WO2021086033A1 - Polycarbonate resin and method for preparing same - Google Patents

Abstract

The present invention relates to a polycarbonate resin and a method for preparing same and, more specifically, to a polycarbonate resin and a method for preparing same, the polycarbonate resin being prepared by interfacial polymerization of a polycarbonate oligomer obtained by melt polymerization with a ketone compound again, and including a repeating unit derived from a carbonic acid diester component, an aromatic/aliphatic/alicyclic diol component, and a ketone compound component, thereby having excellent color, molding processability, heat resistance, and impact resistance.

Description

Polycarbonate resin and its manufacturing method

The present invention relates to a polycarbonate resin and a method for producing the same, and more particularly, to a polycarbonate oligomer obtained by melt polymerization, prepared by interfacial polymerization with a ketone compound again, a carbonic diester component, an aromatic/aliphatic/alicyclic diol component And a polycarbonate resin having excellent color, molding processability, heat resistance, and impact resistance by including a repeating unit derived from a ketone compound component, and a method for producing the same.

Aromatic bisphenol-based polycarbonate has excellent mechanical properties such as tensile strength and impact resistance, and has excellent dimensional safety, heat resistance, and optical transparency, so it is widely used for industrial purposes. Among them, polycarbonates derived from aromatic dihydroxy compounds, such as 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as ``bisphenol A''), are prepared by two methods of interfacial polymerization or melt polymerization. It is industrialized by the method. According to the interfacial polymerization method, polycarbonate is prepared from bisphenol A and phosgene, but phosgene is toxic, so handling and operation are difficult. In addition, when the interfacial polymerization method is used, the manufacturing apparatus may be corroded by chlorine-containing compounds such as hydrogen chloride or sodium chloride and methylene chloride used in a large amount as a solvent, and impurities that may affect polymer properties (for example, , Sodium chloride, etc.) or residual methylene chloride is difficult to remove.

On the other hand, as a method for producing a polycarbonate from an aromatic dihydroxy compound and a diaryl carbonate, for example, bisphenol A and diphenyl carbonate are transesterified in a molten state to produce an aromatic monohydroxy compound (bisphenol A and diphenyl carbonate In the case of, a melt polymerization method in which polymerization is performed while removing phenol) is known. Unlike the interfacial polymerization method, the melt polymerization method has the advantage of not using a solvent, but the viscosity of the polymer in the system increases rapidly as the polymerization proceeds, making it difficult to efficiently remove the aromatic monohydroxy compounds that are by-products out of the system. It has an intrinsic problem that it becomes difficult to increase the polymerization degree due to extremely low reaction rate. Therefore, there is a need for an effective method for producing a high molecular weight aromatic polycarbonate resin using a melt polymerization method.

As a method of solving the above problems, for example, a polycarbonate oligomer containing isosorbide as a repeating unit is produced using a melt polymerization method, and the polycarbonate block copolymer is interfacially polymerized with a polycarbonate oligomer containing bisphenol A as a repeating unit. Although a method for preparing a coalescence (Korean Patent Registration No. 10-1608411) has been proposed, there is a problem in that a high content of phosgene must still be used from the step of preparing a polycarbonate oligomer containing bisphenol A as a repeating unit. When used, there is a limit to increasing the content of isosorbide in the block copolymer.

Accordingly, there is a demand for the development of a technology capable of manufacturing a polycarbonate resin excellent in all physical properties such as color, molding processability, heat resistance and impact resistance while reducing the amount of toxic phosgene used.

The present invention is to solve the problems of the prior art as described above, and is prepared by interfacial polymerization of a polycarbonate oligomer obtained by melt polymerization with a ketone compound again, and a diester carbonate component, an aromatic/aliphatic/alicyclic diol component and a ketone compound It is a technical problem to provide a polycarbonate resin having excellent color, molding processability, heat resistance and impact resistance by including a repeating unit derived from a component, and a method for producing the same.

The present invention to solve the above technical problem, the repeating unit derived from the carbonic acid diester component represented by the following formula (1); A repeating unit derived from a diol component represented by the following formula (2); And as a polycarbonate resin comprising a repeating unit derived from the ketone compound component of Formula 3, it provides a polycarbonate resin comprising the carbonic acid diester component and the ketone compound component in a molar ratio of 1: 0.02 to 1: 0.2:

[Formula 1]

In Formula 1, R ₁ is each independently selected from an unsubstituted or halogen-substituted, C 1 to C 20 alkyl group, a C 6 to C 20 aryl group, or a C 7 to C 25 aralkyl group,

[Formula 2]

In Formula 2, X is a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms; A linear alkylene group having 1 to 15 carbon atoms; A branched alkylene group having 3 to 15 carbon atoms; A cyclic alkylene group having 3 to 15 carbon atoms; Or a divalent organic group derived from anhydrosugar alcohol, and the arylene group, linear alkylene group, branched alkylene group and cyclic alkylene group are halogen atom, alkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryl group, nitro group, or It may be substituted or unsubstituted with a carboxyl group,

[Formula 3]

In Formula 3, R ₂ and R ₃ are each independently a halogen atom; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with O, N, or Cl; Or an aryl group having 3 to 50 carbon atoms substituted or unsubstituted with O, N, or Cl, except that R ₂ and R ₃ are both halogen atoms.

According to another aspect of the present invention, (1) a hydroxy-terminated polycarbonate oligomer having a unit structure represented by the following formula 4 by melt polymerization of a carbonic acid diester represented by the following formula (1) and a diol represented by the following formula (2). Manufacturing a; And (2) interfacially polymerizing the prepared hydroxy-terminated polycarbonate oligomer with a ketone compound represented by the following formula (3) to prepare a polycarbonate resin; including, a carbonic acid diester represented by the following formula (1) and the following formula: The reaction molar ratio of the ketone compound represented by 3 is 1: 0.02 to 1: 0.2,

A method of making a polycarbonate resin is provided:

[Formula 1]

In Formula 1, R ₁ is each independently selected from an unsubstituted or halogen-substituted, C 1 to C 20 alkyl group, a C 6 to C 20 aryl group, or a C 7 to C 25 aralkyl group,

[Formula 2]

In Formula 2, X is a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms; A linear alkylene group having 1 to 15 carbon atoms; A branched alkylene group having 3 to 15 carbon atoms; A cyclic alkylene group having 3 to 15 carbon atoms; Or a divalent organic group derived from anhydrosugar alcohol, and the arylene group, linear alkylene group, branched alkylene group and cyclic alkylene group are halogen atom, alkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryl group, nitro group, or It may be substituted or unsubstituted with a carboxyl group,

[Formula 3]

In Formula 3, R ₂ and R ₃ are each independently a halogen atom; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with O, N, or Cl; Or it represents an aryl group having 3 to 50 carbon atoms substituted or unsubstituted with O, N, or Cl, except that R ₂ and R ₃ are both halogen atoms,

[Formula 4]

In Formula 4, X is as defined in Formula 2, and n represents an integer of 1 to 100.

