KR20220022713A - Copolycarbonate and polycarbonate composition comprising the same - Google Patents

Abstract

The present invention relates to a copolycarbonate and a polycarbonate composition comprising the same. The copolycarbonate exhibits very high surface hardness and improved fluidity while exhibiting excellent impact strength, heat resistance, and transparency of the existing polycarbonate due to a novel structure, thereby being used in various applications requiring high hardness and precision.

Description

Copolycarbonate and polycarbonate composition comprising the same

The present invention relates to a copolycarbonate and a polycarbonate composition comprising the same.

Polycarbonate is produced by polycondensation of an aromatic diol such as bisphenol A and a carbonate precursor such as phosgene, and has excellent impact strength, dimensional stability, heat resistance and transparency. , applied to a wide range of fields such as clothing materials.

In particular, polycarbonate is attracting attention as an interior or exterior material for automobiles or electrical and electronic products or as a replacement material for glass due to its excellent impact resistance. In the case of polycarbonate prepared from bisphenol A, its use is limited due to low surface hardness.

In addition, in the case of general polycarbonate, it has very low fluidity compared to thermoplastic resin, so it is very difficult to apply it to parts that require precision. There was a problem that the impact property was greatly reduced or deformed.

Accordingly, there is an increasing demand for a new material capable of realizing high fluidity and high hardness while exhibiting excellent impact strength, dimensional stability, heat resistance and transparency such as polycarbonate.

The present invention provides a new structure of copolycarbonate having improved fluidity and surface hardness while maintaining the intrinsic properties of the polycarbonate.

The present invention also provides a composition comprising the copolycarbonate.

Hereinafter, a copolycarbonate according to a specific embodiment of the present invention and a polycarbonate composition including the same will be described.

According to an embodiment of the present invention, there is provided a copolycarbonate including a polyester repeating unit including a repeating unit represented by the following Chemical Formulas 1 and 2 and a repeating unit represented by the following Chemical Formulas 3 and 4.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 1 to 4,

R ¹ to R ⁶ are each independently hydrogen, halogen, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or -0COR ¹⁵ ;

Ar ¹ is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene group having 4 to 20 carbon atoms,

Al ¹ and Al ² are each independently a substituted or unsubstituted cycloalkylene group having 4 to 30 carbon atoms, or a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms,

L ¹ is a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO-, or a substituted or unsubstituted C 1 to C 6 alkylene group,

R ⁷ to R ¹⁴ are each independently hydrogen, halogen, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or -0COR ¹⁵ , but at least one is a halogen, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or -0COR ¹⁵ ;

R ¹⁵ is an alkyl group having 1 to 12 carbon atoms.

As used herein, the term "substituted or unsubstituted" may mean unsubstituted or substituted with R', and R' is deuterium, halogen, hydroxy group, carboxyl group, cyano group, nitro group, amino group, or carbon number It may be an alkyl group of 1 to 12.

In the present specification, halogen may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group having 1 to 12 carbon atoms may be a straight chain, branched chain or cyclic alkyl group. Specifically, the alkyl group having 1 to 12 carbon atoms is a straight chain alkyl group having 1 to 12 carbon atoms; Or it may be a branched or cyclic alkyl group having 3 to 12 carbon atoms. More specifically, an alkyl group having 1 to 12 carbon atoms is a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, It may be a neo-pentyl group or a cyclohexyl group. However, the present invention is not limited thereto.

In the present specification, the alkoxy group having 1 to 12 carbon atoms may be a straight chain, branched chain or cyclic alkoxy group. Specifically, the alkoxy group having 1 to 12 carbon atoms is a straight-chain alkoxy group having 1 to 12 carbon atoms; Or it may be a branched or cyclic alkoxy group having 3 to 12 carbon atoms. More specifically, an alkoxy group having 1 to 12 carbon atoms is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, t-butoxy group, n-pentoxy group, iso It may be a -pentoxy group, a neo-pentoxy group or a cyclohexoxy group. However, the present invention is not limited thereto.

In the present specification, the cycloalkylene group having 4 to 30 carbon atoms may be a cycloalkylene group having 4 to 20 carbon atoms, a cycloalkylene group having 4 to 15 carbon atoms, or a cycloalkylene group having 4 to 10 carbon atoms. Specifically, the cycloalkylene group having 4 to 30 carbon atoms may be a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, or a cyclooctylene group. However, the present invention is not limited thereto.

