Biodegradable polycarbonate copolymer containing units derived from anhydrosugar alcohol, anhydrosugar alcohol-alkylene glycol and aromatic diol, its production method and molded article containing same

Abstract

The present invention relates to a polycarbonate copolymer and a production method thereof, and a molded article containing the same. More specifically, the present invention relates to a polycarbonate copolymer which exhibits improved tensile strength and elongation compared to conventional polycarbonate copolymers and is biodegradable due to the inclusion of repeating units derived from a diol component containing an anhydrosugar alcohol, an anhydrosugar alcohol-alkylene glycol, and an aromatic diol in a specific content ratio, and a carbonate diester component, and which also exhibits improved tensile strength and elongation compared to conventional polycarbonate copolymers and is biodegradable, and a production method thereof, and a molded article containing the same.

Description

[Technical field]

[0001] The present invention relates to a polycarbonate copolymer, a method for producing the same, and a molded article containing the same. More specifically, the present invention relates to a polycarbonate copolymer that exhibits improved elongation and elongation compared to conventional polycarbonate copolymers and is biodegradable by containing repeating units derived from a diol component containing an anhydrosugar alcohol, an anhydrosugar alcohol-alkylene glycol, and an aromatic diol in a specific content ratio, and a carbonate diester component, and a method for producing the same, and a molded article containing the same. [Background technology]

[0002] Polycarbonate resin is a general-purpose thermoplastic engineering plastic with a glass transition temperature of about 150° C., and has excellent mechanical properties such as tensile strength and impact strength, as well as dimensional stability, heat resistance, and optical transparency.

[0003] Polycarbonate is usually produced by the condensation polymerization of the petroleum-based raw materials bisphenol A and phosgene. However, due to various reasons such as the accelerating depletion of petroleum resources, the demand for reducing greenhouse gas emissions due to climate change, the soaring prices of raw materials, and the increasing need for renewable raw materials, there is a demand for methods to partially or completely replace the raw materials used to produce polycarbonate with environmentally friendly components.

[0004] Anhydrosugar alcohols are environmentally friendly materials derived from natural products, and can be produced by dehydration of hydrogenated sugars (e.g., hexitols) derived from natural products such as starch. Hydrogenated sugars (also called "sugar alcohols") refer to compounds obtained by adding hydrogen to the reducing end group of sugars, and are generally represented by the formula HOCH2 (CHOH). nIt has the chemical formula CH2OH (where n is an integer between 2 and 5). Hydrogenated sugars are classified into tetritols, pentitols, hexitols and heptitols (having 4, 5, 6 and 7 carbon atoms, respectively) according to the number of carbon atoms. Of these, hexitols with 6 carbon atoms include sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are very useful substances. Thus, anhydrosugar alcohols have attracted great interest due to their wide range of applications, and their level of industrial practical application is gradually increasing.

[0005] A technique for producing polycarbonate using anhydrosugar alcohol has been proposed. For example, Patent Document 1 describes a technique for producing a polycarbonate copolymer using anhydrosugar alcohol isosorbide and a cyclic diol compound as diol components. In addition, Patent Document 2 describes a technique for producing a polycarbonate copolymer using isosorbide and a linear diol compound as diol components.

[0006] However, although the polycarbonate copolymers produced by the above-mentioned conventional techniques have improved environmental compatibility, they have poor mechanical properties (especially tensile strength and / or elongation), making them difficult to actually use as engineering plastics.

[0007] Therefore, there is a need to develop a technology for producing polycarbonate copolymers that can be actually used as engineering plastics by using anhydrosugar alcohols as raw materials, which can improve environmental compatibility, provide biodegradability, and improve mechanical properties such as tensile strength and elongation compared to conventional technologies. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Korea Patent No. 10-2009-0018788 [Patent Document 2] Korean Patent No. 10-1080669 Summary of the Invention [Problem to be solved by the invention]

[0009] The object of the present invention is to provide a polycarbonate copolymer that contains units derived from an anhydrosugar alcohol and its derivatives and thus exhibits good environmental compatibility and biodegradability, and has improved mechanical properties such as tensile strength and elongation compared to conventional anhydrosugar alcohol-containing polycarbonate resins, a method for producing the same, and a molded article containing the same. [Means for solving the problem]

[0010] In order to achieve the above object, the present invention provides a polycarbonate copolymer comprising: a repeating unit derived from a diol component; and a repeating unit derived from a carbonate diester component; wherein the diol component contains, relative to 100 mol % in total of the diol components, (a) 0.3 to 66.9 mol % of anhydrosugar alcohol, (b) 0.3 to 56.9 mol % of anhydrosugar alcohol-alkylene glycol, and (c) 32.1 to 99.4 mol % of an aromatic diol.

[0011] According to another aspect of the present invention, there is provided a method for producing a polycarbonate copolymer, comprising a step of reacting a mixture containing a diol component and a carbonate diester component in the presence of a polymerization catalyst, wherein the diol component contains, relative to 100 mol % in total of the diol components, (a) 0.3 to 66.9 mol % of anhydrosugar alcohol, (b) 0.3 to 56.9 mol % of anhydrosugar alcohol-alkylene glycol, and (c) 32.1 to 99.4 mol % of an aromatic diol.

[0012] According to yet another aspect of the present invention, there is provided a molded article comprising the polycarbonate copolymer of the present invention. Effect of the Invention

[0013] The polycarbonate copolymer according to the present invention exhibits good environmental compatibility and biodegradability as well as significantly improved mechanical properties (particularly tensile strength and elongation) compared to conventional polycarbonate copolymers containing anhydrosugar alcohols. BEST MODE FOR CARRYING OUT THEINVENTION

[0014] The present invention will now be described in more detail. The polycarbonate copolymer of the present invention contains repeating units derived from diol components containing, relative to 100 mol % in total of the diol components, (a) 0.3 to 66.9 mol % of anhydrosugar alcohol, (b) 0.3 to 56.9 mol % of anhydrosugar alcohol-alkylene glycol, and (c) 32.1 to 99.4 mol % of aromatic diol; and repeating units derived from a carbonate diester component.

[0015] [Diol component] (a) Anhydrosugar alcohol In the present invention, the anhydrosugar alcohol may be a monoanhydrosugar alcohol, a dianhydrosugar alcohol or a mixture thereof, and can be obtained during the production of anhydrosugar alcohols by dehydration of hydrogenated sugars. Hydrogenated sugars (also called "sugar alcohols") refer to compounds obtained by adding hydrogen to the reducing end group of sugars, and are generally represented by the formula HOCH2(CHOH). n It has the chemical formula CH2OH (where n is an integer between 2 and 5). Hydrogenated sugars are classified into tetritols, pentitols, hexitols, and heptitols (having 4, 5, 6, and 7 carbon atoms, respectively) according to the number of carbon atoms. Among these, hexitols with 6 carbon atoms include sorbitol, mannitol, iditol, and galactitol.

[0016] The monoanhydrosugar alcohol is an anhydrosugar alcohol produced by removing one molecule of water from the inside of a hydrogenated sugar, and has a tetraol form having four hydroxyl groups in the molecule. The type of monoanhydrosugar alcohol that can be used in the present invention is not particularly limited, and is preferably monoanhydrohexitol, more specifically, 1,4-anhydrohexitol, 3,6-anhydrohexitol, 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more of these.

[0017] The dianhydrosugar alcohol is an anhydrosugar alcohol produced by removing two water molecules from the inside of hydrogenated sugar, and is a diol having two hydroxyl groups in the molecule, and can be produced using hexitol derived from starch. Dianhydrosugar alcohol is an environmentally friendly material obtained from renewable natural resources, so it has attracted much attention for a long time, and research on its production method has been continued. Among such dianhydrosugar alcohols, isosorbide produced from sorbitol is currently the most widely used in industrial applications. The type of dianhydrosugar alcohol that can be used in the present invention is not particularly limited, and is preferably dianhydrohexitol, and more specifically may be 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may be isosorbide (1,4:3,6-dianhydrosorbitol), isomannide (1,4:3,6-dianhydromannitol), isoidide (1,4:3,6-dianhydroiditol) or a mixture of two or more thereof, and more preferably isosorbide.

