Polycarbonate resin and method for producing the same

Abstract

The present application relates to polycarbonate resins comprising units of chemical formula 1, methods for making the same, polycarbonate resin compositions comprising the same, and molded articles comprising the polycarbonate resin compositions.

Description

Technical Field

[0001] This application claims priority and benefit to Korean Patent Application No. 10-2022-0035977, filed with the Korean Intellectual Property Office on March 23, 2022, the entire contents of which are incorporated herein by reference.

[0002] This specification relates to polycarbonate resins and their preparation methods. Background Technology

[0003] The higher the refractive index of an optical material, the thinner the optical lens required to achieve the same level of correction. Therefore, as the refractive index of an optical material increases, thinner and lighter lenses can be manufactured, making it possible to make various devices that use lenses smaller.

[0004] Typically, when the refractive index of an optical material increases, the Abbe number decreases, and a certain level or higher transparency is required for its use as an optical material. Summary of the Invention

[0005] Technical issues

[0006] One exemplary embodiment of this specification aims to provide a polycarbonate resin with a novel structure and a method for preparing the same.

[0007] Another exemplary embodiment of this specification is intended to provide a polycarbonate resin composition comprising a polycarbonate resin having a novel structure and a molding article prepared from said polycarbonate resin composition.

[0008] Technical solution

[0009] An exemplary embodiment of this specification provides a polycarbonate resin comprising units of the following chemical formula 1.

[0010] [Chemical Formula 1]

[0011]

[0012] In chemical formula 1,

[0013] R1 and R2 are distinct from each other and are each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; an unsubstituted or substituted aryl group or a group substituted with deuterium, a halogen group, a hydroxyl group, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryloxy group, an arylthio group, an alkylthio group, an aryl group, or a heteroaryl group; or a substituted or unsubstituted heteroaryl group.

[0014] r1 and r2 are each integers from 1 to 4, and when r1 is 2 or greater, two or more R1s are either the same or different from each other, and when r2 is 2 or greater, two or more R2s are either the same or different from each other.

[0015] L1 and L2 may be the same as or different from each other, and each may be independently a substituted or unsubstituted aryl group.

[0016] X1 to X4 may be the same as or different from each other, and each is independently O or S.

[0017] Z1 and Z2 may be the same as or different from each other, and each is independently a substituted or unsubstituted alkylene or a substituted or unsubstituted cycloalkylene.

[0018] a and b are either the same or different, and are each an independent integer from 1 to 10. Furthermore, when a and b are each 2 or greater, the structures within the parentheses are either the same or different.

[0019] * refers to the part that is connected to the main chain of the resin.

[0020] An exemplary embodiment of this specification provides a method for preparing a polycarbonate resin, the method comprising: polymerizing a composition for preparing a polycarbonate resin, the composition comprising a compound of the following chemical formula 1a and a polycarbonate precursor.

[0021] [Chemical Formula 1a]

[0022]

[0023] In chemical formula 1a,

[0024] R1 and R2 are distinct from each other and are each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; an unsubstituted or substituted aryl group or a group substituted with deuterium, a halogen group, a hydroxyl group, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryloxy group, an arylthio group, an alkylthio group, an aryl group, or a heteroaryl group; or a substituted or unsubstituted heteroaryl group.

[0025] r1 and r2 are each integers from 1 to 4, and when r1 is 2 or greater, two or more R1s are either the same or different from each other, and when r2 is 2 or greater, two or more R2s are either the same or different from each other.

[0026] L1 and L2 may be the same as or different from each other, and each may be independently a substituted or unsubstituted aryl group.

[0027] X1 to X4 may be the same as or different from each other, and each is independently O or S.

[0028] Z1 and Z2 may be the same as or different from each other, and each is independently a substituted or unsubstituted alkylene group, or a substituted or unsubstituted cycloalkylene group, and

[0029] a and b are either the same or different from each other, and each is an independent integer from 1 to 10. When a and b are each 2 or greater, the structures within the parentheses are either the same or different from each other.

[0030] Another exemplary embodiment of this specification provides a polycarbonate resin composition comprising the polycarbonate resin according to the above exemplary embodiment.

[0031] Another exemplary embodiment of this specification provides a molding article comprising a polycarbonate resin composition according to the above exemplary embodiment.

[0032] Beneficial effects

[0033] The polycarbonate resin according to the exemplary embodiments of this specification has a high refractive index and high transparency.

[0034] By using the polycarbonate resin according to the exemplary embodiments of this specification, excellent optical lenses, optical films, optical thin films, or optical resins with small thicknesses can be obtained. Attached Figure Description

[0035] Figure 1 A graph showing the rate of reduction in lens thickness depending on the difference in refractive index. Detailed Implementation

[0036] This instruction manual will be described in more detail below.

[0037] For a polycarbonate resin comprising units of Formula 1 according to an exemplary embodiment of this specification, it can be seen from the relationship between molecular structure and refractive index known from the Lorentz-Lorenz formula that the refractive index of a material composed of molecules can be increased by increasing the electron density of the molecules and decreasing the molecular volume. Furthermore, since the substituents on both sides of the benzene rings of Formula 1 form an asymmetric structure and include R1 and R2 as substituents, the refractive index of a molding article comprising the polycarbonate resin can be improved by increasing the electron density. Therefore, the polycarbonate resin according to an exemplary embodiment of this specification has a high refractive index and high transparency, and optical lenses, optical films, or optical resins using the polycarbonate resin have small thicknesses and can exhibit excellent optical properties.

[0038] Throughout this application, the term "combination thereof" included in the Markush-type expression means a mixture or combination of one or more of the constituent elements described in the Markush-type expression, and means including one or more of the constituent elements described above.

[0039] Examples of substituents used in this specification will be described below, but are not limited thereto.

[0040] In this instruction manual, This refers to the part that needs to be connected.

[0041] In this specification, the term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced by another substituent, and there is no restriction 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), and when two or more are substituted, the two or more substituents can be the same as or different from each other.

[0042] In this specification, the term "substituted or unsubstituted" means substituted with one or more substituents selected from: deuterium, halogen group, hydroxyl, cyano, alkyl, cycloalkyl, alkoxy, alkenyl, aryloxy, arylthio, alkylthio, silyl, aryl, fused ring of aromatic and aliphatic hydrocarbon rings, and heteroaryl, substituted with a substituent connected to two or more of the exemplified substituents, or without substituents.