In the present specification, the heterocycloalkylene group having 3 to 20 carbon atoms may be one in which one or more carbons of the cycloalkylene group are each independently substituted with O, N, Si or S.

In the present specification, the arylene group having 6 to 30 carbon atoms may be a monocyclic arylene group or a polycyclic arylene group. Specifically, the arylene group having 6 to 30 carbon atoms is a monocyclic or polycyclic arylene group having 6 to 25 carbon atoms; Or it may be a monocyclic or polycyclic arylene group having 6 to 20 carbon atoms. More specifically, the arylene group having 6 to 30 carbon atoms may be a phenylene group, a biphenylene group or a terphenylene group as a monocyclic arylene group, and a naphthylene group, an anthracenylene group, or a phenanthrylene group as the polycyclic arylene group. . However, the present invention is not limited thereto.

In the present specification, the heteroarylene group having 2 to 30 carbon atoms may be one in which one or more carbons of the arylene group are each independently substituted with O, N, Si or S.

In the present specification, a single bond means a bond directly connected to each other without a separate atom, and when L ¹ is a single bond in Formula 2, Al ¹ and Al ² are directly connected without a separate atom.

Existing polycarbonate is attracting attention as an interior/exterior material for automobiles or electrical and electronic products or as a replacement material for glass due to its excellent impact strength, heat resistance, and transparency. This was limited.

Accordingly, the present inventors have found that, in the case of a copolycarbonate comprising the polyester repeating units represented by Chemical Formulas 1 and 2 and the repeating units represented by Chemical Formulas 3 and 4 derived from two or more aromatic diols, it is superior to the existing polycarbonate. It was confirmed through experiments that improved fluidity and surface hardness could be exhibited while exhibiting intrinsic physical properties, and the present invention was completed.

Hereinafter, the copolycarbonate according to an embodiment of the present invention will be described in detail.

The copolycarbonate according to the exemplary embodiment includes a polyester repeating unit, wherein the polyester repeating unit includes a diol represented by the following Chemical Formulas A and B and an acid component represented by the following Chemical Formulas C or D. It is derived from the polyester oligomer obtained through the esterification reaction of

[Formula A]

[Formula B]

[Formula C]

[Formula D]

In the above formulas A to D,

R ¹ to R ⁶ , Al ¹ , Al ² , L ¹ and Ar ¹ are the same as defined in Formulas 1 and 2, and X ¹ and X ² are a leaving group and a hydroxyl group, halogen, alkoxy group, or -OCO-alkyl group or the like.

The polyester repeating unit essentially includes the repeating units represented by Chemical Formulas 1 and 2, and, if necessary, additionally using a diol known in the art to which the present invention pertains, and repeating units represented by Chemical Formulas 1 and 2 It may include a repeating unit including other ester bonds.

The copolycarbonate may exhibit improved fluidity and surface hardness while exhibiting intrinsic properties such as excellent impact strength, heat resistance, and transparency of the existing polycarbonate including the polyester repeating unit.

The repeating unit represented by Formula 1 included in the polyester repeating unit is a substituted or unsubstituted 1,4:3,6-dianhydrohexitol represented by Formula A and Formula C or D It can be obtained through an esterification reaction of an acid component.

The substituted or unsubstituted 1,4:3,6-dianhydrohexitol is a substituted or unsubstituted isosorbide, a substituted or unsubstituted isoidide, or a substituted or unsubstituted It may be isomannide (isomannide). The repeating unit obtained through the esterification reaction of each diol with an acid component is as shown in the following Chemical Formulas 1-1 to 1-3.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,

R ¹ to R ⁶ and Ar ¹ are the same as defined in Formula 1, Formula 1-1 is a repeating unit derived from a substituted or unsubstituted child carbide, and Formula 1-2 is a substituted or unsubstituted isoidide-derived of a repeating unit, and Formula 1-3 is a repeating unit derived from substituted or unsubstituted isomannide.