According to another aspect of the present invention, a molded article comprising the polycarbonate resin is provided.

Since the polycarbonate resin according to the present invention is excellent in various physical properties such as color, heat resistance and impact resistance, for example, materials for electric/electronic parts such as TVs and mobile phones; It can be used very suitably for molded articles such as materials for automobile parts such as lamps and lenses. In addition, according to the manufacturing method of the present invention, it is possible to produce eco-friendly polycarbonate by using less phosgene and a solvent than the conventional polycarbonate manufacturing technology, and at the same time, it is possible to manufacture a high molecular weight polycarbonate resin by easily adjusting the molecular weight. Has an advantage.

The term “reaction product” as used herein refers to a material formed by reacting two or more reactants.

In addition, in the present specification, terms such as “first” and “second” are used to describe a polymerization catalyst, but the polymerization catalyst is not limited by these terms. These terms are only used to distinguish polymerization catalysts from each other. For example, the first polymerization catalyst and the second polymerization catalyst may be of the same type or different types of catalysts.

In addition, the English letter "R" used to represent hydrogen, a halogen atom and/or a hydrocarbon group in the formula described in the present specification has a subscript represented by a number, but the "R" is used in such a subscript. Is not limited by. The "R" represents, independently of each other, hydrogen, a halogen atom, and/or a hydrocarbon group. For example, regardless of whether two or more "R"s have the same or different numbers of subscripts, these "Rs" may represent the same hydrocarbon group or different hydrocarbon groups.

Hereinafter, the present invention will be described in more detail.

The polycarbonate resin of the present invention includes a repeating unit derived from a carbonic acid diester component represented by the following formula (1); A repeating unit derived from a diol component represented by the following formula (2); And a repeating unit derived from the ketone compound component of Formula 3, wherein the carbonic acid diester component and the ketone compound component are included in a molar ratio of 1: 0.02 to 1: 0.2:

[Formula 1]

In Formula 1, R ₁ is each independently selected from an unsubstituted or halogen-substituted, C 1 to C 20 alkyl group, a C 6 to C 20 aryl group, or a C 7 to C 25 aralkyl group,

[Formula 2]

In Formula 2, X is a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms; A linear alkylene group having 1 to 15 carbon atoms; A branched alkylene group having 3 to 15 carbon atoms; A cyclic alkylene group having 3 to 15 carbon atoms; Or a divalent organic group derived from anhydrosugar alcohol, and the arylene group, linear alkylene group, branched alkylene group and cyclic alkylene group are halogen atom, alkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryl group, nitro group, or It may be substituted or unsubstituted with a carboxyl group,

[Formula 3]

In Formula 3, R ₂ and R ₃ are each independently a halogen atom; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with O, N, or Cl; Or an aryl group having 3 to 50 carbon atoms substituted or unsubstituted with O, N, or Cl, except that R ₂ and R ₃ are both halogen atoms.

The molar ratio of the diester carbonate component and the ketone compound component is, when the molar ratio of the diester carbonate component is 1, the molar ratio of the ketone compound may be 0.02 or more, 0.04 or more, 0.05 or more, 0.08 or more, or 0.1 or more, 0.2 or less, 0.18 Hereinafter, it may be 0.16 or less, 0.15 or less, 0.12 or less, or 0.1 or less, and for example, it may be 1: 0.02 to 1: 0.2, 1: 0.04 to 1: 0.18 or 1: 0.05 to 1: 0.15. When the molar ratio of the carbonic acid diester component and the ketone compound component is less than the above range, the reactivity decreases and the viscosity average molecular weight of the polycarbonate resin decreases, resulting in poor impact resistance and color. The viscosity average molecular weight of the resin is excessively increased, which may result in poor processability and color.

The viscosity average molecular weight (Mv) of the polycarbonate resin of the present invention is 10,000 to 70,000, preferably 15,000 to 50,000, and more preferably 15,000 to 30,000. If the viscosity average molecular weight is less than 10,000, there is a problem in implementing sufficient mechanical properties, and if the viscosity average molecular weight exceeds 70,000, the molecular weight is too high and the melting property is poor, making processing difficult.

In one embodiment, the carbonic acid diester component represented by Formula 1 may be selected from diphenyl carbonate, bischlorophenyl carbonate, dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate, or a mixture thereof, and more Preferably, diphenyl carbonate or dimethyl carbonate may be used.

In one embodiment, in Formula 2, the halogen atom may be F, Cl, or Br, and the alkyl group is an alkyl group having 1 to 20 carbon atoms (more specifically, an alkyl group having 1 to 13 carbon atoms, for example, methyl, ethyl , Propyl or butyl), and the cycloalkyl group may be a cycloalkyl group having 3 to 10 carbon atoms (more specifically, a cycloalkyl group having 3 to 6 carbon atoms), and the alkenyl group may be an alkenyl group having 2 to 20 carbon atoms (more Specifically, it may be an alkenyl group having 2 to 13 carbon atoms), and the alkoxy group may be an alkoxy group having 1 to 20 carbon atoms (more specifically, an alkoxy group having 1 to 13 carbon atoms, such as methoxy, ethoxy, propoxy Or butoxy), and the aryl group may be an aryl group having 6 to 30 carbon atoms (more specifically, an aryl group having 6 to 20 carbon atoms, for example, a phenyl group, a tolyl group, a xylenyl group, or a naphthyl group). have.

In one embodiment, the diol component represented by Formula 2 may be an aromatic diol, an aliphatic diol, an alicyclic diol, an anhydrosugar alcohol, or a mixture thereof.

As the aromatic diol, for example, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, a nitro group or a carboxyl group substituted or unsubstituted bisphenol (e.g., bisphenol A, bisphenol F, bisphenol TMC, etc.), resorcinol, hydroquinone, biphenol, naphthalene diol, or mixtures thereof, preferably halogen atom, alkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryl group, nitro group or carboxyl group substitution Or unsubstituted, bisphenol A can be used.