[0043] In this specification, the fact that two or more substituents are linked means that the hydrogen of any one substituent is linked to another substituent. For example, when two substituents are linked to each other, phenyl and naphthyl can be linked together to form... The substituents. Furthermore, the connection of three substituents includes not only the sequential connection of (substituent 1)-(substituent 2)-(substituent 3), but also the connection of (substituent 2) and (substituent 3) with (substituent 1). For example, phenyl, naphthyl, and isopropyl can be linked together to form... The above definition also applies to cases where four or more substituents are connected to each other.

[0044] Examples of halogen groups in this specification include fluorine, chlorine, bromine, or iodine.

[0045] In this specification, alkyl groups may be straight-chain or branched, and there is no particular limitation on the number of carbon atoms, but it is preferred to be 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc., but are not limited to these.

[0046] In this specification, there is no particular limitation on cycloalkyl groups, but they are preferably composed of 3 to 30 carbon atoms, and specific examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, adamantyl, etc.

[0047] In this specification, the alkoxy group can be straight-chain, branched, or cyclic. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 30. Specific examples include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexyloxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decoxy, benzyloxy, p-methylbenzyloxy, etc.

[0048] In this specification, the alkenyl group can be linear or branched, and its number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, styryl, styryl, etc., but are not limited thereto.

[0049] In this specification, there are no particular limitations on the aryl group, but it is preferred to have 6 to 50 carbon atoms, and the aryl group can be monocyclic or polycyclic.

[0050] When the aryl group is a monocyclic aryl group, there is no particular limitation on the number of carbon atoms, but it is preferably 6 to 30. Specific examples of monocyclic aryl groups include phenyl, biphenyl, terphenyl, etc., but are not limited to these.

[0051] When the aryl group is a polycyclic aryl group, there is no particular limitation on the number of carbon atoms, but it is preferably 10 to 50. Specific examples of polycyclic aryl groups include naphthyl, anthraceneyl, phenanthreneyl, benzo[a]phenanthreneyl, pyreneyl, finadeninyl, peryleneyl, etc. It includes, but is not limited to, methyl, fluorene, etc.

[0052] In this specification, the fluorene group may be substituted, and adjacent groups may bond to each other to form a ring.

[0053] Examples of fluorene substitution include And so on, but not limited to these.

[0054] In this specification, "adjacent" groups may mean a substituent that substitutes for an atom directly bonded to the atom substituted by the corresponding substituent, a substituent that is spatially closest to the corresponding substituent, or another substituent that substitutes for the atom substituted by the corresponding substituent. For example, two substituents that substitute at the ortho position on a benzene ring and two substituents that substitute for the same carbon atom in an aliphatic ring can be interpreted as groups that are "adjacent" to each other.

[0055] In the specification, the heteroaryl group comprises one or more atoms other than carbon, i.e., one or more heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from O, N, Se, S, etc. The number of carbon atoms is not particularly limited, but is preferably 2 to 30, and the heteroaryl group can be monocyclic or polycyclic. Examples of heteroaryl groups include thiophene, furanyl, pyrrole, imidazolyl, thiazolyl, etc. azole group, Diazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridineyl, pyridazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazenopyrazinyl, isoquinolinyl, indoleyl, carbazoleyl, benzo[] Azolyl, benzimidazolyl, benzothiazolyl, benzocarbazole, benzothiophene, dibenzothiophene, benzofuranyl, phenanthridine, phenanthrolinyl, iso Azolyl, thiadiazolyl, dibenzofuranyl, dibenzothiopyrrolyl, phen Thiol, phen Phenothiazinyl, dihydroindocarbazolyl, spirofluorenyl succinyl, spirofluorenyl thiopheneyl, tetrahydronaphthothiopheneyl, tetrahydronaphthofuranyl, tetrahydrobenzothiopheneyl, tetrahydrobenzofuranyl, etc., but not limited to these.

[0056] In this specification, silane can be alkylsilane, arylsilane, alkylarylsilane, heteroarylsilane, etc. The above examples of alkyl can be applied to alkyl groups in alkylsilane, the above examples of aryl can be applied to aryl groups in arylsilane, the examples of alkyl and aryl can be applied to alkyl and aryl groups in alkylarylsilane, and the examples of heteroaryl can be applied to heteroaryl groups in heteroarylsilane.

[0057] In this specification, the hydrocarbon cyclogroup can be an aromatic hydrocarbon cyclogroup, an aliphatic hydrocarbon cyclogroup, or a fused cyclogroup of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring, and can be selected from examples of cycloalkyl, aryl, and combinations thereof. Examples of hydrocarbon cyclogroups include phenyl, cyclohexyl, adamantyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.1]octyl, tetrahydronaphthyl, tetrahydroanthrayl, 1,2,3,4-tetrahydro-1,4-bridged methylenenaphthyl, 1,2,3,4-tetrahydro-1,4-bridged ethylnaphthyl, spirocyclopentanefluorenyl, spiroadamantanefluorenyl, spirocyclohexanefluorenyl, etc., but are not limited thereto.

[0058] In this specification, aryl groups may be represented by -ORo, and the description of the above aryl groups applies to Ro.

[0059] In this specification, aryl thio groups may be represented by -SRs1, and the description of the above aryl groups applies to Rs1.

[0060] In this specification, alkyl thio groups may be represented by -SRs2, and the description of the above alkyl groups applies to Rs2.

[0061] In this specification, alkylene refers to a group having two bonding positions within an alkyl group, i.e., a divalent group. The above description of alkyl groups can be applied to alkylene groups, except that alkylene groups are divalent.

[0062] In this specification, cycloalkylene refers to a group having two bonding positions in a cycloalkyl group, i.e., a divalent group. The above description of cycloalkyl can be applied to cycloalkylene, except that cycloalkylene is divalent.

[0063] In this specification, arylene refers to a group having two bonding positions within an aryl group, i.e., a divalent group. The above description of aryl groups can be applied to arylene groups, the difference being that arylene groups are divalent.

[0064] In this specification, "divalent fused ring group of aromatic and aliphatic hydrocarbon rings" refers to a group having two bonding positions in the fused ring group of aromatic and aliphatic hydrocarbon rings, i.e., a divalent group. The above description of fused ring groups of aromatic and aliphatic hydrocarbon rings can be applied, except that each of these groups is a divalent group.

[0065] According to one exemplary embodiment of this specification, the polycarbonate resin further comprises a unit of the following chemical formula 2.

[0066] [Chemical Formula 2]

[0067]

[0068] In chemical formula 2,

[0069] L11 can be a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted divalent fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring, or a substituted or unsubstituted arylene group.

[0070] l11 is an integer from 1 to 5, and when l11 is 2 or greater, two or more L11s are either the same or different from each other.