In Formulas 1 and 1-1 to 1-3, R ¹ to R ⁶ are each independently hydrogen, halogen, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; or R ¹ to R ⁶ are each independently hydrogen, halogen, hydroxy group, carboxyl group, methyl group, ethyl group, methoxy group or ethoxy group; or R ¹ to R ⁶ are each independently hydrogen, halogen, a hydroxy group or a methyl group; Alternatively, R ¹ to R ⁶ may be all hydrogen.

The repeating unit represented by Formula 2 included in the polyester repeating unit is obtained through an esterification reaction of a substituted or unsubstituted alicyclic diol represented by Formula B with an acid component represented by Formula C or D. can get

In Formula 2, Al ¹ and Al ² are each independently a cyclohexylene group or an unsubstituted cyclohexylene group substituted with one or more substituents selected from the group consisting of halogen, a hydroxyl group, a methyl group, and a methoxy group; Alternatively, Al ¹ and Al ² may each independently be a 1,4-cyclohexylene group or a 1,3-cyclohexylene group.

In Formula 2, L ¹ is a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO-, methylene group, 1,1-ethylene group, 1,2-ethylene group, 1 , a 3-propylene group, a 2,2-propylene group, a phenylmethylene group, or a diphenylmethylene group; L ¹ is -O-, -S-, -SO-, -SO ₂ -, -CO-, 1,1-ethylene group, 1,2-ethylene group, 1,3-propylene group or 2,2-propylene group; Or L ¹ may be -O-, -S-, 1,1-ethylene group or 2,2-propylene group.

In Formulas 1 and 2, Ar ¹ is the same as one type when the type of the acid component represented by Formula C or D participating in the esterification reaction with the diol represented by Formulas A and B is one type, but When the type of the acid component is two or more, Ar ¹ of each repeating unit may be two or more, and each repeating unit may have a different structure.

In Formulas 1 and 2, Ar ¹ is a phenylene group substituted with one or more substituents selected from the group consisting of halogen, a hydroxyl group, a methyl group, and a methoxy group, or an unsubstituted phenylene group; Alternatively, Ar ¹ may be a 1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene group.

The copolycarbonate comprises 1 to 50% by weight, 1 to 40% by weight, 1 to 30% by weight, 1 to 20% by weight or 3 to 15% by weight of the polyester repeating unit based on the total repeating unit, It is possible to improve the flowability and surface hardness while maintaining the intrinsic properties of polycarbonate at an excellent level.

In addition, the polyester repeating unit includes 60 to 99% by weight or 65 to 95% by weight of the repeating unit represented by Chemical Formula 1, based on the total weight of the polyester repeating unit, and the repeating unit represented by Chemical Formula 2 By including 1 to 40% by weight or 5 to 35% by weight, the above-described effect can be further maximized.

The copolycarbonate may be prepared by reacting the above-described polyester oligomer, aromatic diol, and carbonate precursor.

The copolycarbonate according to the embodiment is a repeating unit represented by Chemical Formulas 3 and 4 by using an aromatic diol including a substituted bisphenol A and unsubstituted bisphenol A represented by the following Chemical Formula E as the aromatic diol. By including, it is possible to exhibit high surface hardness while exhibiting various physical properties such as excellent impact strength, heat resistance and transparency.

[Formula E]

In Formula E, R ⁷ to R ¹⁴ are the same as defined in Formula 3.

In Formula 3 or Formula E, a substituent may be introduced at any position of R ⁷ to R ¹⁴ , but among them, it may be introduced at positions R ⁷ , R ⁹ , R ¹² and R ¹⁴ .

Specifically, in Formula 3 or Formula E, at least one of R ⁷ , R ⁹ , R ¹² and R ¹⁴ is a halogen, a carboxyl group, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group or a propoxy group, The remainder may be hydrogen, and R ⁸ , R ¹⁰ , R ¹¹ and R ¹³ may be hydrogen.

More specifically, in Formula 3 or Formula E, R ⁷ and R ¹² are halogen, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹³ and R ¹⁴ are hydrogen. can

The aromatic diol includes substituted bisphenol A and unsubstituted bisphenol A, and may further include various aromatic diols known in the art to which the present invention pertains. As a non-limiting example, the aromatic diol may include, in addition to the substituted bisphenol A and unsubstituted bisphenol A, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl) )sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, bisphenol A , 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane and bis( It may further include one type of diol selected from the group consisting of 4-hydroxyphenyl) diphenylmethane.