The aliphatic diol may be, for example, an aliphatic diol having 2 to 10 carbon atoms, unsubstituted or substituted with a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, a nitro group or a carboxyl group, for example For example, ethylene glycol, diethylene glycol, triethylene glycol, propane diol (1,2-propane diol and 1,3-propane diol, etc.), butane diol (1,2-butane diol, 1,3-butane diol and 1 ,4-butane diol, etc.), pentane diol (1,2-pentane diol, 1,3-pentane diol, 1,4-pentane diol and 1,5-pentane diol, etc.), hexane diol (1,2-hexane diol, etc.) , 1,3-hexane diol, 1,4-hexane diol, 1,5-hexane diol and 1,6-hexane diol, etc.), neopentyl glycol, or a mixture thereof, preferably butane diol. have.

As the alicyclic diol, for example, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, a nitro group or a carboxyl group substituted or unsubstituted, cyclohexane diol (1,2-cyclohexane diol, 1,3-cyclohexane diol and 1,4-cyclohexane diol, etc.), cyclohexane dimethanol (1,2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol and 1,4-cyclohexane dimethanol, etc.) ), tetramethylcyclobutane diol, or a mixture thereof, preferably cyclohexane diol.

As the anhydrosugar alcohol, dianhydrose hexitol may be used. For example, isosorbide, isomannide, isoidide, or a mixture thereof may be used, preferably isosorbide.

In one embodiment, X in Formula 2 is substituted or unsubstituted bisphenol (e.g., bisphenol A, bisphenol F or bisphenol TMC, etc.), substituted or unsubstituted resorcinol, substituted or unsubstituted hydroquinone (e.g. For example, hydroquinone, 2-nitro hydroquinone, 2-sulfonyl hydroquinone, etc.), substituted or unsubstituted biphenol, substituted or unsubstituted naphthalenediol, or arylene which may be derived from substituted or unsubstituted diphenylphenol. It may be a group, for example, it may be represented by the following formulas 2a to 2h.

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

[Formula 2e]

[Formula 2f]

[Chemical Formula 2g]

[Formula 2h]

In one embodiment, in Formula 2, X may be an alkylene group that may be derived from substituted or unsubstituted ethylene glycol, substituted or unsubstituted propylene glycol, or substituted or unsubstituted butanediol, for example, It may be an ethylene group, a propylene group, or a butylene group.

In one embodiment, in Formula 2, X is a cycloalkylene group that may be derived from a substituted or unsubstituted cyclohexane diol, a substituted or unsubstituted cyclohexane dimethanol, or a substituted or unsubstituted tetramethylcyclobutane diol. It can be, for example, it can be represented by the following formulas 2i to 2k.

[Formula 2i]

[Formula 2j]

[Formula 2k]

In one embodiment, in Chemical Formula 2, X may be a divalent organic group derived from anhydrosugar alcohol, and may be, for example, represented by the following Chemical Formulas 2l to 2n.

[Formula 2l]

[Chemical Formula 2m]

[Formula 2n]

In one embodiment, the ketone compound represented by Formula 3 is except for phosgene (that is, except _{when both R 2} and R ₃ are halogen atoms in Formula 3), specifically from the compounds represented by the following Formulas 3a to 3d Can be chosen.

[Formula 3a]

[Formula 3b]

[Formula 3c]

[Chemical Formula 3d]

According to another aspect of the present invention, a method of manufacturing the polycarbonate resin is provided, and the manufacturing method includes (1) melt polymerization of a diester carbonate represented by the following Formula 1 and a diol represented by the following Formula 2, Preparing a hydroxy-terminated polycarbonate oligomer having a unit structure represented by 4; And (2) interfacial polymerization of the prepared hydroxy-terminated polycarbonate oligomer and a ketone compound represented by the following formula (3) to prepare a polycarbonate resin; and

The reaction molar ratio of the carbonic acid diester represented by the following Formula 1 and the kenon compound represented by the following Formula 3 may be 1:0.02 to 1:0.2.

[Formula 1]

In Formula 1, R ₁ is each independently selected from an unsubstituted or halogen-substituted, C 1 to C 20 alkyl group, a C 6 to C 20 aryl group, or a C 7 to C 25 aralkyl group,

[Formula 2]

In Formula 2, X is a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms; A linear alkylene group having 1 to 15 carbon atoms; A branched alkylene group having 3 to 15 carbon atoms; A cyclic alkylene group having 3 to 15 carbon atoms; Or a divalent organic group derived from anhydrosugar alcohol, and the arylene group, linear alkylene group, branched alkylene group and cyclic alkylene group may be unsubstituted or substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group, and ,

[Formula 3]

In Formula 3, R ₂ and R ₃ are each independently a halogen atom; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with O, N, or Cl; Or it represents an aryl group having 3 to 50 carbon atoms substituted or unsubstituted with O, N, or Cl, except that R ₂ and R ₃ are both halogen atoms,

[Formula 4]

In Formula 4, X is as defined in Formula 2, and n represents an integer of 1 to 100.

(A) Preparation of hydroxy-terminated polycarbonate oligomer (melt polymerization)

The manufacturing method of the present invention comprises (1) melt polymerization of the carbonic acid diester represented by Formula 1 and the diol represented by Formula 2 to prepare a hydroxy-terminated polycarbonate oligomer having a unit structure represented by Formula 4 It includes the step of.

The carbonic acid diester represented by Formula 1 and the diol represented by Formula 2 used in the manufacturing method of the present invention are as described above in the polycarbonate resin part.

The hydroxy-terminated polycarbonate oligomer contained as a repeating unit of the polycarbonate resin of the present invention has a unit structure represented by the following formula (4).

[Formula 4]

In Formula 4, X is as defined in Formula 2, and n represents an integer of 1 to 100.

The hydroxy-terminated polycarbonate oligomer having a unit structure represented by Formula 4 may have a viscosity average molecular weight (Mv) of 1,000 to 20,000, more preferably 5,000 to 15,000. .

If the viscosity average molecular weight of the hydroxy-terminated polycarbonate oligomer is less than 1,000, the effect of reducing the amount of toxic phosgene or its substitute material in the interfacial polymerization step may be insignificant, and if the viscosity average molecular weight exceeds 20,000, in the interfacial polymerization step There is a difficulty in synthesizing with a desired molecular weight because the reactivity of is lowered.