[0071] X11 to X14 may be the same as or different from each other, and each is independently O or S.

[0072] Z11 and Z12 may be the same as or different from each other, and each is independently a substituted or unsubstituted alkylene group or a substituted or unsubstituted cycloalkylene group.

[0073] a' and b' are either the same or different from each other, and are each an independent integer from 0 to 10. Furthermore, when a' and b' are each 2 or greater, the structures within the parentheses are either the same or different from each other.

[0074] * refers to the part that is connected to the main chain of the resin.

[0075] By further incorporating units represented by Formula 2, polycarbonate resins can supplement the glass transition temperature (Tg) of units of Formula 1 or make the chain behavior of units of Formula 1 more flexible, and have technical effects that are beneficial to the injection molding of molded articles.

[0076] An exemplary embodiment of this specification provides a polycarbonate resin comprising units of chemical formula 1 and units of chemical formula 2.

[0077] According to one exemplary embodiment of this specification, r1 is 1.

[0078] According to an exemplary embodiment of this specification, chemical formula 1 is any one of the following chemical formulas 1-1 to 1-4.

[0079] [Chemical Formula 1-1]

[0080]

[0081] [Chemical Formula 1-2]

[0082]

[0083] [Chemical Formulas 1-3]

[0084]

[0085] [Chemical Formulas 1-4]

[0086]

[0087] In chemical formulas 1-1 to 1-4,

[0088] The definitions of Z1, Z2, X1 to X4, a, b, L1, L2 and R1 are the same as those defined in Formula 1.

[0089] According to an exemplary embodiment of this specification, R1 and R2 are different from each other and are each independently hydrogen or an unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; L1 and L2 are the same as or different from each other and are each independently a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms; X1 to X4 are O; and Z1 and Z2 are the same as or different from each other and are each independently a straight-chain or branched alkylene group having 1 to 30 carbon atoms.

[0090] According to an exemplary embodiment of this specification, R1 and R2 are different from each other and are each independently hydrogen or an unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0091] According to an exemplary embodiment of this specification, R1 and R2 are different from each other and are each independently hydrogen or an unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0092] According to an exemplary embodiment of this specification, R1 and R2 are different from each other and are each independently hydrogen or an unsubstituted polycyclic aryl group having 10 to 30 carbon atoms.

[0093] According to an exemplary embodiment of this specification, R1 and R2 are different from each other and are each independently hydrogen or an unsubstituted polycyclic aryl group having 10 to 20 carbon atoms.

[0094] According to one exemplary embodiment of this specification, R1 and R2 are different from each other and are each independently hydrogen or naphthyl.

[0095] According to one exemplary embodiment of this specification, R1 is a naphthyl group.

[0096] According to one exemplary embodiment of this specification, R2 is hydrogen.

[0097] According to one exemplary embodiment of this specification, L1 and L2 may be the same as or different from each other, and each is independently a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms.

[0098] According to one exemplary embodiment of this specification, L1 and L2 may be the same as or different from each other, and each is independently a monocyclic or polycyclic arylene group having 6 to 20 carbon atoms.

[0099] According to one exemplary embodiment of this specification, L1 and L2 may be the same as or different from each other, and each is independently a polycyclic aryl group having 10 to 30 carbon atoms.

[0100] According to one exemplary embodiment of this specification, L1 and L2 may be the same as or different from each other, and each is independently a polycyclic aryl group having 10 to 20 carbon atoms.

[0101] According to an exemplary embodiment of this specification, L1 and L2 are divalent naphthyl groups.

[0102] According to one exemplary embodiment of this specification, X1 is 0.

[0103] According to one exemplary embodiment of this specification, X2 is 0.

[0104] According to one exemplary embodiment of this specification, X3 is 0.

[0105] According to one exemplary embodiment of this specification, X4 is 0.

[0106] According to one exemplary embodiment of this specification, Z1 and Z2 may be the same as or different from each other, and each is independently a straight-chain or branched alkylene group having 1 to 30 carbon atoms.

[0107] According to one exemplary embodiment of this specification, Z1 and Z2 may be the same as or different from each other, and each is independently a straight-chain or branched alkylene group having 1 to 20 carbon atoms.

[0108] According to an exemplary embodiment of this specification, Z1 and Z12 are ethylene.

[0109] According to one exemplary embodiment of this specification, a is 1.

[0110] According to one exemplary embodiment of this specification, b is 1.

[0111] According to one exemplary embodiment of this specification, a is 0.

[0112] According to one exemplary embodiment of this specification, b is 0.

[0113] According to an exemplary embodiment of this specification, L11 is a straight-chain or branched alkylene group having 1 to 30 carbon atoms; a fused ring group consisting of a divalent monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aliphatic hydrocarbon ring having 3 to 30 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 50 carbon atoms, which is unsubstituted or substituted with a straight-chain or branched alkyl group having 1 to 30 carbon atoms or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0114] According to an exemplary embodiment of this specification, L11 is a straight-chain or branched alkylene group having 1 to 20 carbon atoms; a fused ring group consisting of a divalent monocyclic or polycyclic aromatic hydrocarbon ring having 6 to 20 carbon atoms and an aliphatic hydrocarbon ring having 3 to 20 carbon atoms; or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms, which is unsubstituted or substituted with a straight-chain or branched alkyl group having 1 to 20 carbon atoms or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0115] According to an exemplary embodiment of this specification, L11 is an unsubstituted or methyl-substituted methylene; isopropylidene; an unsubstituted or methyl- or phenyl-substituted phenylene; a divalent naphthyl; or a divalent fluorene.

[0116] According to one exemplary embodiment of this specification, l11 is 1.

[0117] According to one exemplary embodiment of this specification, l11 is 2, and the two L11 are the same as or different from each other.

[0118] According to one exemplary embodiment of this specification, l11 is 3, and the three L11s may be the same as or different from each other.

[0119] According to one exemplary embodiment of this specification, X11 is 0.

[0120] According to one exemplary embodiment of this specification, X12 is 0.

[0121] According to one exemplary embodiment of this specification, X13 is 0.

[0122] According to one exemplary embodiment of this specification, X14 is 0.

[0123] According to an exemplary embodiment of this specification, Z11 and Z12 may be the same as or different from each other, and each is independently a straight-chain or branched alkylene group having 1 to 30 carbon atoms.

[0124] According to an exemplary embodiment of this specification, Z11 and Z12 may be the same as or different from each other, and each is independently a straight-chain or branched alkylene group having 1 to 20 carbon atoms.

[0125] According to an exemplary embodiment of this specification, Z11 and Z12 are ethylene.

