KR20230101140A - Polycarbonate copolymer with improved heat resistance and scratch resistance and method for preparing the same - Google Patents

Abstract

The present invention relates to a polycarbonate copolymer and a method for producing the same, and more particularly, to a repeating unit derived from an acenaphthoquinone-based diol compound; And a polycarbonate repeating unit; and relates to a polycarbonate copolymer having improved heat resistance and scratch resistance compared to conventional linear polycarbonate and polycarbonate copolymer, while maintaining excellent transparency and flowability, and a method for producing the same. .

Description

Polycarbonate copolymer with improved heat resistance and scratch resistance and manufacturing method thereof

The present invention relates to a polycarbonate copolymer and a method for producing the same, and more particularly, to a repeating unit derived from an acenaphthoquinone-based diol compound; And a polycarbonate repeating unit; and relates to a polycarbonate copolymer having improved heat resistance and scratch resistance compared to conventional linear polycarbonate and polycarbonate copolymer, while maintaining excellent transparency and flowability, and a method for producing the same. .

Polycarbonate has excellent mechanical properties such as tensile strength and impact resistance, and is widely used for industrial purposes because of its excellent dimensional stability, heat resistance, and optical transparency. In order to improve the physical properties of polycarbonate, research on various copolymers continues, and for example, a polysiloxane-polycarbonate copolymer has been proposed to improve low-temperature impact resistance (US Patent Publication No. 2003-0105226).

The chemical structure of polycarbonate prepared using bisphenol A and phosgene basically has a hydroxyl group at the end group, and a new type of polymer can be prepared using a method of activating the hydroxyl group at both terminal groups. At this time, polymerization may be performed in an aqueous solution, at an interface, or in a non-aqueous solution.

However, polycarbonates, especially made from bisphenol A, have limited scratch resistance. Therefore, in order to prevent or minimize the scratch damage, a hard coat must be applied as a surface modification, but this hard coat involves additional processes and costs, and has poor durability.

Korean Patent Registration No. 10-1815930 discloses a polycarbonate copolymer with improved scratch resistance and anti-fogging properties, and the polycarbonate copolymer disclosed herein exhibits excellent anti-fogging properties, but also has anti-scratch properties. needs to be further improved.

Therefore, there is a demand for the development of a polycarbonate copolymer with improved heat resistance and scratch resistance while excellently maintaining transparency and fluidity, which are properties inherent in polycarbonate.

The present invention is to solve the problems of the prior art as described above, while having improved heat resistance and scratch resistance compared to conventional linear polycarbonate and conventional polycarbonate copolymers, while maintaining excellent transparency and flowability polycarbonate air It is a technical task to provide a synthesis and a manufacturing method thereof.

In order to solve the above technical problems, one aspect of the present invention is a repeating unit derived from a substituted or unsubstituted acenaphthoquinone-based diol compound; And polycarbonate repeating units; it provides a polycarbonate copolymer comprising a.

According to one preferred embodiment of the present invention, the present invention, a repeating unit derived from a compound represented by Formula 1; And polycarbonate repeating units; provides a polycarbonate copolymer comprising:

[Formula 1]

In Formula 1,

R and R' each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

Another aspect of the present invention is a diol component containing a substituted or unsubstituted acenaphthoquinone-based diol compound; And a carbonic acid diester compound or a carbonate precursor; It provides a method for producing a polycarbonate copolymer comprising the step of copolymerizing.

According to one preferred embodiment of the present invention, the present invention, a diol component containing the compound represented by the formula (1); And a carbonic acid diester compound or a carbonate precursor; It provides a method for producing a polycarbonate copolymer comprising the step of copolymerizing.

Another aspect of the present invention provides a molded article comprising the polycarbonate copolymer according to the present invention.

Since the polycarbonate copolymer according to the present invention exhibits improved heat resistance and scratch resistance while maintaining excellent transparency and fluidity, molded products including the polycarbonate copolymer (eg, films, sheets, lenses, cover glasses, interior and exterior materials, etc.) It can be used very suitably for optical use in industry and for use as a substitute for lightweight materials.