The hydroxy-terminated polycarbonate oligomer having a unit structure represented by Chemical Formula 4 includes a carbonic acid diester component represented by Chemical Formula 1 and a diol component represented by Chemical Formula 2 (aromatic diol, aliphatic diol, alicyclic diol, anhydrosugar. Alcohol or a mixture thereof) can be prepared by melt polymerization.

The diester carbonate component and the diol component are as described above in the polycarbonate resin portion.

The amount of the diester carbonate component is preferably 0.8 to 1.2 moles per 1 mole of the diol component. If the amount of the diester carbonate component exceeds 1.02 moles per 1 mole of the diol component, it may be difficult to obtain a hydroxy-terminated polycarbonate oligomer having a sufficient molecular weight as the carbonic ester residue acts as a terminal terminator, and the amount of the diester carbonate component is a diol component. If it is less than 0.8 mol per 1 mol, the diol component acts as an end terminator, and it may be difficult to obtain a hydroxy-terminated polycarbonate oligomer having a sufficient molecular weight.

The carbonic acid diester and diol may be melt-polymerized in the presence of a polymerization catalyst.

Examples of the polymerization catalyst include alkali metal salt compounds (eg, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium carbonate, etc.); Alkaline earth metal salt compounds (eg, calcium hydroxide, barium oxide, magnesium oxide, etc.); Nitrogen-containing basic compounds (eg, tetramethyl ammonium hydroxide, tetraethylammonium hydroxide and triethylamine, etc.); Alternatively, a mixture of these and the like may be used, and these may be used alone or in combination of two or more. Among these, it is more preferable to use a nitrogen-containing basic compound and an alkali metal salt compound in combination.

The amount of the polymerization catalyst used may be preferably 1×10 ^-9 to 1×10 ^-3 molar equivalent, more preferably 1×10 ^-8 to 5×10 ^-4 molar equivalent, based on 1 mol of carbonic acid diester.

The melt polymerization may be performed under elevated temperature conditions, for example, 180°C to 240°C, more specifically, 200°C to 220°C, under normal pressure or reduced pressure (eg, 0.1 torr to 50 torr).

According to an embodiment of the present invention, melt polymerization is performed by mixing the carbonic acid diester component represented by Formula 1, the diol component represented by Formula 2, and the polymerization catalyst at normal pressure, and at a temperature of 180°C to 240°C (for example, , Reacting after raising the temperature to 200° C.; And alcohol (eg, phenol or methanol) as a side reactant at a temperature of 180° C. to 240° C. under reduced pressure of 50 torr or less (eg, 0.1 torr to 50 torr) It can be carried out by a process including the step of reacting while removing.

(B) Preparation of polycarbonate resin (interfacial polymerization)

The polycarbonate resin of the present invention contains a repeating unit derived from the ketone compound component of Formula 3 described above.

The manufacturing method of the present invention includes the step of interfacial polymerization of the prepared hydroxy-terminated polycarbonate oligomer and the ketone compound represented by Chemical Formula 3 to prepare a polycarbonate resin.

The ketone compound represented by Chemical Formula 3 is as described in the polycarbonate resin part.

In the production method of the present invention, the carbonic acid diester component represented by Formula 1 and the ketone compound component represented by Formula 3 may be used in a molar ratio of 1: 0.02 to 1: 0.2.

The molar ratio of the diester carbonate component and the ketone compound component is, when the molar ratio of the diester carbonate component is 1, the molar ratio of the ketone compound may be 0.02 or more, 0.04 or more, 0.05 or more, 0.08 or more, or 0.1 or more, 0.2 or less, 0.18 Hereinafter, it may be 0.16 or less, 0.15 or less, 0.12 or less, or 0.1 or less, and for example, it may be 1: 0.02 to 1: 0.2, 1: 0.04 to 1: 0.18 or 1: 0.05 to 1: 0.15. When the molar ratio of the carbonic acid diester component and the ketone compound component is less than the above range, the reactivity decreases and the viscosity average molecular weight of the polycarbonate resin decreases, resulting in poor impact resistance and color. The viscosity average molecular weight of the resin is excessively increased, which may result in poor processability and color.

The interfacial polymerization reaction may be carried out under interfacial reaction conditions consisting of an aqueous alkali solution and an organic phase.

For the interfacial polymerization reaction, a hydroxy-terminated polycarbonate oligomer having a unit structure represented by Formula 4 and a ketone compound represented by Formula 3 were added to a reactor, and a molecular weight modifier, a first polymerization catalyst, a phase transfer catalyst, and a pH modifier (Eg, NaOH) and methylene chloride (MC) may be additionally added. Specifically, it can be prepared by adding the ketone compound to an organic phase-aqueous mixture containing the hydroxy-terminated polycarbonate oligomer, and adding a molecular weight modifier and a catalyst in stages.

As the molecular weight modifier, a monofunctional compound similar to a monomer used for preparing polycarbonate may be used. The monofunctional substances are, for example, p-isopropylphenol, p-tert-butylphenol (p-tert-butylphenol, PTBP), p-cumyl phenol, p-isooctylphenol, and p-iso Derivatives based on phenol such as nonylphenol; Or it may be an aliphatic alcohol. Preferably, p-tert-butylphenol (PTBP) may be used.

As the catalyst, a polymerization catalyst and/or a phase transfer catalyst may be used. As a polymerization catalyst, for example, triethylamine (TEA) may be used, and as a phase transfer catalyst, a compound represented by the following Formula 5 may be used, for example.

[Formula 5]

^{_{(R 4) 4 Q + Y}} -

In Formula 5, R ₄ represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and Y represents a halogen atom or -OR ₅ . Here, R ₅ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

Specifically, the phase transfer catalyst is, for example, [CH ₃ (CH ₂ ) ₃ ] ₄ NY, [CH ₃ (CH ₂ ) ₃ ] ₄ PY, [CH ₃ (CH ₂ ) ₅ ] ₄ NY, [CH ₃ (CH ₂ ) ₆ ] ₄ NY, [CH ₃ (CH ₂ ) ₄ ] ₄ NY, CH ₃ [CH ₃ (CH ₂ ) ₃ ] ₃ NY or CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NY days have. In the above formulas, Y represents Cl, Br or -OR ₅ , wherein R ₅ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

The content of the phase transfer catalyst is preferably about 0.01 to 10% by weight, more preferably 0.1 to 10% by weight, based on the total weight of the hydroxy-terminated polycarbonate oligomer. If the content is less than 0.01% by weight, reactivity may decrease, and if the content is more than 10% by weight, it may precipitate as a precipitate or decrease in transparency.

