Polycarbonate copolymer comprising units derived from anhydrocarbon alcohol, aromatic glycol and hydroxy-terminated

Abstract

The present invention relates to a polycarbonate copolymer, a method for producing the same, and a molded article comprising the same, and more specifically, to: a polycarbonate copolymer having significantly improved mechanical properties (such as impact strength) compared to conventional polycarbonate copolymers; the present invention relates to a composition comprising repeating units derived from a diol component and a diester carbonate component, the diol component comprising an anhydrosugar alcohol, an aromatic diol, and a hydroxyl-terminated siloxane in a specific content ratio; a method for the production thereof; and a molded article comprising the polycarbonate copolymer.

Description

Technical Field

[0001] The present invention relates to a polycarbonate copolymer, a method for preparing the same, and a molded article comprising the copolymer. More specifically, the present invention relates to a polycarbonate copolymer comprising repeating units derived from a diol component and a carbonate diol component, wherein the diol component comprises a sugar alcohol, an aromatic diol, and a hydroxyl-terminated polysiloxane in a specific content ratio, and thus has significantly improved mechanical properties (such as impact strength) compared to conventional polycarbonate copolymers. The present invention also relates to a method for preparing the copolymer and a molded article comprising the copolymer. Background Art

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

[0003] Polycarbonate is usually prepared by polycondensation of phosgene and bisphenol A, a petroleum-based raw material. However, due to various reasons, such as the accelerating consumption of petroleum resources, the demand for reducing greenhouse gas emissions to address climate change, the rising prices of raw materials, and the increasing demand for recyclable raw materials, a method for partially or completely replacing the raw materials for preparing polycarbonate with environmentally friendly components is being sought.

[0004] Sugar alcohol is an environmentally friendly material derived from natural resources and can be produced by the dehydration reaction of hydrogenated sugars (such as hexitols) 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 usually have the chemical formula HOCH2(CHOH) n CH2OH, where n is an integer from 2 to 5. According to the number of carbon atoms, hydrogenated sugars are classified into butanediol, pentanediol, hexanediol, and heptanediol (4, 5, 6, and 7 carbon atoms, respectively). Among them, hexanediols with 6 carbon atoms include sorbitol, mannitol, iditol, galactitol, etc. In particular, sorbitol and mannitol are very useful materials. Therefore, sugar alcohol has attracted much attention due to its wide applicability, and its actual industrial application level is gradually increasing.

[0005] Techniques for preparing polycarbonate using sugar alcohol have been proposed. For example, Korean Patent Publication No. 10-2009-0018788 discloses a technique for preparing a polycarbonate copolymer using sugar alcohol isosorbide and a cyclic diol compound as the diol component. In addition, Korean Patent No. 10-1080669 discloses a technique for preparing a polycarbonate copolymer using isosorbide and a linear diol compound as the diol component.

[0006] However, despite the improved environmental friendliness, the polycarbonate copolymers prepared by the above prior art are actually difficult to be used in engineering plastic applications due to poor mechanical properties (especially impact strength).

[0007] Therefore, it is necessary to develop a technology that can use sugar alcohols as raw materials to improve environmental friendliness and improve mechanical properties such as impact strength compared with the prior art, and prepare a polycarbonate copolymer that can be actually used in engineering plastic applications. Summary of the Invention

[0008] Technical Problems to be Solved

[0009] The object of the present invention is to provide a polycarbonate copolymer which contains repeating units derived from sugar alcohols, thus having good environmental friendliness, and at the same time showing significantly improved mechanical properties such as impact strength compared with existing polycarbonate resins containing sugar alcohols, and to provide a method for preparing the copolymer and a molded article containing the copolymer.

[0010] Technical Solutions

[0011] To achieve the above object, the present invention provides a polycarbonate copolymer which comprises: repeating units derived from a diol component; and repeating units derived from a carbonate diester component; wherein, based on a total of 100 mol% of the diol component, the diol component comprises (a) 79.8 to 96.9 mol% of a sugar alcohol, (b) 2.6 to 19.9 mol% of an aromatic diol, and (c) 0.11 to 1.99 mol% of a hydroxyl-terminated polysiloxane.

[0012] According to another aspect, the present invention provides a method for preparing a polycarbonate copolymer, which comprises: reacting a mixture containing a diol component and a carbonate diester component in the presence of a polymerization catalyst, wherein based on a total of 100 mol% of the diol component, the diol component comprises (a) 79.8 to 96.9 mol% of a sugar alcohol, (b) 2.6 to 19.9 mol% of an aromatic diol, and (c) 0.11 to 1.99 mol% of a hydroxyl-terminated polysiloxane.

[0013] According to another aspect, the present invention provides a molded article containing the polycarbonate copolymer of the present invention.

[0014] Advantageous Effects

[0015] The polycarbonate copolymer according to the present invention has good environmental friendliness, and at the same time shows significantly improved mechanical properties (especially impact strength) compared with existing polycarbonate copolymers containing sugar alcohols. Detailed Description of the Invention

[0016] The present invention will be explained in more detail below.

[0017] The polycarbonate copolymer of the present invention comprises repeating units derived from a diol component which, based on a total of 100 mol% of the diol component, comprises (a) 79.8 to 96.9 mol% of a dehydrosugar alcohol, (b) 2.6 to 19.9 mol% of an aromatic diol and (c) 0.11 to 1.99 mol% of a hydroxyl-terminated polysiloxane; and repeating units derived from a carbonate diester component.