[0018] The content of the anhydrosugar alcohol in the diol component contained as a repeating unit in the polycarbonate copolymer of the present invention is 0.3 to 66.9 mol% relative to 100 mol% of the total of the diol components. If the content of the anhydrosugar alcohol in the diol component is less than 0.3 mol% relative to 100 mol% of the total of the diol components, the tensile strength of the copolymer is poor, and conversely, if it exceeds 66.9 mol%, the tensile strength and elongation of the copolymer are poor.

[0019] In one embodiment, the anhydrosugar alcohol content in the diol component may be 0.3 mol% or more, 0.4 mol% or more, or 0.5 mol% or more, relative to 100 mol% of the total of the diol components, and may be 66.9 mol% or less, 66 mol% or less, 65 mol% or less, 64 mol% or less, 63 mol% or less, 62 mol% or less, 61 mol% or less, 60 mol% or less, 59 mol% or less, 58 mol% or less, 57 mol% or less, 56 mol% or less, or 55 mol% or less.

[0020] (b) Anhydrosugar alcohol-alkylene glycol In the present invention, the anhydrosugar alcohol-alkylene glycol is obtained by an addition reaction between an anhydrosugar alcohol and an alkylene oxide. In one embodiment, the alkylene oxide may be a linear alkylene oxide having 2 to 18 carbon atoms or a branched alkylene oxide having 3 to 18 carbon atoms, and more specifically, may be ethylene oxide, propylene oxide, or a combination thereof.

[0021] In the present invention, the term "anhydrosugar alcohol-alkylene glycol" refers to an adduct obtained by reacting a hydroxy group at a terminal (e.g., one or more terminals) of a monoanhydrosugar alcohol or a dianhydrosugar alcohol with an alkylene oxide (e.g., a C2-C18 alkylene oxide, more specifically, ethylene oxide, propylene oxide, or a mixture thereof), and refers to a compound in which the hydrogen of the hydroxy group at the terminal (e.g., one or more terminals) of the monoanhydrosugar alcohol or the dianhydrosugar alcohol is replaced with a hydroxyalkyl group which is a ring-opened form of the alkylene oxide.

[0022] In one embodiment, the anhydrosugar alcohol-alkylene glycol has the following formula (A): [ka] (wherein, each R1 is independently hydrogen or an alkyl group, more specifically hydrogen or an alkyl group having 1 to 18 carbon atoms, and each m and n is independently an integer of 0 to 15, with the proviso that m+n is an integer of 1 to 25, more specifically an integer of 2 to 20, and even more specifically an integer of 3 to 15).

[0023] In another embodiment, the anhydrosugar alcohol-alkylene glycol is represented by the following formula (B): [ka] (In the formula, R 1 and R 2 each independently represents a linear alkylene group having 2 to 18 carbon atoms or a branched alkylene group having 3 to 18 carbon atoms, and m and n each independently represent an integer of 0 to 15, with the proviso that m+n represents an integer of 1 to 30 or an integer of 1 to 25.

[0024] More specifically, in the formula (B), R 1 and R 2each independently represents an ethylene group, a propylene group, or an isopropylene group, and more specifically, R 1 and R 2 are the same, and m and n each independently represent an integer of 0 to 14, with the proviso that m+n is an integer of 1 to 25, an integer of 2 to 20, or an integer of 3 to 15.

[0025] In one embodiment, the anhydrosugar alcohol-alkylene glycol may be the following isosorbide-propylene glycol, isosorbide-ethylene glycol, or a mixture thereof.

[0026] [Isosorbide-propylene glycol] [ka] In the formula, a and b each independently represent an integer of 0 to 15, provided that a+b is an integer of 1 to 30 or an integer of 1 to 25; more specifically, a and b each independently represent an integer of 0 to 14, provided that a+b is an integer of 1 to 25, an integer of 2 to 20, or an integer of 3 to 15.

[0027] [Isosorbide-Ethylene Glycol] [ka] In the formula, c and d each independently represent an integer of 0 to 15, with the proviso that c+d may be an integer of 1 to 30 or an integer of 1 to 25, and more specifically, c and d each independently represent an integer of 0 to 14, with the proviso that c+d may be an integer of 1 to 25, an integer of 2 to 20, or an integer of 3 to 15.

[0028] The content of the anhydrosugar alcohol-alkylene glycol in the diol component contained as a repeating unit in the polycarbonate copolymer of the present invention is 0.3 to 56.9 mol% relative to 100 mol% of the total diol components. If the content of the anhydrosugar alcohol-alkylene glycol in the diol component is less than 0.3 mol% relative to 100 mol% of the total diol components, the tensile strength and biodegradability of the copolymer are poor, and conversely, if it exceeds 56.9 mol%, the tensile strength and heat resistance of the copolymer are poor. In one embodiment, the anhydrosugar alcohol-alkylene glycol content in the diol component may be 0.3 mol% or more, 0.4 mol% or more, or 0.5 mol% or more, based on 100 mol% of the total diol components, and may be 56.9 mol% or less, 56 mol% or less, 55 mol% or less, 54 mol% or less, 53 mol% or less, 52 mol% or less, 51 mol% or less, 50 mol% or less, 49 mol% or less, 48 ​​mol% or less, 47 mol% or less, 46 mol% or less, 45 mol% or less, 44 mol% or less, 43 mol% or less, 42 mol% or less, 41 mol% or less, or 40 mol% or less.

[0029] (c) Aromatic diol In the present invention, the aromatic diol means an aromatic compound having two hydroxy groups.

[0030] In one embodiment, the aromatic diol may be at least one selected from the group consisting of bisphenol-based diol compounds, fluorene-based diol compounds, benzene-based diol compounds, furan-based diol compounds, pyridine-based diol compounds, or combinations thereof.

[0031] In one embodiment, the aromatic diol is 2,2-bis(4-hydroxyphenyl)propane [hereinafter referred to as bisphenol A], an alkylene oxide adduct of bisphenol A (for example, an adduct in which 1 mole to 25 moles of C2-C18 alkylene oxide are added per mole of bisphenol A), 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3,5- 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-4-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether, 9,9-bis(4-(2-hydroxyethoxy-2-methyl)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-2-methyl) The fluorene may be, but is not limited to, one or more selected from the group consisting of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 1,4-bis(2-hydroxymethyl)benzene, 1,3-bis(2-hydroxymethyl)benzene, 1,4-bis(2-hydroxyethyl)benzene, 2,5-bis(hydroxymethyl)furan, 2,5-bis(hydroxyethyl)furan, 2,6-bis(hydroxymethyl)pyridine, or combinations thereof.

[0032] More specifically, the aromatic diol may be, but is not limited to, one or more selected from the group consisting of bisphenol A, an alkylene oxide adduct of bisphenol A, 9,9-bis-(4-(2-hydroxyethoxy)phenyl)fluorene, 1,4-bis(2-hydroxymethyl)benzene, 1,3-bis(2-hydroxymethyl)benzene, 1,4-bis(2-hydroxyethyl)benzene, 2,5-bis(hydroxymethyl)furan, 2,5-bis(hydroxyethyl)furan, 2,6-bis(hydroxymethyl)pyridine, or combinations thereof.

[0033] The content of the aromatic diol in the diol component contained as a repeating unit in the polycarbonate copolymer of the present invention is 32.1 to 99.4 mol% relative to 100 mol% of the total of the diol components. If the content of the aromatic diol in the diol component is less than 32.1 mol% relative to 100 mol% of the total of the diol components, the tensile strength and elongation of the copolymer are inferior, and conversely, if it exceeds 99.4 mol%, the tensile strength and biodegradability of the copolymer are inferior.

[0034] In one embodiment, the aromatic diol content in the diol component may be 32.1 mol% or more, 32.5 mol% or more, 33 mol% or more, 33.5 mol% or more, 34 mol% or more, 34.5 mol% or more, or 35 mol% or more, relative to 100 mol% of the total of the diol components, and may be 99.4 mol% or less, 99.3 mol% or less, 99.2 mol% or less, 99.1 mol% or less, or 99 mol% or less.

