparison, it was compared with the results of measuring the biodegradability of cellulose (Sigma aldrich, Cellulose, Cat. No. 310697), a standard material.

[0298]

[0299] The biodegradability of cellulose, which was previously known to have excellent biodegradability, was found to be 100%.

[0300]

[0301] Compared to the biodegradability of cellulose, the copolymers of Examples 1 and 2 were measured for decomposition, and it was confirmed that they were decomposed by more than 68% and 46%, respectively, based on the initial mass of the sample after 180 days. Through this, it was confirmed that the copolymers of Examples 1 and 2 have biodegradable properties under industrial composting conditions.

Claims

1. Contains a repeating unit represented by the following chemical formula 1, a repeating unit represented by the following chemical formula 2, and a repeating unit represented by the following chemical formula 3, A copolymer comprising 20 mol or more and 200 mol or less of repeating units represented by the above chemical formula 2 per 1 mol of repeating units represented by the above chemical formula 1: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In the above chemical formula 1, L1 is a substituted or unsubstituted alkylene group having 3 or fewer carbon atoms, n is an integer greater than or equal to 5, In the above chemical formula 2, L2 is a substituted or unsubstituted alkylene group having 2 or more carbon atoms, In the above chemical formula 3 L3 is a substituted or unsubstituted alkylene group having 1 or more carbon atoms or an arylene group having 1 or more carbon atoms.

2. In paragraph 1, A copolymer comprising a repeating unit represented by the above chemical formula 1, wherein the repeating unit is represented by the following chemical formula 1-1: [Chemical Formula 1-1] In the above chemical formula 1-1, R1 to R6 are each independently hydrogen or an alkyl group, n is an integer greater than or equal to 5.

3. In paragraph 1, The above copolymer is a copolymer comprising a repeating unit represented by the following chemical formula 10: [Chemical Formula 10] In the above chemical formula 10, p is an integer greater than or equal to 2.

4. In paragraph 1, The copolymer is a copolymer having a structure in which repeating units represented by the following chemical formula 10 are bonded to both terminals of the functional group of the following chemical formula 11: [Chemical Formula 10] In the above chemical formula 10, p is an integer greater than or equal to 2, [Chemical Formula 11] In the above chemical formula 11 n is an integer greater than or equal to 5.

5. In paragraph 1, The above copolymer is a copolymer comprising a repeating unit represented by the following chemical formula 4: [Chemical Formula 4] In the above chemical formula 4, q is an integer greater than or equal to 2, L4 is a substituted or unsubstituted alkylene group having 2 or more carbon atoms, L5 is a substituted or unsubstituted alkylene group having 1 or more carbon atoms or an arylene group having 1 or more carbon atoms.

6. In paragraph 1, The above copolymer is a copolymer comprising a repeating unit represented by the following chemical formula 5: [Chemical Formula 5] In the above chemical formula 5, L6 and L8 are each independently a substituted or unsubstituted alkylene group having 2 or more carbon atoms, L7 is a substituted or unsubstituted alkylene group having 3 or fewer carbon atoms, L9 is a substituted or unsubstituted alkylene group having 1 or more carbon atoms or an arylene group having 1 or more carbon atoms, n1 is an integer greater than or equal to 5, q1 is an integer greater than or equal to 2, q2 is an integer greater than or equal to 2.

7. In paragraph 1, A copolymer in which n in the above chemical formula 1 is an integer of 5 or more and 5000 or less.

8. In paragraph 1, A copolymer comprising 1.0 mol or less of a repeating unit represented by the chemical formula 3 per 1 mol of a repeating unit represented by the chemical formula 2.

9. In paragraph 1, The above copolymer is a copolymer having a tensile elongation of 400% or more.

10. In paragraph 1, The above copolymer is a copolymer having a tensile strength of 10 Mpa or more and 50 Mpa or less.

11. A step of preparing a prepolymer by ring-opening polymerizing a monomer represented by the following chemical formula 7 in the presence of a compound represented by the following chemical formula 6; and A step of preparing a copolymer by reacting the above prepolymer with a monomer represented by the following chemical formula 8; A method for producing a copolymer, wherein 20 mol or more and 200 mol or less of a compound represented by the chemical formula 7 is added to 1 mol of a compound represented by the chemical formula 6: [Chemical Formula 6] In the above chemical formula 6, L1 is a substituted or unsubstituted alkylene group having 3 or fewer carbon atoms, n is an integer greater than or equal to 5, [Chemical Formula 7] In the above chemical formula 7, L2 is a substituted or unsubstituted alkylene group having 2 or more carbon atoms, [Chemical Formula 8] In the above chemical formula 8, L3 is a substituted or unsubstituted alkylene group having 1 or more carbon atoms or an arylene group having 1 or more carbon atoms.

12. In paragraph 11, A method for producing a copolymer, wherein the step of producing a prepolymer by ring-opening polymerizing a monomer represented by the above chemical formula 7 in the presence of a compound represented by the above chemical formula 6 is performed in the presence of a catalyst represented by the following chemical formula 9: [Chemical Formula 9] MA 1 q A 2 2-q In the above chemical formula 9, M is Al, Mg, Zn, Ca, Sn, Fe, Y, Sm, Lu, Ti or Zr, q is an integer from 0 to 2, A 1 and A 2 are each independently an alkoxy or carboxyl group.

13. In paragraph 12, In the step of producing a prepolymer by ring-opening polymerizing a monomer represented by the above chemical formula 7 in the presence of a compound represented by the above chemical formula 6; A method for producing a copolymer, wherein the catalyst represented by the above chemical formula 9 is included in an amount of 0.001 parts by weight or less based on 100 parts by weight of the total of the compound represented by the above chemical formula 6 and the monomer represented by the above chemical formula 7.

14. A molded product molded from a resin composition containing the copolymer of paragraph 1.

15. In paragraph 14, A molded product comprising at least one molded product selected from the group consisting of injection molded products, extrusion molded products, inflation molded products, fibers, nonwovens, foams, films, and sheets.

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