In a preferred embodiment, the interfacial polymerization of the hydroxy-terminated polycarbonate oligomer and the ketone compound may be performed stepwise over the first and second steps. Specifically, the first step of polymerizing from a mixture into which the hydroxy-terminated polycarbonate oligomer, the ketone compound, the first polymerization catalyst, a phase transfer catalyst, a molecular weight modifier, a pH modifier (e.g., NaOH) and methylene chloride (MC) are added. After performing, the second polymerization step may be performed by sequentially adding a second polymerization catalyst. Here, the second polymerization step may be performed by providing a second polymerization catalyst to the resulting mixture after the first polymerization step is completed.

In one embodiment, a polymer is prepared through a melt polymerization step and an interfacial polymerization step as described above, and then the organic phase dispersed in methylene chloride is alkali washed and then separated. Subsequently, the organic phase is washed with 0.1N hydrochloric acid solution, and then washed with distilled water 2 to 3 times. When washing is complete, the concentration of the organic phase dispersed in methylene chloride is constantly adjusted, and granulation is performed using a certain amount of distilled water in the range of 30°C to 100°C, preferably in the range of 60°C to 80°C. If the temperature of distilled water is less than 30°C, the assembling speed may be slow and the assembling time may be very long, and if the temperature of distilled water exceeds 100°C, it may be difficult to obtain a shape of polycarbonate in a certain size. When the assembly is completed, it is preferable to dry it at 100°C to 120°C for 5 to 10 hours, and more preferably firstly at 100°C to 110°C for 5 to 10 hours, and secondly at 110°C to 120°C. It can be dried for up to 10 hours.

Since the polycarbonate resin according to the present invention has excellent properties such as color, molding processability, heat resistance and impact resistance, for example, materials for electric/electronic parts such as mobile phones and TVs; Or it can be very suitably used for molded articles such as materials for automobile parts such as lamps and lenses.

Accordingly, according to another aspect of the present invention, a molded article comprising the polycarbonate resin of the present invention is provided.

A method of molding the polycarbonate resin of the present invention into a molded article is not particularly limited, and a molded article may be manufactured using a method generally used in the plastic molding field.

Hereinafter, the present invention will be described in more detail through examples according to the present invention and comparative examples not according to the present invention. However, the scope of the present invention is not limited to these.

[Example]

Example 1

<Step 1: Preparation of bisphenol A polycarbonate oligomer>

Bisphenol A 275 g (1.2 mol), diphenyl carbonate 215 g (1 mol), and cesium carbonate (cesium carbonate) 0.0001 g were added to a 2 L three-neck reactor, and the temperature was raised to 200° C. while slowly stirring in a nitrogen gas atmosphere. The pressure was gradually lowered to 0.1 torr over 90 minutes and the temperature was raised to 220° C. under reduced pressure to remove phenol, a side reactant. After that, the reduced pressure was released, and 240 g (0.16 mol) of a hydroxy-terminated aromatic polycarbonate oligomer represented by the following formula (6) having a number average molecular weight (Mn) of 1,510 was obtained.

[Formula 6]

<Second step: Preparation of high molecular weight bisphenol A polycarbonate resin>

In a 2L three-neck reactor, 240 g of the polycarbonate oligomer obtained in the first step, 16 g (0.05 mol) of triphosgene of formula 3b, 350 g of 5% by weight sodium hydroxide aqueous solution, 1 L of methylene chloride, p-tert-butyl phenol (PTBP) ) 1 g (0.007 mol) and 250 μL of a 15% by weight trimethylamine (TEA) aqueous solution were mixed, and then reacted for 60 minutes. To the reaction result, 0.3 L of methylene chloride and 300 μL of a 15% by weight aqueous triethylamine solution were mixed, and then reacted for an additional 1 hour.

After layer separation, the organic phase having an increased viscosity was washed with alkali and separated. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution, and then washed repeatedly 2 to 3 times with distilled water. After the washing was completed, the organic phase was assembled at 76° C. using a certain amount of distilled water. After the assembly was completed, it was first dried at 110° C. for 8 hours, and secondarily dried at 120° C. for 10 hours, thereby preparing a high molecular weight polycarbonate resin. The physical properties of the prepared polycarbonate resin were measured and described in Table 1 below.

Example 2

<Step 1: Preparation of bisphenol A polycarbonate oligomer>

Except that the reaction time under reduced pressure was changed from 90 minutes to 60 minutes to remove the side-reactant phenol, the number average molecular weight (Mn) of Formula 7 was 740. 235 g (0.32 mol) of a hydroxy-terminated aromatic polycarbonate oligomer was prepared.

[Formula 7]

<Second step: Preparation of high molecular weight bisphenol A polycarbonate resin>

In place of 240 g (0.16 mol) of the polycarbonate oligomer of Formula 6 obtained in Example 1, 235 g (0.32 mol) of the polycarbonate oligomer of Formula 7 obtained in the first step was used, and the content of triphosgene of Formula 3b Was changed from 16 g (0.05 mol) to 33 g (0.11 mol), and the content of the 5 wt% sodium hydroxide aqueous solution was changed from 350 g to 700 g, and a high molecular weight poly A carbonate resin was prepared. The physical properties of the prepared polycarbonate resin were measured and described in Table 1 below.

Example 3

<Step 1: Preparation of bisphenol A polycarbonate oligomer>

In the same manner as in Example 1, 240 g (0.16 mol) of a hydroxy-terminated aromatic polycarbonate oligomer of Formula 6 was obtained.

[Formula 6]

<Second step: Preparation of high molecular weight bisphenol A polycarbonate resin>

A high molecular weight polycarbonate resin was prepared in the same manner as in Example 1, except that 26 g (0.16 mol) of carbonyldiimidazole of formula 3c was used in place of 16 g (0.05 mol) of triphosgene of formula 3b. I did. The physical properties of the prepared polycarbonate resin were measured and described in Table 1 below.