[0035] (d) any additional diol component In one embodiment, the diol component can further include (d) an additional diol selected from an aliphatic diol, an alicyclic diol other than anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol, or a mixture thereof. In one embodiment, the aliphatic diol may be selected from, but is not limited to, ethylene glycol, propanediol (such as 1,2-propanediol and 1,3-propanediol), butanediol (such as 1,2-butanediol, 1,3-butanediol and 1,4-butanediol), pentanediol (such as 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol and 1,5-pentanediol), hexanediol (such as 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol and 1,5-hexanediol and 1,6-hexanediol), diethylene glycol, triethylene glycol, tetraethyl glycol, or mixtures thereof.

[0036] In one embodiment, the alicyclic diol other than the anhydrosugar alcohol and the anhydrosugar alcohol-alkylene glycol may be selected from, but is not limited to, cyclohexanedimethanol (e.g., 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, etc.), 2-methyl-1,4-cyclohexanediol, decalin dimethanol (e.g., 2,6-decalin dimethanol, 1,5-decalin dimethanol, and 2,3-decalin dimethanol, etc.), norbornane dimethanol (e.g., 2,3-norbornane dimethanol, and 2,5-norbornane dimethanol, etc.), adamantane diol (e.g., 1,2-adamantanediol, 1,3-adamantanediol, and 1,4-adamantanediol, etc.), or a mixture thereof.

[0037] The (d) additional diol compound used in the present invention is not limited to the above examples, and the additional diol compound may be used alone or in combination of two or more.

[0038] In one embodiment, the content of the (d) additional diol in the diol component may be, relative to 100 mol% in total of the diol components, 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, 5 mol% or more, 6 mol% or more, 7 mol% or more, 8 mol% or more, 9 mol% or more, or 10 mol% or more, and may be, but is not limited to, 30 mol% or less, 29 mol% or less, 28 mol% or less, 27 mol% or less, 26 mol% or less, 25 mol% or less, 24 mol% or less, 23 mol% or less, 22 mol% or less, 21 mol% or less, or 20 mol% or less.

[0039] [Carbonate diester component] In the present invention, the type of the carbonate diester component is not particularly limited as long as the effects of the present invention are not lost, and can be selected from, for example, dialkyl carbonates, diaryl carbonates, alkylene carbonates, or combinations thereof.

[0040] In one embodiment, examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl n-butyl carbonate, and ethyl isobutyl carbonate. Examples of the diaryl carbonate include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and di(m-cresyl) carbonate. Examples of the alkylene carbonate include Examples of the carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate, and neopentylene carbonate.

[0041] In one embodiment, the carbonate diester component may be selected from dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, or a combination thereof, and more preferably may be diphenyl carbonate.

[0042] In one embodiment, the carbonate diester component is represented by the following formula (C): [ka] (wherein A and A' are each independently selected from an unsubstituted or halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 25 carbon atoms, and A and A' may be the same or different).

[0043] In one embodiment, the carbonate diester component represented by the formula (C) may be selected from diphenyl carbonate, ditolyl carbonate, bischlorophenyl carbonate, dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate, or a mixture thereof, and preferably diphenyl carbonate or dimethyl carbonate may be used.

[0044] When producing the polycarbonate copolymer of the present invention, the carbonic acid diester component can be used in a molar equivalent of 0.90 to 1.10, preferably 0.96 to 1.04, relative to 1 molar equivalent of the total diol components. If the molar equivalent of the carbonic acid diester component relative to 1 molar equivalent of the total diol components is less than 0.90, the number of OH groups at the terminals of the produced polycarbonate copolymer increases, the thermal stability of the polycarbonate copolymer deteriorates, or the desired high molecular weight cannot be obtained. On the other hand, if the molar equivalent of the carbonic acid diester component exceeds 1.10, the transesterification reaction rate under the same conditions decreases, the desired high molecular weight cannot be obtained, and the amount of residual carbonic acid diester in the produced polycarbonate copolymer increases, and such residual carbonic acid diester may cause a bad odor during the molding process using the polycarbonate copolymer or cause a bad odor in the molded product, which is not preferable.

[0045] In one embodiment, the polycarbonate copolymer of the present invention is represented by the following formula (1): [ka] A repeating unit having a structure represented by the following formula: The following formula (2) [ka] (wherein, each R1 independently represents hydrogen or an alkyl group, more specifically, hydrogen or an alkyl group having 1 to 18 carbon atoms; and each m and n independently represents an integer of 0 to 15, with the proviso that m+n represents an integer of 1 to 25, more specifically, an integer of 2 to 20, and even more specifically, an integer of 3 to 15); and The following formula (3) [ka] (wherein R is an arylene group having 6 to 40 carbon atoms; or a heteroarylene group having 5 to 40 carbon atoms containing one or more heteroatoms selected from the group consisting of N, O, and S), a repeating unit having a structure represented by the following formula: may include. In one embodiment, the polycarbonate copolymer of the present invention is represented by the following formula (4): [ka] (wherein R' is an alkylene group having 2 to 12 carbon atoms, a cycloalkylene group having 3 to 30 carbon atoms, or a combination thereof).

[0046] The present invention also provides a method for producing a polycarbonate copolymer, which comprises a step of reacting a mixture containing a diol component and a carbonate diester component in the presence of a polymerization catalyst, wherein the diol component contains, relative to 100 mol % in total of the diol components, (a) 0.3 to 66.9 mol % of anhydrosugar alcohol, (b) 0.3 to 56.9 mol % of anhydrosugar alcohol-alkylene glycol, and (c) 32.1 to 99.4 mol % of an aromatic diol.

[0047] In one embodiment, the diol component used in the method for producing the polycarbonate copolymer may further include (d) an additional diol selected from an aliphatic diol, an alicyclic diol other than anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol, or a mixture thereof.

[0048] The types and amounts of the anhydrosugar alcohol, anhydrosugar alcohol-alkylene glycol, aromatic diol, additional diol and carbonate diester components that can be used in the method for producing the polycarbonate copolymer of the present invention are as described above.

[0049] In the method for producing a polycarbonate copolymer of the present invention, a transesterification catalyst can be used as the polymerization catalyst. For example, an alkali metal salt compound, an alkaline earth metal salt compound, or a mixture thereof can be used.

[0050] In one embodiment, a polymerization catalyst selected from an alkali metal salt compound, an alkaline earth metal salt compound, or a mixture thereof may be used in combination with a basic compound selected from a basic boron compound, a basic phosphorus compound, a basic ammonium compound, an amine compound, or a mixture thereof. However, it is preferable to use only the polymerization catalyst without using a basic compound in combination.

[0051] In one embodiment, the alkali metal salt compound used as the polymerization catalyst is, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, tantalum, cesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium phenylborohydride, potassium phenylborohydride, ... Examples of the lithium boron, cesium phenyl boron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphite, dilithium hydrogen phosphite, disodium hydrogen phosphite, dipotassium hydrogen phosphite, dilithium hydrogen phosphite, disodium hydrogen phosphite, dipotassium phenyl phosphate, dilithium phenyl phosphate, dicesium phenyl phosphate, sodium, potassium, lithium, and cesium alcoholates, phenolates, and disodium, dipotassium, dilithium, and dicesium salts of bisphenol A.

[0052] In one embodiment, examples of the alkaline earth metal salt compound used as the polymerization catalyst include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.

[0053] The above alkali metal salt compounds and alkaline earth metal salt compounds may be used alone or in combination of two or more kinds.

[0054] In one embodiment, examples of the basic boron compound used in combination with the polymerization catalyst include sodium salts, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, or strontium salts of tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl boron, tributylphenyl boron, tetraphenyl boron, benzyltriphenyl boron, methyltriphenyl boron, and butyltriphenyl boron.

[0055] In one embodiment, the basic phosphorus compound may be, for example, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, or a quaternary phosphonium salt.

[0056] In one embodiment, the basic ammonium compound may be, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, or butyltriphenylammonium hydroxide.

[0057] In one embodiment, examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, and aminoquinoline.

[0058] The basic compounds used in combination with the polymerization catalyst may be used alone or in combination of two or more kinds.

