Polycarbonate copolymer containing units derived from anhydrosugar alcohol, aromatic diol and hydroxy-terminated polysiloxane, method for producing the same, and molded article containing the same

Abstract

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 has significantly improved mechanical properties (e.g., impact strength) compared to conventional polycarbonate copolymers by containing repeating units derived from a diol component containing an anhydrosugar alcohol, an aromatic diol, and a hydroxy-terminated polysiloxane in a specific content ratio, and a carbonate diester component, a method for producing the same, 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 has significantly improved mechanical properties (e.g., impact strength) compared to conventional polycarbonate copolymers by containing repeating units derived from a diol component containing an anhydrosugar alcohol, an aromatic diol, and a hydroxy-terminated polysiloxane in a specific content ratio, and a carbonate diester component, 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 around 150°C. It has excellent mechanical properties such as tensile strength and impact strength, as well as dimensional stability, heat resistance, and optical transparency.

[0003] Polycarbonate is typically produced by the condensation polymerization of petroleum-based raw materials bisphenol A and phosgene. However, due to various reasons, including the accelerating depletion of petroleum resources, the need to reduce greenhouse gas emissions due to climate change, rising raw material prices, and the growing 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") are compounds obtained by adding hydrogen to the reducing end group of sugars, and are generally referred to as HOCH2(CHOH). nThe chemical formula is CHOH (where n is an integer between 2 and 5). Hydrogenated sugars are classified into tetritols, pentitols, hexitols, and heptitols (4, 5, 6, and 7 carbon atoms, respectively) based on the number of carbon atoms. Among these, hexitols with 6 carbon atoms include sorbitol, mannitol, iditol, and galactitol, with sorbitol and mannitol being very useful substances. As such, anhydrosugar alcohols have attracted great interest due to their wide range of applications, and their level of industrial practical application is gradually increasing.

[0005] Techniques for producing polycarbonates using anhydrosugar alcohols have 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. Furthermore, 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 friendliness, they have poor mechanical properties (especially impact strength), making them difficult to actually use as engineering plastics. Therefore, there is a need to develop a technology to produce polycarbonate copolymers that can actually be used as engineering plastics by using anhydrosugar alcohols as raw materials, thereby increasing environmental friendliness and improving mechanical properties such as impact strength compared to conventional technologies. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Korean Patent No. 10-2009-0018788 [Patent Document 2] Korean Patent No. 10-1080669 Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a polycarbonate copolymer that is environmentally friendly and has significantly improved mechanical properties such as impact strength compared to conventional anhydrosugar alcohol-containing polycarbonate resins due to the inclusion of units derived from an anhydrosugar alcohol, a method for producing the same, and a molded article containing the same. [Means for solving the problem]

[0009] 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) 79.8 to 96.9 mol % of an anhydrosugar alcohol, (b) 2.6 to 19.9 mol % of an aromatic diol, and (c) 0.11 to 1.99 mol % of a hydroxy-terminated polysiloxane.

[0010] 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 component, (a) 79.8 to 96.9 mol % of an anhydrosugar alcohol, (b) 2.6 to 19.9 mol % of an aromatic diol, and (c) 0.11 to 1.99 mol % of a hydroxy-terminated polysiloxane.

[0011] According to yet another aspect of the present invention, there is provided a molded article comprising the polycarbonate copolymer of the present invention. [Effects of the Invention]

[0012] The polycarbonate copolymer of the present invention is environmentally friendly and exhibits significantly improved mechanical properties (especially impact strength) compared to conventional polycarbonate copolymers containing anhydrosugar alcohols. BEST MODE FOR CARRYING OUT THE INVENTION

[0013] The present invention will now be described in more detail.

[0014] The polycarbonate copolymer of the present invention contains repeating units derived from a diol component containing (a) 79.8 to 96.9 mol % of anhydrosugar alcohol, (b) 2.6 to 19.9 mol % of aromatic diol, and (c) 0.11 to 1.99 mol % of hydroxy-terminated polysiloxane, relative to 100 mol % in total of the diol component; 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 in the process of producing an anhydrosugar alcohol by dehydration of a hydrogenated sugar. A hydrogenated sugar (also called a "sugar alcohol") refers to a compound obtained by adding hydrogen to the reducing end group of a sugar, and is generally represented by HOCH2(CHOH). n It has the chemical formula CHOH (where n is an integer between 2 and 5). Hydrogenated sugars are classified into tetritols, pentitols, hexitols, and heptitols (4, 5, 6, and 7 carbon atoms, respectively) based on the number of carbon atoms. Of 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 interior of a hydrogenated sugar, and is in the form of a tetraol having four hydroxy 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 thereof. The dianhydrosugar alcohol is an anhydrosugar alcohol produced by removing two water molecules from the interior of a hydrogenated sugar. It is a diol with two hydroxyl groups in the molecule and can be produced using starch-derived hexitol. Dianhydrosugar alcohols are environmentally friendly materials obtained from renewable natural resources, and have long attracted much attention, leading to ongoing research into their production methods. Among these dianhydrosugar alcohols, isosorbide produced from sorbitol currently has the widest range of industrial applications. The type of dianhydrosugar alcohol that can be used in the present invention is not particularly limited, but is preferably dianhydrohexitol, more specifically, 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.