[0018] [Diol component]

[0019] (a) Dehydrosugar alcohol

[0020] In the present invention, the dehydrosugar alcohol may be a mono-dehydrosugar alcohol, a di-dehydrosugar alcohol or a mixture thereof, and may be obtained by a method for preparing a dehydrosugar alcohol by a dehydration reaction of a hydrogenated sugar. The hydrogenated sugar (also referred to as "sugar alcohol") refers to a compound obtained by adding hydrogen to the reducing end group in a sugar, and generally has the chemical formula HOCH2(CHOH) n CH2OH (where n is an integer from 2 to 5), and it is classified into butanediol, pentanediol, hexanediol and heptanediol (4, 5, 6 and 7 carbon atoms respectively) according to the number of carbon atoms. Among them, hexanediol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol and the like.

[0021] The mono-dehydrosugar alcohol is a dehydrosugar alcohol formed by removing one molecule of water from inside the hydrogenated sugar, and it has the form of a tetrahydric alcohol having four hydroxyl groups in the molecule. The kind of mono-dehydrosugar alcohol that can be used in the present invention is not particularly limited, and it may preferably be a mono-dehydrosugar alcohol, and more specifically, it may be 1,4-dehydrosorbitol, 3,6-dehydrosorbitol, 2,5-dehydrosorbitol, 1,5-dehydrosorbitol, 2,6-dehydrosorbitol or a mixture of two or more of the above.

[0022] The di-dehydrosugar alcohol is a dehydrosugar alcohol formed by removing two molecules of water from inside the hydrogenated sugar, and it has the form of a dihydric alcohol having two hydroxyl groups in the molecule, and can be produced by using a hexanediol derived from starch. Since the di-dehydrosugar alcohol is an environmentally friendly material extracted from recyclable natural resources, it has attracted much attention for a long time, and research on its production has been continuously carried out. Among these di-dehydrosugar alcohols, isosorbide currently produced from sorbitol has the widest industrial applicability. The kind of di-dehydrosugar alcohol that can be used in the present invention is not particularly limited, and it may preferably be a di-dehydrosugar alcohol, and more specifically, it may be 1,4:3,6-di-dehydrosorbitol. 1,4:3,6-di-dehydrosorbitol may be isosorbide (1,4:3,6-di-dehydrosorbitol), isomannide (1,4:3,6-di-dehydromannitol), isoidide (1,4:3,6-di-dehydroiditol) or a mixture of two or more of the above, and more preferably may be isosorbide.

[0023] In one embodiment, the polycarbonate copolymer of the present invention may include repeating units having the following structure:

[0024]

[0025] In the polycarbonate copolymer of the present invention, the content of the sugar alcohol in the diol component included as a repeating unit is 79.8 to 96.9 mol% based on the total 100 mol% of the diol component. Based on the total 100 mol% of the diol component, if the content of the sugar alcohol in the diol component is less than 79.8 mol%, the surface hardness of the copolymer deteriorates. On the contrary, if it is greater than 96.9 mol%, the impact strength of the copolymer deteriorates.

[0026] In one embodiment, based on the total 100 mol% of the diol component, the content of the sugar alcohol in the diol component may be 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 also be 96.5 mol% or less, 96 mol% or less, 95.5 mol% or less, or 95 mol% or less, but is not limited thereto.

[0027] (b) Aromatic diol

[0028] In the present invention, the aromatic diol refers to an aromatic compound having two hydroxyl groups.

[0029] In one embodiment, the aromatic diol may be one or more selected from the group consisting of bisphenol diol compounds, fluoro diol compounds, phenyl diol compounds, furan diol compounds, pyridine diol compounds, or combinations thereof.

[0030] In one embodiment, the aromatic diol can be selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane [hereinafter referred to as bisphenol A], an alkylene oxide adduct of bisphenol A (e.g., an adduct obtained by adding 1 to 25 moles of C2-C18 alkylene oxide 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-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 2,4'-dihydroxydiphenylmethane, 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)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-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-methylphenyl)fluorene, 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, but is not limited thereto.

[0031] More specifically, the aromatic diol can be 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, but is not limited thereto.

[0032] Based on 100 mol% of the total diol component, the content of the aromatic diol in the diol component included as a repeating unit in the polycarbonate copolymer of the present invention is 2.6 to 19.9 mol%. Based on 100 mol% of the total diol component, if the content of the aromatic diol in the diol component is less than 2.6 mol%, the impact strength of the copolymer deteriorates. On the contrary, if it is greater than 19.9 mol%, the surface hardness of the copolymer deteriorates.

[0033] In one embodiment, based on a total of 100 mol% of the diol component, the content of the aromatic diol in the diol component may be 2.7 mol% or more, 2.8 mol% or more, 2.9 mol% or more, or 3 mol% or more, and may also 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 thereto.

[0034] (c) hydroxy-terminated polysiloxane

[0035] In the present invention, the hydroxy-terminated polysiloxane is a polysiloxane compound having hydroxyl groups at both ends.

[0036] In one embodiment, the hydroxy-terminated polysiloxane may be a hydroxy-phenyl-terminated polysiloxane represented by the following Chemical Formula 1:

[0037] [Chemical Formula 1]

[0038]

[0039] In the above Chemical Formula 1,

[0040] R5 independently represents a hydrogen atom, a halogen atom, a hydroxyl 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;

[0041] R6 independently represents a hydrocarbon group having 1 to 13 carbon atoms or a hydroxyl group;

[0042] R7 independently represents an alkylene group having 2 to 8 carbon atoms;

[0043] A is X or NH-X-NH, where X represents a straight-chain 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 by a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a carboxyl group;

[0044] m independently represents an integer from 0 to 4; and

[0045] n independently represents an integer from 2 to 1000, preferably an integer from 2 to 500, more preferably an integer from 5 to 100.