[0126] According to one exemplary embodiment of this specification, a' is 1.

[0127] According to one exemplary embodiment of this specification, b' is 1.

[0128] According to one exemplary embodiment of this specification, a' is 0.

[0129] According to one exemplary embodiment of this specification, b' is 0.

[0130] According to an exemplary embodiment of this specification, the polycarbonate resin may each have -OH, -SH, -CO2CH3, -Cl, or -OC6H5 as two end groups.

[0131] In one exemplary embodiment of this specification, the weight-average molecular weight of the polycarbonate resin is from 5,000 g / mol to 500,000 g / mol, preferably from 8,000 g / mol to 400,000 g / mol, 10,000 g / mol to 350,000 g / mol, or 11,000 g / mol to 300,000 g / mol. More preferably, the weight-average molecular weight of the polycarbonate resin is from 12,000 g / mol to 250,000 g / mol, 13,000 g / mol to 200,000 g / mol, 14,000 g / mol to 150,000 g / mol, or 15,000 g / mol to 100,000 g / mol.

[0132] In one exemplary embodiment of this specification, the number average molecular weight of the polycarbonate resin is 2,000 g / mol to 300,000 g / mol, 4,000 g / mol to 250,000 g / mol, 5,000 g / mol to 210,000 g / mol, 6,000 g / mol to 180,000 g / mol, 6,500 g / mol to 150,000 g / mol, 7,000 g / mol to 120,000 g / mol, 7,000 g / mol to 90,000 g / mol, and preferably 8,000 g / mol to 60,000 g / mol.

[0133] When the polycarbonate resin meets the above-mentioned weight-average molecular weight range and number-average molecular weight range, the polycarbonate resin can have the best flowability and processability.

[0134] In this specification, the weight-average molecular weight (Mw) of the polycarbonate resin and the oligomers used to prepare it can be measured using gel permeation chromatography (GPC) with polystyrene (PS) standards on an Agilent 1200 series instrument. Specifically, the weight-average molecular weight can be measured using an Agilent 1200 series instrument with a Polymer Laboratories PLgel MIX-B 300 mm column, and in this case, the measurement temperature is 40 °C, the solvent used is tetrahydrofuran (THF), and the flow rate is 1 mL / min. Samples of polycarbonate resin or oligomers are each prepared at a concentration of 10 mg / 10 mL, then fed in 10 μL increments, and the weight-average molecular weight (Mw) value is obtained using a calibration curve formed using polystyrene standards. In this case, nine types of standard polystyrene products 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 are used.

[0135] In one exemplary embodiment of this specification, the glass transition temperature (Tg) of the polycarbonate resin can be from 90°C to 200°C. Alternatively, the glass transition temperature can be from 110°C to 190°C. The glass transition temperature is preferably from 100°C to 190°C, or from 120°C to 180°C, and specifically from 126.3°C to 178.4°C. When the polycarbonate resin meets the above glass transition temperature range, the glass transition temperature can be easily adjusted to meet the physical properties desired in this specification when preparing a polycarbonate resin composition by mixing it with a resin having excellent heat resistance and injection moldability and a glass transition temperature different from the above range.

[0136] The glass transition temperature (Tg) can be measured using differential scanning calorimetry (DSC). Specifically, the glass transition temperature can be measured by a graph obtained by heating a polycarbonate resin sample of 5.5 mg to 8.5 mg to 270 °C under a nitrogen atmosphere, then cooling it, and scanning the resin sample during a second heating process while heating it at a heating rate of 10 °C / min.

[0137] In one exemplary embodiment of this specification, the polycarbonate resin has a refractive index of 1.50 to 1.75 measured at a wavelength of 587 nm. The refractive index may preferably be 1.64 to 1.712, and more preferably 1.6456 to 1.7015. When the resin meets the above refractive index, thin and lightweight optical lenses can be manufactured when the resin is applied to molding articles such as optical lenses.

[0138] In one exemplary embodiment of this specification, the Abbe number of the resin, measured and calculated at wavelengths of 486 nm, 587 nm, and 656 nm, can be between 5 and 45. The Abbe number is preferably between 10 and 25, and more preferably between 15 and 23, or between 15.0 and 21.3. When the resin meets the above Abbe number range, when the resin is applied to molded products such as optical lenses, there is an effect of reduced dispersion and increased sharpness. Specifically, the Abbe number can be determined by measuring the refractive index (n) at wavelengths of D (587 nm), F (486 nm), and C (656 nm) at 20°C. D n F and n C It is obtained through the following equation.

[0139] Abbe number = (n D -1) / (n F -n C )

[0140] The refractive index can be measured by the prism coupler method, and for example, the SPA-3DR manufactured by SAIRON Technology Inc. can be used, but is not limited to this.

[0141] The refractive index of the resin can be calculated by measuring the change in the amount of light reflected from a sample prepared by flattening the resin by placing a glass slide on a heated plate at 200°C using a prism coupler. When the prepared sample is brought into contact with a prism and a laser is incident on it, most of the incident laser light is totally internally reflected. However, under specific incident angles and conditions, light is coupled due to the evanescent field generated at the boundary surface. By measuring the angle at which coupling occurs, the intensity of the light detected by the detector decreases sharply. The refractive index of the film can then be automatically calculated using the prism coupler from parameters related to the polarization mode of the light and the refractive indices of the prism and the substrate.

[0142] An exemplary embodiment of the present invention provides a method for preparing a polycarbonate resin, the method comprising: polymerizing a composition for preparing a polycarbonate resin, the composition comprising a compound of the following chemical formula 1a and a polycarbonate precursor.

[0143] [Chemical Formula 1a]

[0144]

[0145] In chemical formula 1a,

[0146] R1 and R2 are distinct from each other and are each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; an unsubstituted or substituted aryl group or a group substituted with deuterium, a halogen group, a hydroxyl group, a cyano group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryloxy group, an arylthio group, an alkylthio group, an aryl group, or a heteroaryl group; or a substituted or unsubstituted heteroaryl group.

[0147] r1 and r2 are each integers from 1 to 4, and when r1 is 2 or greater, two or more R1s are either the same or different from each other, and when r2 is 2 or greater, two or more R2s are either the same or different from each other.

[0148] L1 and L2 may be the same as or different from each other, and each may be independently a substituted or unsubstituted aryl group.

[0149] X1 to X4 may be the same as or different from each other, and each is independently O or S.

[0150] Z1 and Z2 may be the same as or different from each other, and each is independently a substituted or unsubstituted alkylene group, or a substituted or unsubstituted cycloalkylene group, and

[0151] a and b are either the same or different from each other, and each is an independent integer from 1 to 10. When a and b are each 2 or greater, the structures within the parentheses are either the same or different from each other.