[0017] In one embodiment, the polycarbonate copolymers of the present invention may include repeat units having the following structure: [ka]

[0018] The amount of the anhydrosugar alcohol in the diol component contained as a repeating unit in the polycarbonate copolymer of the present invention is 79.8 to 96.9 mol % relative to 100 mol % of the total diol components. If the amount of the anhydrosugar alcohol in the diol component is less than 79.8 mol % relative to 100 mol % of the total diol components, the copolymer will have poor surface hardness, and conversely, if it exceeds 96.9 mol %, the copolymer will have poor impact strength.

[0019] In one embodiment, the amount of anhydrosugar alcohol in the diol component may be, relative to 100 mol% of the total diol components, 80 mol% or more, 81 mol% or more, 82 mol% or more, 83 mol% or more, 84 mol% or more, 85 mol% or more, or 86 mol% or more, and may be, but is not limited to, 96.5 mol% or less, 96 mol% or less, 95.5 mol% or less, or 95 mol% or less.

[0020] (b) Aromatic diol In the present invention, the aromatic diol means an aromatic compound having two hydroxy groups.

[0021] In one embodiment, the aromatic diol may be one or more 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.

[0022] 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)ethane 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 alkyl group 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.

[0023] More specifically, the aromatic diol may be, but is not limited to, one or more selected from the group consisting of bisphenol A, alkylene oxide adducts 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.

[0024] The content of the aromatic diol in the diol component contained as a repeating unit in the polycarbonate copolymer of the present invention is 2.6 to 19.9 mol % relative to 100 mol % of the total diol components. If the amount of aromatic diol in the diol component is less than 2.6 mol % relative to 100 mol % of the total diol components, the copolymer will have poor impact strength, and conversely, if it exceeds 19.9 mol %, the copolymer will have poor surface hardness.

[0025] In one embodiment, the amount of aromatic diol in the diol component may be, relative to 100 mol% of the total of the diol components, 2.7 mol% or more, 2.8 mol% or more, 2.9 mol% or more, or 3 mol% or more, and may be 19 mol% or less, 18 mol% or less, 17 mol% or less, 16 mol% or less, 15 mol% or less, 14 mol% or less, 13 mol% or less, 12 mol% or less, 11 mol% or less, 10 mol% or less, 9 mol% or less, or 8 mol% or less, but is not limited to these.

[0026] (c) Hydroxy-terminated polysiloxane In the present invention, the hydroxy-terminated polysiloxane is a polysiloxane compound having hydroxy groups at both ends.

[0027] In one embodiment, the hydroxy-terminated polysiloxane has the following formula (1): [ka] (In the formula, R5 independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R6 independently represents a hydrocarbon group having 1 to 13 carbon atoms or a hydroxy group; R7 independently represents an alkylene group having 2 to 8 carbon atoms; A is X or NH-X-NH, where X represents a linear or branched aliphatic group having 1 to 20 carbon atoms; a cycloalkylene group having 3 to 20 carbon atoms; or a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms which is unsubstituted or substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a carboxyl group; m independently represents an integer of 0 to 4; n independently represents an integer of 2 to 1,000, preferably an integer of 2 to 500, and more preferably an integer of 5 to 100.

[0028] More specifically, in R5 in formula (1), the halogen atom is Cl or Br; the alkyl group is an alkyl group having 1 to 13 carbon atoms, such as methyl, ethyl, or propyl; the alkoxy group is an alkoxy group having 1 to 13 carbon atoms, such as methoxy, ethoxy, or propoxy; and the aryl group is an aryl group having 6 to 10 carbon atoms, such as phenyl, chlorophenyl, or tolyl; In R6 in formula (1), the hydrocarbon group having 1 to 13 carbon atoms is an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, an alkenyl group having 2 to 13 carbon atoms, an alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, an aralkoxy group having 7 to 13 carbon atoms, an alkaryl group having 7 to 13 carbon atoms, or an alkaryloxy group having 7 to 13 carbon atoms; In A in formula (1), X may be, for example, an unsubstituted or halogen-substituted aliphatic group having 1 to 20 carbon atoms, an aliphatic group having 1 to 20 carbon atoms and containing an oxygen, nitrogen, or sulfur atom in the main chain, a cycloalkylene group having 3 to 6 carbon atoms, or an arylene group that can be derived from bisphenol A, resorcinol, hydroquinone, or diphenylphenol, and for example, X can be represented by any of the following formulas (Aa) to (Ah). [ka]