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

As used herein, any compound, group or structure “substituted” means that the compound, group or structure is a halogen atom (eg, F, Cl or Br), a hydroxy group, an alkyl group (eg, 1 to 10 carbon atoms or 1 to 10 carbon atoms). 1 to 6 alkyl group), an alkoxy group (eg, 1 to 10 carbon atoms or 1 to 6 carbon atoms alkoxy group), a cycloalkyl group (eg, 3 to 10 carbon atoms or 3 to 6 carbon atoms cycloalkyl group), an aryl group ( For example, an aryl group having 6 to 12 carbon atoms or 6 carbon atoms) or a combination thereof.

The copolymer of the present invention includes a repeating unit derived from a substituted or unsubstituted acenaphthoquinone-based diol compound; and polycarbonate repeating units.

In the present specification, the acenaphthoquinone-based diol compound refers to a compound having at least one “acenaphthoquinone-based” structure and having hydroxyl groups at both ends, and the acenaphthoquinone-based diol compound may be substituted or unsubstituted. can

In one embodiment, the acenaphthoquinone-based diol compound may be a compound represented by Formula 2 below:

[Formula 1]

In Formula 1,

R and R' each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

More specifically, the acenaphthoquinone-based diol compound may have a structure represented by Formula 2 below:

[Formula 2]

In a preferred embodiment, the copolymer of the present invention comprises a repeating unit derived from the compound represented by Formula 1; and polycarbonate repeating units.

According to one embodiment of the present invention, the copolymer of the present invention is a diol compound other than the substituted or unsubstituted acenaphthoquinone-based diol compound (more specifically, the compound of Formula 1) (hereinafter referred to as “additional diol compound”). Also referred to as) may further include a repeating unit derived from.

In one embodiment, the additional diol compound may be a dihydric phenolic compound.

More specifically, the dihydric phenolic compound may be a compound having a structure represented by Formula 3 below:

[Formula 3]

In Formula 3,

A is a straight, branched or cyclic alkylene group having no functional group; Or a straight, branched or cyclic alkylene group (e.g., 1 carbon atom) containing at least one functional group selected from the group consisting of a sulfide group, an ether group, a sulfoxide group, a sulfone group, a ketone group, a phenyl group, an isobutylphenyl group, or a naphthyl group. to 10 linear alkylene groups, C3 to 10 branched alkylene groups, or C3 to 10 cyclic alkylene groups),

R ₁ and R ₂ are each independently a halogen atom (eg, Cl or Br); Or a straight, branched or cyclic alkyl group (e.g., a straight alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms),

m and n each independently represents an integer of 0 to 4;

Specifically, the compound of Formula 3, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl) -Hydroxyphenyl)-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl -1,1-bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1, 10-bis (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis ( 4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) nonane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane, 4-methyl-2,2-bis(4-hydroxy hydroxyphenyl) pentane, 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) methane, resorcinol, hydroquinone, 4,4'- Dihydroxyphenyl ether [bis(4-hydroxyphenyl)ether], 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3' -Dichlorodiphenyl ether, bis(3,5-dimethyl-4-hydroxyphenyl) ether, bis(3,5-dichloro-4-hydroxyphenyl) ether, 1,4-dihydroxy-2,5- Dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p,p'-dihydroxyphenyl], 3,3'-dichloro-4,4'- Dihydroxyphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3, 5-dichloro-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)cyclododecane , 1,1-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) decane, 1,4-bis (4-hydroxyphenyl) propane, 1,4-bis (4 -hydroxyphenyl) butane, 1,4-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3-chloro-4-hydroxy Phenyl) propane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3,5-dichloro-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4- Hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2, 4-bis(4-hydroxyphenyl)-2-methyl-butane, 4,4'-thiodiphenol [bis(4-hydroxyphenyl)sulfone], bis(3,5-dimethyl-4-hydroxyphenyl )sulfone, bis(3-chloro-4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(3-methyl-4-hydroxyphenyl) Sulfide, bis(3,5-dimethyl-4-hydroxyphenyl)sulfide, bis(3,5-dibromo-4-hydroxyphenyl)sulfoxide, 4,4'-dihydroxybenzophenone, 3, 3',5,5'-tetramethyl-4,4'-dihydroxybenzophenone, 4,4'-dihydroxy diphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene or 2,6-di It may be selected from hydroxynaphthalene, but is not necessarily limited thereto. Representatively, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) is exemplified. Other functional dihydric phenols may be referred to US Patents US 2,999,835, US 3,028,365, US 3,153,008 and US 3,334,154, and the dihydric phenols may be used alone or in combination of two or more. can be used