The type of carbonate precursor for reacting with the polyester oligomer and the aromatic diol to provide a copolycarbonate is not particularly limited, and for example, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, di Phenyl carbonate, ditoryl carbonate, bis(chlorophenyl) carbonate, di-m-cresyl carbonate, dynaphthyl carbonate, bis(diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene and bishalophosgene One or more selected from the group consisting of mates may be used. Preferably, triphosgene or phosgene can be used.

The copolycarbonate is obtained by polymerizing the polyester oligomer, the aromatic diol, and the carbonate precursor, and the polymerization may be performed by interfacial polymerization. Interfacial polymerization has the advantage that polymerization can be performed at normal pressure and low temperature, and molecular weight can be easily controlled. In addition, the interfacial polymerization may include, for example, a step of adding a coupling agent after pre-polymerization and then polymerization again, in this case, a high molecular weight copolycarbonate may be obtained.

The polymerization temperature is preferably 0 °C to 40 °C, and the reaction time is preferably 10 minutes to 24 hours. In addition, the pH during the reaction is preferably maintained at 9 or more or 11 or more.

The solvent that can be used for the polymerization is not particularly limited as long as it is a solvent used for polymerization of polycarbonate in the art. For example, halogenated hydrocarbons such as dichloromethane and chlorobenzene may be used.

In addition, the polymerization is preferably performed in the presence of an acid binder, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as triethylamine and pyridine may be used as the acid binder.

In addition, in order to control the molecular weight of the polycarbonate during the polymerization, it is preferable to perform polymerization in the presence of a molecular weight modifier. C _1-20 alkylphenol may be used as the molecular weight modifier, and specific examples thereof include p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eico sylphenol, docosylphenol, or triacontylphenol is mentioned. The molecular weight regulator may be added before polymerization, during polymerization, or after polymerization. The molecular weight modifier is, for example, 0.01 parts by weight or more, 0.1 parts by weight or more, or 1 part by weight or more, 10 parts by weight or less, 6 parts by weight when the total weight of the polyester oligomer and the aromatic diol is 100 parts by weight. or less, or 5 parts by weight or less, and a desired molecular weight can be obtained within this range.

In addition, in order to promote the polymerization reaction, a reaction such as a tertiary amine compound such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound Accelerators may additionally be used.

The copolycarbonate comprises 1 to 50% by weight, 1 to 40% by weight, 1 to 30% by weight, 1 to 20% by weight or 3 to 15% by weight of the polyester repeating unit based on the total weight, 1 to 80% by weight, 1 to 60% by weight, 1 to 50% by weight, 1 to 30% by weight, 1 to 20% by weight or 1 to 10% by weight of the repeating unit represented by Formula 3, wherein Formula 4 1 to 98% by weight, 30 to 98% by weight, 50 to 95% by weight, 60 to 95% by weight, 70 to 95% by weight, or 75 to 90% by weight of the repeating unit represented by may be included. Within this range, it can exhibit excellent impact strength and heat resistance while exhibiting high fluidity and high hardness.

The copolycarbonate may have a weight average molecular weight (g/mol) of 20,000 to 60,000, or 30,000 to 50,000.

The copolycarbonate has a flow index (MI) of 30 to 90 g/10min, 35 to 90 g/10min, 40 to 85 g/10min, 45 to 75 g measured at 300° C. and 1.2 kg according to ASTM D1238. High fluidity may be exhibited at /10min or 50 to 70 g/10min. In addition, the copolycarbonate may exhibit high hardness such that a pencil hardness measured according to ASTM D 3363 with respect to a specimen formed therefrom is F or more. In addition, the copolycarbonate has a transmittance of 85% to 100%, 87% to 100%, 88% to 100% or 89% to 89% in the range of 350 to 1050 nm measured according to ASTM D1003 with respect to the specimen formed therefrom It can be 100%. For detailed measurement methods of the flow index, pencil hardness, and transmittance, reference may be made to the contents described in Test Examples to be described later.

On the other hand, according to another embodiment of the invention, there is provided a polycarbonate composition comprising the copolycarbonate.