[0029] In one embodiment, the hydroxyphenyl-terminated polysiloxane of formula (1) may be a reaction product of a hydroxyphenyl-terminated siloxane of formula (1a) below with an acyl compound (i.e., a hydroxyphenyl-terminated siloxane having an ester bond): [ka] (In the formula, R5, R6, R7, m, and n are defined as in formula (1).) The hydroxy-terminated siloxane of formula (1a) can be produced, for example, by synthesizing a compound of formula (1b) below, which has a hydroxy group and a double bond, with a compound of formula (1c) below, which contains silicone, in a molar ratio of 2:1 using a platinum-based catalyst. [ka] (In the formula, R5 and m are defined as in the formula (1), and k represents an integer of 1 to 7.) [ka] (In the formula, R6 and n are defined as in formula (1) above.)

[0030] Specifically, the hydroxy-terminated siloxane of the formula (1a) is a siloxane monomer manufactured by Dow Corning. [ka] For a method for producing the hydroxy-terminated siloxane of formula (1a), reference may be made to U.S. Pat. No. 6,072,011.

[0031] The acyl compound used in producing the hydroxyphenyl-terminated polysiloxane of formula (1) may have, for example, an aromatic, aliphatic, or mixed structure containing both aromatic and aliphatic groups. If the acyl compound has an aromatic or mixed structure, it may have 6 to 30 carbon atoms, and if it is aliphatic, it may have 1 to 20 carbon atoms. The acyl compound may further contain a halogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom.

[0032] In another embodiment, the hydroxyphenyl-terminated polysiloxane of formula (1) may be a reaction product of the hydroxyphenyl-terminated siloxane of formula (1a) with a diisocyanate compound (i.e., a hydroxyphenyl-terminated siloxane having a urethane bond).

[0033] Here, the diisocyanate compound may be, for example, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, or 4,4'-methylenediphenyl diisocyanate.

[0034] The amount of the hydroxy-terminated polysiloxane in the diol component contained as a repeating unit in the polycarbonate copolymer of the present invention is 0.11 to 1.99 mol% relative to 100 mol% of the total diol components. If the amount of hydroxy-terminated polysiloxane in the diol component is less than 0.11 mol% relative to 100 mol% of the total diol components, the impact strength of the copolymer will be poor, and conversely, if it exceeds 1.99 mol%, synthesis of the copolymer may become difficult.

[0035] In one embodiment, the amount of hydroxy-terminated polysiloxane in the diol component may be, based on 100 mol% of the total diol component, 0.12 mol% or more, 0.13 mol% or more, 0.14 mol% or more, 0.15 mol% or more, 0.16 mol% or more, 0.17 mol% or more, 0.18 mol% or more, 0.19 mol% or more, or 0.2 mol% or more, and may be 1.9 mol% or less, 1.8 mol% or less, 1.7 mol% or less, 1.6 mol% or less, 1.5 mol% or less, 1.4 mol% or less, 1.3 mol% or less, 1.2 mol% or less, 1.1 mol% or less, or 1 mol% or less, but is not limited to these.

[0036] (d) any additional diol component In one embodiment, the diol component may further comprise (d) an additional diol selected from an aliphatic diol, an alicyclic diol other than anhydrosugar alcohol, or a mixture thereof.

[0037] 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, 1,5-hexanediol and 1,6-hexanediol), diethylene glycol, triethylene glycol, tetraethyl glycol, or a mixture thereof.

[0038] In one embodiment, the alicyclic diol other than the anhydrosugar alcohol 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, decalindimethanol (e.g., 2,6-decalindimethanol, 1,5-decalindimethanol, and 2,3-decalindimethanol, etc.), norbornanedimethanol (e.g., 2,3-norbornanedimethanol and 2,5-norbornanedimethanol, etc.), adamantanediol (e.g., 1,2-adamantanediol, 1,3-adamantanediol, and 1,4-adamantanediol, etc.), or a mixture thereof.

[0039] The (d) additional diol compound used in the present invention is not limited to the examples given above, and the additional diol compound may be used alone or in combination of two or more.

[0040] In one embodiment, the amount of the (d) additional diol in the diol component may be, relative to 100 mol% of the 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.

[0041] [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.

[0042] 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.

[0043] In one embodiment, the carbonic acid diester component may be selected from dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, or a combination thereof, and more preferably diphenyl carbonate.

[0044] In one embodiment, the carbonate diester component is represented by the following formula (2): [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 from each other.)

[0045] In one embodiment, the carbonate diester component represented by the formula (2) may be selected from diphenyl carbonate (DPC), 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.