[0046] More specifically,

[0047] For R5 in Chemical Formula 1, the halogen atom can be Cl or Br; the alkyl group can be an alkyl group having 1 to 13 carbon atoms, such as methyl, ethyl or propyl; the alkoxy group can be an alkoxy group having 1 to 13 carbon atoms, such as methoxy, ethoxy or propoxy; the aryl group can be an aryl group having 6 to 10 carbon atoms, such as phenyl, chlorophenyl or tolyl;

[0048] For R6 in Chemical Formula 1, the hydrocarbon group having 1 to 13 carbon atoms can be 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 aralkyloxy 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; and

[0049] In A of Chemical Formula 1, X can be, for example, an aliphatic group having 1 to 20 carbon atoms which is unsubstituted or substituted by a halogen atom; an aliphatic group having 1 to 20 carbon atoms and containing an oxygen, nitrogen or sulfur atom in the main chain; a sub-cycloalkyl group having 3 to 6 carbon atoms; or an arylene group derivable from bisphenol A, resorcinol, hydroquinone or diphenylphenol. For example, X can be represented by one of the following Chemical Formulas Aa to Ah:

[0050] [Chemical Formula Aa]

[0051]

[0052] [Chemical Formula Ab]

[0053]

[0054] [Chemical Formula Ac]

[0055]

[0056] [Chemical Formula Ad]

[0057]

[0058] [Chemical Formula Ae]

[0059]

[0060] [Chemical Formula Af]

[0061]

[0062] [Chemical Formula Ag]

[0063]

[0064] [Chemical Formula Ah]

[0065]

[0066] In one embodiment, the hydroxy phenyl - terminated polysiloxane of Chemical Formula 1 can be a reaction product of a hydroxy - terminated siloxane of the following Chemical Formula 1a and an acyl compound (i.e., a hydroxy - terminated polysiloxane having an ester bond):

[0067] [Chemical Formula 1a]

[0068]

[0069] In the above Chemical Formula 1a, R5, R6, R7, m, and n are the same as those defined in the above Chemical Formula 1.

[0070] The hydroxy - terminated siloxane of the above Chemical Formula 1a can be prepared, for example, by synthesizing a compound having a hydroxy group and a double bond of the following Chemical Formula 1b and a silicon - containing compound of the following Chemical Formula 1c in a molar ratio of 2:1 using a platinum - based catalyst:

[0071] [Chemical Formula 1b]

[0072]

[0073] In the above Chemical Formula 1b, R5 and m are the same as those defined in the above Chemical Formula 1, and k represents an integer from 1 to 7.

[0074] [Chemical Formula 1c]

[0075]

[0076] In the above Chemical Formula 1c, R6 and n are the same as those defined in the above Chemical Formula 1.

[0077] Specifically, as the hydroxy - terminated siloxane of the above Chemical Formula 1a, a siloxane monomer from Dow Corning can be used but is not limited thereto. In addition, for the preparation of the hydroxy - terminated siloxane of the above Chemical Formula 1a, reference can be made to U.S. Patent No. US 6,072,011.

[0078] The acyl compound used to prepare the hydroxy phenyl - terminated polysiloxane of Chemical Formula 1 can have, for example, an aromatic structure, an aliphatic structure, or a mixed - form structure containing both an aromatic structure and an aliphatic structure. If the acyl compound is aromatic or of the mixed form, it can have 6 to 30 carbon atoms, and if it is of the aliphatic form, it can have 1 to 20 carbon atoms. In addition, the acyl compound can also contain halogen, oxygen, nitrogen, or sulfur atoms.

[0079] In another embodiment, the hydroxy phenyl-terminated polysiloxane of Chemical Formula 1 may be a reaction product of the above-mentioned hydroxy-terminated siloxane of Chemical Formula 1a and a diisocyanate compound (i.e., a hydroxy-terminated polysiloxane having a urethane bond).

[0080] The diisocyanate compound described above may be, for example, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, or 4,4'-methylenediphenyl diisocyanate.

[0081] Based on a total of 100 mol% of the diol component, the content of the hydroxy-terminated polysiloxane in the diol component included as a repeating unit in the polycarbonate copolymer of the present invention is 0.11 to 1.99 mol%. Based on a total of 100 mol% of the diol component, if the content of the hydroxy-terminated polysiloxane in the diol component is less than 0.11 mol%, the impact strength of the copolymer deteriorates. On the contrary, if it is greater than 1.99 mol%, copolymer synthesis may become difficult.

[0082] In one embodiment, based on a total of 100 mol% of the diol component, the content of the hydroxy-terminated polysiloxane in the diol component may be 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 it may also 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 thereto.

[0083] (d) Optional other diols

[0084] In one embodiment, the diol component may further include (d) other diols selected from aliphatic diols, alicyclic diols other than anhydro sugar alcohols, or mixtures thereof.

[0085] In one embodiment, the aliphatic diol may be selected from ethylene glycol, propylene glycol (such as 1,2-propylene glycol and 1,3-propylene glycol, etc.), butylene glycol (such as 1,2-butylene glycol, 1,3-butylene glycol, and 1,4-butylene glycol, etc.), pentylene glycol (such as 1,2-pentylene glycol, 1,3-pentylene glycol, 1,4-pentylene glycol, and 1,5-pentylene glycol, etc.), hexylene glycol (such as 1,2-hexylene glycol, 1,3-hexylene glycol, 1,4-hexylene glycol, 1,5-hexylene glycol, and 1,6-hexylene glycol, etc.), diethylene glycol, triethylene glycol, tetraethylene glycol, or mixtures thereof, but is not limited thereto.

[0086] In one embodiment, the alicyclic diol other than the dehydrosorbitol may be selected from cyclohexanedimethanol (e.g., 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, etc.), 2-methyl-1,4-cyclohexanediol, decahydronaphthalenedimethanol (e.g., 2,6-decahydronaphthalenedimethanol, 1,5-decahydronaphthalenedimethanol, 2,3-decahydronaphthalenedimethanol, etc.), norbornanedimethanol (e.g., 2,3-norbornanedimethanol, 2,5-norbornanedimethanol, etc.), adamantanediol (e.g., 1,2-adamantanediol, 1,3-adamantanediol, 1,4-adamantanediol, etc.) or a mixture thereof, but is not limited thereto.