Example 4

<Step 1: Preparation of isosorbide polycarbonate oligomer>

Except that 177 g (1.2 mol) of isosorbide was used in place of 275 g (1.2 mol) of bisphenol A, and the reaction time under reduced pressure was changed from 90 minutes to 120 minutes to remove the side-reactant phenol, In the same manner as in Example 1, 220 g (0.21 mol) of a hydroxy-terminated aliphatic polycarbonate oligomer represented by the following Formula 8 having a number average molecular weight (Mn) of 1,050 was obtained.

[Formula 8]

<Second step: Preparation of high molecular weight isosorbide polycarbonate resin>

In place of 240 g (0.16 mol) of the polycarbonate oligomer of Formula 6 obtained in Example 1, 220 g (0.21 mol) of the polycarbonate oligomer of Formula 8 obtained in the first step was used, and 16 g of triphosgene of Formula 3b ( 0.05 mol) instead of 33 g (0.2 mol) of carbonyldiimidazole of formula 3c, and the same method as in Example 1, except that the content of the 5% by weight aqueous sodium hydroxide solution was changed from 350 g to 550 g. To prepare a high molecular weight polycarbonate resin. The physical properties of the prepared polycarbonate resin were measured and described in Table 1 below.

Example 5

<Step 1: Preparation of bisphenol A polycarbonate oligomer and isosorbide polycarbonate oligomer>

Bisphenol A 138 g (0.6 mol), diphenyl carbonate 108 g (0.5 mol), and cesium carbonate (cesium carbonate) 0.00005 g were added to a 2 L three-neck reactor, and the temperature was raised to 200° C. while slowly stirring in a nitrogen gas atmosphere. The pressure was gradually lowered to 0.1 torr over 90 minutes and the temperature was raised to 220° C. under reduced pressure to remove phenol, a side reactant. After that, the reduced pressure was released, and 117 g (0.08 mol) of a hydroxy-terminated aromatic polycarbonate oligomer represented by the following formula 6 having a number average molecular weight (Mn) of 1,530 was obtained.

[Formula 6]

In addition, 89 g (0.6 mol) of isosorbide, 108 g (0.5 mol) of diphenyl carbonate, and 0.00005 g of cesium carbonate (cesium carbonate) were added to a 2 L three-neck reactor, and the temperature was raised to 200° C. while slowly stirring in a nitrogen gas atmosphere. The pressure was gradually lowered to 0.1 torr over 120 minutes and the temperature was raised to 220° C. under reduced pressure to remove phenol, a side reactant. Thereafter, the reduced pressure was released, and 105 g (0.1 mol) of a hydroxy-terminated aliphatic polycarbonate oligomer represented by the following formula (8) having a number average molecular weight (Mn) of 1,020 was obtained.

[Formula 8]

<Second step: Preparation of high molecular weight poly(isosorbide carbonate-bisphenol A carbonate) copolymer resin>

In a 2L three-neck reactor, 105 g of bisphenol A polycarbonate oligomer of Formula 6 obtained in the first step and 105 g of isosorbide polycarbonate oligomer of Formula 8, 16 g (0.05 mol) of triphosgene of Formula 3b, 5% by weight of hydroxide 350 g of sodium aqueous solution, 1 L of methylene chloride, 1 g (0.007 mol) of p-tert-butyl phenol (PTBP), and 250 μL of a 15% by weight triethylamine aqueous solution were mixed, and then reacted for 60 minutes. To the reaction result, 0.3 L of methylene chloride and 300 μL of a 15% by weight aqueous triethylamine solution were mixed, and then reacted for an additional 1 hour.

After layer separation, the organic phase having an increased viscosity was washed with alkali and separated. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution, and then washed repeatedly 2 to 3 times with distilled water. Washing was completed, and the organic phase was granulated at 76° C. using a certain amount of pure water. After the assembly was completed, firstly dried at 110° C. for 8 hours, and secondly dried at 120° C. for 10 hours, thereby preparing a high molecular weight poly(isosorbide carbonate-bisphenol A carbonate) copolymer resin. The physical properties of the prepared polycarbonate resin were measured and described in Table 1 below.

Comparative Example 1

<Step 1: Preparation of bisphenol A polycarbonate oligomer>

Bisphenol A 230 g (1 mol), 33 wt% sodium hydroxide aqueous solution 240 g, triphosgene 100 g (0.34 mol), and methylene chloride 1 L were added to a 2 L three-neck reactor and reacted at room temperature for 30 minutes, resulting in a number average molecular weight (Mn) of 1,480 Phosphorus 250 g (0.17 mol) of the hydroxy-terminated aromatic polycarbonate oligomer of Formula 6 was obtained in a dissolved state in 1.3 Kg of methylene chloride.

<Second step: Preparation of high molecular weight bisphenol A polycarbonate resin>

In a 2 L three-neck reactor, the obtained polycarbonate oligomer solution, 1.2 g (0.008 mol) of p-tert-butyl phenol (PTBP), and 250 μL of a 15% by weight triethylamine aqueous solution were mixed, and then reacted for 60 minutes. To the reaction result, 360 g of methylene chloride and 300 μL of a 15% by weight triethylamine aqueous solution were mixed, and then reacted for an additional 30 minutes.

After layer separation, the organic phase having an increased viscosity was washed with alkali and separated. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution, and then washed repeatedly 2 to 3 times with distilled water. Washing was completed, and the organic phase was granulated at 76° C. using a certain amount of pure water. After the assembly was completed, it was first dried at 110° C. for 8 hours, and secondarily dried at 120° C. for 10 hours, thereby preparing a high molecular weight polycarbonate resin. The physical properties of the prepared polycarbonate resin were measured and described in Table 1 below.

Comparative Example 2

Bisphenol A 251 g (1.1 mol), diphenyl carbonate 215 g (1 mol), and cesium carbonate (cesium carbonate) 0.0001 g were added to a 2 L three-neck reactor, and the temperature was raised to 200° C. while slowly stirring in a nitrogen gas atmosphere. The pressure was gradually lowered to 0.1 torr over 180 minutes, and the temperature was raised to 240° C. under reduced pressure to remove phenol as a side reactant, thereby preparing an aromatic polycarbonate resin having a high molecular weight. The physical properties of the prepared polycarbonate resin were measured and described in Table 1 below.

Comparative Example 3

Except that 177 g (1.2 mol) of isosorbide was used in place of 251 g (1.1 mol) of bisphenol A, and the reaction time under reduced pressure was changed from 180 minutes to 200 minutes to remove the side-reactant phenol, In the same manner as in Comparative Example 2, a high molecular weight aliphatic polycarbonate resin was prepared. The physical properties of the prepared polycarbonate resin were measured and described in Table 1 below.