[0046] When producing the polycarbonate copolymer of the present invention, the carbonate diester component can be used in a molar equivalent of 0.90 to 1.10, preferably 0.96 to 1.04, relative to the molar equivalent of all diol components. If the molar equivalent of the carbonate diester component relative to the molar equivalent of all diol components is less than 0.90, the number of terminal OH groups in the produced polycarbonate copolymer increases, resulting in a decrease in the thermal stability of the polycarbonate copolymer or in failure to obtain the desired molecular weight. Conversely, if the molar equivalent of the carbonate diester component exceeds 1.10, the transesterification reaction rate under the same conditions decreases, the desired molecular weight cannot be obtained, or the amount of residual carbonate diester in the produced polycarbonate copolymer increases. This residual carbonate diester can cause unpleasant odors during the molding process using the polycarbonate copolymer or in the molded product, which is undesirable.

[0047] In one embodiment, the polycarbonate copolymer of the present invention contains a polycarbonate block having the structure of the following formula (3) as a repeating unit. [ka] (In the formula, R8 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which is unsubstituted or substituted with an alkyl group (for example, an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 13 carbon atoms), a cycloalkyl group (for example, a cycloalkyl group having 3 to 20 carbon atoms, preferably a cycloalkyl group having 3 to 6 carbon atoms), an alkenyl group (for example, an alkenyl group having 2 to 20 carbon atoms, preferably an alkenyl group having 2 to 13 carbon atoms), an alkoxy group (for example, an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 13 carbon atoms), a halogen atom (for example, Cl or Br), or nitro. Here, the aromatic hydrocarbon group may be derived from a compound of the following formula (4), for example: [ka] (In the formula, X represents a linear, branched, or cyclic alkylene group containing no functional group; or a linear, branched, or cyclic alkylene group containing one or more functional groups selected from the group consisting of sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, or isobutylphenyl (for example, a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms), R9 and R 10 each independently represents a halogen atom (e.g., Cl or Br), or a linear, branched, or cyclic alkyl group (e.g., a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms), p and q each independently represent an integer of 0 to 4.

[0048] Specifically, the compound of the formula (4) includes, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4-hydroxyphenyl)-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)ethane, 1,10-bis(4-hydroxyphenyl)decane, 2-methyl-1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)nonane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane, 4-methyl 4,4'-dihydroxyphenyl ether [bis(4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, bis(3,5-dimethyl-4-hydroxyphenyl) ether ...4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, ether, bis(3,5-dichloro-4-hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p,p'-dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dichloro-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)decane, 1,4-bis(4-hydroxyphenyl)propane, 1,4-bis(4-hydroxyphenyl)butane, 1,4-bis(4-hydroxyphenyl)isobutane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3,5-dichloro-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,4 Examples of suitable hydroxybenzoates include, but are not limited to, bis(4-hydroxyphenyl)-2-methylbutane, 4,4'-thiodiphenol [bis(4-hydroxyphenyl)sulfone], bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, bis(3-chloro-4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(3-methyl-4-hydroxyphenyl)sulfide, bis(3,5-dimethyl-4-hydroxyphenyl)sulfide, bis(3,5-dibromo-4-hydroxyphenyl)sulfoxide, 4,4'-dihydroxybenzophenone, 3,3',5,5'-tetramethyl-4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. A representative example is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). For other functional dihydric phenols, see U.S. Pat. Nos. 2,999,835, 3,028,365, 3,153,008, and 3,334,154. The dihydric phenols may be used alone or in combination.

[0049] As other monomers for the polycarbonate blocks, for example, carbonate precursors such as carbonyl chloride (phosgene), carbonyl bromide, bishaloformates, diphenyl carbonate or dimethyl carbonate can be used.

[0050] 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) 79.8 to 96.9 mol % of an anhydrosugar alcohol, (b) 2.6 to 19.9 mol % of an aromatic diol, and (c) 0.11 to 1.99 mol % of a hydroxy-terminated polysiloxane.

[0051] 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, or a mixture thereof.

[0052] The types and amounts of the anhydrosugar alcohol, aromatic diol, hydroxy-terminated polysiloxane, additional diol and carbonate diester components that can be used in the method for producing the polycarbonate copolymer of the present invention are the same as those described above. In the method for producing a polycarbonate copolymer of the present invention, a transesterification catalyst can be used as the polymerization catalyst, and for example, an alkali metal salt compound, an alkaline earth metal salt compound, or a mixture thereof can be used.

[0053] In one embodiment, a polymerization catalyst selected from an alkali metal salt compound, an alkaline earth metal salt compound, or a mixture thereof can 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 as an auxiliary. However, it is preferable to use the polymerization catalyst alone without using the auxiliary basic compound.