[0152] According to an exemplary embodiment of this specification, the composition for preparing a polycarbonate resin further comprises a compound of formula 2a, wherein the compound of formula 1a and the compound of formula 2a are included in an amount of 0.01 mol% to 100 mol%: 99.99 mol% to 0 mol%. Specifically, the compound is included in an amount of 0.01 mol% to 99.99 mol%: 99.99 mol% to 0.01 mol%. More specifically, the compound is included in amounts of 0.1 mol% to 99.9 mol%: 99.9 mol% to 0.1 mol%, 1 mol% to 99 mol%: 99 mol% to 1 mol%, and 5 mol% to 90 mol%: 5 mol% to 90 mol%.

[0153] [Chemical Formula 2a]

[0154]

[0155] In chemical formula 2a,

[0156] L11 can be a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted divalent fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring, or a substituted or unsubstituted arylene group.

[0157] l11 is an integer from 1 to 5, and when l11 is 2 or greater, two or more L11s are either the same or different from each other.

[0158] X11 to X14 may be the same as or different from each other, and each is independently O or S.

[0159] Z11 and Z12 may be the same as or different from each other, and each is independently a substituted or unsubstituted alkylene group or a substituted or unsubstituted cycloalkylene group.

[0160] a' and b' are either the same or different from each other, and are each an independent integer from 0 to 10. When a' and b' are each 2 or greater, the structures within the parentheses are either the same or different from each other.

[0161] An exemplary embodiment of the present invention provides a method for preparing a polycarbonate resin, the method comprising: polymerizing a composition for preparing the polycarbonate resin, said composition comprising a compound of formula 1a and a polycarbonate precursor. When the compound of formula 1a is included, said compound readily polymerizes, has a wide range of refractive indices or high refractive indices depending on the substituents, and has a wide range of glass transition temperatures.

[0162] An exemplary embodiment of the present invention provides a method for preparing a polycarbonate resin, the method comprising: polymerizing a composition for preparing the polycarbonate resin, said composition comprising a compound of formula 1a, a compound of formula 2a, and a polycarbonate precursor. The compounds of formula 1a and formula 2a are included in an amount of 0.01 mol% to 100 mol%: 99.99 mol% to 0 mol%. Specifically, the compounds are included in an amount of 0.01 mol% to 99.99 mol%: 99.99 mol% to 0.01 mol%. More specifically, the compounds are included in amounts of 0.1 mol% to 99.9 mol%: 99.9 mol% to 0.1 mol%, 1 mol% to 99 mol%: 99 mol% to 1 mol%, and 5 mol% to 90 mol%: 5 mol% to 90 mol%.

[0163] When chemical formulas 1a and 2a are included in the above amounts, the compound readily polymerizes, exhibits a wide range of refractive indices or high refractive indices depending on the substituents, and has a wide range of glass transition temperatures. Furthermore, the glass transition temperature (Tg) and refractive index can be adjusted, and the chain behavior of the polycarbonate resin can be made flexible, resulting in technical effects favorable for injection molding of molded articles. The composition used to prepare the polycarbonate resin may also contain a solvent.

[0164] The solvent may be, for example, diphenyl ether, dimethylacetamide or methanol, but is not limited thereto, and any solvent used in the art may be suitably employed.

[0165] The solvent may be included in an amount of 5 to 60 parts by weight relative to 100 parts by weight of the composition for preparing the resin.

[0166] The solvent may be included in an amount of preferably 5 to 50 parts by weight, 7 to 45 parts by weight, or 8 to 40 parts by weight relative to 100 parts by weight of the composition for preparing the resin.

[0167] In one exemplary embodiment of this specification, the compound may be a compound of chemical formula 1a, but is not limited thereto.

[0168]

[0169] In one exemplary embodiment of this specification, the compound of chemical formula 2a may be any of, but is not limited to, the following compounds.

[0170]

[0171] In one exemplary embodiment of this specification, the compound of formula 1a may be included in an amount of 1 to 100 parts by weight or 1 to 99 parts by weight relative to 100 parts by weight of the composition for preparing polycarbonate resin.

[0172] The compound of formula 1a may be included in an amount preferably from 1 to 60 parts by weight, 1 to 50 parts by weight, 1 to 40 parts by weight, 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight, relative to 100 parts by weight of the composition for preparing polycarbonate resin.

[0173] In one exemplary embodiment of this specification, the compound of formula 2a may be included in an amount of 0 to 99 parts by weight or 1 to 99 parts by weight relative to 100 parts by weight of the composition for preparing polycarbonate resin.

[0174] The compound of formula 2a may be included in an amount preferably from 1 to 60 parts by weight, 1 to 50 parts by weight, 1 to 40 parts by weight, 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight, relative to 100 parts by weight of the composition for preparing polycarbonate resin.

[0175] In one exemplary embodiment of this specification, the polycarbonate precursor may be included in an amount of 1 to 60 parts by weight relative to 100 parts by weight of the composition for preparing the polycarbonate resin.

[0176] The polycarbonate precursor may be included in an amount preferably from 1 to 60 parts by weight, 1 to 55 parts by weight, 1 to 50 parts by weight, 1 to 45 parts by weight, or 1 to 40 parts by weight, relative to 100 parts by weight of the composition for preparing the polycarbonate resin.

[0177] According to one exemplary embodiment of this specification, the polycarbonate precursor is of the following chemical formula A.

[0178] [Chemical Formula A]

[0179]

[0180] In chemical formula A,

[0181] Rb1 and Rb2 may be the same as or different from each other, and each is independently a halogen group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

[0182] a1 and a2 are each 0 or 1.

[0183] According to an exemplary embodiment of this specification, Rb1 and Rb2 may be the same as or different from each other, and each is independently a halogen group, a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0184] According to an exemplary embodiment of this specification, Rb1 and Rb2 may be the same as or different from each other, and each is independently a halogen group, a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0185] According to an exemplary embodiment of this specification, Rb1 and Rb2 may be the same as or different from each other, and each is independently a halogen group, a straight-chain or branched alkyl group having 1 to 30 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

[0186] According to an exemplary embodiment of this specification, Rb1 and Rb2 may be the same as or different from each other, and each is independently a halogen group, a straight-chain or branched alkyl group having 1 to 20 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms.

[0187] According to one exemplary embodiment of this specification, Rb1 and Rb2 may be the same as or different from each other, and each is independently -Cl, methyl, ethyl, n-propyl, isopropyl, n-butyl, or phenyl.