[0087] The (d) other diol compounds used in the present invention are not limited to the above examples, and the other diol compounds may be used alone or as a mixture of two or more of them.

[0088] In one embodiment, based on a total of 100 mol% of the diol component, the content of the (d) other diol in the diol component may be 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 also be 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, but is not limited thereto.

[0089] [Carbonate ester component]

[0090] In the present invention, as long as the effects of the present invention are not lost, the type of the carbonate ester component is not particularly limited. For example, it may be selected from dialkyl carbonates, diaryl carbonates, alkylene carbonates or a combination thereof.

[0091] In one embodiment, examples of the dialkyl carbonate may include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl n-butyl carbonate, ethyl isobutyl carbonate, etc.; examples of the diaryl carbonate may include diphenyl carbonate, dimethylphenyl carbonate, bis(chlorophenyl) carbonate, di(m-tolyl) carbonate, etc.; examples of the alkylene carbonate may 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, neopentylene carbonate, etc.

[0092] 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, it may be diphenyl carbonate.

[0093] In one embodiment, the carbonate diester component may be selected from compounds represented by the following Chemical Formula 2:

[0094] [Chemical Formula 2]

[0095]

[0096] In Chemical Formula 2 above, 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 as or different from each other.

[0097] In one embodiment, the carbonate diester component represented by Chemical Formula 2 above may be selected from diphenyl carbonate (DPC), dimethylphenyl carbonate, dichlorophenyl carbonate, dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate or a mixture thereof, and preferably diphenyl carbonate or dimethyl carbonate may be used.

[0098] When preparing the polycarbonate copolymer of the present invention, based on 1 molar equivalent of the total diol component, the molar equivalent of the carbonate diester component may be 0.90 to 1.10, preferably 0.96 to 1.04. Based on 1 molar equivalent of the total diol component, if the molar equivalent of the carbonate diester component is less than 0.90, the OH groups at the ends of the prepared polycarbonate copolymer increase, so the thermal stability of the polycarbonate copolymer deteriorates or the desired high molecular weight cannot be obtained. On the contrary, if the molar equivalent of the carbonate diester component is greater than 1.10, the rate of the transesterification reaction decreases or the desired high molecular weight cannot be obtained under the same conditions, and the content of the residual carbonate diester in the prepared polycarbonate copolymer also increases. This residual carbonate diester produces an unpleasant odor during the molding process of using the polycarbonate copolymer, or causes an unpleasant odor in the molded product - which is not desirable.

[0099] In one embodiment, the polycarbonate copolymer of the present invention contains a polycarbonate block having the structure of the following Chemical Formula 3 as a repeating unit:

[0100] [Chemical Formula 3]

[0101]

[0102] In Chemical Formula 3 above,

[0103] R8 represents an aryl hydrocarbon group having 6 to 30 carbon atoms, which group is unsubstituted or substituted by the following groups: alkyl (e.g., alkyl having 1 to 20 carbon atoms, preferably alkyl having 1 to 13 carbon atoms), cycloalkyl (e.g., cycloalkyl having 3 to 20 carbon atoms, preferably cycloalkyl having 3 to 6 carbon atoms), alkenyl (e.g., alkenyl having 2 to 20 carbon atoms, preferably alkenyl having 2 to 13 carbon atoms), alkoxy (e.g., alkoxy having 1 to 20 carbon atoms, preferably alkoxy having 1 to 13 carbon atoms), halogen atom (e.g., Cl or Br) or nitro, wherein the aryl hydrocarbon group may be derived from a compound of the following Chemical Formula 4:

[0104] [Chemical Formula 4]

[0105]

[0106] In the above Chemical Formula 4,

[0107] X represents a straight-chain, branched-chain or cyclic alkylene group without functional groups; or a straight-chain, branched-chain or cyclic alkylene group containing one or more functional groups selected from thioether, ether, sulfoxide, sulfone, ketone, naphthyl or isobutylphenyl (e.g., straight-chain alkylene having 1 to 10 carbon atoms, branched-chain alkylene having 3 to 10 carbon atoms or cyclic alkylene having 3 to 10 carbon atoms),

[0108] R9 and R 10 each independently represents a halogen atom (e.g., Cl or Br) or a straight-chain, branched-chain or cyclic alkyl group (e.g., straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms or cyclic alkyl having 3 to 10 carbon atoms), and

[0109] p and q each independently represent an integer from 0 to 4.

[0110] Specifically, the compound of the above chemical formula 4 can be, 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, 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-2,2-bis(4-hydroxyphenyl)pentane, 4,4-bis(4-hydroxyphenyl)heptane, diphenyl-bis(4-hydroxyphenyl)methane, resorcinol, hydroquinone, 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, bis(3,5-dichloro-4-hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-toluene, 4,4'-dihydroxybiphenol [p,p'-dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxybenzene, 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-bis(4-hydroxyphenyl)-2-methyl-butane, 4,4'-thiobiphenol [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'-dihydroxybiphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene or 2,6-dihydroxynaphthalene, but not limited thereto. Among them, representative is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). For other functional dihydroxyphenols, reference can be made to U.S. Patent Nos. 2,999,835, 3,028,365, 3,153,008 and 3,334,154. The above dihydroxyphenols can be used alone or in combination of two or more of them.,

[0111] As another monomer for the polycarbonate block, a carbonate precursor such as carbonyl chloride (phosgene), carbonyl bromide, bishaloformate, diphenyl carbonate or dimethyl carbonate can be used.