[0054] In one embodiment, examples of the alkali metal salt compound used as the polymerization catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium stearate, 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 phenyl boron phenylate include lithium phenyl boron phenylate, cesium phenyl boron phenylate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium hydrogen phosphite, potassium hydrogen phosphite, dilithium hydrogen phosphite, dicesium hydrogen phosphite, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, alcoholates and phenolates of sodium, potassium, lithium and cesium, and the disodium salt, dipotassium salt, dilithium salt and dicesium salt of bisphenol A.

[0055] 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 hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, 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.

[0056] The above-mentioned alkali metal salt compounds and alkaline earth metal salt compounds may be used alone or in combination of two or more kinds.

[0057] 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.

[0058] In one embodiment, examples of basic phosphorus compounds include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, or quaternary phosphonium salts.

[0059] In one embodiment, examples of basic ammonium compounds include 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.

[0060] In one embodiment, examples of the amine-based 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, or aminoquinoline.

[0061] The basic compounds used in combination with the polymerization catalyst may be used alone or in combination of two or more.

[0062] By using the polycarbonate copolymer of the present invention, it is possible to obtain molded articles that are superior in environmental friendliness and have significantly improved mechanical properties (especially impact strength) compared to conventional anhydrosugar alcohol-containing polycarbonate copolymers.

[0063] Therefore, according to yet another aspect of the present invention, there is provided a molded article comprising the polycarbonate copolymer of the present invention.

[0064] The molded article can be produced by subjecting the polycarbonate copolymer of the present invention to known molding processes such as extrusion molding and injection molding.

[0065] 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.

[0066] Example <Production of Polysiloxane> Production Example 1: Production of linear polysiloxane Under a nitrogen atmosphere, 0.4 mol of monomer BY16-799 (Dow Corning) was dissolved in 300 mL of chloroform in a 500 mL three-neck flask equipped with a condenser, and 67 mL of triethylamine (TEA) catalyst was added. While the solution was refluxing, 0.2 mol of terephthaloyl chloride (TCL) dissolved in 1,000 mL of chloroform was slowly added over 1 hour, and the mixture was refluxed for 12 hours. The solvent was then removed from the reaction solution, and the product was dissolved in acetone, washed with hot distilled water, and dried in a vacuum oven for 24 hours to produce the hydroxy-terminated siloxane having an ester bond of formula (5) below. [ka]

[0067] <Production of polysiloxane-polycarbonate copolymer containing anhydrosugar alcohol> Example 1 A 250 mL four-neck reactor equipped with a nitrogen line, a by-product removal trap, a vacuum pump for pressure reduction, a stirrer capable of monitoring the stirring torque, a thermometer, and a heater was charged with 1770 mmol of isosorbide (ISB), 1867 mmol of diphenyl carbonate (DPC), 93 mmol of bisphenol A ethylene oxide 5-mol adduct (BPA-EO5), 3.73 mmol of the hydroxy-terminated siloxane of formula (5) (hereinafter referred to as "siloxane oligomer"), and 87 ppm of sodium carbonate. The temperature was raised to 120 °C under a nitrogen atmosphere, and the reactants were dissolved with stirring as needed. After dissolving the reactants, the reactor temperature was raised to 170 °C and the reaction was allowed to proceed for 1 hour. The pressure was then reduced from atmospheric pressure to 20 torr to remove a portion of the phenol by-product. The reactor temperature was then raised to 230 °C, the pressure was reduced to less than 1 torr, and the reaction was continued for another hour. The reaction was terminated when the stirring torque of the stirrer reached a predetermined stirring torque, to obtain a polycarbonate resin having the structure of the following formula (6). [ka]

[0068] Example 2 A polycarbonate resin was obtained in the same manner as in Example 1, except that 1768 mmol of isosorbide and 5.6 mmol of siloxane oligomer were used.

[0069] Example 3 A polycarbonate resin was obtained in the same manner as in Example 1, except that 1764 mmol of isosorbide and 9.34 mmol of siloxane oligomer were used.

[0070] Example 4 A polycarbonate resin was obtained in the same manner as in Example 1, except that 1675 mmol of isosorbide and 13.07 mmol of siloxane oligomer were used.

[0071] Example 5 A polycarbonate resin was obtained in the same manner as in Example 1, except that 1755 mmol of isosorbide and 18.67 mmol of siloxane oligomer were used.

[0072] Example 6 A 250 mL four-neck reactor equipped with a nitrogen line, a by-product removal trap, and a vacuum pump for pressure reduction, a stirrer capable of monitoring the stirring torque, a thermometer, and a heater, was charged with 1675 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 93.36 mmol of cyclohexanedimethanol (CHDM), 93.36 mmol of ethylene oxide 5-mol adduct of bisphenol A, 5.6 mmol of siloxane oligomer, and 87 ppm of sodium carbonate. The temperature was raised to 120 °C under a nitrogen atmosphere, and the reactants were dissolved with stirring as needed. After dissolving the reactants, the temperature of the reactor was raised to 170 °C and the reaction was allowed to proceed for 1 hour. The pressure was then reduced from atmospheric pressure to 20 torr to remove a portion of the phenol by-product. The reactor temperature was then raised to 230 °C, the pressure was reduced to 1 torr or less, and the reaction was continued for another hour. The reaction was terminated when the stirring torque of the stirrer reached the predetermined value, yielding a polycarbonate resin.

