Polycarbonates and methods of making the same

Abstract

The present application relates to polycarbonates comprising units of formula 1a; and units of formula 1b, compositions comprising the same, and molded articles prepared from the compositions.

Description

Technical Field

[0001] This invention relates to polycarbonate and its preparation method. More specifically, this invention relates to polycarbonate having high hardness and / or heat resistance, and its preparation method.

[0002] This invention claims priority and benefit to Korean Patent No. 10-2021-0012478, filed with the Korean Intellectual Property Office on January 28, 2021, the entire contents of which are incorporated herein by reference. Background Technology

[0003] Polycarbonate resin is a polymer material that has been used in a variety of fields, such as exterior materials for electrical and electronic products, automotive parts, building materials, and optical components.

[0004] Polycarbonate is a material extracted from bisphenol A petroleum. The problem with it is that in order to increase its hardness, additional processes such as hard coatings are required, which increases costs and reduces durability.

[0005] Therefore, there is a need to develop polycarbonates that have improved durability while maintaining the excellent physical properties of polycarbonate itself. Summary of the Invention

[0006] [Technical Issues]

[0007] An exemplary embodiment of the present invention attempts to provide a polycarbonate having a novel structure and a method for preparing the same.

[0008] Another exemplary embodiment of the present invention seeks to provide a composition comprising a polycarbonate having a novel structure, and a molding article prepared from the composition.

[0009] [Technical Solution]

[0010] An exemplary embodiment of the present invention provides a polycarbonate comprising units represented by the following chemical formula 1a; and units represented by the following chemical formula 1b.

[0011] [Chemical Formula 1a]

[0012]

[0013] [Chemical Formula 1b]

[0014]

[0015] In chemical formulas 1a and 1b,

[0016] A is a substituted or unsubstituted phenylene group; or an arylene group consisting of two or more substituted or unsubstituted benzene rings linked or fused by a single bond.

[0017] L1 and L2 may be the same as or different from each other, and each may be a substituted or unsubstituted straight-chain or branched alkylene group.

[0018] L3 and L4 may be the same as or different from each other, and each is selected from one of substituted or unsubstituted straight-chain or branched alkylene groups, substituted or unsubstituted cycloalkylene groups, and substituted or unsubstituted aryl groups, or two or more of them connected by a single bond as divalent groups.

[0019] L5 and L6 may be the same as or different from each other, and each is a single bond; or they may be selected from one of substituted or unsubstituted straight-chain or branched alkylene groups, substituted or unsubstituted cycloalkylene groups, and substituted or unsubstituted aryl groups, or two or more of them connected by single bonds.

[0020] The polycarbonate contains units of formula 1a that may be the same or different from each other.

[0021] The polycarbonate contains units of chemical formula 1b that may be the same as or different from each other.

[0022] * indicates the location on the polycarbonate main chain.

[0023] An exemplary embodiment of the present invention provides a method for preparing polycarbonate according to the above exemplary embodiment, the method comprising: polymerizing a composition comprising a compound of the following chemical formula 11a, a compound of the following chemical formula 11b, and a carbonate precursor.

[0024] [Chemical Formula 11a]

[0025] HO-L3-OL1-A-L2-O-L4-OH

[0026] [Chemical Formula 11b]

[0027]

[0028] In chemical formulas 11a and 11b,

[0029] A is a substituted or unsubstituted phenylene group; or an arylene group consisting of two or more substituted or unsubstituted benzene rings linked or fused by a single bond.

[0030] L1 and L2 may be the same as or different from each other, and each may be a substituted or unsubstituted straight-chain or branched alkylene group.

[0031] L3 and L4 may be the same as or different from each other, and each is selected from one of substituted or unsubstituted straight-chain or branched alkylene groups, substituted or unsubstituted cycloalkylene groups, and substituted or unsubstituted aryl groups, or two or more of them connected by a single bond as divalent groups.

[0032] L5 and L6 may be the same as or different from each other and each is a single bond; or they may be selected from one of substituted or unsubstituted straight-chain or branched alkylene groups, substituted or unsubstituted cycloalkylene groups and substituted or unsubstituted arylene groups, or two or more of them connected by single bonds.

[0033] Another exemplary embodiment of the present invention provides a composition comprising the polycarbonate according to the above exemplary embodiment.

[0034] Another exemplary embodiment of the present invention provides a molding article prepared from a composition comprising polycarbonate according to the above exemplary embodiments.

[0035] [Beneficial Effects]

[0036] The polycarbonate according to some exemplary embodiments of the present invention has high hardness.

[0037] Polycarbonates according to some exemplary embodiments of the present invention have excellent heat resistance.

[0038] Therefore, by using polycarbonate with high hardness or excellent heat resistance, polycarbonate can be used in a wide range of fields that require excellent mechanical strength or heat resistance, such as lenses, glass, optical components and vehicle parts. Detailed Implementation

[0039] Specific exemplary implementations will be described in more detail below.

[0040] In this specification, the cycloalkylene group can be a monocyclic or polycyclic cycloalkylene group. Specifically, the cycloalkylene group can be a cycloalkylene group having 3 to 20 carbon atoms; a monocyclic or polycyclic cycloalkylene group having 6 to 18 carbon atoms; or a monocyclic or polycyclic cycloalkylene group having 6 to 12 carbon atoms. More specifically, the cycloalkylene group can be a divalent group derived from an alicyclic hydrocarbon as a monocyclic cycloalkylene group, such as cyclopentylene, cyclohexylene, or cycloheptylene, and can be adamantanediyl, norbornanediyl, etc., as a polycyclic cycloalkylene group. However, the cycloalkylene group is not limited to these. Furthermore, the cycloalkylene group can be unsubstituted or substituted with one or more of an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen.

[0041] In this specification, the description of cycloalkylene can be applied to cycloalkylene, except that cycloalkylene is a monovalent group rather than a divalent group.