[0112] The present invention also provides a method for preparing a polycarbonate copolymer, which includes: reacting a mixture containing a diol component and a carbonate diester component in the presence of a polymerization catalyst, wherein based on a total of 100 mol% of the diol component, the diol component contains (a) 79.8 to 96.9 mol% of a dehydrated sugar alcohol, (b) 2.6 to 19.9 mol% of an aromatic diol and (c) 0.11 to 1.99 mol% of a hydroxyl-terminated polysiloxane.

[0113] In one embodiment, the diol component used in the method for preparing the polycarbonate copolymer may further contain (d) other diols selected from aliphatic diols, alicyclic diols other than dehydrated sugar alcohols or mixtures thereof.

[0114] The types and amounts of the dehydrated sugar alcohol, aromatic diol, hydroxyl-terminated polysiloxane, other diols and carbonate diester component that can be used in the method for preparing the polycarbonate copolymer of the present invention are the same as those described above.

[0115] In the method for preparing the 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.

[0116] In one embodiment, together with a polymerization catalyst selected from an alkali metal salt compound, an alkaline earth metal salt compound or a mixture thereof, a basic compound selected from a basic boron compound, a basic phosphorus compound, a basic ammonium compound, an amino compound or a mixture thereof can also be used as an auxiliary, but it is preferred to use the polymerization catalyst alone without using a basic compound as an auxiliary.

[0117] In one embodiment, the alkali metal salt compound used as a polymerization catalyst may be, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, 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 phenylborate, potassium phenylborate, lithium phenylborate, cesium phenylborate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium hydrogen phosphite, dipotassium hydrogen phosphite, dilithium hydrogen phosphite, dicesium hydrogen phosphite, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, alcoholates or phenolates of sodium, potassium, lithium or cesium, disodium salt, dipotassium salt, dilithium salt or dicesium salt of bisphenol A, etc.

[0118] In one embodiment, the alkaline earth metal salt compound used as a polymerization catalyst may be, for example, 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 or strontium stearate, etc.

[0119] The above alkali metal salt compounds and alkaline earth metal salt compounds can be used alone or in combination of two or more of them.

[0120] In one embodiment, the basic boron compound used in combination with the above polymerization catalyst may be, for example, sodium salts, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts or strontium salts of tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron and butyltriphenylboron, etc.

[0121] In one embodiment, the basic phosphorus compound may be, for example, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine or quaternary phosphonium salts, etc.

[0122] In one embodiment, the alkaline ammonium compound can 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, etc.

[0123] In one embodiment, the amino compound can be, for example, 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, etc.

[0124] The above-mentioned basic compounds used in combination with the polymerization catalyst can be used alone or in combination of two or more of them.

[0125] By using the polycarbonate copolymer of the present invention, a molded article having good environmental friendliness and showing significantly improved mechanical properties (especially impact strength) compared with the existing polycarbonate copolymer containing dehydrosorbitol can be obtained.

[0126] Therefore, according to another aspect of the present invention, there is provided a molded article comprising the polycarbonate copolymer of the present invention.

[0127] The molded article can be manufactured by processing the polycarbonate copolymer of the present invention with known extrusion, injection, or other molding methods.

[0128] The present invention will be explained in more detail by the following examples and comparative examples. However, the scope of the present invention is not limited in any way.

[0129] Examples

[0130] Preparation of polysiloxane

[0131] Preparation Example 1: Preparation of linear polysiloxane

[0132] In a 500 mL three-necked flask equipped with a condenser, under a nitrogen atmosphere, 0.4 mol of monomer BY16-799 (Dow Corning) was dissolved in 300 mL of chloroform, and then 67 mL of triethylamine (TEA) catalyst was added. While the solution was refluxing, 0.2 mol of terephthaloyl chloride (TCL) dissolved in 1000 mL of chloroform was slowly added over 1 hour, and the mixture was refluxed for 12 hours. Then, the solvent of the reaction solution was removed, the product was dissolved in acetone, washed with hot distilled water, and dried in a vacuum oven for 24 hours to prepare a hydroxyl-terminated siloxane with an ester bond of the following Chemical Formula 5.

[0133] [Chemical Formula 5]

[0134]

[0135] <Preparation of a Polysiloxane-Polycarbonate Copolymer Containing Anhydrosugar Alcohol>

[0136] Example 1

[0137] 1770 mmol of isosorbide (ISB), 1867 mmol of diphenyl carbonate (DPC), 93 mmol of the 5-mole ethylene oxide adduct of bisphenol A (BPA-EO5), 3.73 mmol of the hydroxyl-terminated siloxane of the above Chemical Formula 5 (hereinafter referred to as "siloxane oligomer"), and 87 ppm of sodium carbonate were added to a 250 mL four-necked reactor, which was connected to a nitrogen pipeline and a vacuum pump for decompression equipped with a trap for removing by-products, and was equipped with a stirrer, a thermometer, and a heater capable of confirming the stirring torque. Then, the temperature was raised to 120 °C under a nitrogen atmosphere, and the reaction raw materials were dissolved by stirring if necessary. After the reaction raw materials were dissolved, the temperature of the reactor was raised to 170 °C and reacted for 1 hour, and then the pressure was reduced from atmospheric pressure to 20 Torr to remove some by-product phenol. Then, the temperature of the reactor was raised to 230 °C, the pressure was reduced to below 1 Torr, and the reaction was further carried out for 1 hour. After the stirring torque of the stirrer reached a predetermined stirring torque, the reaction was terminated to obtain a polycarbonate resin having the structure of the following Chemical Formula 6.

[0138] [ISB]

[0139]

[0140] [DPC]

[0141]

[0142] [BPA-EO5]

[0143] (a + b = 5)

[0144] [Chemical Formula 6]

[0145]

[0146] (n = 27; a + b = 5)

[0147] Example 2

[0148] A polycarbonate resin was obtained in the same manner as in Example 1, except that 1768 mmol of isosorbide and 5.6 mmol of the above-mentioned silicone oligomer were used.