Since the copolycarbonate has been described in detail above, a detailed description thereof will be omitted herein. In addition, the polycarbonate composition may include various additives and solvents known in the art.

As the polycarbonate composition according to the other embodiment includes the copolycarbonate, it is expected to be used in various fields requiring high hardness or precision as it exhibits improved fluidity and surface hardness as well as excellent intrinsic properties of the existing polycarbonate. do.

The copolycarbonate of a novel structure according to an embodiment of the present invention exhibits very high surface hardness and improved fluidity while exhibiting excellent impact strength, heat resistance and transparency of the existing polycarbonate, and various uses requiring high hardness or precision. expected to be used for

Hereinafter, the action and effect of the invention will be described in more detail through specific examples of the invention. However, this is presented as an example of the invention and the scope of the invention is not limited in any way by this.

Preparation Example 1: Preparation of polyester oligomer

In a 500 mL three-necked flask, 14.8 g (101 mmol) of isosorbide, 2.7 g (12 mmol) of 4,4'-isopropylidene dicyclohexanol, 12 g (59 mmol) of isophthalic acid, 12 g of terephthalic acid (59 mmol), 200 mL of dichloromethane was added, and 32 mL (230 mmol) of triethylamine was slowly added to the flask at room temperature. The resulting mixture was then stirred at room temperature for 24 hours. After completion of the reaction, the obtained product was washed with distilled water, and then the solvent was removed using a rotary vacuum distiller to obtain 38 g of polyester oligomer A (PE-A).

Preparation Example 2: Preparation of polyester oligomer

In a 500 mL 3-neck flask, 15.7 g (107 mmol) of isosorbide, 1.4 g (6 mmol) of 4,4'-isopropylidene dicyclohexanol, 12 g (59 mmol) of isophthalic acid, 12 g (59 mmol) of terephthalic acid mmol), 200 mL of dichloromethane was added, and 32 mL (230 mmol) of triethylamine was slowly added to the flask at room temperature. The resulting mixture was then stirred at room temperature for 24 hours. After the reaction was completed, the obtained product was washed with distilled water, and then the solvent was removed using a rotary vacuum distiller to obtain 39 g of polyester oligomer B (PE-B).

Preparation Example 3: Preparation of polyester oligomer

In a 500 mL 3-neck flask, 13.2 g (90 mmol) of isosorbide, 5.4 g (23 mmol) of 4,4'-isopropylidene dicyclohexanol, 12 g (59 mmol) of isophthalic acid, 12 g of terephthalic acid (59 mmol), 200 mL of dichloromethane was added, and 32 mL (230 mmol) of triethylamine was slowly added to the flask at room temperature. The resulting mixture was then stirred at room temperature for 24 hours. After completion of the reaction, the obtained product was washed with distilled water, and then the solvent was removed using a rotary vacuum distiller to obtain 40 g of polyester oligomer C (PE-C).

Comparative Preparation Example 4: Preparation of polyester oligomer

Put 16.4 g (112 mmol) of isosorbide, 12 g (59 mmol) of isophthalic acid, 12 g (59 mmol) of terephthalic acid, and 200 mL of dichloromethane in a 500 mL 3-neck flask, and triethylamine at room temperature in the flask 32 mL (230 mmol) was added slowly. The resulting mixture was then stirred at room temperature for 24 hours. After the reaction was completed, the obtained product was washed with distilled water, and then the solvent was removed using a rotary vacuum distiller to obtain 37 g of polyester oligomer D (PE-D).

Comparative Preparation Example 5: Preparation of polyester oligomer

26.7 g (112 mmol) of 4,4'-isopropylidene dicyclohexanol, 12 g (59 mmol) of isophthalic acid, 12 g (59 mmol) of terephthalic acid, and 200 mL of dichloromethane in a 500 mL three-necked flask , 32 mL (230 mmol) of triethylamine was slowly added to the flask at room temperature. The resulting mixture was then stirred at room temperature for 24 hours. After the reaction was completed, the obtained product was washed with distilled water, and then the solvent was removed using a rotary vacuum distiller to obtain 44 g of polyester oligomer E (PE-E).