[0188] According to one exemplary embodiment of this specification, the compound of chemical formula A is selected from any of the following compounds.

[0189]

[0190] In the case of polyester resins, the precursor (terephthalate) (etc.) has a higher content than polycarbonate resin precursors (carbonates) It has a higher molecular weight and accounts for a large proportion of the resin's weight.

[0191] Because the precursor reduces the concentration of the diol monomers that achieve high refractive indices, polycarbonate resins have a relatively higher refractive index than polyester resins. Furthermore, compared to polycarbonate resins, polyester resins have long conjugated bonds due to their structural characteristics and typically have a higher yellowness index due to intramolecular hydrogen bonding.

[0192] If necessary, the polycarbonate precursor is used to link additional comonomers, and other specific examples of its application, besides compounds represented by chemical formula A, include phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, xylene carbonate, bis(chlorophenyl) carbonate, m-cresol carbonate, dinaphthalene carbonate, bis(diphenyl) carbonate, dihalocarbamate, etc., and any one or a mixture of two or more of them may be used.

[0193] In one exemplary embodiment of this specification, it is preferred that the polycarbonate resin is polymerized from a compound of formula 1a and a polycarbonate precursor of formula A.

[0194] The unit of the above-mentioned chemical formula 1 can be formed by polymerizing the compound of chemical formula 1a and the polycarbonate precursor of chemical formula A.

[0195] The compound of formula 1a may be used in amounts from 1 to 100 mol parts and from 1 to 99 mol parts, relative to 100 mol parts of a polycarbonate resin comprising units of formula 1.

[0196] The polycarbonate precursor of formula A can be used in amounts of 50 to 150 mol parts relative to 100 mol parts of all monomers of the compound of formula 1a constituting the resin.

[0197] In one exemplary embodiment of this specification, the polycarbonate resin may also comprise a unit of chemical formula 2.

[0198] The unit of the above-mentioned chemical formula 2 can be formed by polymerizing the compound of chemical formula 2a and the polycarbonate precursor of chemical formula A.

[0199] The compound of formula 2a can be used in amounts of 0 to 99 mol parts and 1 to 99 mol parts, relative to 100 mol parts of all monomers of a polycarbonate resin comprising units of formula 2.

[0200] The polycarbonate precursor of formula A can be used in amounts of 50 to 150 mol parts relative to 100 mol parts of all monomers of the compound of formula 2a constituting the resin.

[0201] For the polymerization of the resin according to this specification, methods known in the art can be used.

[0202] Preferably, polymerization is carried out by melt polycondensation.

[0203] In melt polycondensation, a composition for preparing polycarbonate resin can be used, with a catalyst applied as needed, and melt polycondensation can be carried out under heating and further under atmospheric or reduced pressure via transesterification, while removing byproducts. Materials commonly used in the art can be used as catalysts.

[0204] Specifically, in the melt polycondensation method, it is preferable to melt the compound of formula 1a and the polycarbonate precursor in a reaction vessel, and then carry out the reaction while the byproduct compound is in a stationary state. The composition used to prepare the polycarbonate resin may also contain a compound of formula 2a.

[0205] To allow byproduct compounds to remain in the reactor, the pressure can be controlled by shutting down the reaction apparatus or by reducing or increasing the pressure.

[0206] The reaction time of the process is 20 minutes or longer and 600 minutes or shorter, preferably 40 minutes or longer and 450 minutes or shorter, and more preferably 60 minutes or longer and 300 minutes or shorter.

[0207] In this scenario, when the byproduct compounds are distilled off immediately after their formation, the resulting resin has a low content of high molecular weight material. However, when the byproduct compounds are allowed to remain in the reaction vessel for a certain period of time, the resulting resin is obtained as having a high content of high molecular weight material.

[0208] Melt polycondensation can be carried out continuously or intermittently. The reaction apparatus used to perform the reaction can be a vertical type equipped with anchor-type impellers, maxblend impellers, spiral belt impellers, etc., or a horizontal type equipped with paddle blades, grid blades, spectacle-shaped blades, etc., or an extruder type equipped with a screw. Furthermore, considering the viscosity of the polymer, it is desirable to use a reaction apparatus with an appropriate combination of these reaction devices.

[0209] In the methods for preparing polycarbonate resins used in this specification, the catalyst can be removed or deactivated after the polymerization reaction is complete to maintain thermal and hydrolytic stability. Preferably, the catalyst can be deactivated by adding an acidic material known in the art.

[0210] As acidic materials, esters are preferably used, such as butyl benzoate; aromatic sulfonic acids, such as p-toluenesulfonic acid; aromatic sulfonates, such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids, such as phosphorous acid, phosphoric acid, and phosphonic acid; phosphite esters, such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite; phosphate esters, such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonic acids, such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonate esters, such as diethyl phenylphosphonate; phosphine derivatives, such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids, such as boric acid and phenylboronic acid; and aromatic sulfonates, such as tetrabutyl dodecylbenzenesulfonate. Salts; organohalides, such as stearic acid chloride, benzoyl chloride and p-toluenesulfonyl chloride; alkyl sulfuric acid, such as dimethyl sulfuric acid; organohalides, such as benzyl chloride, etc.

[0211] The acidic material can be used in amounts of 0.1 mol to 5 mol, preferably 0.1 mol to 1 mol, relative to 100 mol of catalyst.

[0212] When the amount of acidic material is less than 0.1 mol, the deactivation effect becomes insufficient, which is not preferred. Furthermore, when the amount exceeds 5 mol, the heat resistance of the resin deteriorates and the molded articles are prone to staining, which is also not preferred.

[0213] After catalyst deactivation, a further process can be carried out at a pressure of 0.1 mmHg to 1 mmHg and a temperature of 200°C to 350°C to remove low-boiling-point compounds from the resin. In this process, a horizontal apparatus or thin-film evaporator equipped with stirring blades having excellent surface renewal capabilities, such as paddle blades, grid blades, and spectacle-shaped blades, is preferably used.

[0214] Preferably, the resin in this specification contains as few foreign matter as possible, and preferably, the molten raw materials are filtered, the catalyst solution is filtered, etc.

[0215] The sieve aperture of the filter used for filtration is preferably 5 μm or smaller, and more preferably 1 μm or smaller. Furthermore, a polymer filter is preferably used to filter the produced resin. The sieve aperture of the polymer filter is preferably 100 μm or smaller, and more preferably 30 μm or smaller. In addition, the process of obtaining the resin granules needs to be carried out in a low-dust environment, preferably level 6 or lower, and more preferably level 5 or lower.