[0073] Example 7 A polycarbonate resin was obtained in the same manner as in Example 6, except that 1619 mmol of isosorbide, 149.38 mmol of an ethylene oxide 5-mol adduct of bisphenol A, and 5.60 mmol of a siloxane oligomer were used.

[0074] Example 8 A polycarbonate resin was obtained in the same manner as in Example 6, except that 1755 mmol of isosorbide, 46.68 mmol of cyclohexanedimethanol, 56 mmol of an ethylene oxide 5-mol adduct of bisphenol A, and 9.34 mmol of a siloxane oligomer were used.

[0075] Example 9 A polycarbonate resin was obtained in the same manner as in Example 1, except that 1712 mmol of isosorbide, 149.38 mmol of an ethylene oxide 5-mol adduct of bisphenol A, and 5.6 mmol of a siloxane oligomer were used.

[0076] Comparative Example 1 A 250 mL four-neck reactor equipped with a nitrogen line, a by-product removal trap, and a vacuum pump for pressure reduction, a stirrer capable of monitoring the stirring torque, a thermometer, and a heater, was charged with 1867 mmol of isosorbide, 1867 mmol of diphenyl carbonate, and 87 ppm of sodium carbonate. The temperature was raised to 120 °C under a nitrogen atmosphere, and the reactants were dissolved with stirring as needed. After dissolving the reactants, the temperature of the reactor was raised to 170 °C and the reaction was allowed to proceed for 1 hour. The pressure was then reduced from atmospheric pressure to 20 torr to remove a portion of the phenol by-product. The reactor was then heated to 230 °C, the pressure was reduced to 1 torr or less, and the reaction was continued for another hour. The reaction was terminated when the stirring torque of the stirrer reached the predetermined value, yielding a polycarbonate resin.

[0077] Comparative Example 2 A 250 mL four-neck reactor equipped with a nitrogen line, a by-product removal trap, and a vacuum pump for pressure reduction, a stirrer capable of monitoring the stirring torque, a thermometer, and a heater, was charged with 1861 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 5.6 mmol of siloxane oligomer, and 87 ppm of sodium carbonate. The temperature was raised to 120 °C under a nitrogen atmosphere, and the reactants were dissolved with stirring as needed. After dissolving the reactants, the temperature of the reactor was raised to 170 °C and the reaction was allowed to proceed for 1 hour. The pressure was then reduced from atmospheric pressure to 20 torr to partially remove the phenol by-product. The reactor was then heated to 230 °C, the pressure was reduced to 1 torr or less, and the reaction was continued for another hour. The reaction was terminated when the stirring torque of the stirrer reached the predetermined value, yielding a polycarbonate resin.

[0078] Comparative Example 3 A 250 mL four-neck reactor equipped with a nitrogen line, a by-product removal trap, a vacuum pump for pressure reduction, a stirrer capable of monitoring the stirring torque, a thermometer, and a heater was charged with 1811 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 46.68 mmol of the ethylene oxide 5-mol adduct of bisphenol A, 9.34 mmol of siloxane oligomer, and 87 ppm of sodium carbonate. The temperature was raised to 120 °C under a nitrogen atmosphere, and the reactants were dissolved with stirring as needed. After dissolving the reactants, the temperature of the reactor was raised to 170 °C and the reaction was allowed to proceed for 1 hour. The pressure was then reduced from atmospheric pressure to 20 torr to remove a portion of the phenol by-product. The reactor was then heated to 230 °C, the pressure was reduced to below 1 torr, and the reaction was continued for another hour. The reaction was then terminated when the stirring torque of the stirrer reached the predetermined value, yielding a polycarbonate resin.

[0079] Comparative Example 4 A 250 mL four-neck reactor equipped with a nitrogen line, a by-product removal trap, a vacuum pump for pressure reduction, a stirrer capable of monitoring the stirring torque, a thermometer, and a heater was charged with 1488 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 373 mmol of the 5-mol ethylene oxide adduct of bisphenol A, 5.6 mmol of siloxane oligomer, and 87 ppm of sodium carbonate. The temperature was raised to 120 °C under a nitrogen atmosphere, and the reactants were dissolved with stirring as needed. After dissolving the reactants, the reactor temperature was raised to 170 °C and the reaction was allowed to proceed for 1 hour. The pressure was then reduced from atmospheric pressure to 20 torr to remove a portion of the phenol by-product. The reactor temperature was then raised to 230 °C, the pressure was reduced to 1 torr or less, and the reaction was continued for another hour. The reaction was terminated when the stirring torque of the stirrer reached the predetermined value, yielding a polycarbonate resin.