[0042] In this specification, heterocyclic alkyl groups can be monocyclic or polycyclic heterocyclic alkyl groups including O, S, Se, or N as heteroatoms. Specifically, heterocyclic alkyl groups can be heterocyclic alkyl groups having 1 to 20 carbon atoms; monocyclic or polycyclic heterocyclic alkyl groups having 2 to 18 carbon atoms; or monocyclic or polycyclic heterocyclic alkyl groups having 2 to 12 carbon atoms. More specifically, examples of heterocyclic alkyl groups include dioxanecyclohexylene, dithiohexylene, etc.

[0043] In this specification, the description of heterocyclic alkyl groups can be applied to heterocyclic alkyl groups, except that heterocyclic alkyl groups are monovalent groups rather than divalent groups.

[0044] In this specification, straight-chain or branched alkylene groups can be straight-chain or branched alkylene groups derived from aliphatic hydrocarbons having 1 to 10, or 1 to 5, carbon atoms, as divalent groups. Specific examples of alkylene groups include methylene, ethylene, propylene, n-propylene, isopropylene, butylene, n-butylene, isobutylene, tert-butylene, sec-butylene, 1-methyl-butylene, 1-ethyl-butylene, pentylene, n-pentylene, isopentylene, neopentylene, tert-pentylene, hexylene, n-hexylene, 1-methylpentylene, 2-methylpentylene, 4-methyl-2-pentylene, 3,3-dimethyl Butylene, 2-ethylbutylene, heptylene, n-heptylene, 1-methylhexylene, octylene, n-octylene, tert-octylene, 1-methylheptylene, 2-ethylhexylene, 2-propylpentylene, n-nonylene, 2,2-dimethylheptylene, 1-ethyl-propylene, 1,1-dimethyl-propylene, isohexylene, 2-methylpentylene, 4-methylhexylene, 5-methylhexylene, etc., but not limited to these.

[0045] In this specification, the description of straight-chain or branched alkylene groups can be applied to straight-chain or branched alkyl groups, the difference being that straight-chain or branched alkyl groups are monovalent groups rather than divalent groups.

[0046] In this specification, unless otherwise specified, alkyl includes straight-chain alkyl and branched-chain alkyl.

[0047] In this specification, the arylene group can be monocyclic or polycyclic, and its number of carbon atoms is not particularly limited, but preferably 6 to 30, and can be 6 to 20. Specific examples of monocyclic arylene groups include phenylene, biphenylene, and triphenylene, but are not limited thereto. When the arylene group is polycyclic, its number of carbon atoms is not particularly limited, but preferably 10 to 30, and can be 10 to 20. Specific examples of polycyclic arylene groups include naphthylene, anthracene, phenanthrene, triphenylenylene, pyrene, phenalenylene, perylene, and so on. Examples include, but are not limited to, basalt, fluorene, etc.

[0048] In this specification, the description of aryl groups can be applied to aryl groups, except that aryl groups are monovalent groups rather than divalent groups.

[0049] In this specification, a heteroaryl group comprises one or more atoms other than carbon (i.e., one or more heteroatoms), specifically, the heteroatoms comprise one or more atoms selected from O, N, Se, S, etc. The number of carbon atoms in the heteroaryl group is not particularly limited, but is preferably from 1 to 30, and can be from 1 to 20. The heteroaryl group can be monocyclic or polycyclic. Examples of heteroaryl groups include, but are not limited to, divalent thiophene, divalent furanyl, divalent pyrrole, divalent imidazolyl, divalent thiazolyl, divalent oxazolyl, divalent oxadiazolyl, divalent pyridyl, divalent bipyridyl, divalent pyrimidinyl, divalent triazinyl, divalent triazolyl, divalent acridinel, divalent pyridazinyl, divalent quinolinyl, divalent quinazolinyl, divalent quinoxalinyl, divalent phthalazinyl, divalent pyridopyrimidinyl, divalent pyridopyrazinyl, divalent pyrazenopyrazinyl, divalent isoquinolinyl, divalent indolyl, and divalent carbazoleyl.

[0050] In this specification, the description of heteroaryl groups can be applied to heteroaryl groups, except that heteroaryl groups are monovalent groups rather than divalent groups.

[0051] In this specification, divalent aliphatic hydrocarbon groups refer to the aforementioned straight-chain or branched alkylene groups, cycloalkylene groups, heteroalkylene groups, etc.

[0052] In this specification, an alkoxy group can be an alkoxy group having 1 to 10 or 1 to 5 carbon atoms. Specific examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, 1-methyl-butoxy, 1-ethyl-butoxy, pentoxy, etc.

[0053] In this specification, halogen is a fluorine, chlorine, bromine, or iodine group.

[0054] In this specification, the descriptions of the above-mentioned cycloalkyl or heteroalkylene compounds can be applied to aliphatic rings, and the descriptions of aryl or heteroaryl compounds can be applied to aromatic rings.

[0055] The term "substitution" refers to the replacement of a hydrogen atom bonded to a carbon atom in a compound with another substituent. There are no restrictions on the position to be substituted, as long as the position is where the hydrogen atom is substituted (i.e., the position where the substituent can be substituted). When two or more substituents are substituted, the two or more substituents can be the same as or different from each other.

[0056] In this specification, the term "substituted or unsubstituted" means substituted by one or more substituents selected from deuterium, halogen, nitro (NO2), nitrile (CN), haloalkyl, COOR, alkyl, cycloalkyl, heterocycloalkyl, alkoxy, aryl, and heteroaryl, substituted by substituents linked to two or more of the exemplified substituents, or without substituents. Here, R is alkyl, cycloalkyl, heterocycloalkyl, alkoxy, aryl, or heteroaryl.

[0057] In this specification, * indicates the connection point with another structure.

[0058] An exemplary embodiment of the present invention provides a polycarbonate comprising units represented by the following chemical formula 1a; and units represented by the following chemical formula 1b.

[0059] [Chemical Formula 1a]

[0060]

[0061] [Chemical Formula 1b]

[0062]

[0063] In chemical formulas 1a and 1b, the definitions of each substituent are the same as those mentioned above.

[0064] Polycarbonates composed of isosorbide groups in related technologies have advantages such as high heat resistance, high scratch resistance, and transparency. However, due to the rigidity of the monomers themselves, polycarbonates in related technologies have the disadvantage of lower impact strength than commercially available polycarbonates. To solve this problem, the inventors have investigated a method for improving the impact strength of polycarbonates by copolymerizing monomers with flexible properties other than isosorbide groups.