Example 1: Preparation of copolycarbonate

619.33 g of water, 2,2-bis(4-hydroxy-3-methylphenyl)propane (BPC) 6.5 g (25 mmol), bisphenol A (BPA) 110 g (473 mmol), 16.5 g of polyester oligomer A (PE-A) prepared in Preparation Example 1, 102.5 g of 40 wt% NaOH aqueous solution, 200 mL of dichloromethane, and , and stirred for several minutes.

Stop purging with nitrogen and put 63 g (212 mmol) of triphosgene (TPG) and 120 mL of dichloromethane in a 1 L round-bottom flask to dissolve triphosgene, and then slowly introduce the dissolved triphosgene solution into the main reactor, When this was completed, 3.26 g of PTBP (p-tert-butylphenol) was added and stirred for 10 minutes. Thereafter, 40 wt% of an aqueous NaOH solution was added, and then 1.08 g of triethylamine was added as a coupling agent. At this time, the reaction pH was maintained at 11 to 13.

In order to complete the reaction with sufficient time to allow the reaction to take place, HCl was added to drop the pH to 3-4. Then, the stirring was stopped to separate the organic layer and the water layer, the water layer was removed, pure H ₂ O was added again, and the process of washing with water was repeated 3 to 5 times.

When water washing was completed, only the organic layer was extracted and copolycarbonate was obtained by reprecipitation using a non-solvent using methanol, H ₂ O, and the like.

Examples 2 to 3 and Comparative Examples 1 to 3: Preparation of copolycarbonate

A copolycarbonate was prepared in the same manner as in Example 1, except that the type of polyester oligomer and the type and content of "?hyang?* diol were changed as shown in Table 1 below."

polyester oligomer BPC BPA PE-A PE-B PE-C PE-D PE-E Example 1 12.4 4.9 82.7 Example 2 12.4 4.9 82.7 Example 3 12.4 4.9 82.7 Comparative Example 1 12.4 4.9 82.7 Comparative Example 2 12.4 4.9 82.7 Comparative Example 3 12.4 87.6

(Unit: % by weight)

Test Example: Evaluation of physical properties of copolycarbonate

The physical properties of the polycarbonate prepared in Examples and Comparative Examples were evaluated in the following manner, and the results are shown in Table 2.

<Preparation of specimen>

To 1 part by weight of the copolycarbonate prepared in Examples and Comparative Examples, 0.050 parts by weight of tris(2,4-di-tert-butylphenyl)phosphite was added, and pelletized using a vented Φ19 mm twin-screw extruder. After that, the specimen was prepared by injection molding at a cylinder temperature of 300 °C and a mold temperature of 90 °C using a HAAKE Minijet injection molding machine.

1) Weight average molecular weight (Mw): The weight average molecular weight of copolycarbonate was measured by GPC using PS standard (Standard) using Agilent 1200 series.

2) Fluidity (Melt Index; MI): The MI value of the copolycarbonate was measured according to ASTM D1238 (300° C., 1.2 kg conditions).

3) Surface hardness: Pencil hardness was measured in accordance with ASTM D 3363. Specifically, after fixing the angle of the pencil at 45°, the surface of the specimen was scraped by about 6.5 mm to evaluate whether scratches were observed with the naked eye, and the strength of the pencil was evaluated. The experiment was repeated.

4) Transparency: Transmittance in the range of about 350 to 1050 nm was measured using UltraScan PRO (manufactured by HunterLab) according to ASTM D1003.

Mw (g/mol) MI (g/10min) surface hardness transparency (%) Example 1 43,000 47 F 89 Example 2 42,000 40 F 88 Example 3 42,000 65 F 89 Comparative Example 1 43,000 22 F 88 Comparative Example 2 43,000 80 B 89 Comparative Example 3 41,000 52 HB 87

Referring to Table 2, an embodiment comprising a copolycarbonate including the polyester repeating units represented by Chemical Formulas 1 and 2 and the repeating units represented by Chemical Formulas 3 and 4 derived from two or more aromatic diols In the case of 1 to 3, it was confirmed that high fluidity of 40 g/10 min or more and high surface hardness were exhibited.

However, in Comparative Examples 1 and 2 in which the polyester repeating unit does not have the repeating unit represented by Chemical Formulas 1 or 2, high fluidity and high hardness were not simultaneously satisfied, and the polyester repeating represented by Chemical Formulas 1 and 2 In the case of Comparative Example 3 without the repeating unit represented by Chemical Formula 3, even if all units are included, it is confirmed that the high hardness of the Example level is not exhibited.