[0080] Comparative Example 5 A 250 mL four-neck reactor equipped with a nitrogen line, a by-product removal trap, a vacuum pump for pressure reduction, a stirrer capable of monitoring the stirring torque, a thermometer, and a heater was charged with 1774 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 93 mmol of the ethylene oxide 5-mol adduct of bisphenol A, and 87 ppm of sodium carbonate. The temperature was raised to 120 °C under a nitrogen atmosphere, and the reactants were dissolved with stirring as needed. After dissolving the reactants, the temperature of the reactor was raised to 170 °C and the reaction was allowed to proceed for 1 hour. The pressure was then reduced from atmospheric pressure to 20 torr to remove a portion of the phenol by-product. The reactor was then heated to 230 °C, the pressure was reduced to 1 torr or less, and the reaction was continued for another hour. The reaction was terminated when the stirring torque of the stirrer reached the predetermined value, yielding a polycarbonate resin.

[0081] Comparative Example 6 A 250 mL four-neck reactor equipped with a nitrogen line, a by-product removal trap, a vacuum pump for pressure reduction, a stirrer capable of monitoring the stirring torque, a thermometer, and a heater was charged with 1772 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 93 mmol of the ethylene oxide 5-mol adduct of bisphenol A, 1.87 mmol of siloxane oligomer, and 87 ppm of sodium carbonate. The temperature was raised to 120 °C under a nitrogen atmosphere, and the reactants were dissolved with stirring as needed. After dissolving the reactants, the temperature of the reactor was raised to 170 °C and the reaction was allowed to proceed for 1 hour. The pressure was then reduced from atmospheric pressure to 20 torr to partially remove the phenol by-product. The reactor was then heated to 230 °C, the pressure was reduced to below 1 torr, and the reaction was continued for another hour. The reaction was terminated when the stirring torque of the stirrer reached the predetermined value, yielding a polycarbonate resin.

[0082] Comparative Example 7 A 250 mL four-neck reactor equipped with a nitrogen line, a by-product removal trap, a vacuum pump for pressure reduction, a stirrer capable of monitoring the stirring torque, a thermometer, and a heater was charged with 1867 mmol of bisphenol A, 1867 mmol of diphenyl carbonate, and 87 ppm of sodium carbonate. The temperature was raised to 120 °C under a nitrogen atmosphere, and the reactants were dissolved with stirring as needed. After dissolving the reactants, the temperature of the reactor was raised to 170 °C and the reaction was allowed to proceed for 1 hour. The pressure was then reduced from atmospheric pressure to 20 torr to partially remove the phenol by-product. The reactor was then heated to 230 °C, the pressure was reduced to less than 1 torr, and the reaction was continued for another hour. The reaction was terminated when the stirring torque of the stirrer reached the predetermined value, yielding a polycarbonate resin.

[0083] Comparative Example 8 A 250 mL four-neck reactor equipped with a nitrogen line, a by-product removal trap, a vacuum pump for pressure reduction, a stirrer capable of monitoring the stirring torque, a thermometer, and a heater was charged with 1768 mmol of bisphenol A, 1867 mmol of diphenyl carbonate, 5.6 mmol of siloxane oligomer, and 87 ppm of sodium carbonate. The temperature was raised to 120 °C under a nitrogen atmosphere, and the reactants were dissolved with stirring as needed. After dissolving the reactants, the temperature of the reactor was raised to 170 °C and the reaction was allowed to proceed for 1 hour. The pressure was then reduced from atmospheric pressure to 20 torr to partially remove the phenol by-product. The reactor was then heated to 230 °C, the pressure was reduced to below 1 torr, and the reaction was continued for another hour. The reaction was terminated when the stirring torque of the stirrer reached the predetermined value, yielding a polycarbonate resin.

[0084] Comparative Example 9 A 250 mL four-neck reactor equipped with a nitrogen line, a by-product removal trap, a vacuum pump for pressure reduction, a stirrer capable of monitoring the stirring torque, a thermometer, and a heater was charged with 1680 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 93.36 mmol of cyclohexanetimethanol, 93.36 mmol of the ethylene oxide 5-mol adduct of bisphenol A, and 87 ppm of sodium carbonate. The temperature was raised to 120 °C under a nitrogen atmosphere, and the reactants were dissolved with stirring as needed. After dissolving the reactants, the temperature of the reactor was raised to 170 °C and the reaction was allowed to proceed for 1 hour. The pressure was then reduced from atmospheric pressure to 20 torr to partially remove the phenol by-product. The reactor was then heated to 230 °C, the pressure was reduced to less than 1 torr, and the reaction was continued for another hour. The reaction was terminated when the stirring torque of the stirrer reached the predetermined value, yielding a polycarbonate resin.