[0059] By using the polycarbonate copolymer according to the present invention, it is possible to obtain a molded article which is environmentally friendly, exhibits biodegradability, and exhibits improved mechanical properties (particularly tensile strength and elongation) compared to conventional anhydrosugar alcohol-containing polycarbonate copolymers.

[0060] Therefore, according to yet another aspect of the present invention, there is provided a molded article comprising the polycarbonate copolymer of the present invention.

[0061] The molded article can be produced by processing the polycarbonate copolymer of the present invention by a known molding method such as extrusion molding or injection molding.

[0062] The present invention will be described in more detail below with reference to examples and comparative examples, but the scope of the present invention is not limited thereto.

[0063] Working Example Example 1 In a 1,000mL 4-neck reactor connected to a nitrogen gas pipe, a trap for removing by-products, and a vacuum pump for reducing pressure, and including a stirrer capable of checking the stirring torque, a thermometer, and a heater, 95.8mmol of isosorbide, 95.8mmol of ethylene oxide 1 mole adduct of isosorbide, 1,724.4mmol of ethylene oxide 2 mole adduct of bisphenol A, 1,916.0mmol of diphenyl carbonate, and calcium chloride (100ppm relative to the total diol amount) were added, and the temperature was raised to 100°C under a nitrogen atmosphere, and the reactants were dissolved while stirring as necessary. After dissolving the reactants, the temperature of the reactor was raised to 160°C, and the reaction was carried out for 1 hour, and then the pressure was reduced from normal pressure to 20 torr to remove some of the phenol, a by-product generated.

[0064] Next, the reactor temperature was raised to 240°C, the pressure was reduced to 3 torr or less, and the reaction was continued for another hour. After the stirring torque of the stirrer reached a predetermined value, the reaction was terminated. As a result of the reaction, about 410 g of a transparent polycarbonate copolymer having a number average molecular weight of 24,200 g / mol, a PDI of 2.9, and a glass transition temperature of 123°C was obtained.

[0065] Five identical tensile specimens were prepared from the polycarbonate resin obtained above according to ASTM D638, and the tensile strength and elongation of the five tensile specimens were measured using a universal testing machine (UTM). The average tensile strength of the five tensile strength measurements was 78.7 MPa, the average elongation of the five elongation measurements was 84.1%, and the average weight loss of the three biodegradable measurements was 4.8% and 6.8% after 3 months and 6 months, respectively. The results are shown in Table 1 below.

[0066] Example 2 A polycarbonate copolymer having a number average molecular weight of 25,500 g / mol, a PDI of 3.1, and a glass transition temperature of 110° C. was obtained in the same manner as in Example 1, except that 95.8 mmol of an ethylene oxide 5-mol adduct of isosorbide was used instead of 95.8 mmol of an ethylene oxide 1-mol adduct of isosorbide. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 85.7 MPa, the average elongation was 92.2%, and the average weight loss rates after 3 months and 6 months were 8.3% and 15.2%, respectively. The results are shown in Table 1 below.

[0067] Example 3 A polycarbonate copolymer having a number average molecular weight of 22,100 g / mol, a PDI of 3.2, and a glass transition temperature of 115° C. was obtained in the same manner as in Example 1, except that 95.8 mmol of a propylene oxide 5-mol adduct of isosorbide was used instead of 95.8 mmol of an ethylene oxide 1-mol adduct of isosorbide. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 91.1 MPa, the average elongation was 88.5%, and the average weight loss rates after 3 months and 6 months were 7.2% and 13.9%, respectively. The results are shown in Table 1 below.

[0068] Example 4 A polycarbonate copolymer having a number average molecular weight of 23,800 g / mol, a PDI of 4.5, and a glass transition temperature of 92° C. was obtained in the same manner as in Example 1, except that the isosorbide content was changed from 95.8 mmol to 89.0 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 1,779.1 mmol, the content of the ethylene oxide 2 mole adduct of bisphenol A was changed from 1,724.4 mmol to 1,601.2 mmol, and 89.0 mmol of a propylene oxide 25 mole adduct of isosorbide was used instead of 95.8 mmol of an ethylene oxide 1 mole adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 73.6 MPa, the average elongation was 110.9%, and the average weight loss rates after 3 months and 6 months were 13.8% and 28.0%, respectively. The results are shown in Table 1 below.

[0069] Example 5 A polycarbonate copolymer having a number average molecular weight of 23,800 g / mol, a PDI of 3.2, and a glass transition temperature of 104° C. was obtained in the same manner as in Example 1, except that the isosorbide content was changed from 95.8 mmol to 219.0 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 2,189.7 mmol, 1,532.8 mmol of bisphenol A was used instead of 1,724.4 mmol of the 2-mol ethylene oxide adduct of bisphenol A, and 437.9 mmol of the 5-mol ethylene oxide adduct of isosorbide was used instead of 95.8 mmol of the 1-mol ethylene oxide adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 85.3 MPa, the average elongation was 77.9%, and the average weight loss rates after 3 months and 6 months were 16.1% and 30.5%, respectively. The results are shown in Table 1 below.

[0070] Example 6 A polycarbonate copolymer having a number average molecular weight of 27,300 g / mol, a PDI of 4.2, and a glass transition temperature of 83° C. was obtained in the same manner as in Example 1, except that the isosorbide content was changed from 95.8 mmol to 157.4 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 1,573.8 mmol, 1,101.7 mmol of bisphenol A was used instead of 1,724.4 mmol of an ethylene oxide 2-mol adduct of bisphenol A, and 314.8 mmol of an ethylene oxide 25-mol adduct of isosorbide was used instead of 95.8 mmol of an ethylene oxide 1-mol adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 73.5 MPa, the average elongation was 96.0%, and the average weight loss rates after 3 months and 6 months were 19.3% and 33.4%, respectively. The results are shown in Table 1 below.

[0071] Example 7 A polycarbonate copolymer having a number average molecular weight of 21,600 g / mol, a PDI of 3.4, and a glass transition temperature of 151° C. was obtained in the same manner as in Example 1, except that the isosorbide content was changed from 95.8 mmol to 479.0 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 2,395.0 mmol, 1,676.5 mmol of bisphenol A was used instead of 1,724.4 mmol of the ethylene oxide 2-mol adduct of bisphenol A, and 239.5 mmol of a propylene oxide 1-mol adduct of isosorbide was used instead of 95.8 mmol of the ethylene oxide 1-mol adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 75.4 MPa, the average elongation was 42.4%, and the average weight loss rates after 3 months and 6 months were 5.6% and 7.3%, respectively. The results are shown in Table 1 below.

[0072] Example 8 A polycarbonate copolymer having a number average molecular weight of 23,200 g / mol, a PDI of 3.4, and a glass transition temperature of 118° C. was obtained in the same manner as in Example 1, except that the isosorbide content was changed from 95.8 mmol to 479.0 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 2,395.0 mmol, 1,676.5 mmol of bisphenol A was used instead of 1,724.4 mmol of the ethylene oxide 2-mol adduct of bisphenol A, and 239.5 mmol of a propylene oxide 5-mol adduct of isosorbide was used instead of 95.8 mmol of the ethylene oxide 1-mol adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 83.7 MPa, the average elongation was 56.3%, and the average weight loss rates after 3 months and 6 months were 8.9% and 16.8%, respectively. The results are shown in Table 1 below.

[0073] Example 9 The isosorbide content was changed from 95.8 mmol to 786.9 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 1,967.3 mmol, 688.6 mmol of 9,9-bis-(4-(2-hydroxyethoxy)phenyl)fluorene was used instead of 1,724.4 mmol of the 2-mol ethylene oxide adduct of bisphenol A, and 491.8 mmol of the 5-mol ethylene oxide adduct of isosorbide was used instead of 95.8 mmol of the 1-mol ethylene oxide adduct of isosorbide. In the same manner as in Example 1, 471 g of a polycarbonate copolymer having a number average molecular weight of 24,200 g / mol, a PDI of 3.1, and a glass transition temperature of 105° C. was obtained. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured by the same method as in Example 1, and it was confirmed that the average tensile strength was 96.4 MPa, the average elongation was 49.9%, and the average weight loss rate after 3 months and 6 months was 17.6% and 32.2%, respectively. The results are shown in Table 1 below.