[0149] Example 3

[0150] A polycarbonate resin was obtained in the same manner as in Example 1, except that 1764 mmol of isosorbide and 9.34 mmol of the above-mentioned silicone oligomer were used.

[0151] Example 4

[0152] A polycarbonate resin was obtained in the same manner as in Example 1, except that 1675 mmol of isosorbide and 13.07 mmol of the above-mentioned silicone oligomer were used.

[0153] Example 5

[0154] A polycarbonate resin was obtained in the same manner as in Example 1, except that 1755 mmol of isosorbide and 18.67 mmol of the above-mentioned silicone oligomer were used.

[0155] Example 6

[0156] 1675 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 93.36 mmol of cyclohexanedimethanol (CHDM), 93.36 mmol of a 5-mole ethylene oxide adduct of bisphenol A, 5.6 mmol of the above-mentioned silicone oligomer, and 87 ppm of sodium carbonate were added to a 250 mL four-necked reactor, which was connected to a nitrogen gas pipeline and a vacuum pump for decompression equipped with a trap for removing by-products, and was equipped with a stirrer, a thermometer, and a heater capable of confirming the stirring torque. Then, the temperature was raised to 120 °C under a nitrogen atmosphere, and the reaction raw materials were dissolved by stirring if necessary. After the reaction raw materials were dissolved, the temperature of the reactor was raised to 170 °C and reacted for 1 hour, then the pressure was reduced from atmospheric pressure to 20 Torr to remove some by-product phenol. Then, the temperature of the reactor was raised to 230 °C, the pressure was reduced to below 1 Torr, and the reaction was further carried out for 1 hour. The reaction was terminated after the stirring torque of the stirrer reached a predetermined stirring torque to obtain a polycarbonate resin.

[0157] Example 7

[0158] A polycarbonate resin was obtained in the same manner as in Example 6, except that 1619 mmol of isosorbide, 149.38 mmol of a 5-molar ethylene oxide adduct of bisphenol A, and 5.60 mmol of the above-mentioned silicone oligomer were used.

[0159] Example 8

[0160] 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 a 5-molar ethylene oxide adduct of bisphenol A, and 9.34 mmol of the above-mentioned silicone oligomer were used.

[0161] Example 9

[0162] A polycarbonate resin was obtained in the same manner as in Example 1, except that 1712 mmol of isosorbide, 149.38 mmol of a 5-molar ethylene oxide adduct of bisphenol A, and 5.6 mmol of the above-mentioned silicone oligomer were used.

[0163] Comparative Example 1

[0164] 1867 mmol of isosorbide, 1867 mmol of diphenyl carbonate, and 87 ppm of sodium carbonate were added to a 250 mL four-necked reactor, which was connected to a nitrogen gas pipeline and a vacuum pump for pressure reduction equipped with a trap for removing by-products, and was equipped with a stirrer, a thermometer, and a heater capable of confirming the stirring torque. Then, the temperature was raised to 120 °C under a nitrogen atmosphere, and the reaction raw materials were dissolved by stirring if necessary. After the reaction raw materials were dissolved, the temperature of the reactor was raised to 170 °C and reacted for 1 hour, then the pressure was reduced from atmospheric pressure to 20 Torr to remove some by-product phenol. Then, the temperature of the reactor was raised to 230 °C, the pressure was reduced to below 1 Torr, and the reaction was further continued for 1 hour. After the stirring torque of the stirrer reached a predetermined stirring torque, the reaction was terminated to obtain a polycarbonate resin.

[0165] Comparative Example 2

[0166] 1861 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 5.6 mmol of the above-mentioned silicone oligomer, and 87 ppm of sodium carbonate were added to a 250 mL four-necked reactor, which was connected to a nitrogen pipeline and a vacuum pump for decompression equipped with a trap for removing by-products, and was equipped with a stirrer, a thermometer, and a heater capable of confirming the stirring torque. Then, the temperature was raised to 120 °C under a nitrogen atmosphere, and the reaction raw materials were dissolved by stirring if necessary. After the reaction raw materials were dissolved, the temperature of the reactor was raised to 170 °C and reacted for 1 hour, and then the pressure was reduced from atmospheric pressure to 20 Torr to remove some by-product phenol. Then, the temperature of the reactor was raised to 230 °C, and the pressure was reduced to below 1 Torr, and the reaction was further continued for 1 hour. After the stirring torque of the stirrer reached a predetermined stirring torque, the reaction was terminated to obtain a polycarbonate resin.

[0167] Comparative Example 3

[0168] 1811 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 46.68 mmol of a 5-mole ethylene oxide adduct of bisphenol A, 9.34 mmol of the above-mentioned silicone oligomer, and 87 ppm of sodium carbonate were added to a 250 mL four-necked reactor, which was connected to a nitrogen pipeline and a vacuum pump for decompression equipped with a trap for removing by-products, and was equipped with a stirrer, a thermometer, and a heater capable of confirming the stirring torque. Then, the temperature was raised to 120 °C under a nitrogen atmosphere, and the reaction raw materials were dissolved by stirring if necessary. After the reaction raw materials were dissolved, the temperature of the reactor was raised to 170 °C and reacted for 1 hour, and then the pressure was reduced from atmospheric pressure to 20 Torr to remove some by-product phenol. Then, the temperature of the reactor was raised to 230 °C, and the pressure was reduced to below 1 Torr, and the reaction was further continued for 1 hour. After the stirring torque of the stirrer reached a predetermined stirring torque, the reaction was terminated to obtain a polycarbonate resin.