[0065] By incorporating the units shown in chemical formulas 1a and 1b of this invention, the free volume of the polycarbonate chain can be reduced, thereby improving the heat resistance of the polycarbonate. Furthermore, the segmental rotation of the isosorbide groups can be restricted to exhibit an effect of improving the hardness of the polycarbonate.

[0066] According to an exemplary embodiment of the present invention, when the polycarbonate contains two or more units of chemical formula 1a, the units of the plurality of chemical formula 1a may be the same as or different from each other.

[0067] According to an exemplary embodiment of the present invention, when the polycarbonate contains two or more units of chemical formula 1b, the units of the plurality of chemical formula 1b may be the same as or different from each other.

[0068] According to an exemplary embodiment of the present invention, A in chemical formula 1a may be phenylene, biphenylene, or naphthylene.

[0069] According to an exemplary embodiment of the present invention, A in chemical formula 1a may be selected from the following structural formula.

[0070]

[0071] In these structural formulas, * refers to the binding position.

[0072] According to an exemplary embodiment of the present invention, A in chemical formula 1a may be selected from the following structural formula.

[0073]

[0074] In these structural formulas, * refers to the binding position.

[0075] According to an exemplary embodiment of the present invention, L1 and L2 in chemical formula 1a may be the same as or different from each other, and each is a straight-chain or branched alkylene group.

[0076] According to an exemplary embodiment of the present invention, L1 and L2 in chemical formula 1a may be the same as or different from each other, and each is a straight-chain or branched C1 to C20 alkylene group.

[0077] According to an exemplary embodiment of the present invention, L1 and L2 in chemical formula 1a may be the same or different from each other, and each is a straight-chain C1 to C10 alkylene, preferably a straight-chain C1 to C5 alkylene.

[0078] According to an exemplary embodiment of the present invention, L1 and L2 in chemical formula 1a may be the same as or different from each other, and each is methylene or ethylene.

[0079] According to an exemplary embodiment of the present invention, L1 and L2 in chemical formula 1a are identical to each other and are methylene or ethylene.

[0080] According to an exemplary embodiment of the present invention, chemical formula 1a may be represented by the following chemical formula 1a-1.

[0081] [Chemical Formula 1a-1]

[0082]

[0083] In chemical formula 1a-1,

[0084] n and m may be the same or different from each other, and each is an integer from 1 to 20.

[0085] The definitions of other substituents are the same as those defined in chemical formula 1a.

[0086] According to an exemplary embodiment of the present invention, n and m in chemical formula 1a-1 may be the same or different from each other, and each may be an integer from 1 to 10, an integer from 1 to 5, or an integer from 1 to 3.

[0087] According to an exemplary embodiment of the present invention, L3 and L4 in formula 1a may be the same as or different from each other, and each is a straight-chain or branched alkylene, cycloalkylene, arylene, straight-chain or branched alkylene-cycloalkylene, cycloalkylene-straight-chain or branched alkylene, straight-chain or branched alkylene-cycloalkylene-straight-chain or branched alkylene, straight-chain or branched alkylene-arylene, arylene-straight-chain or branched alkylene, or straight-chain or branched alkylene-aryl-straight-chain or branched alkylene, and here, the straight-chain or branched alkylene, cycloalkylene and arylene are each unsubstituted or substituted with alkoxy, COOR, alkyl or aryl, and R is hydrogen, alkyl or aryl.

[0088] For example, cycloalkylene-straight-chain or branched alkylene refers to a divalent group to a cycloalkylene group and a straight-chain or branched alkylene group connected by a single bond.

[0089] According to an exemplary embodiment of the present invention, L3 and L4 in chemical formula 1a may be the same as or different from each other, and each is arylene, straight-chain or branched alkylene-arylene, arylene-straight-chain or branched alkylene, or straight-chain or branched alkylene-arylene-straight-chain or branched alkylene.

[0090] For example, straight-chain or branched alkylene-arylene-straight-chain or branched alkylene refers to a divalent group in which straight-chain or branched alkylene, arylene, and straight-chain or branched alkylene are linked by a single bond in that order.

[0091] According to an exemplary embodiment of the present invention, L3 and L4 in formula 1a may be the same as or different from each other, and each is arylene, straight-chain or branched alkylene-arylene, arylene-straight-chain or branched alkylene, or straight-chain or branched alkylene-arylene-straight-chain or branched alkylene, and here, the arylene is C6 to C20, and the straight-chain or branched alkylene is C1 to C6.

[0092] According to an exemplary embodiment of the present invention, L3 and L4 in chemical formula 1a may be the same as or different from each other, and each is C6 to C20 arylene, C1 to C6 alkylene-C6 to C20 arylene, or C6 to C20 arylene-C1 to C6 alkylene.

[0093] According to an exemplary embodiment of the present invention, L3 and L4 in chemical formula 1a may be the same as or different from each other, and are each phenylene, alkylene-phenylene, or phenylene-alkylene, and here, the alkylene is methylene or ethylene.

[0094] According to an exemplary embodiment of the present invention, L3 in chemical formula 1a is alkylene-phenylene, L4 is phenylene-alkylene, and here, the alkylene is methylene or ethylene.

[0095] According to an exemplary embodiment of the present invention, chemical formula 1a may be represented by the following chemical formulas 1a-2.

[0096] [Chemical Formula 1a-2]

[0097]

[0098] In chemical formula 1a-2,

[0099] L7 and L8 may be the same as or different from each other, and each may be a straight-chain or branched alkylene group.

[0100] The definitions of A, n, and m are the same as those defined in chemical formulas 1a and 1a-1.

[0101] According to one example, L7 and L8 are C1 to C20 straight-chain or branched alkylene groups, specifically C1 to C6 straight-chain alkylene groups, and are, for example, methylene or ethylene.

[0102] According to an exemplary embodiment of the present invention, L5 and L6 in chemical formula 1b may be the same as or different from each other, and each is a single bond, or a straight chain or a branched alkylene group.