[0074] Example 10 The isosorbide content was changed from 95.8 mmol to 786.9 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 1,967.3 mmol, and 688.6 mmol of 9,9-bis-(4-(2-hydroxyethoxy)phenyl)fluorene was used instead of 1,724.4 mmol of the 2-mol ethylene oxide adduct of bisphenol A, and 491.8 mmol of the 5-mol propylene oxide adduct of isosorbide was used instead of 95.8 mmol of the 1-mol ethylene oxide adduct of isosorbide. In the same manner as in Example 1, 463 g of a polycarbonate copolymer having a number average molecular weight of 21,600 g / mol, a PDI of 3.4, and a glass transition temperature of 108° C. was obtained. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 98.1 MPa, the average elongation was 45.6%, and the average weight loss rates after 3 months and 6 months were 13.3% and 24.5%, respectively. The results are shown in Table 1 below.

[0075] Example 11 The content of isosorbide was changed from 95.8 mmol to 479.0 mmol, 670.6 mmol of 9,9-bis-(4-(2-hydroxyethoxy)phenyl)fluorene was used instead of 1,724.4 mmol of ethylene oxide 2 mole adduct of bisphenol A, and 766.4 mmol of ethylene oxide 5 mole adduct of isosorbide was used instead of 95.8 mmol of ethylene oxide 1 mole adduct of isosorbide. The same method as in Example 1 was used to obtain 466 g of a polycarbonate copolymer having a number average molecular weight of 26,100 g / mol, a PDI of 3.5, and a glass transition temperature of 81° C. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured by the same method as in Example 1, and it was confirmed that the average tensile strength was 77.0 MPa, the average elongation was 77.2%, and the average weight loss rates after 3 months and 6 months were 27.9% and 43.6%, respectively. The results are shown in Table 1 below.

[0076] Example 12 The content of isosorbide was changed from 95.8 mmol to 479.0 mmol, 670.6 mmol of 9,9-bis-(4-(2-hydroxyethoxy)phenyl)fluorene was used instead of 1,724.4 mmol of ethylene oxide 2 mole adduct of bisphenol A, and 766.4 mmol of propylene oxide 5 mole adduct of isosorbide was used instead of 95.8 mmol of ethylene oxide 1 mole adduct of isosorbide. The same method as in Example 1 was used to obtain 472 g of a polycarbonate copolymer having a number average molecular weight of 25,500 g / mol, a PDI of 3.6, and a glass transition temperature of 80°C. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured by the same method as in Example 1, and it was confirmed that the average tensile strength was 74.6 MPa, the average elongation was 78.1%, and the average weight loss rates after 3 months and 6 months were 23.7% and 40.3%, respectively. The results are shown in Table 1 below.

[0077] Example 13 A polycarbonate copolymer having a number average molecular weight of 25,300 g / mol, a PDI of 3.2, and a glass transition temperature of 86° C. was obtained in the same manner as in Example 1, except that the content of isosorbide was changed from 95.8 mmol to 1,026.4 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 1,866.2 mmol, the content of 2-mol ethylene oxide adduct of bisphenol A was changed from 1,724.4 mmol to 653.2 mmol, and 186.6 mmol of 5-mol ethylene oxide adduct of isosorbide was used instead of 95.8 mmol of 1-mol ethylene oxide adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 81.0 MPa, the average elongation was 48.7%, and the average weight loss rates after 3 months and 6 months were 14.9% and 26.1%, respectively. The results are shown in Table 1 below.

[0078] Example 14 A polycarbonate copolymer having a number average molecular weight of 24,700 g / mol, a PDI of 3.4, and a glass transition temperature of 83° C. was obtained in the same manner as in Example 1, except that the isosorbide content was changed from 95.8 mmol to 1,026.4 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 1,866.2 mmol, the content of the ethylene oxide 2-mol adduct of bisphenol A was changed from 1,724.4 mmol to 653.2 mmol, and 186.6 mmol of a propylene oxide 5-mol adduct of isosorbide was used instead of 95.8 mmol of an ethylene oxide 1-mol adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 83.4 MPa, the average elongation was 39.5%, and the average weight loss rates after 3 months and 6 months were 13.2% and 21.8%, respectively. The results are shown in Table 1 below.

[0079] Example 15 A polycarbonate copolymer having a number average molecular weight of 24,600 g / mol, a PDI of 3.0, and a glass transition temperature of 101° C. was obtained in the same manner as in Example 1, except that the isosorbide content was changed from 95.8 mmol to 1,060.6 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 1,928.4 mmol, 674.9 mmol of bisphenol A was used instead of 1,724.4 mmol of an ethylene oxide 2-mol adduct of bisphenol A, and 192.8 mmol of an ethylene oxide 5-mol adduct of isosorbide was used instead of 95.8 mmol of an ethylene oxide 1-mol adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 84.9 MPa, the average elongation was 35.6%, and the average weight loss rates after 3 months and 6 months were 12.1% and 24.5%, respectively. The results are shown in Table 1 below.

[0080] Example 16 A polycarbonate copolymer having a number average molecular weight of 22,800 g / mol, a PDI of 3.2, and a glass transition temperature of 100° C. was obtained in the same manner as in Example 1, except that the isosorbide content was changed from 95.8 mmol to 1,060.6 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 1,928.4 mmol, 674.9 mmol of bisphenol A was used instead of 1,724.4 mmol of an ethylene oxide 2-mol adduct of bisphenol A, and 192.8 mmol of a propylene oxide 5-mol adduct of isosorbide was used instead of 95.8 mmol of an ethylene oxide 1-mol adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 85.4 MPa, the average elongation was 34.1%, and the average weight loss rates after 3 months and 6 months were 10.2% and 22.2%, respectively. The results are shown in Table 1 below.

[0081] Example 17 The content of isosorbide was changed from 95.8 mmol to 9.6 mmol, the content of ethylene oxide 2 mole adduct of bisphenol A was changed from 1,724.4 mmol to 1,896.8 mmol, and ethylene oxide 5 mole adduct of isosorbide 9.6 mmol was used instead of ethylene oxide 1 mole adduct of isosorbide 95.8 mmol, but the same method as in Example 1 was used to obtain 669 g of a polycarbonate copolymer having a number average molecular weight of 27,900 g / mol, a PDI of 2.7, and a glass transition temperature of 120 ° C. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured by the same method as in Example 1, and it was confirmed that the average tensile strength was 73.2 MPa, the average elongation was 94.9%, and the average weight loss rate after 3 months and 6 months was 4.5% and 9.9%, respectively. The results are shown in Table 1 below.

[0082] Example 18 The content of isosorbide was changed from 95.8 mmol to 11.6 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 2,326.5 mmol, bisphenol A was used instead of 1,724.4 mmol of ethylene oxide 2 mole adduct of bisphenol A, and propylene oxide 5 mole adduct of isosorbide was used instead of 95.8 mmol of ethylene oxide 1 mole adduct of isosorbide. Except for this, 585 g of polycarbonate copolymer having a number average molecular weight of 29,500 g / mol, PDI of 2.2, and glass transition temperature of 146 ° C. was obtained in the same manner as in Example 1. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 74.4 MPa, the average elongation was 88.3%, and the average weight loss rate after 3 months and 6 months was 2.9% and 6.8%, respectively. The results are shown in Table 1 below.

[0083] Example 19 A polycarbonate copolymer having a number average molecular weight of 25,000 g / mol, a PDI of 2.8, and a glass transition temperature of 93° C. was obtained in the same manner as in Example 1, except that the content of isosorbide was changed from 95.8 mmol to 615.9 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 2,052.8 mmol, the content of 2-mol ethylene oxide adduct of bisphenol A was changed from 1,724.4 mmol to 1,026.4 mmol, and 410.6 mmol of 5-mol ethylene oxide adduct of isosorbide was used instead of 95.8 mmol of 1-mol ethylene oxide adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 86.7 MPa, the average elongation was 64.7%, and the average weight loss rates after 3 months and 6 months were 17.1% and 30.8%, respectively. The results are shown in Table 1 below.