[0216] In addition to injection molding, examples of methods for molding molded articles containing polycarbonate resin include compression molding, casting, rolling, extrusion molding, stretching, etc., but are not limited to these.

[0217] Another exemplary embodiment of this specification provides a polycarbonate resin composition comprising the resin according to the above exemplary embodiment.

[0218] In one exemplary embodiment of this specification, based on 100 parts by weight of the polycarbonate resin composition, the polycarbonate resin may be included in an amount from 1 part by weight to 80 parts by weight.

[0219] In one exemplary embodiment of this specification, the polycarbonate resin composition may further comprise a solvent. The solvent may be, for example, dimethylacetamide or 1,2-dichlorobenzene.

[0220] Based on 100 parts by weight of the polycarbonate resin composition, the solvent may be included in an amount of 20 to 99 parts by weight.

[0221] In addition to the compounds of Formula 1a, the polycarbonate resin composition may also contain other monomers. There are no particular limitations on the other monomers, and monomers commonly used in the field of polycarbonate may be appropriately used, as long as they do not alter the main physical properties of the polycarbonate resin composition. The additional monomers may be used in amounts from 1 to 50 mol parts relative to all monomers constituting a resin comprising units of Formula 1, 1 mol parts per unit volume.

[0222] If necessary, in addition to resins containing units of Formula 1, polycarbonate resin compositions may also contain one or more additives selected from the following: for example, antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent whitening agents, UV absorbers, pigments, and dyes.

[0223] Based on 100 parts by weight of the polycarbonate resin composition, the additives may be included in an amount from 1 part by weight to 99 parts by weight.

[0224] There are no particular restrictions on the types of antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent whitening agents, UV absorbers, pigments or dyes, and those used in the art may be appropriately employed.

[0225] Another exemplary embodiment of this specification provides a molding article comprising a resin composition according to the above exemplary embodiment.

[0226] In one exemplary embodiment of this specification, the molding article may be prepared from a polycarbonate resin composition or its cured product.

[0227] As an example of a method for preparing a molded article, it may include: thoroughly mixing a resin and an additive containing a unit of chemical formula 1 using a mixer, preparing the resulting mixture into granules by extruding the mixture using an extruder, drying the granules, and then injection molding the granules using an injection molding machine.

[0228] In one exemplary embodiment of this specification, the molded article is an optical lens.

[0229] In one exemplary embodiment of this specification, the thickness of the optical lens is from 0.1 μm to 30 mm.

[0230] Due to differences in the refractive index of optical lenses, the focal point of light can differ between lenses of the same thickness. This is because... Figure 1 This is illustrated in the diagram. This changes the position of the focal point between the camera lens and the image sensor, and between the spectacle lens and the human pupil, and as the refractive index increases, the thickness of the lens and the film decreases to adjust the focal point at the same position. An exemplary embodiment of the optical lens according to this specification has a high refractive index, and therefore an optical lens with a small thickness can be achieved.

[0231] The optical lens is made using the polycarbonate resin, has a small thickness, high refractive index and high transparency, and can be preferably used in cameras.

[0232] In one exemplary embodiment of this specification, the molding article is an optical film or optical thin film. The optical film or optical thin film is made of polycarbonate resin, has a small thickness and excellent light-catching and light-diffusing effects, and can be preferably applied to backlight modules of liquid crystal displays, planar lenses and superlenses, etc.

[0233] In one exemplary embodiment of this specification, the thickness of the optical film or optical thin film is from 0.1 nm to 10 mm.

[0234] In one exemplary embodiment of this specification, the molding article is an optical resin. The optical resin is made of polycarbonate resin and has low optical loss due to its small thickness, high refractive index, and low birefringence.

[0235] The optical resin according to an exemplary embodiment of this specification exhibits low optical loss due to its high refractive index and low birefringence. The optical resin according to an exemplary embodiment of this specification has a glass transition temperature of 90°C to 200°C, which is not particularly high or low in terms of heat resistance compared to general optical materials in the relevant art, thus making it easy to process and exhibiting excellent heat resistance. When the glass transition temperature exceeds 200°C, it becomes difficult to process the optical resin due to the increased melt flow index, while when the glass transition temperature is below 90°C, the low heat resistance results in poor weather resistance due to the external environment. Therefore, optical resins according to an exemplary embodiment of this specification that possess suitable thermal properties and achieve a high refractive index are rare.

[0236] Invention Embodiments

[0237] The present specification will be illustrated in more detail below by way of examples.

[0238] Preparation Example 1: Preparation of Resin 1

[0239] 66.48 g (0.1009 mol) of monomer 1-1 and 21.422 g (0.100 mmol) of diphenyl carbonate were melted and reacted at 250 °C for 5 hours. Phenol was produced as a byproduct during the reaction, and the pressure was adjusted up to 1 Torr to remove the phenol. After the reaction was complete, resin 1, the polymer melt resin, was obtained by blowing nitrogen into the reactor to create an atmospheric pressure atmosphere.

[0240] Monomer 1-1:

[0241] Preparation Examples 2 to 17: Preparation of Resins 2 to 17

[0242] Resins 2 to 17 were prepared in the same manner as in Preparation Example 1, except that monomers in Table 1 below were used instead of monomers 1-1 in Preparation Example 1 in the following molar amounts.

[0243]

[0244] [Table 1]

[0245]

[0246] Experimental example.

[0247] The molecular weight and molecular weight distribution of the polymerized resin sample were determined by gel permeation chromatography (GPC), and thermal properties were studied by obtaining thermograms using differential scanning calorimetry (DSC). After forming a film to measure the refractive index and Abbe number, ellipsometry was used to obtain values ​​based on the wavelength of light.

[0248] For molecular weight determination by gel permeation chromatography (GPC), the resin sample was dissolved in tetrahydrofuran (THF, stabilized with butylated hydroxytoluene (BHT)) at a concentration of 1.0 mg / 1 mL. The dissolved resin sample was filtered through a syringe filter to obtain the solution, and the molecular weight was measured at 40 °C. The results are shown in Table 2 below. A Waters RI detector was used, and two Agilent PLgel MIXED-B columns were employed.

[0249] Differential scanning calorimetry (DSC) was used to determine the glass transition temperature (Tg) of the resin. The glass transition temperature (Tg) was obtained from the following graph: 5.5 mg to 8.5 mg of resin sample was heated to 270 °C under N2 flow, the resin sample was cooled, and then the resin sample was scanned while being heated at a heating rate of 10 °C / min during a second heating period. The glass transition temperature (Tg) is shown in Table 2 below.