Comparative Example 4

<Step 1: Preparation of bisphenol A polycarbonate oligomer>

In the same manner as in Example 1, 240 g (0.16 mol) of a hydroxy-terminated aromatic polycarbonate oligomer of Formula 6 was obtained.

[Formula 6]

<Second step: Preparation of high molecular weight bisphenol A polycarbonate resin>

A high molecular weight polycarbonate resin was prepared in the same manner as in Example 1, except that the content of triphosgene of Formula 3b was changed from 16 g (0.05 mol) to 70 g (0.22 mol). The physical properties of the prepared polycarbonate resin were measured and described in Table 1 below.

Comparative Example 5

<Step 1: Preparation of bisphenol A polycarbonate oligomer>

In the same manner as in Example 1, 240 g (0.16 mol) of a hydroxy-terminated aromatic polycarbonate oligomer of Formula 6 was obtained.

[Formula 6]

<Second step: Preparation of high molecular weight bisphenol A polycarbonate resin>

A high molecular weight polycarbonate resin was prepared in the same manner as in Example 1, except that the content of triphosgene of Formula 3b was changed from 16 g (0.05 mol) to 3.2 g (0.01 mol). The physical properties of the prepared polycarbonate resin were measured and described in Table 1 below.

Comparative Example 6

<Preparation of hydroxy terminal (isosorbide carbonate-aromatic carbonate) oligomer and bisphenol A polycarbonate oligomer>

Diphenyl carbonate 238 g (1 mol), isosorbide 155 g (1.1 mol), and cesium carbonate (cesium carbonate) 0.0001 g were added to a 2 L three-neck condensation reactor, and the temperature was raised while stirring slowly at 200° C. under a nitrogen gas atmosphere. The pressure was gradually lowered to 0.1 torr over 1 hour to remove the side-reactant phenol under reduced pressure. After that, the reduced pressure was released, and 25 g (0.1 mol) of bisphenol A was additionally added, followed by lowering it to 0.1 torr at 220° C. and reacting for 30 minutes while applying the reduced pressure again. As a result, a hydroxy-terminated (isosorbide carbonate-aromatic carbonate) oligomer of the following formula (9) was obtained.

[Formula 9]

In addition, 230 g (1 mol) of bisphenol A, 240 g of 33 wt% sodium hydroxide aqueous solution, 100 g (0.34 mol) of triphosgene, and 1 L of methylene chloride were added to a 2 L three-neck reactor and reacted at room temperature for 30 minutes to obtain a number average molecular weight (Mn). 250 g (0.17 mol) of a hydroxy-terminated aromatic polycarbonate oligomer represented by the following formula 6, which is 1,480, was obtained in a state dissolved in 1.3 Kg of methylene chloride.

[Formula 6]

<Preparation of high molecular weight poly(isosorbide carbonate-bisphenol A carbonate) copolymer>

250 g of the bisphenol A polycarbonate oligomer of Formula 6 dissolved in the methylene chloride in a 2L three-neck reactor, and 50 g of the hydroxy terminal (isosorbide carbonate-aromatic carbonate) oligomer of Formula 9 dissolved in methylene chloride After mixing the bisphenol A polycarbonate oligomer content equivalent to 20% by weight based on 100% by weight), p-tert-butyl phenol (PTBP) 1.2 g (0.008 mol) and 15% by weight of triethylamine aqueous solution 250 μL of 60 It was allowed to react for a minute. To the reaction result, 360 g of methylene chloride and 300 μL of a 15% by weight triethylamine aqueous solution were mixed, and then reacted for an additional 30 minutes.

After layer separation, the organic phase having an increased viscosity was washed with alkali and separated. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution, and then washed repeatedly 2 to 3 times with distilled water. Washing was completed, and the organic phase was granulated at 76° C. using a certain amount of pure water. After the assembly is completed, by first drying at 110°C for 8 hours and secondly at 120°C for 10 hours, [poly(isosorbide carbonate-bisphenol A carbonate)]-[polycarbonate] block copolymer resin Was prepared. The physical properties of the prepared polycarbonate resin were measured and described in Table 1 below.

Comparative Example 7

<Preparation of hydroxy terminal (isosorbide carbonate-aromatic carbonate) oligomer and bisphenol A polycarbonate oligomer>

In the same manner as in Comparative Example 6, a hydroxy-terminated (isosorbide carbonate-bisphenol A carbonate) oligomer of Formula 9 was obtained, and the hydroxy-terminated aromatic polycarbonate of Formula 6 was carried out in the same manner as in Comparative Example 6. 250 g (0.17 mol) oligomer was obtained in a state dissolved in 1.3 Kg methylene chloride.

[Formula 9]

[Formula 6]

<Preparation of high molecular weight poly(isosorbide carbonate-bisphenol A carbonate) copolymer>

The content of the hydroxy-terminated (isosorbide carbonate-aromatic carbonate) oligomer of Formula 9 is 50 g (a content corresponding to 20% by weight based on 100% by weight of the bisphenol A polycarbonate oligomer of Formula 6) to 125 g (bisphenol A polycarbonate). [Poly(isosorbide carbonate-bisphenol A carbonate)]-[polycarbonate] block by performing the same method as in Comparative Example 6, except that the content corresponding to 50% by weight based on 100% by weight of the oligomer) was changed. A copolymer resin was prepared. The physical properties of the prepared polycarbonate resin were measured and described in Table 1 below.

<Method of measuring physical properties>

(a) Viscosity Average Molecular Weight (Mv): Using an Ubbelohde Viscometer, the viscosity of the methylene chloride solution was measured at 20°C, and the intrinsic viscosity [η] was calculated by the following equation:

[η]=1.23x10 ^-5 Mv ^0.83

(b) Impact strength: According to ASTM D256, a notch cut specimen was prepared from the polycarbonate resin of each Example and Comparative Example, and the impact of the specimen was performed using an impact tester (CEAST, IT-98). The strength was measured.

(c) YI (Yellowness Index): According to ASTM D1925, the YI value was measured using a Color Meter (CM-3700D). The lower the YI value, the lower the yellowing phenomenon.