[0084] Example 20 A polycarbonate copolymer having a number average molecular weight of 23,800 g / mol, a PDI of 2.5, and a glass transition temperature of 111° C. was obtained in the same manner as in Example 1, except that the isosorbide content was changed from 95.8 mmol to 650.1 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 2,166.9 mmol, 1,083.4 mmol of bisphenol A was used instead of 1,724.4 mmol of an ethylene oxide 2-mol adduct of bisphenol A, and 433.4 mmol of a propylene oxide 5-mol adduct of isosorbide was used instead of 95.8 mmol of an ethylene oxide 1-mol adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 88.8 MPa, the average elongation was 66.2%, and the average weight loss rates after 3 months and 6 months were 14.2% and 28.3%, respectively. The results are shown in Table 1 below.

[0085] Example 21 The isosorbide content was changed from 95.8 mmol to 143.7 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 2,874.0 mmol, and 2,586.6 mmol of 1,4-bis(2-hydroxymethyl)benzene was used instead of 1,724.4 mmol of the 2-mol ethylene oxide adduct of bisphenol A, and 143.7 mmol of the 5-mol ethylene oxide adduct of isosorbide was used instead of 95.8 mmol of the 1-mol ethylene oxide adduct of isosorbide. In the same manner as in Example 1, 500 g of a polycarbonate copolymer having a number average molecular weight of 28,400 g / mol, a PDI of 2.3, and a glass transition temperature of 101° C. was obtained. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured by the same method as in Example 1, and it was confirmed that the average tensile strength was 81.6 MPa, the average elongation was 94.8%, and the average weight loss rate after 3 months and 6 months was 6.9% and 14.1%, respectively. The results are shown in Table 1 below.

[0086] Example 22 A polycarbonate copolymer having a number average molecular weight of 21,500 g / mol, a PDI of 3.0, and a glass transition temperature of 109° C. was obtained in the same manner as in Example 1, except that the content of isosorbide was changed from 95.8 mmol to 260.0 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 2,600.3 mmol, 1,820.2 mmol of 2,5-bis(hydroxymethyl)furan was used instead of 1,724.4 mmol of the 2-mol ethylene oxide adduct of bisphenol A, and 520.1 mmol of the 5-mol propylene oxide adduct of isosorbide was used instead of 95.8 mmol of the 1-mol ethylene oxide adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 80.2 MPa, the average elongation was 62.7%, and the average weight loss rates after 3 months and 6 months were 9.4% and 18.9%, respectively. The results are shown in Table 1 below.

[0087] Example 23 The isosorbide content was changed from 95.8 mmol to 992.2 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 2,480.5 mmol, and 868.2 mmol of 2,6-bis(hydroxymethyl)pyridine was used instead of 1,724.4 mmol of the 2-mol ethylene oxide adduct of bisphenol A, and 620.1 mmol of the 5-mol ethylene oxide adduct of isosorbide was used instead of 95.8 mmol of the 1-mol ethylene oxide adduct of isosorbide. In the same manner as in Example 1, 558 g of a polycarbonate copolymer having a number average molecular weight of 26,600 g / mol, a PDI of 3.3, and a glass transition temperature of 99°C was obtained. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 90.5 MPa, the average elongation was 57.8%, and the average weight loss rates after 3 months and 6 months were 16.7% and 35.3%, respectively. The results are shown in Table 1 below.

[0088] Comparative Example Comparative Example 1 The content of isosorbide was changed from 95.8 mmol to 157.4 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 1,573.8 mmol, the content of 2 ethylene oxide mole adduct of bisphenol A was changed from 1,724.4 mmol to 1,416.5 mmol, and 1 ethylene oxide mole adduct of isosorbide was not used, and 458 g of polycarbonate copolymer having a number average molecular weight of 28,800 g / mol, a PDI of 2.7, and a glass transition temperature of 118 ° C. was obtained in the same manner as in Example 1. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 68.1 MPa, the average elongation was 73.9%, and the average weight loss rate after 3 months and 6 months was 0% and 0%, respectively. The results are shown in Table 2 below.

[0089] Comparative Example 2 A polycarbonate copolymer having a number average molecular weight of 26,100 g / mol, a PDI of 2.2, and a glass transition temperature of 141° C. was obtained in the same manner as in Example 1, except that the content of isosorbide was changed from 95.8 mmol to 184.8 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 1,847.5 mmol, 1,662.8 mmol of bisphenol A was used instead of 1,724.4 mmol of ethylene oxide 2 mole adduct of bisphenol A, and 1 mole adduct of ethylene oxide of isosorbide was not used. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 59.7 MPa, the average elongation was 70.4%, and the average weight loss rate after 3 months and 6 months was 0% and 0%, respectively. The results are shown in Table 2 below.

[0090] Comparative Example 3 The content of isosorbide was changed from 95.8 mmol to 136.9 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 1,368.55 mmol, 1,231.7 mmol of 9,9-bis-(4-(2-hydroxyethoxy)phenyl)fluorene was used instead of 1,724.4 mmol of ethylene oxide 2 mole adduct of bisphenol A, and 1 mole adduct of ethylene oxide of isosorbide was not used, and 450 g of polycarbonate copolymer having a number average molecular weight of 23,100 g / mol, a PDI of 2.5, and a glass transition temperature of 168 ° C. was obtained in the same manner as in Example 1. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 61.2 MPa, the average elongation was 10.2%, and the average weight loss rate after 3 months and 6 months was 0% and 0%, respectively. The results are shown in Table 2 below.

[0091] Comparative Example 4 The content of isosorbide was changed from 95.8 mmol to 506.4 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 1,687.9 mmol, the content of 2 ethylene oxide mole adduct of bisphenol A was changed from 1,724.4 mmol to 1,181.5 mmol, and 1 ethylene oxide mole adduct of isosorbide was not used, and 454 g of polycarbonate copolymer having a number average molecular weight of 27,500 g / mol, a PDI of 2.6, and a glass transition temperature of 120 ° C. was obtained in the same manner as in Example 1. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 70.0 MPa, the average elongation was 22.4%, and the average weight loss rate after 3 months and 6 months was 0% and 0%, respectively. The results are shown in Table 2 below.

[0092] Comparative Example 5 A polycarbonate copolymer having a number average molecular weight of 27,300 g / mol, a PDI of 2.3, and a glass transition temperature of 146° C. was obtained in the same manner as in Example 1, except that the content of isosorbide was changed from 95.8 mmol to 581.6 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 1,938.8 mmol, 1,357.2 mmol of bisphenol A was used instead of 1,724.4 mmol of ethylene oxide 2 mole adduct of bisphenol A, and 1 mole adduct of ethylene oxide of isosorbide was not used. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 62.1 MPa, the average elongation was 20.1%, and the average weight loss rate after 3 months and 6 months was 0% and 0%, respectively. The results are shown in Table 2 below.

[0093] Comparative Example 6 The content of isosorbide was changed from 95.8 mmol to 444.8 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 1,482.6 mmol, 1,037.8 mmol of 9,9-bis-(4-(2-hydroxyethoxy)phenyl)fluorene was used instead of 1,724.4 mmol of 2-mol ethylene oxide adduct of bisphenol A, and 436 g of polycarbonate copolymer having a number average molecular weight of 23,900 g / mol, a PDI of 2.5, and a glass transition temperature of 158°C was obtained in the same manner as in Example 1, except that the tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 63.8 MPa, the average elongation was 2.5%, and the average weight loss rate after 3 months and 6 months was 0% and 0%, respectively. The results are shown in Table 2 below.

[0094] Comparative Example 7 The content of isosorbide was changed from 95.8 mmol to 8.2 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 1,642.3 mmol, the content of 2 ethylene oxide mole adduct of bisphenol A was changed from 1,724.4 mmol to 1,634.1 mmol, and 1 ethylene oxide mole adduct of isosorbide was not used, and 441 g of polycarbonate copolymer having a number average molecular weight of 29,400 g / mol, a PDI of 2.6, and a glass transition temperature of 117 ° C. was obtained in the same manner as in Example 1. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 60.4 MPa, the average elongation was 74.1%, and the average weight loss rate after 3 months and 6 months was 0% and 0%, respectively. The results are shown in Table 2 below.

