WO2021086033A1 - Résine de polycarbonate et son procédé de préparation - Google Patents

Résine de polycarbonate et son procédé de préparation Download PDF

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WO2021086033A1
WO2021086033A1 PCT/KR2020/014875 KR2020014875W WO2021086033A1 WO 2021086033 A1 WO2021086033 A1 WO 2021086033A1 KR 2020014875 W KR2020014875 W KR 2020014875W WO 2021086033 A1 WO2021086033 A1 WO 2021086033A1
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formula
group
polycarbonate resin
carbon atoms
represented
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PCT/KR2020/014875
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Korean (ko)
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신경무
이재훈
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주식회사 삼양사
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Publication of WO2021086033A1 publication Critical patent/WO2021086033A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/305—General preparatory processes using carbonates and alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/22—General preparatory processes using carbonyl halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/22—General preparatory processes using carbonyl halides
    • C08G64/226—General preparatory processes using carbonyl halides and alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • 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.
  • polycarbonates derived from aromatic dihydroxy compounds such as 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as ⁇ bisphenol A'')
  • ⁇ bisphenol A'' 2,2-bis(4-hydroxyphenyl)propane
  • 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.
  • chlorine-containing compounds such as hydrogen chloride or sodium chloride and methylene chloride used in a large amount as a solvent
  • impurities that may affect polymer properties for example, , Sodium chloride, etc.
  • residual methylene chloride is difficult to remove.
  • 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
  • a melt polymerization method in which polymerization is performed while removing phenol
  • 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.
  • 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.
  • a method for preparing a coalescence 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.
  • 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.
  • 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,
  • 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,
  • 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 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:
  • 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,
  • 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,
  • 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,
  • X is as defined in Formula 2, and n represents an integer of 1 to 100.
  • a molded article comprising the polycarbonate resin is provided.
  • 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.
  • 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.
  • reaction product refers to a material formed by reacting two or more reactants.
  • 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.
  • the first polymerization catalyst and the second polymerization catalyst may be of the same type or different types of catalysts.
  • 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.
  • 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:
  • 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,
  • 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,
  • 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.
  • 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.
  • 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.
  • the halogen atom may be F, Cl, or Br
  • 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)
  • 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)
  • 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)
  • 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)
  • the aryl group may be an aryl group having 6 to 30 carbon atoms
  • 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.
  • 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.
  • bisphenol A bisphenol F, bisphenol TMC, etc.
  • resorcinol hydroquinone
  • biphenol bisphenol
  • naphthalene diol or mixtures thereof
  • halogen atom alkyl group, cycloalkyl group
  • 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
  • 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.
  • cyclohexane diol 1,2-cyclohexane diol, 1,3-cyclohexane diol and 1,4-cyclohex
  • dianhydrose hexitol may be used as the anhydrosugar alcohol.
  • isosorbide, isomannide, isoidide, or a mixture thereof may be used, preferably isosorbide.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a method of manufacturing the polycarbonate resin 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.
  • 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,
  • 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 ,
  • 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,
  • X is as defined in Formula 2, and n represents an integer of 1 to 100.
  • 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).
  • 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. .
  • 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.
  • the polymerization catalyst examples 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.
  • 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.
  • 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).
  • 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).
  • 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.
  • alcohol eg, phenol or methanol
  • 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.
  • 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.
  • 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.
  • 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.
  • a molecular weight modifier e.g, NaOH
  • MC methylene chloride
  • 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.
  • p-tert-butylphenol (PTBP) may be used.
  • a polymerization catalyst and/or a phase transfer catalyst may be used.
  • 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.
  • TAA triethylamine
  • R 4 represents an alkyl group having 1 to 10 carbon atoms
  • Q represents nitrogen or phosphorus
  • Y represents a halogen atom or -OR 5
  • 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 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.
  • 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.
  • the interfacial polymerization of the hydroxy-terminated polycarbonate oligomer and the ketone compound may be performed stepwise over the first and second steps.
  • 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.
  • the second polymerization step may be performed by sequentially adding a second polymerization catalyst.
  • the second polymerization step may be performed by providing a second polymerization catalyst to the resulting mixture after the first polymerization step is completed.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Mn number average molecular weight
  • 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.
  • 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.
  • 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.
  • Mn number average molecular weight
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • a copolymer resin was prepared. The physical properties of the prepared polycarbonate resin were measured and described in Table 1 below.
  • Viscosity Average Molecular Weight (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 [ ⁇ ] was calculated by the following equation:
  • YI Yellowness Index
  • 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)
  • 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
  • a high molecular weight polycarbonate resin having a viscosity average molecular weight of 20,000 or more was obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne une résine de polycarbonate et son procédé de préparation et, plus particulièrement, une résine de polycarbonate et son procédé de préparation, la résine de polycarbonate étant préparée par polymérisation interfaciale d'un oligomère de polycarbonate obtenu par polymérisation à l'état fondu avec un composé cétone de nouveau, et comprenant une unité de répétition dérivée d'un composant de diester d'acide carbonique, un composant diol aromatique/aliphatique/alicyclique, et un composant de composé cétone, présentant ainsi une excellente couleur, une excellente aptitude au moulage, une excellente résistance à la chaleur et une excellente résistance aux chocs.
PCT/KR2020/014875 2019-10-30 2020-10-29 Résine de polycarbonate et son procédé de préparation WO2021086033A1 (fr)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
KR20030029509A (ko) * 2001-10-05 2003-04-14 바이엘 악티엔게젤샤프트 폴리에스테르 카르보네이트의 제조
KR20050048609A (ko) * 2002-08-16 2005-05-24 제너럴 일렉트릭 캄파니 투명한 실리콘-함유 코폴리카보네이트의 제조방법
JP2006511667A (ja) * 2002-12-20 2006-04-06 ゼネラル・エレクトリック・カンパニイ ポリカーボネートの製造方法
KR20150004085A (ko) * 2013-07-02 2015-01-12 주식회사 삼양사 [폴리(아이소소바이드 카보네이트-방향족 카보네이트)]-[폴리카보네이트] 블록 공중합체 및 그 제조방법
KR20170005227A (ko) * 2015-07-01 2017-01-12 주식회사 엘지화학 폴리카보네이트 수지, 이의 제조방법 및 이를 포함하는 성형품

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2123692B1 (fr) * 2007-03-08 2012-05-23 Teijin Limited Polycarbonate à terminaison modifiée et son procédé de fabrication
EP2532697B1 (fr) * 2010-02-05 2014-03-26 Teijin Limited Résine polycarbonate et procédé pour produire celle-ci

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030029509A (ko) * 2001-10-05 2003-04-14 바이엘 악티엔게젤샤프트 폴리에스테르 카르보네이트의 제조
KR20050048609A (ko) * 2002-08-16 2005-05-24 제너럴 일렉트릭 캄파니 투명한 실리콘-함유 코폴리카보네이트의 제조방법
JP2006511667A (ja) * 2002-12-20 2006-04-06 ゼネラル・エレクトリック・カンパニイ ポリカーボネートの製造方法
KR20150004085A (ko) * 2013-07-02 2015-01-12 주식회사 삼양사 [폴리(아이소소바이드 카보네이트-방향족 카보네이트)]-[폴리카보네이트] 블록 공중합체 및 그 제조방법
KR20170005227A (ko) * 2015-07-01 2017-01-12 주식회사 엘지화학 폴리카보네이트 수지, 이의 제조방법 및 이를 포함하는 성형품

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