[0169] Comparative Example 4

[0170] 1488 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 373 mmol of 5-mole ethylene oxide adduct of bisphenol A, 5.6 mmol of the above-mentioned silicone oligomer, and 87 ppm of sodium carbonate were added to a 250 mL four-necked reactor, which was connected to a nitrogen pipeline and a vacuum pump for decompression equipped with a trap for removing by-products, and was equipped with a stirrer, a thermometer, and a heater capable of confirming the stirring torque. Then, the temperature was raised to 120 °C under a nitrogen atmosphere, and the reaction raw materials were dissolved by stirring if necessary. After the reaction raw materials were dissolved, the temperature of the reactor was raised to 170 °C and reacted for 1 hour, and then the pressure was reduced from atmospheric pressure to 20 Torr to remove some by-product phenol. Then, the temperature of the reactor was raised to 230 °C, and the pressure was reduced to below 1 Torr, and further reacted for 1 hour. After the stirring torque of the stirrer reached a predetermined stirring torque, the reaction was terminated to obtain a polycarbonate resin.

[0171] Comparative Example 5

[0172] 1774 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 93 mmol of 5-mole ethylene oxide adduct of bisphenol A, and 87 ppm of sodium carbonate were added to a 250 mL four-necked reactor, which was connected to a nitrogen pipeline and a vacuum pump for decompression equipped with a trap for removing by-products, and was equipped with a stirrer, a thermometer, and a heater capable of confirming the stirring torque. Then, the temperature was raised to 120 °C under a nitrogen atmosphere, and the reaction raw materials were dissolved by stirring if necessary. After the reaction raw materials were dissolved, the temperature of the reactor was raised to 170 °C and reacted for 1 hour, and then the pressure was reduced from atmospheric pressure to 20 Torr to remove some by-product phenol. Then, the temperature of the reactor was raised to 230 °C, and the pressure was reduced to below 1 Torr, and further reacted for 1 hour. After the stirring torque of the stirrer reached a predetermined stirring torque, the reaction was terminated to obtain a polycarbonate resin.

[0173] Comparative Example 6

[0174] 1772 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 93 mmol of the 5-mole ethylene oxide adduct of bisphenol A, 1.87 mmol of the above-mentioned silicone oligomer, and 87 ppm of sodium carbonate were added to a 250 mL four-necked reactor. The reactor was connected to a nitrogen gas pipeline and a vacuum pump for decompression equipped with a trap for removing by-products, and was equipped with a stirrer, a thermometer, and a heater capable of confirming the stirring torque. Then, the temperature was raised to 120 °C under a nitrogen atmosphere, and the reaction raw materials were dissolved by stirring if necessary. After the reaction raw materials were dissolved, the temperature of the reactor was raised to 170 °C and reacted for 1 hour, and then the pressure was reduced from atmospheric pressure to 20 Torr to remove some by-product phenol. Then, the temperature of the reactor was raised to 230 °C, the pressure was reduced to below 1 Torr, and the reaction was further continued for 1 hour. After the stirring torque of the stirrer reached a predetermined stirring torque, the reaction was terminated to obtain a polycarbonate resin.

[0175] Comparative Example 7

[0176] 1867 mmol of bisphenol A, 1867 mmol of diphenyl carbonate, and 87 ppm of sodium carbonate were added to a 250 mL four-necked reactor. The reactor was connected to a nitrogen gas pipeline and a vacuum pump for decompression equipped with a trap for removing by-products, and was equipped with a stirrer, a thermometer, and a heater capable of confirming the stirring torque. Then, the temperature was raised to 120 °C under a nitrogen atmosphere, and the reaction raw materials were dissolved by stirring if necessary. After the reaction raw materials were dissolved, the temperature of the reactor was raised to 170 °C and reacted for 1 hour, and then the pressure was reduced from atmospheric pressure to 20 Torr to remove some by-product phenol. Then, the temperature of the reactor was raised to 230 °C, and the pressure was reduced to below 1 Torr, and the reaction was further continued for 1 hour. After the stirring torque of the stirrer reached a predetermined stirring torque, the reaction was terminated to obtain a polycarbonate resin.

[0177] Comparative Example 8

[0178] 1768 mmol of bisphenol A, 1867 mmol of diphenyl carbonate, 5.6 mmol of the above-mentioned silicone oligomer, and 87 ppm of sodium carbonate were added to a 250 mL four-necked reactor. The reactor was connected to a nitrogen gas pipeline and a vacuum pump for decompression equipped with a trap for removing by-products, and was equipped with a stirrer, a thermometer, and a heater capable of confirming the stirring torque. Then, the temperature was raised to 120 °C under a nitrogen atmosphere, and the reaction raw materials were dissolved by stirring if necessary. After the reaction raw materials were dissolved, the temperature of the reactor was raised to 170 °C and reacted for 1 hour, and then the pressure was reduced from atmospheric pressure to 20 Torr to remove some by-product phenol. Then, the temperature of the reactor was raised to 230 °C, the pressure was reduced to below 1 Torr, and the reaction was further continued for 1 hour. After the stirring torque of the stirrer reached a predetermined stirring torque, the reaction was terminated to obtain a polycarbonate resin.

[0179] Comparative Example 9

[0180] 1680 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 93.36 mmol of cyclohexanedimethanol, 93.36 mmol of the 5-mole ethylene oxide adduct of bisphenol A, and 87 ppm of sodium carbonate were added to a 250 mL four-necked reactor, which was connected to a nitrogen gas pipeline and a vacuum pump for decompression equipped with a trap for removing by-products, and was equipped with a stirrer, a thermometer, and a heater capable of confirming the stirring torque. Then, the temperature was raised to 120 °C under a nitrogen atmosphere, and the reaction raw materials were dissolved by stirring if necessary. After the reaction raw materials were dissolved, the temperature of the reactor was raised to 170 °C and reacted for 1 hour, and then the pressure was reduced from atmospheric pressure to 20 Torr to remove some by-product phenol. Then, the temperature of the reactor was raised to 230 °C, the pressure was reduced to below 1 Torr, and the reaction was further continued for 1 hour. After the stirring torque of the stirrer reached a predetermined stirring torque, the reaction was terminated to obtain a polycarbonate resin.