[0095] Comparative Example 8 The content of isosorbide was changed from 95.8 mmol to 8.9 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 1,779.1 mmol, 1,770.2 mmol of bisphenol A was used instead of 1,724.4 mmol of ethylene oxide 2 mole adduct of bisphenol A, and 450 g of polycarbonate copolymer having a number average molecular weight of 27,700 g / mol, a PDI of 2.3, and a glass transition temperature of 142 ° C. was obtained in the same manner as in Example 1, except that the ethylene oxide 1 mole adduct of isosorbide was not used. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 56.5 MPa, the average elongation was 71.5%, and the average weight loss rate after 3 months and 6 months was 0% and 0%, respectively. The results are shown in Table 2 below.

[0096] Comparative Example 9 The content of isosorbide was changed from 95.8 mmol to 3.8 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 1,505.4 mmol, the content of 2 ethylene oxide mole adduct of bisphenol A was changed from 1,724.4 mmol to 1,497.9 mmol, and 3.8 mmol of 5 ethylene oxide mole adduct of isosorbide was used instead of 95.8 mmol of 1 ethylene oxide mole adduct of isosorbide. Except for this, 459 g of polycarbonate copolymer having a number average molecular weight of 26,200 g / mol, a PDI of 2.7, and a glass transition temperature of 115 ° C. was obtained in the same manner as in Example 1. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 61.7 MPa, the average elongation was 74.7%, and the average weight loss rate after 3 months and 6 months was 1.9% and 4.1%, respectively. The results are shown in Table 2 below.

[0097] Comparative Example 10 The content of isosorbide was changed from 95.8 mmol to 4.5 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 1,779.1 mmol, bisphenol A was used instead of 1,724.4 mmol of ethylene oxide 2 mole adduct of bisphenol A, and propylene oxide 5 mole adduct of isosorbide was used instead of 95.8 mmol of ethylene oxide 1 mole adduct of isosorbide. Except for this, 460 g of polycarbonate copolymer having a number average molecular weight of 28,100 g / mol, PDI of 2.3, and glass transition temperature of 140 ° C. was obtained in the same manner as in Example 1. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 59.4 MPa, the average elongation was 72.6%, and the average weight loss rate after 3 months and 6 months was 1.3% and 3.5%, respectively. The results are shown in Table 2 below.

[0098] Comparative Example 11 The content of isosorbide was changed from 95.8 mmol to 1,642.3 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 2,451.1 mmol, the content of 2 mol ethylene oxide adduct of bisphenol A was changed from 1,724.4 mmol to 784.4 mmol, and 24.5 mmol of 5 mol ethylene oxide adduct of isosorbide was used instead of 95.8 mmol of 1 mol ethylene oxide adduct of isosorbide. Except for this, 545 g of polycarbonate copolymer having a number average molecular weight of 26,400 g / mol, a PDI of 2.5, and a glass transition temperature of 113 ° C. was obtained in the same manner as in Example 1. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 67.6 MPa, the average elongation was 10.4%, and the average weight loss rate after 3 months and after 6 months was 2.5% and 5.7%, respectively. The results are shown in Table 2 below.

[0099] Comparative Example 12 The content of isosorbide was changed from 95.8 mmol to 1,779.1 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 2,655.4 mmol, bisphenol A was used instead of 1,724.4 mmol of ethylene oxide 2 mole adduct of bisphenol A, and propylene oxide 5 mole adduct of isosorbide was used instead of 95.8 mmol of ethylene oxide 1 mole adduct of isosorbide, but 568 g of polycarbonate copolymer having a number average molecular weight of 28,700 g / mol, PDI of 2.3, and glass transition temperature of 132 ° C. was obtained in the same manner as in Example 1. The tensile strength, elongation, and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 64.9 MPa, the average elongation was 9.1%, and the average weight loss rate after 3 months and 6 months was 2.2% and 4.0%, respectively. The results are shown in Table 2 below.

[0100] Comparative Example 13 A polycarbonate copolymer having a number average molecular weight of 27,100 g / mol, a PDI of 3.8, and a glass transition temperature of 48° C. was obtained in the same manner as in Example 1, except that the content of isosorbide was changed from 95.8 mmol to 150.5 mmol, the content of diphenyl carbonate was changed from 1,916.0 mmol to 1,881.7 mmol, the content of 2-mol ethylene oxide adduct of bisphenol A was changed from 1,724.4 mmol to 658.6 mmol, and 1,072.6 mmol of 5-mol ethylene oxide adduct of isosorbide was used instead of 95.8 mmol of 1-mol ethylene oxide adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 46.8 MPa, the average elongation was 110.1%, and the average weight loss rates after 3 months and 6 months were 32.9% and 56.7%, respectively. The results are shown in Table 2 below.

[0101] Comparative Example 14 A polycarbonate copolymer having a number average molecular weight of 23,400 g / mol, a PDI of 3.8, and a glass transition temperature of 55° C. was obtained in the same manner as in Example 1, except that the isosorbide content was changed from 95.8 mmol to 150.5 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 1,881.8 mmol, 658.6 mmol of bisphenol A was used instead of 1,724.4 mmol of an ethylene oxide 2-mol adduct of bisphenol A, and 1,072.6 mmol of a propylene oxide 5-mol adduct of isosorbide was used instead of 95.8 mmol of an ethylene oxide 1-mol adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 51.7 MPa, the average elongation was 103.8%, and the average weight loss rates after 3 months and 6 months were 30.2% and 46.3%, respectively. The results are shown in Table 2 below.

[0102] Comparative Example 15 A polycarbonate copolymer having a number average molecular weight of 29,700 g / mol, a PDI of 3.1, and a glass transition temperature of 125° C. was obtained in the same manner as in Example 1, except that the isosorbide content was changed from 95.8 mmol to 2,463.4 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 2,737.1 mmol, 136.9 mmol of 1,4-cyclohexanedimethanol was used instead of 1,724.4 mmol of ethylene oxide 2-mol adduct of bisphenol A, and 136.9 mmol of ethylene oxide 5-mol adduct of isosorbide was used instead of 95.8 mmol of ethylene oxide 1-mol adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 88.1 MPa, the average elongation was 12.8%, and the average weight loss rates after 3 months and 6 months were 3.0% and 4.9%, respectively. The results are shown in Table 2 below.

[0103] Comparative Example 16 A polycarbonate copolymer having a number average molecular weight of 24,300 g / mol, a PDI of 2.3, and a glass transition temperature of 115° C. was obtained in the same manner as in Example 1, except that the isosorbide content was changed from 95.8 mmol to 2,463.4 mmol, the diphenyl carbonate content was changed from 1,916.0 mmol to 2,737.1 mmol, and 1,4-butanediol was used instead of 1,724.4 mmol of an ethylene oxide 2-mol adduct of bisphenol A, and 136.9 mmol of a propylene oxide 5-mol adduct of isosorbide was used instead of 95.8 mmol of an ethylene oxide 1-mol adduct of isosorbide. The tensile strength, elongation and biodegradability of the obtained polycarbonate copolymer were measured in the same manner as in Example 1, and it was confirmed that the average tensile strength was 72.6 MPa, the average elongation was 16.5%, and the average weight loss rates after 3 months and 6 months were 14.4% and 27.2%, respectively. The results are shown in Table 2 below.