[0250] The refractive index can be measured using the prism coupler method, and for example, the SPA-3DR manufactured by SAIRON Technology Inc. can be used, but is not limited to this.

[0251] The refractive index of a resin can be calculated by measuring the change in the amount of light reflected from a sample prepared by flattening the resin by placing a glass slide on a heating plate at 200°C using a prism coupler. When the prepared sample is brought into contact with a prism and a laser is incident on it, most of the incident laser is totally internally reflected. However, under specific incident angles and conditions, the light is coupled due to the evanescent field generated at the boundary surface. By measuring the angle at which coupling occurs, the intensity of the light detected by the detector decreases sharply. The refractive index of the film can be automatically calculated using the prism coupler from parameters related to the polarization mode of the light and the refractive indices of the prism and the substrate. The refractive index and Abbe number are shown in Table 2 below. Specifically, the refractive index is measured at a wavelength of 587 nm, and for the Abbe number, the refractive index (n) is measured at wavelengths of D (587 nm), F (486 nm), and C (656 nm), respectively. D n F and n C The Abbe number is obtained from the following equation.

[0252] Abbe number = (n D -1) / (nF -n C )

[0253] [Table 2]

[0254]

[0255] In Table 2, Mn represents the index-average molecular weight, Mw represents the weight-average molecular weight, PDI represents the polydispersity index, RI represents the refractive index, Tg represents the glass transition temperature, and the refractive index is the value measured at a wavelength of 587 nm.

[0256] According to Table 2, the resin according to an exemplary embodiment of the present invention comprises a unit of Formula 1, and in particular, the benzene ring of the fluorene core structure of Formula 1 is also substituted with an electron-rich R1 substituent, such that the refractive index of the polycarbonate resin comprising the fluorene core structure is improved due to the high electron density of the fluorene core structure.

[0257] Furthermore, since polycarbonate resin also contains units of chemical formula 2, the glass transition temperature (Tg) and refractive index can be adjusted, and the chain behavior of polycarbonate resin can be made flexible, resulting in technical effects that are beneficial to the injection molding process of molded products.

Claims

1. A polycarbonate resin comprising units of the following chemical formula 1: [Chemical Formula 1] in, In chemical formula 1, R1 is a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms. R2 is hydrogen. r1 is 1. r2 is an integer from 1 to 4. L1 and L2 may be the same as or different from each other, and each may be independently a substituted or unsubstituted aryl group. X1 to X4 are 0, Z1 and Z2 may be the same as or different from each other, and each is independently a substituted or unsubstituted alkylene or a substituted or unsubstituted cycloalkylene. a and b are either the same or different, and are each an independent integer from 1 to 10. Furthermore, when a and b are each 2 or greater, the structures within the parentheses are either the same or different. This refers to the portion connected to the main chain of the resin.

2. The polycarbonate resin according to claim 1, further comprising units of chemical formula 2: [Chemical Formula 2] In chemical formula 2, L11 can be a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted divalent fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring, or a substituted or unsubstituted arylene group. l11 is an integer from 1 to 5, and when l11 is 2 or greater, two or more L11s are either the same or different from each other. X11 to X14 may be the same as or different from each other, and each is independently O or S. Z11 and Z12 may be the same as or different from each other, and each is independently a substituted or unsubstituted alkylene group or a substituted or unsubstituted cycloalkylene group. a' and b' are either the same or different from each other, and are each an independent integer from 0 to 10. Furthermore, when a' and b' are each 2 or greater, the structures within the parentheses are either the same or different from each other. This refers to the portion connected to the main chain of the resin.

3. The polycarbonate resin according to claim 1, wherein: L1 and L2 may be the same as or different from each other, and each is independently a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms. X1 to X4 are 0, and Z1 and Z2 may be the same as or different from each other, and each is independently a straight-chain or branched alkylene group having 1 to 30 carbon atoms.

4. The polycarbonate resin according to claim 1, wherein the weight-average molecular weight Mw of the polycarbonate resin is from 5,000 g / mol to 500,000 g / mol.

5. The polycarbonate resin according to claim 1, wherein the refractive index of the polycarbonate resin measured at a wavelength of 587 nm is from 1.50 to 1.

75.

6. The polycarbonate resin according to claim 1, wherein the glass transition temperature Tg of the polycarbonate resin is 90°C to 200°C.

7. The polycarbonate resin according to claim 1, wherein the Abbe number of the polycarbonate resin measured at wavelengths of 486 nm, 587 nm, and 656 nm is 5 to 45.

8. A method for preparing a polycarbonate resin according to any one of claims 1 to 7, the method comprising: Polymerization of a composition for preparing a polycarbonate resin, wherein the composition for preparing a polycarbonate resin comprises a compound of the following chemical formula 1a and a polycarbonate precursor: [Chemical Formula 1a] In chemical formula 1a, R1 is a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms. R2 is hydrogen. r1 is 1 r2 is an integer from 1 to 4. L1 and L2 may be the same as or different from each other, and each may be independently a substituted or unsubstituted aryl group. X1 to X4 are 0, Z1 and Z2 may be the same as or different from each other, and each is independently a substituted or unsubstituted alkylene or a substituted or unsubstituted cycloalkylene. a and b are either the same or different from each other, and each is an independent integer from 1 to 10. When a and b are each 2 or greater, the structures within the parentheses are either the same or different from each other.

9. The method according to claim 8, wherein the composition for preparing the polycarbonate resin further comprises a compound of formula 2a, and the compound of formula 1a and the compound of formula 2a are included in an amount of 0.01 mol% to 100 mol%: 99.99 mol% to 0 mol%: [Chemical Formula 2a] In chemical formula 2a, L11 can be a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted divalent fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring, or a substituted or unsubstituted arylene group. l11 is an integer from 1 to 5, and when l11 is 2 or greater, two or more L11s are either the same or different from each other. X11 to X14 may be the same as or different from each other, and each is independently O or S. Z11 and Z12 may be the same as or different from each other, and each is independently a substituted or unsubstituted alkylene group or a substituted or unsubstituted cycloalkylene group. a' and b' are either the same or different from each other, and are each an independent integer from 0 to 10. When a' and b' are each 2 or greater, the structures within the parentheses are either the same or different from each other.

10. The method of claim 8, wherein the polycarbonate precursor is a compound of the following chemical formula A: [Chemical Formula A] In chemical formula A, Rb1 and Rb2 may be the same as or different from each other, and each is independently a halogen group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. a1 and a2 are each 0 or 1.

11. A polycarbonate resin composition comprising the polycarbonate resin according to any one of claims 1 to 7.

12. A molding article comprising the polycarbonate resin composition according to claim 11.

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