[0103] According to an exemplary embodiment of the present invention, L5 and L6 in chemical formula 1b may be the same as or different from each other, and each is a single bond, or a straight-chain or branched C1 to C6 alkylene group.

[0104] According to an exemplary embodiment of the present invention, L5 and L6 in chemical formula 1b may be the same as or different from each other, and each is a single bond, methylene, ethylene, propylene or butylene.

[0105] According to an exemplary embodiment of the present invention, based on the total weight of the polycarbonate, the polycarbonate may contain 10% or more by weight, preferably 15% or more by weight, more preferably 20% or more by weight and less than 50% by weight, less than 45% by weight, or less than 40% by weight of the unit represented by chemical formula 1a.

[0106] According to an exemplary embodiment of the invention, based on the total weight of the polycarbonate, the polycarbonate may contain 40% or more by weight, preferably 50% or more by weight, more preferably 60% or more by weight and less than 90% by weight, for example less than 85% by weight, or less than 70% by weight of the unit represented by chemical formula 1b.

[0107] In this invention, the content of the structure contained in the polycarbonate can be calculated by general methods from the results of nuclear magnetic resonance (NMR) analysis of the polycarbonate.

[0108] The weight-average molecular weight (Mw) of the polycarbonate according to an exemplary embodiment of the present invention can be appropriately adjusted according to the purpose and use, and with regard to the fact that it can exhibit improved weather resistance while maintaining the excellent properties of polycarbonate itself, such as transparency and impact strength, the weight-average molecular weight of the polycarbonate can be 30,000 g / mol or more, or 40,000 g / mol or more and 60,000 g / mol or less, or 55,000 g / mol or less, or 50,000 g / mol or less.

[0109] In this invention, the weight-average molecular weight (Mw) of polycarbonate and the oligomers used in its preparation can be measured using a gel permeation chromatography (GPC) instrument with polystyrene (PS) standards on an Agilent 1200 series instrument. Specifically, it can be measured using an Agilent 1200 series instrument with a Polymer Laboratories PLgel MIX-B 300 mm column, at a measurement temperature of 160 °C, using 1,2,4-trichlorobenzene as the solvent, and at a flow rate of 1 mL / min. Samples of polycarbonate or oligomers are prepared at a concentration of 10 mg / 10 mL and subsequently injected in 200 μL volumes. The Mw value is derived from a calibration curve formed using polystyrene standards. In this case, nine types of polystyrene standards with molecular weights (g / mol) of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000 were used.

[0110] According to an exemplary embodiment of the present invention, the polycarbonate further comprises a unit of the following chemical formula 2.

[0111] [Chemical Formula 2]

[0112]

[0113] In chemical formula 2,

[0114] X1 and X3 may be the same as or different from each other, and each may be a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent isosorbide group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.

[0115] X2 is a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent isosorbide group, a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, O, S, SO, SO2, or CO.

[0116] k1 is either 0 or 1, and is 1 when X2 directly bonded to X1 is O, S, SO, SO2, or CO.

[0117] l is an integer from 1 to 5, and when l is 2 or greater, X2 are either the same or different from each other.

[0118] k2 is either 0 or 1, and is 1 when X2 directly bonded to X3 is O, S, SO, SO2, or CO.

[0119] Polycarbonate contains units of chemical formula 2 that may be the same or different from each other.

[0120] * indicates the location on the polycarbonate main chain.

[0121] According to an exemplary embodiment of the present invention, when polycarbonate contains two or more units of chemical formula 2, the units of chemical formula 2 may be the same as or different from each other.

[0122] According to an exemplary embodiment of the invention, based on the total weight of the polycarbonate, the polycarbonate contains 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight of the unit represented by Chemical Formula 2. The polycarbonate may contain less than 70% by weight, for example less than 50% by weight of the unit represented by Chemical Formula 2.

[0123] According to an exemplary embodiment of the present invention, chemical formula 2 may be represented by one of the following chemical formulas 3 to 6.

[0124] [Chemical Formula 3]

[0125]

[0126] [Chemical Formula 4]

[0127]

[0128] [Chemical Formula 5]

[0129]

[0130] [Chemical Formula 6]

[0131]

[0132] In chemical formulas 3 to 6,

[0133] Y1 and Y2 are respectively a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent isosorbide group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.

[0134] Y3 and Y4 are each a substituted or unsubstituted straight-chain or branched alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted aryl group, O, S, SO, SO2, or CO.

[0135] R1 through R4 may be the same as or different from each other, and each may be hydrogen, halogen, substituted or unsubstituted alkyl, or substituted or unsubstituted alkoxy.

[0136] a and b are both integers between 0 and 4.

[0137] c, d, e, and f are each integers from 1 to 4.

[0138] g, h, i, and j are each integers from 0 to 4.

[0139] When g, h, i, and j are each greater than or equal to 2, each of R1 to R4 is either the same as or different from each other.

[0140] Polycarbonate contains units of chemical formulas 3 to 6 that may be the same as or different from each other.

[0141] * indicates the location on the polycarbonate main chain.

[0142] According to an exemplary embodiment of the present invention, when each polycarbonate comprises two or more units of chemical formula 3 to 6, the units of chemical formula 3 to 6 may be the same as or different from each other.

[0143] According to an exemplary embodiment of the present invention, Y1 in Formula 3 may be a substituted or unsubstituted cycloalkylene, a substituted or unsubstituted heterocycloalkylene, a substituted or unsubstituted arylene, or a substituted or unsubstituted heteroarylene.

[0144] According to an exemplary embodiment of the present invention, Y1 in Formula 3 may be a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroalkylene group having 2 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms.

[0145] According to an exemplary embodiment of the present invention, Y1 in Formula 3 may be a substituted or unsubstituted cycloalkylene group having 3 to 15 carbon atoms, a substituted or unsubstituted heteroalkylene group having 2 to 15 carbon atoms, a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 15 carbon atoms.