Accordingly, it is confirmed that the copolycarbonate according to an embodiment of the present invention can implement high fluidity and high hardness by including all of the repeating units of Chemical Formulas 1 to 4.

Claims (14)

A polyester repeating unit comprising a repeating unit represented by the following Chemical Formulas 1 and 2, and
A copolycarbonate comprising a repeating unit represented by the following Chemical Formulas 3 and 4:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 1 to 4,
R ¹ to R ⁶ are each independently hydrogen, halogen, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or -0COR ¹⁵ ;
Ar ¹ is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene group having 4 to 20 carbon atoms,
Al ¹ and Al ² are each independently a substituted or unsubstituted cycloalkylene group having 4 to 30 carbon atoms, or a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms,
L ¹ is a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO-, or a substituted or unsubstituted C 1 to C 6 alkylene group,
R ⁷ to R ¹⁴ are each independently hydrogen, halogen, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or -0COR ¹⁵ , but at least one is a halogen, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or -0COR ¹⁵ ;
R ¹⁵ is an alkyl group having 1 to 12 carbon atoms.
The copolycarbonate according to claim 1, wherein the repeating unit represented by Chemical Formula 1 is a repeating unit represented by the following Chemical Formulas 1-1 to 1-3:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,
R ¹ to R ⁶ are each independently hydrogen, halogen, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or -0COR ¹⁵ ;
Ar ¹ is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene group having 4 to 20 carbon atoms,
R ¹⁵ is an alkyl group having 1 to 12 carbon atoms.
The copolycarbonate according to claim 1, wherein R ¹ to R ⁶ are each independently hydrogen, halogen, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.
The method of claim 1, wherein Al ¹ and Al ² are each independently a cyclohexylene group substituted with one or more substituents selected from the group consisting of halogen, a hydroxyl group, a methyl group, and a methoxy group, or an unsubstituted cyclohexylene group. Gin, copolycarbonate.
According to claim 1, wherein L ¹ Is a single bond, -O-, -S-, -SO-, -SO ₂ -, -CO-, methylene group, 1,1-ethylene group, 1,2-ethylene group , 1,3-propylene group, 2,2-propylene group, phenylmethylene group or diphenylmethylene group, copolycarbonate.
The copolycarbonate according to claim 1, wherein Ar ¹ is a phenylene group substituted with one or more substituents selected from the group consisting of halogen, a hydroxyl group, a methyl group, and a methoxy group, or an unsubstituted phenylene group.
The copolycarbonate according to claim 1, wherein the copolycarbonate comprises 1 to 50% by weight of the polyester repeating unit based on the total repeating unit.
According to claim 1, Based on the total weight of the polyester repeating unit,
The repeating unit represented by Formula 1 is 60 to 99% by weight and
The repeating unit represented by Formula 2 is included in an amount of 1 to 40% by weight, copolycarbonate.
According to claim 1, wherein at least one of R ⁷ , R ⁹ , R ¹² and R ¹⁴ is a halogen, a carboxyl group, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, or a propoxy group, the rest is hydrogen , R ⁸ , R ¹⁰ , R ¹¹ and R ¹³ are hydrogen.
According to claim 1, with respect to the total weight of the copolycarbonate,
The polyester repeating unit is 1 to 50% by weight,
The repeating unit represented by Formula 3 is 1 to 80% by weight and
The repeating unit represented by Formula 4 is included in an amount of 1 to 98% by weight, copolycarbonate.
The copolycarbonate according to claim 1, wherein the flow index (MI) measured at 300° C. and 1.2 kg according to ASTM D1238 is 30 to 90 g/10 min.
The copolycarbonate according to claim 1, wherein the specimen formed from the copolycarbonate has a pencil hardness of F or more as measured in accordance with ASTM D 3363.
The copolycarbonate according to claim 1, wherein the specimen formed from the copolycarbonate has a transmittance of 85% to 100% in a range of 350 to 1050 nm measured according to ASTM D1003.
A polycarbonate composition comprising the copolycarbonate of claim 1.