[0104] [Ingredients] ISB: Isosorbide EI 1: 1 mole ethylene oxide adduct of isosorbide EI 5: 5 mole adduct of ethylene oxide with isosorbide EI 25: 25 moles of ethylene oxide adduct of isosorbide PI 1: 1 mole propylene oxide adduct of isosorbide PI 5: 5 mole propylene oxide adduct of isosorbide PI 25: 25 moles of propylene oxide adduct of isosorbide BPA(EO)2: Bisphenol A with 2 moles of ethylene oxide BPA: Bisphenol A BHEPF: 9,9-bis-(4-(2-hydroxyethoxy)phenyl)fluorene 1,4-BHMB: 1,4-bis(2-hydroxymethyl)benzene 2,5-BHMF: 2,5-bis(hydroxymethyl)furan 2,6-BHMP: 2,6-bis(hydroxymethyl)pyridine CHDM: 1,4-cyclohexanedimethanol 1,4-BD: 1,4-butanediol DPC: Diphenyl carbonate CaCl2: Calcium chloride

[0105] [Physical property measurement method] Number average molecular weight (Mn, g / mol) and polydispersity index (PDI): Each polycarbonate copolymer prepared in the above examples and comparative examples was dissolved in chloroform at 1-3 wt%, and the number average molecular weight (Mn) and polydispersity index (PDI) were measured using a gel permeation chromatography (GPC) device (Agilent). The column used was PLgel 5μM IXED-D 300×7.5mm (Agilent), the column temperature was 35°C, the elution solvent was chloroform, the flow rate was 0.5mL / min, and the standard substance was polystyrene (Sigma-Aldrich).

[0106] Glass transition temperature (Tg): Using a differential scanning calorimeter (DSC Q100, manufactured by TA Instruments), the glass transition temperature was measured under the following specific conditions: increasing the temperature from 20°C to 300°C at a heating rate of 10°C / min, then rapidly cooling to 20°C, and increasing the temperature again to 300°C.

[0107] Tensile strength and elongation: Tensile strength and elongation were measured at a speed of 5 mm / min using a UTM (Instron 5967, manufactured by Instron) in accordance with ASTM D638. Specifically, the tensile strength and elongation were measured five times for each specimen prepared in the examples and comparative examples, and the average value of the five measurement results for each specimen was calculated. -Biodegradability evaluation: The polycarbonate copolymers obtained in the above examples and comparative examples were processed into a film with a thickness of about 100 μm using a hot press (Mini Test Press-10, manufactured by Toyoseiki Co., Ltd.), and cut into a size of 8 cm wide x 4 cm long to prepare a test specimen for measuring biodegradability.

[0108] To measure biodegradation under compost conditions, the biodegradability test specimens were buried in compost in a thermostatic chamber maintained at a temperature of 50°C and a humidity of 60%, and biodegradability was measured every two weeks for six months. The compost and burial conditions were as follows, and biodegradability (%) was measured as the weight loss rate (%) of each specimen according to the following formula, and the average value of the measurements of three specimens was calculated.

[0109] [Biodegradable]

number

[0110] [Composting and burial conditions] Compost was produced using a microbial fermentation and decomposition device (Wrinkle, Hanmi Flexible Co., Ltd.) from a starter culture composition of Bacillus smithii, a thermophilic bacterium used for organic waste treatment (Food Cleaner, Hanmi Flexible Co., Ltd.). In order to maintain the activity of the microorganisms continuously, the compost used for measuring biodegradability was replaced with freshly produced compost every week.

[0111] To confirm the reliability of this biodegradability evaluation, cellulose (α-cellulose, ≥98%) was used as the reference substance and the biodegradability was measured in the same manner as in the biodegradability evaluation method described above. As a result, it was confirmed that weight loss began after 4 weeks, and biodegradation had progressed to a level where recovery was impossible after 10 weeks.

[0112] [Table 1-1] [Table 1-2] [Table 2-1] [Table 2-2]

[0113] As shown in Table 1, the polycarbonate copolymers of Examples 1 to 23 according to the present invention contain anhydrosugar alcohol, anhydrosugar alcohol-alkylene glycol, and aromatic diol as diol components in specific content ranges, and exhibit good, well-balanced physical properties in terms of tensile strength, elongation, heat resistance, and biodegradability, such as an average tensile strength of 73.2 MPa or more, an average elongation of 34.1% or more, a glass transition temperature of 80°C or more, and a high biodegradability after 6 months of 6.8% or more.

[0114] However, as shown in Table 2, the polycarbonate copolymers of Comparative Examples 1 to 8 had poor average tensile strength of 70.0 MPa or less, and the biodegradability after 6 months was 0%, that is, no biodegradation was observed. In particular, the polycarbonate copolymers of Comparative Examples 3 to 6 also had poor average elongation of 22.4% or less. The polycarbonate copolymers of Comparative Examples 9 and 10 had very poor average tensile strength of 61.7 MPa or less, and poor biodegradability after 6 months of 4.1% or less, compared to the polycarbonate copolymers of the Examples. The polycarbonate copolymers of Comparative Examples 11 and 12 had poor average tensile strength of 67.6 MPa or less, and poor average elongation of 10.4% or less. The polycarbonate copolymers of Comparative Examples 13 and 14 had very poor average tensile strength and glass transition temperature, and the polycarbonate copolymers of Comparative Examples 15 and 16 had very poor average elongation.

Claims

1. comprising a repeat unit derived from a diol component; and a repeat unit derived from a carbonate diester component; A polycarbonate copolymer, wherein the diol component contains, relative to 100 mol % of the total of the diol components, (a) 0.3 to 55 mol % of an anhydrosugar alcohol, (b) 0.3 to 40 mol % of an anhydrosugar alcohol-alkylene glycol, and (c) 35 to 99 mol % of an aromatic diol.

2. 2. The polycarbonate copolymer according to claim 1, wherein the anhydrosugar alcohol is a dianhydrohexitol.

3. 2. The polycarbonate copolymer of claim 1, wherein the anhydrosugar alcohol is selected from isosorbide, isomannide, isoidide, or mixtures thereof.

4. 2. The polycarbonate copolymer according to claim 1, wherein the anhydrosugar alcohol-alkylene glycol is obtained by an addition reaction between an anhydrosugar alcohol and an alkylene oxide.

5. 5. The polycarbonate copolymer according to claim 4, wherein the alkylene oxide is a linear alkylene oxide having 2 to 18 carbon atoms or a branched alkylene oxide having 3 to 18 carbon atoms.

6. 2. The polycarbonate copolymer according to claim 1, wherein the aromatic diol is at least one selected from the group consisting of bisphenol-based diol compounds, fluorene-based diol compounds, benzene-based diol compounds, furan-based diol compounds, pyridine-based diol compounds, and combinations thereof.

7. 2. The polycarbonate copolymer according to claim 1, wherein the aromatic diol is at least one selected from the group consisting of bisphenol A, an alkylene oxide adduct of bisphenol A, 9,9-bis-(4-(2-hydroxyethoxy)phenyl)fluorene, 1,4-bis(2-hydroxymethyl)benzene, 1,3-bis(2-hydroxymethyl)benzene, 1,4-bis(2-hydroxyethyl)benzene, 2,5-bis(hydroxymethyl)furan, 2,5-bis(hydroxyethyl)furan, 2,6-bis(hydroxymethyl)pyridine, or a combination thereof.

8. 2. The polycarbonate copolymer of claim 1, wherein the carbonate diester component is selected from a dialkyl carbonate, a diaryl carbonate, an alkylene carbonate, or a combination thereof.

9. The carbonate diester component is represented by the following formula (C): 【Chemistry 1】 (wherein A and A' are each independently selected from an unsubstituted or halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 25 carbon atoms, and A and A' may be the same or different from each other.)

10. The following formula (1) 【Chemistry 2】 A repeating unit having a structure represented by the formula: The following formula (2) 【Transformation 3】 (In the formula, R 1 each independently represents hydrogen or an alkyl group, and m and n each independently represents an integer of 0 to 15, with the proviso that m+n represents an integer of 1 to 25; and The following formula (3) 【Chemistry 4】 (wherein R is an arylene group having 6 to 40 carbon atoms; or a heteroarylene group having 5 to 40 carbon atoms and containing one or more heteroatoms selected from the group consisting of N, O, and S); The polycarbonate copolymer of claim 1 comprising:

11. A method for producing a polycarbonate copolymer, comprising: a step of reacting a mixture containing a diol component and a carbonate diester component in the presence of a polymerization catalyst, The diol component contains, relative to a total of 100 mol% of the diol components, (a) 0.3 to 55 mol% of an anhydrosugar alcohol, (b) 0.3 to 40 mol% of an anhydrosugar alcohol-alkylene glycol, and (c) 35 to 99 mol% of an aromatic diol.

12. A molded article comprising the polycarbonate copolymer according to any one of claims 1 to 10.

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