[0146] According to an exemplary embodiment of the present invention, Y1 in Formula 3 may be a substituted or unsubstituted cyclobutylene, a substituted or unsubstituted cyclopentylene, a substituted or unsubstituted cyclohexylene, a substituted or unsubstituted divalent tetrahydrofuran, a substituted or unsubstituted biphenylene, or a substituted or unsubstituted divalent furan.

[0147] According to an exemplary embodiment of the present invention, Y2 in Formula 4 may be a substituted or unsubstituted cycloalkylene group or a substituted or unsubstituted arylene group.

[0148] According to an exemplary embodiment of the present invention, Y2 in Formula 4 may be a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

[0149] According to an exemplary embodiment of the present invention, Y2 in Formula 4 may be a substituted or unsubstituted cycloalkylene group having 3 to 15 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms.

[0150] According to an exemplary embodiment of the present invention, Y2 in Formula 4 may be a substituted or unsubstituted cyclobutylene, a substituted or unsubstituted cyclopentylene, a substituted or unsubstituted cyclohexylene, or a substituted or unsubstituted biphenylene.

[0151] According to an exemplary embodiment of the present invention, Y3 in Formula 5 may be a substituted or unsubstituted alkylene, a substituted or unsubstituted cycloalkylene, a substituted or unsubstituted arylene, or SO2.

[0152] According to an exemplary embodiment of the present invention, Y3 in Formula 5 may be a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or SO2.

[0153] According to an exemplary embodiment of the present invention, Y3 in Formula 5 may be a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 15 carbon atoms, a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, or SO2.

[0154] According to an exemplary embodiment of the present invention, Y3 in Formula 5 may be a substituted or unsubstituted straight-chain or branched alkylene, a substituted or unsubstituted cyclohexylene, a substituted or unsubstituted phenylene, or SO2 having 1 to 5 carbon atoms.

[0155] According to an exemplary embodiment of the present invention, Y4 in Formula 6 may be a substituted or unsubstituted alkylene, a substituted or unsubstituted cycloalkylene, a substituted or unsubstituted arylene, or SO2.

[0156] According to an exemplary embodiment of the present invention, Y4 in Formula 6 may be a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or SO2.

[0157] According to an exemplary embodiment of the present invention, Y4 in Formula 6 may be a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 15 carbon atoms, a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, or SO2.

[0158] According to an exemplary embodiment of the present invention, Y4 in Formula 6 may be a substituted or unsubstituted straight-chain or branched alkylene, a substituted or unsubstituted cyclohexylene, a substituted or unsubstituted phenylene, or SO2 having 1 to 5 carbon atoms.

[0159] According to an exemplary embodiment of the present invention, R1 to R4 in chemical formulas 5 and 6 may be hydrogen or substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms.

[0160] According to an exemplary embodiment of the present invention, R1 to R4 in chemical formulas 5 and 6 may be hydrogen or substituted or unsubstituted alkyl groups having 1 to 5 carbon atoms.

[0161] According to an exemplary embodiment of the present invention, R1 to R4 in chemical formulas 5 and 6 may be hydrogen, or substituted or unsubstituted methyl groups.

[0162] According to an exemplary embodiment of the present invention, R1 to R4 in chemical formulas 5 and 6 may be substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms.

[0163] According to an exemplary embodiment of the present invention, R1 to R4 in chemical formulas 5 and 6 may be substituted or unsubstituted alkyl groups having 1 to 5 carbon atoms.

[0164] According to an exemplary embodiment of the present invention, R1 to R4 in chemical formulas 5 and 6 may be substituted or unsubstituted methyl groups.

[0165] According to an exemplary embodiment of the present invention, chemical formula 3 may be represented by any of the following units.

[0166]

[0167] According to an exemplary embodiment of the present invention, chemical formula 4 can be represented by any of the following units.

[0168]

[0169] According to an exemplary embodiment of the present invention, chemical formula 5 may be represented by any of the following units.

[0170]

[0171] According to an exemplary embodiment of the present invention, chemical formula 6 may be represented by any of the following units.

[0172]

[0173] According to an exemplary embodiment of the present invention, the polycarbonate may have hydroxyl groups as end groups, but is not limited thereto.

[0174] According to an exemplary embodiment of the present invention, when the impact strength of polycarbonate is measured at 23°C according to ASTM D256 (1 / 8 inch, notched cantilever beam), the impact strength can be above 245 J / m, above 250 J / m, or above 280 J / m. There is no particular upper limit to this impact strength, but it can be, for example, below 500 J / m or below 450 J / m.

[0175] Specifically, the cantilever beam impact strength measurement method uses a pendulum with a predetermined weight to obtain the impact strength by dividing the absorbed energy obtained when the sample is struck and rotated by the pendulum as the return height by the cross-sectional area at the notch of the sample.

[0176] According to an exemplary embodiment of the present invention, when the pencil hardness of polycarbonate is measured at a temperature of 23°C and at an angle of 45° under a load of 50 grams using a pencil hardness tester (Cometech) according to ASTM D3363, the pencil hardness can be HB or higher.

[0177] Another exemplary embodiment of the present invention provides a method for preparing a polycarbonate comprising the unit shown in chemical formula 1a and the unit shown in chemical formula 1b, the method comprising: polymerizing a composition comprising a compound of chemical formula 11a, a compound of chemical formula 11b and a carbonate precursor.

[0178] [Chemical Formula 11a]

[0179] HO-L3-O-L1-A-L2-O-L4-OH

[0180] [Chemical Formula 11b]

[0181]

[0182] In chemical formulas 11a and 11b,

[0183] A is a substituted or unsubstituted phenylene group; or an arylene group consisting of two or more substituted or unsubstituted benzene rings linked or fused by a single bond.

[0184] L1 and L2 may be the same as or different from each other, and each may be a substituted or unsubstituted straight-chain or branched alkylene group.

[0185] L3 and L4 may be the same as or different from each other, and each is selected from one of substituted or unsubstituted straight-chain or branched alkylene groups, substituted or unsubstituted cycloalkylene groups, and substituted or unsubstituted aryl groups, or two or more of their divalent groups linked by single bonds.