[Table 1]

[Table 1]

As shown in Table 1, the polycarbonate resin of Examples 1 to 5 according to the present invention significantly reduced the amount of phosgene-based material used compared to the polycarbonate resin of Comparative Example 1 (when prepared by the conventional interfacial polymerization method) In addition, the impact strength was 35 Kg _f /cm ² or more, YI value was 2.4 or less, which provided excellent impact resistance and color, and a high molecular weight polycarbonate resin having a viscosity average molecular weight of 20,000 or more was obtained.

On the other hand, in the case of the polycarbonate resin of Comparative Example 1 (when prepared by the conventional interfacial polymerization method), the use of toxic phosgene-based materials was very high, and the workability was poor, and in the case of Comparative Examples 2 and 3 (conventional melt polymerization Method), the color was poor with a YI value of 3.0 or more due to thermal decomposition and residual catalyst due to a high-temperature reaction.

In addition, in the case of Comparative Example 4, the content of the ketone compound was relatively high compared to the carbonic acid diester, and the viscosity average molecular weight of the polycarbonate resin was excessively increased. As a result, the processability was decreased, and the YI value was severely observed to be 5.2, and yellowing was severely observed. In the case of Comparative Example 5, the content of the ketone compound was relatively small compared to the diester carbonate, so that the reactivity was lowered, and the viscosity average molecular weight of the polycarbonate resin was less than 15,000, so that a high molecular weight polycarbonate resin could not be obtained, and the impact strength was lowered And yellowing was observed severely with a YI value of 4.2.

In addition, in the case of Comparative Example 6, the workability was poor due to the large amount of toxic phosgene-based compound used, the impact strength was also relatively low, the color was poor with a YI value of 3.0 or more, and the isosorbide content in the copolymer was low. It was not suitable for use as an eco-friendly material.

In the case of Comparative Example 7, as the isosorbide content was increased, the use of toxic phosgene-based compounds was large, resulting in poor workability, and the reactivity was lowered to obtain a high molecular weight polycarbonate resin with a viscosity average molecular weight of less than 15,000. There was no, the impact strength was very poor, the YI value was 4.8, and yellowing was observed severely.

Claims (9)

A repeating unit derived from a carbonic acid diester component represented by the following formula (1); A repeating unit derived from a diol component represented by the following formula (2); And As a polycarbonate resin comprising a repeating unit derived from the ketone compound component of Formula 3, Polycarbonate resin comprising the carbonic acid diester component and the ketone compound component in a molar ratio of 1: 0.02 to 1: 0.2: [Formula 1]

In Formula 1, R ₁ is each independently selected from an unsubstituted or halogen-substituted, C 1 to C 20 alkyl group, a C 6 to C 20 aryl group, or a C 7 to C 25 aralkyl group, [Formula 2]

In Formula 2, X is a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms; A linear alkylene group having 1 to 15 carbon atoms; A branched alkylene group having 3 to 15 carbon atoms; A cyclic alkylene group having 3 to 15 carbon atoms; Or a divalent organic group derived from anhydrosugar alcohol, and the arylene group, linear alkylene group, branched alkylene group and cyclic alkylene group are halogen atom, alkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryl group, nitro group, or It may be substituted or unsubstituted with a carboxyl group, [Formula 3]

In Formula 3, R ₂ and R ₃ are each independently a halogen atom; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with O, N, or Cl; Or an aryl group having 3 to 50 carbon atoms substituted or unsubstituted with O, N, or Cl, except that R ₂ and R ₃ are both halogen atoms. The polycarbonate resin according to claim 1, having a viscosity average molecular weight of 10,000 to 70,000. (1) preparing a hydroxy-terminated polycarbonate oligomer having a unit structure represented by the following formula (4) by melt polymerization of a carbonic acid diester represented by the following formula (1) and a diol represented by the following formula (2); And (2) interfacial polymerization of the prepared hydroxy-terminated polycarbonate oligomer and a ketone compound represented by the following formula (3) to prepare a polycarbonate resin; including, The reaction molar ratio of the carbonic acid diester represented by the following Formula 1 and the ketone compound represented by the following Formula 3 is 1: 0.02 to 1: 0.2, Method for producing polycarbonate resin: [Formula 1]

In Formula 1, R ₁ is each independently selected from an unsubstituted or halogen-substituted, C 1 to C 20 alkyl group, a C 6 to C 20 aryl group, or a C 7 to C 25 aralkyl group, [Formula 2]

In Formula 2, X is a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms; A linear alkylene group having 1 to 15 carbon atoms; A branched alkylene group having 3 to 15 carbon atoms; A cyclic alkylene group having 3 to 15 carbon atoms; Or a divalent organic group derived from anhydrosugar alcohol, and the arylene group, linear alkylene group, branched alkylene group and cyclic alkylene group are halogen atom, alkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryl group, nitro group, or It may be substituted or unsubstituted with a carboxyl group, [Formula 3]

In Formula 3, R ₂ and R ₃ are each independently a halogen atom; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with O, N, or Cl; Or it represents an aryl group having 3 to 50 carbon atoms substituted or unsubstituted with O, N, or Cl, except that R ₂ and R ₃ are both halogen atoms, [Formula 4]

In Formula 4, X is as defined in Formula 2, and n represents an integer of 1 to 100. The method of claim 3, wherein the polycarbonate resin has a viscosity average molecular weight of 10,000 to 70,000. The method for producing a polycarbonate resin according to claim 3, wherein the hydroxy-terminated polycarbonate oligomer has a viscosity average molecular weight of 1,000 to 20,000, having a unit structure represented by Chemical Formula 4. The method of claim 3, wherein the melt polymerization in step (1) is carried out in the presence of a polymerization catalyst selected from the group consisting of an alkali metal salt compound, an alkaline earth metal salt compound, a nitrogen-containing basic compound, or a mixture thereof. A method for producing a carbonate resin. The reaction of claim 3, wherein in the melt polymerization of step (1), a carbonic acid diester represented by Formula 1, a diol represented by Formula 2, and a polymerization catalyst are mixed and heated to a temperature of 180°C to 240°C. Letting go; And reacting while removing alcohol as a side reactant at a temperature of 180° C. to 240° C. under a reduced pressure of 50 torr or less. The method for producing a polycarbonate resin according to claim 3, wherein the interfacial polymerization in step (2) is performed under interfacial reaction conditions consisting of an aqueous alkali solution and an organic phase. A molded article comprising the polycarbonate resin of claim 1 or 2.