[0085] Comparative Example 10 A 250 mL four-neck reactor equipped with a nitrogen pipe, a by-product removal trap, and a vacuum pump for pressure reduction, a stirrer capable of checking the stirring torque, a thermometer, and a heater, was charged with 1737 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 93.36 mmol of the ethylene oxide 5-mol adduct of bisphenol A, 37.35 mmol of siloxane oligomer, and 87 ppm of sodium carbonate, and the temperature was raised to 120°C under a nitrogen atmosphere, and the reactants were dissolved with stirring as necessary. After dissolving the reactants, the temperature of the reactor was raised to 170°C and the reaction was carried out, but the reaction did not proceed, and physical properties could not be measured.

[0086] <Physical property measurement> The specimens prepared using the polycarbonate resins prepared in Examples 1 to 9 and Comparative Examples 1 to 9 were measured for the following physical properties, and the results are shown in Tables 1 and 2 below.

[0087] Room temperature impact strength The room temperature impact strength was evaluated in accordance with STM D256 using notched specimens at room temperature of 23°C. The final test result was calculated as the average of the test results of 10 specimens.

[0088] Low temperature impact strength Low-temperature impact strength was evaluated in accordance with ASTM D256 using notched specimens at a temperature of -20°C. The final test result was calculated as the average of the test results of 10 specimens.

[0089] pencil hardness The pencil hardness of each specimen was measured at 23°C using a 553-M1 pencil hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). Specifically, the surface was scratched at a 45-degree angle, and the hardest pencil density code just before the surface ruptured and the scratch occurred was recorded as the pencil hardness value.

[0090] The hardness of pencils decreases in the following order: 9H (highest) - 8H - 7H - 6H - 5H - 4H - 3H - 2H - HF - HB - B - 2B - 3B - 4B - 5B - 6B - 7B - 8B - 9B (lowest).

[0091] Miscibility with BPA-PC A miscibility test was conducted with linear polycarbonate resin TRIREX 3022PJ (manufactured by SAMYANG CORPORATION) to test its compatibility with general PC. After extrusion molding at 240°C, if the surface was smooth and the color was uniform, it was judged to be miscible. If phase separation occurred on the surface and the color was uneven after extrusion molding, it was judged to be incompatible.

[0092] [Table 1] [Table 2]

[0093] As shown in Tables 1 and 2 above, the polycarbonate copolymers of Examples 1 to 9 according to the present invention had significantly improved impact strength compared to the resins of Comparative Examples 1 to 3, 5 to 7, and 9, improved surface hardness compared to the resins of Comparative Examples 4 and 8, and also had good miscibility with general PC.

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 % in total of the diol components, (a) 79.8 to 96.9 mol % of an anhydrosugar alcohol, (b) 2.6 to 19.9 mol % of an aromatic diol, and (c) 0.11 to 1.99 mol % of a hydroxy-terminated polysiloxane.

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

3. 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.

4. The hydroxy-terminated polysiloxane is represented by the following formula (1): 【Chemistry 1】 (In the formula, R 5 each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R 6 each independently represents a hydrocarbon group having 1 to 13 carbon atoms or a hydroxy group, R 7 each independently represents an alkylene group having 2 to 8 carbon atoms, A is X or NH-X-NH, where X represents a linear or branched aliphatic group having 1 to 20 carbon atoms; a cycloalkylene group having 3 to 20 carbon atoms; or a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms which is unsubstituted or substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a carboxyl group; m independently represents an integer of 0 to 4; and n independently represents an integer of 2 to 1,000.

5. 2. The polycarbonate copolymer of claim 1, wherein the diol component further comprises (d) an additional diol selected from an aliphatic diol, an alicyclic diol other than anhydrosugar alcohol, or a mixture thereof.

6. the aliphatic diol is selected from ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, diethylene glycol, triethylene glycol, tetraethyl glycol or mixtures thereof; 6. The polycarbonate copolymer according to claim 5, wherein the alicyclic diol other than the anhydrosugar alcohol is selected from cyclohexanedimethanol, 2-methyl-1,4-cyclohexanediol, decalindimethanol, norbornanedimethanol, adamantanediol, or a mixture thereof.

7. 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.

8. 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 comprises, relative to 100 mol% of the total of the diol components, (a) 79.8 to 96.9 mol% of an anhydrosugar alcohol, (b) 2.6 to 19.9 mol% of an aromatic diol, and (c) 0.11 to 1.99 mol% of a hydroxy-terminated polysiloxane.

9. A molded article comprising the polycarbonate copolymer according to any one of claims 1 to 7.

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