[0186] L5 and L6 may be the same as or different from each other and each is a single bond; or they may be selected from one of substituted or unsubstituted straight-chain or branched alkylene groups, substituted or unsubstituted cycloalkylene groups and substituted or unsubstituted arylene groups, or two or more of them connected by single bonds.

[0187] Preferred examples of substituents in chemical formula 11a are the same as those described above involving chemical formula 1a.

[0188] Preferred examples of substituents in chemical formula 11b are the same as those described above involving chemical formula 1b.

[0189] According to another exemplary embodiment of the present invention, chemical formula 11a may be represented by the following chemical formula 11a-1.

[0190] [Chemical Formula 11a-1]

[0191]

[0192] In chemical formula 11a-1, the definition of each substituent is the same as in chemical formula 1a-1.

[0193] According to another exemplary embodiment of the present invention, chemical formula 11a-1 may be represented by the following chemical formula 11a-2.

[0194] [Chemical Formula 11a-2]

[0195]

[0196] In chemical formula 11a-2, the definition of each substituent is the same as in chemical formula 1a-2.

[0197] According to an exemplary embodiment of the present invention, a compound of chemical formula 11a can be represented by the following structure.

[0198]

[0199] According to an exemplary embodiment of the present invention, the compound of chemical formula 11a can be prepared by the following reaction formula.

[0200]

[0201] In this reaction formula, the definitions of A and L1 to L3 are the same as those in chemical formula 11a.

[0202] After dissolving 1 equivalent of a dichloro compound, 2.2 equivalents of a diol compound, and potassium carbonate (K₂CO₃) in dimethylformamide (DMF), the resulting solution was stirred at 80 °C. Upon completion of the reaction, the mixture was extracted with ethyl acetate (EA) and water, followed by removal of water from the separated organic layer using anhydrous magnesium sulfate (MgSO₄). After concentrating the water-free organic layer under reduced pressure by distillation, the compound of formula 11a was synthesized by column chromatography.

[0203] Compounds of chemical formula 11b can be prepared and used by methods known in the art, or can be used by purchasing commercially available products.

[0204] According to an exemplary embodiment of the present invention, the carbonate precursor may be represented by the following chemical formula 12.

[0205] [Chemical Formula 12]

[0206]

[0207] In chemical formula 12,

[0208] R5 and R6 may be the same as or different from each other, and each may be a substituted or unsubstituted straight-chain or branched alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl.

[0209] Carbonate precursors are used to link compounds of formula 11a and formula 11b, or, where necessary, to add comonomers such as compounds of formula 21. Specific examples include phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, ditolyl carbonate, dinaphthalene carbonate, bis(biphenyl) carbonate, dihalocarbamates, etc., and any one or a mixture of two or more of them may be used.

[0210] In one exemplary embodiment of this specification, the carbonate precursor may be diphenyl carbonate.

[0211] The unit of the above-mentioned chemical formula 1a can be formed by polymerizing the compound of chemical formula 11a and the carbonate precursor of chemical formula 12, and the unit of the above-mentioned chemical formula 1b can be formed by polymerizing the compound of chemical formula 11b and the carbonate precursor of chemical formula 12.

[0212] In other words, polycarbonates containing units of formula 1a and formula 1b can be prepared by polymerizing compounds of formula 11a, compounds of formula 11b, and carbonate precursors of formula 12.

[0213] Based on the total weight of the composition, the compound of chemical formula 11a may be included in amounts of 5% to 50% by weight, 10% to 40% by weight, more than 15% by weight, and 30% by weight.

[0214] Based on the total weight of the composition, the compound of chemical formula 11b may be included in amounts of 20% to 70% by weight, 30% to 60% by weight, and 35% to 50% by weight.

[0215] Based on the total weight of the composition, the carbonate precursor of Formula 12 may be included in amounts of 20% to 70% by weight, 30% to 60% by weight, and 35% to 50% by weight.

[0216] For polymerization, methods known in the art can be used, and ideally, polymerization can be carried out by melt polymerization.

[0217] Specifically, a composition comprising a compound of formula 11a, a compound of formula 11b, and a carbonate precursor is melted under a nitrogen atmosphere at a pressure of 700 to 800 Torr and a temperature of 120 to 170°C. The temperature is then increased to 180 to 200°C at a pressure of 80 to 120 Torr to remove the phenol generated during the reaction. The temperature is then increased to above 200°C at a pressure of 20 to 40 Torr, and finally increased to above 220°C at a pressure of 0.05 to 0.2 Torr. The composition is then polymerizable by terminating the reaction.

[0218] In addition, reaction catalysts such as lithium hydroxide, cesium carbonate, sodium hydroxide, and sodium methoxide can be used to promote the polymerization reaction.

[0219] According to an exemplary embodiment of the present invention, the composition used in the polymerization step may further comprise a compound of the following chemical formula 21.

[0220] [Chemical Formula 21]

[0221]

[0222] In chemical formula 21,

[0223] X1 and X3 may be the same as or different from each other, and each may be a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent isosorbide group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.

[0224] X2 is a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent isosorbide group, a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, O, S, SO, SO2, or CO.

[0225] k1 is either 0 or 1, and is 1 when X2 directly bonded to X1 is O, S, SO, SO2, or CO.

[0226] l is an integer from 1 to 5, and when l is 2 or greater, X2 are either the same or different from each other.

[0227] k2 is 0 or 1, provided that when X2 directly bonded to X3 is O, S, SO, SO2 or CO, k2 is 1.

[0228] The compound of formula 21 can be polymerized to form the unit of formula 2 described above. Based on 100 molar parts of the carbonate precursor of formula 12, the compound of formula 21 may be included in amounts of 30 molar parts or more, 40 molar parts or more, 90 molar parts or less, or 80 molar parts or less.

[0229] According to an exemplary embodiment of the present invention, chemical formula 21 may be represented by the following chemical formulas 31, 41, 51 or 61.

[0230] [Chemical Formula 31]

[0231]

[0232] [Chemical Formula 41]

[0233]

[0234] [Chemical Formula 51]

[0235]

[0236] [Chemical Formula 61]

[0237]

[0238] In chemical formulas 31, 41, 51, and 61,

[0239] Y1 and Y2 may be the same as or different from each other, and each may be a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent isosorbide group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.