[0181] Comparative Example 10

[0182] 1737 mmol of isosorbide, 1867 mmol of diphenyl carbonate, 93.36 mmol of the 5-mole ethylene oxide adduct of bisphenol A, 37.35 mmol of the above-mentioned silicone oligomer, and 87 ppm of sodium carbonate were added to a 250 mL four-necked reactor, which was connected to a nitrogen gas pipeline and a vacuum pump for decompression equipped with a trap for removing by-products, and was equipped with a stirrer, a thermometer, and a heater capable of confirming the stirring torque. Then, the temperature was raised to 120 °C under a nitrogen atmosphere, and the reaction raw materials were dissolved by stirring if necessary. After the reaction raw materials were dissolved, the temperature of the reactor was raised to 170 °C for reaction, but it was not conducive to the reaction, so the performance could not be measured.

[0183] <Performance Measurement>

[0184] For each sample prepared from each polycarbonate resin prepared in Examples 1 to 9 and Comparative Examples 1 to 9, the following properties were measured, and the results are shown in Table 1 and Table 2 below, respectively.

[0185] Room temperature impact strength

[0186] According to ASTM D256, at room temperature conditions of 23 °C, the room temperature impact strength of the notched samples was evaluated. The final test result was calculated as the average of the test results of 10 samples.

[0187] Low temperature impact strength

[0188] At a temperature condition of -20 °C, the low temperature impact strength of the notched samples was evaluated according to ASTM D256. The final test result was calculated as the average of the test results of 10 samples.

[0189] Pencil Hardness

[0190] At 23 °C, the pencil hardness of each sample was measured using a 553-M1 pencil hardness tester (YASUDA SEIKI). Specifically, the surface was scratched at a 45-degree angle, and the hardest pencil concentration code before surface cracking and scratch generation was expressed as the pencil hardness value.

[0191] The pencil hardness decreases in the order of 9H (highest) - 8H - 7H - 6H - 5H - 4H - 3H - 2H - H - F - HB - B - 2B - 3B - 4B - 5B - 6B - 7B - 8B - 9B (lowest).

[0192] Miscibility with BPA-PC

[0193] It was blended with the linear polycarbonate resin TRIREX 3022PJ (Samyang Corporation) to test the miscibility with ordinary PC. After extrusion at 240 °C, if the surface was smooth and the color was uniform, it was judged to be miscible, while if phase separation occurred on the surface and the color was uneven after extrusion, it was indicated as immiscible.

[0194] [Table 1]

[0195] (D)*: Ductility

[0196]

[0197]

[0198] [Table 2]

[0199] (D)*: Ductility

[0200] (B)*: Brittleness

[0201] As shown in Table 1 and Table 2, the polycarbonate copolymers of Examples 1 to 9 showed significantly improved impact strength compared to the resins of Comparative Examples 1 to 3, Comparative Examples 5 to 7, and Comparative Example 9, improved surface hardness compared to the resins of Comparative Examples 4 and 8, and they also had good miscibility with ordinary PC.

Claims

1. A polycarbonate copolymer, comprising: Repeating units derived from a diol component; And Repeating units derived from a carbonate diester component; Wherein, based on the total 100 mol% of the diol component, the diol component comprises (a) 79.8 to 96.9 mol% of an anhydro sugar alcohol, (b) 2.6 to 19.9 mol% of an aromatic diol, and (c) 0.11 to 1.99 mol% of a hydroxyl-terminated polysiloxane.

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

3. The polycarbonate copolymer according to claim 1, wherein the aromatic diol is one or more selected from the group consisting of bisphenol diol compounds, fluoro diol compounds, phenyl diol compounds, furan diol compounds, pyridine diol compounds, or combinations thereof.

4. The polycarbonate copolymer according to claim 1, wherein the hydroxyl-terminated polysiloxane is a hydroxyl phenyl-terminated polysiloxane represented by the following Chemical Formula 1: [Chemical Formula 1] Among them, In the above Chemical Formula 1, R5 independently represents a hydrogen atom, a halogen atom, a hydroxyl 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 hydroxyl group; R7 independently represents an alkylene group having 2 to 8 carbon atoms; A is X or NH-X-NH, where X represents a straight-chain 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 by a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a carboxyl group; m independently represents an integer from 0 to 4; and n independently represents an integer from 2 to 1000.

5. The polycarbonate copolymer according to claim 1, wherein the diol component further comprises (d) other diols selected from aliphatic diols, cycloaliphatic diols other than anhydro sugar alcohols, or mixtures thereof.

6. The polycarbonate copolymer according to claim 5, wherein: The aliphatic diols are selected from ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, or mixtures thereof; and The cycloaliphatic diols other than anhydro sugar alcohols are selected from cyclohexanedimethanol, 2-methyl-1,4-cyclohexanediol, decahydronaphthalenedimethanol, norbornanedimethanol, adamantanediol, or mixtures thereof.

7. The polycarbonate copolymer according to claim 1, wherein the carbonate diester component is selected from dialkyl carbonates, diaryl carbonates, alkylene carbonates, or combinations thereof.

8. A method for preparing a polycarbonate copolymer, comprising: Reacting a mixture comprising a diol component and a carbonate diester component in the presence of a polymerization catalyst, Wherein, based on the total 100 mol% of the diol component, the diol component comprises (a) 79.8 to 96.9 mol% of an anhydro sugar alcohol, (b) 2.6 to 19.9 mol% of an aromatic diol, and (c) 0.11 to 1.99 mol% of a hydroxyl-terminated polysiloxane.

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

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