[0240] Y3 and Y4 may be the same as or different from each other, and each may be a substituted or unsubstituted straight-chain or branched alkylene, a substituted or unsubstituted cycloalkylene, a substituted or unsubstituted arylene, O, S, SO, SO2, or CO.

[0241] R1 through R4 may be the same as or different from each other, and each may be hydrogen, halogen, substituted or unsubstituted alkyl, or substituted or unsubstituted alkoxy.

[0242] a and b are both integers between 0 and 4.

[0243] c, d, e, and f are each integers from 1 to 4.

[0244] g, h, i, and j are each integers from 0 to 4.

[0245] When g, h, i, and j are each greater than 2, each of R1 to R4 is either the same as or different from each other.

[0246] According to an exemplary embodiment of the present invention, the descriptions in chemical formulas 3 to 6 are applicable to Y1 to Y4 and R1 to R4 of chemical formulas 31, 41, 51 and 61.

[0247] According to an exemplary embodiment of the present invention, chemical formula 31 may be represented by any of the following structures.

[0248]

[0249] According to an exemplary embodiment of the present invention, chemical formula 41 may be represented by any of the following structures.

[0250]

[0251] According to an exemplary embodiment of the present invention, chemical formula 51 may be represented by any of the following structures.

[0252]

[0253] According to an exemplary embodiment of the present invention, chemical formula 61 may be represented by any of the following structures.

[0254]

[0255] Another exemplary embodiment of the present invention provides a composition comprising the polycarbonate according to the above exemplary embodiment.

[0256] According to one example, the composition containing the polycarbonate may further contain a heat stabilizer to prevent a decrease in the molecular weight or a deterioration in the color of the resin molding.

[0257] Examples of heat stabilizers include phosphoric acid, phosphoric acid, phosphonic acid, phosphonic acid, and their esters, etc. Specific examples include triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tri-octadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and 2,2-methylenebis(4,6-di-tert-butylphenyl)phosphite. Butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearate pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenylmonoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butyl phenyl), dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, or mixtures of two or more thereof.

[0258] Based on 100 parts by weight of polycarbonate resin, this heat stabilizer can be used in amounts of 0.0001 parts by weight to 1 part by weight, 0.005 parts by weight to 0.5 parts by weight, or 0.01 parts by weight to 0.2 parts by weight. When the stabilizer is used in the above amounts, it can prevent the molecular weight of the resin from decreasing or discoloring, without causing additive leaching, etc.

[0259] According to another example, the composition containing the polycarbonate may further contain commonly known antioxidants.

[0260] Specific examples of antioxidants include pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-lauryl thiopropionate), glyceryl-3-stearyl thiopropionate, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. 5-Di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 4,4′-biphenyldiphosphonate tetra(2,4-di-tert-butylphenyl), 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane or a mixture of two or more thereof.

[0261] Based on 100 parts by weight of polycarbonate, the antioxidant can be used in amounts of 0.0001 parts by weight to 1 part by weight, 0.001 parts by weight to 0.5 parts by weight, or 0.005 parts by weight to 0.1 parts by weight.

[0262] According to another example, the composition containing the polycarbonate may further contain a lubricant and may contain, for example, pentaerythritol tetrastearate.

[0263] Based on 100 parts by weight of polycarbonate, the lubricant can be used in amounts of 0.0001 parts by weight to 1 part by weight, 0.005 parts by weight to 0.5 parts by weight, or 0.01 parts by weight to 0.2 parts by weight.

[0264] Another exemplary embodiment of the present invention provides a molding article prepared from a composition comprising the polycarbonate according to the above exemplary embodiment. As described above, since the polycarbonate comprising the unit shown in Formula 1a and the unit shown in Formula 1b has excellent hardness or heat resistance, the molding article according to the present invention has a wider range of applications than molding articles prepared from polycarbonate used in the related art. Furthermore, when the polycarbonate further comprises repeating units shown in Formula 2, the range of applications can be further expanded since the desired physical properties can be achieved by adjusting the weight ratio of the units shown in Formulas 1a, 1b and 2.

[0265] If desired, in addition to the aforementioned polycarbonate, the composition or molding may further comprise one or more selected from antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent whitening agents, UV absorbers, pigments, and dyes.

[0266] As an example of a method for preparing molded articles, the method may include the following steps: thoroughly mixing the aforementioned polycarbonate and other additives using a mixer, extruding the mixture using an extruder to prepare the resulting mixture into granules, drying the granules, and then injection molding the granules using an injection molding machine.

[0267] Experimental Example 1. Preparation of Polycarbonate

[0268] Example 1

[0269] 1) Preparation of monomer 1(2,2′-(((1,4-phenylenebis(methylene))bis(oxy))bis(4,1-phenylene))bis(ethanol-1-ol) monomer)

[0270]

[0271] After dissolving 1 equivalent of 1,4-bis(chloromethyl)benzene, 2.2 equivalents of 4-(2-hydroxyethyl)phenol, and potassium carbonate (K₂CO₃) in dimethylformamide (DMF), the resulting solution was stirred at 80 °C. Upon completion of the reaction, the mixture was extracted with ethyl acetate (EA) and water, followed by removal of water from the separated organic layer using anhydrous magnesium sulfate (MgSO₄). After concentrating the water-removed organic layer under reduced pressure by distillation, monomer 1 was obtained by column chromatography.

[0272] 2) Preparation of polycarbonate resin

[0273] After cleaning the reaction vessel to remove all moisture, it was purged with nitrogen. 105 parts by weight of diphenyl carbonate (DPC) based on 100 parts by weight of isosorbide (Roquette Freres) and 40 parts by weight of monomer 1 (a compound of formula 11a) were introduced into a 1-liter glass reaction vessel along with 0.02 wt% (based on the weight of isosorbide) of lithium hydroxide as a catalyst. The introduced materials were dissolved by stirring for 20 minutes under a nitrogen atmosphere at a pressure of 760 Torr and a temperature of 150°C. Subsequently, the pressure was reduced to 100 Torr to remove the phenol generated during the reaction, and the reaction temperature was increased to 190°C over 60 minutes. Then, the pressure was reduced to 30 Torr, and the temperature was increased to 210°C over 40 minutes. Subsequently, as the stirrer torque increased and the viscosity increased, the pressure was finally reduced to 0.1 Torr, and the temperature was increased to 230°C. The reaction was terminated after the stirrer reached the required stirring torque, and the resulting melt was granulated to prepare a carbonate resin.

[0274] Example 2

[0275]

[0276] Monomer 2 was prepared in the same manner as in Example 1, except that 1,4-bis(2-chloroethyl)benzene was used instead of 1,4-bis(chloromethyl)benzene in Example 1, and polycarbonate was prepared in the same manner as in Example 1, except that monomer 2 was used instead of monomer 1.

[0277] Example 3

[0278]

[0279] Monomer 3 was prepared in the same manner as in Example 1, except that 4,4′-bis(chloromethyl)-1,1′-biphenyl was used instead of 1,4-bis(chloromethyl)benzene in Example 1, and polycarbonate was prepared in the same manner as in Example 1, except that monomer 3 was used instead of monomer 1.

[0280] Example 4

[0281]

[0282] Monomer 4 was prepared in the same manner as in Example 1, except that 4-(hydroxymethyl)phenol was used instead of 4-(2-hydroxyethyl)phenol in Example 1, and polycarbonate was prepared in the same manner as in Example 1, except that monomer 4 was used instead of monomer 1.

[0283] Comparative Example 1

[0284] Except for monomer 1 in Example 1, polycarbonate was prepared in the same manner as in Example 1 by using only isosorbide for polymerization.

[0285] Experimental Example 2. Evaluation of the physical properties of polycarbonate

[0286] 0.050 parts by weight of tris(2,4-di-tert-butylphenyl) phosphite, 0.010 parts by weight of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and 0.030 parts by weight of pentaerythritol tetrastearate were added to 100 parts by weight of each polycarbonate prepared in the examples and comparative examples. The resulting mixture was granulated using a HAAKE Mini CTW with an attached vent, and samples were prepared by injection molding the granules using a HAAKE Minijet injection molding system at a cylinder temperature of 300°C and a mold temperature of 120°C.

[0287] The properties of these injection-molded specimens or polycarbonates were measured using the following methods, and the results are shown in Table 1.

[0288] -Weight-average molecular weight (g / mol): Measured using an Agilent 1200 series calibrated with PC standards.

[0289] - Flowability (MI): Measured according to ASTM D1238 (at 300°C and 1.2 kg).

[0290] - Cantilever beam room temperature impact strength (J / m): Measured at 23°C according to ASTM D256 (1 / 8 inch, notched cantilever beam).

[0291] - Pencil hardness: Measured at 23°C using a pencil hardness tester (Cometech) according to ASTM D3363 at a 45° angle under a 50g load with pencils of strength 2B, B, and HB.

[0292] [Table 1]

[0293]

[0294] Referring to Table 1, it was confirmed that the compounds in the examples exhibited higher impact strength and higher hardness compared to the comparative examples.

[0295] Specifically, it can be seen that, compared with Comparative Example 1, which does not contain the unit of Chemical Formula 1a of the present invention and only contains the unit of Chemical Formula 1b, the Example has a pencil hardness of HB and a high impact strength of 250 J / m or more.

[0296] Therefore, it can be determined that the polycarbonate of the present invention comprising units of chemical formula 1a and chemical formula 1b can achieve improved impact resistance and high hardness.

Claims

1. A polycarbonate comprising units represented by the following Chemical Formula 1a-2; and units represented by the following Chemical Formula 1b, wherein the polycarbonate comprising 10 to 50% by weight of the units represented by the Chemical Formula 1a-2, based on the total weight of the polycarbonate, wherein the polycarbonate comprises 40 to 90% by weight of the units represented by the Chemical Formula 1b, based on the total weight of the polycarbonate, wherein the polycarbonate has a weight average molecular weight of 40,000 to 60,000 g / mol: [Chemical Formula 1a-2] [Chemical Formula 1b] in the Chemical Formula 1a-2 and the Chemical Formula 1b, A is a substituted or unsubstituted phenylene; or an arylene group linked by a single bond or fused of two or more substituted or unsubstituted benzene rings, L5 and L6 are the same as or different from each other, and each is a single bond; or a substituted or unsubstituted straight chain or branched chain alkylene, L7 and L8 are the same as or different from each other, and each is a straight chain or branched chain alkylene, the units of the Chemical Formula 1a-2 contained in the polycarbonate are the same as or different from each other, the units of the Chemical Formula 1b contained in the polycarbonate are the same as or different from each other, n and m are the same as or different from each other, and each is an integer of 1 to 20, refers to the position of attachment to the main chain of the polycarbonate.

2. The polycarbonate of claim 1, wherein, A in the Chemical Formula 1a-2 is selected from the following structural formulas: 。 3.A method of preparing the polycarbonate according to claim 1, the method comprising: polymerizing a composition comprising a compound represented by the following Chemical Formula 11a-2, a compound represented by the following Chemical Formula 11b, and a carbonate precursor: [Chemical Formula 11a-2] [Chemical Formula 11b] in the Chemical Formula 11a-2 and the Chemical Formula 11b, A is a substituted or unsubstituted phenylene; or an arylene group linked by a single bond or fused of two or more substituted or unsubstituted benzene rings, L5 and L6 are the same as or different from each other, and each is a single bond; or a substituted or unsubstituted straight chain or branched chain alkylene, L7 and L8 are the same as or different from each other, and each is a straight chain or branched chain alkylene, n and m are the same as or different from each other, and each is an integer of 1 to 20.

4. The method of claim 3, wherein, the carbonate precursor is represented by the following Chemical Formula 12: [Chemical Formula 12] in the Chemical Formula 12, R5 and R6 are the same as or different from each other, and each is a substituted or unsubstituted straight chain or branched chain alkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl. 5.A composition comprising the polycarbonate according to claim 1 or 2. 6.A molded article prepared from a composition comprising the polycarbonate according to claim 1 or 2.

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