According to one embodiment, in the copolymer of the present invention, the molar ratio of repeating units derived from substituted or unsubstituted acenaphthoquinone-based diol compounds (more specifically, the compound of Formula 1) per 1 mole of repeating units derived from all diol components is 0.05 0.06 or more, 0.07 or more, 0.08 or more, 0.09 or more, or 0.1 or more, or 0.9 or less, 0.89 or less, 0.88 or less, 0.87 or less, 0.86 or less, 0.85 or less, 0.84 or less, 0.83 or less, 0.82 or less, 0.81 or less, or It may be 0.8 or less. Specifically, the molar ratio of repeating units derived from the compound of Formula 1 per 1 mole of repeating units derived from all diol components may be 0.05 to 0.9, more specifically, 0.06 to 0.89, 0.08 to 0.85, or 0.1 to 0.8. there is.

In the copolymer of the present invention, if the relative content of the repeating unit derived from the substituted or unsubstituted acenaphthoquinone-based diol compound (more specifically, the compound of Formula 1), compared to the repeating unit derived from all diol components, is excessively less than the above level Heat resistance of the copolymer may be lowered or scratch resistance may be deteriorated, and conversely, if the amount exceeds the above level, the fluidity of the copolymer may be very deteriorated.

The polycarbonate repeating unit included in the copolymer of the present invention may be derived from a carbonic acid diester compound or a carbonate precursor.

In one embodiment, the carbonic acid diester compound may be selected from dialkyl carbonates, diaryl carbonates, alkylene carbonates, or combinations thereof.

In one embodiment, examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl normal butyl carbonate, and ethyl isobutyl carbonate. Examples of the lyl carbonate include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and di(m-cresyl) carbonate, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, and tetramethylene Carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1 ,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate, neopentylene carbonate and the like.

In one embodiment, the carbonic acid diester compound may be selected from dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, or a combination thereof, more preferably diphenyl carbonate.

In one embodiment, the carbonic acid diester compound may be selected from compounds represented by Formula 4 below.

[Formula 4]

In Formula 4, Y and Y' are each independently selected from an unsubstituted or halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 25 carbon atoms, and Y and Y' may be the same as or different from each other.

In one embodiment, the carbonic acid diester compound represented by Formula 4 is selected from diphenyl carbonate, ditolyl carbonate, bischlorophenyl carbonate, dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate, or mixtures thereof may be used, but diphenyl carbonate or dimethyl carbonate may be preferably used.

In one embodiment, the carbonate precursor may be selected from the group consisting of phosgene (carbonyl chloride), carbonyl bromide, bishalo formate, diphenyl carbonate, dimethyl carbonate, or a combination thereof.

According to one embodiment, in the copolymer of the present invention, the molar ratio of polycarbonate repeating units per 1 mol of all diol component-derived repeating units may be 0.9 or more, 0.95 or more, or 0.98 or more, and also 1.1 or less, 1.05 or less, or 1.02 or less. can

In the copolymer of the present invention, if the relative content of the polycarbonate repeating unit compared to all the diol component-derived repeating units is too low, the thermal stability of the copolymer may be deteriorated or a desired level of molecular weight may not be obtained, Conversely, if the amount exceeds the above level, toxic gas may be generated during molding of the copolymer or it may cause decomposition.

In one embodiment, the viscosity average molecular weight of the copolymer of the present invention may be 10,000 to 80,000, but is not limited thereto. If the viscosity average molecular weight of the copolymer is excessively less than the above level, mechanical properties such as impact strength and tensile strength may be deteriorated, and conversely, if it is excessively greater than the above level, moldability may be deteriorated.

The copolymer of the present invention is a random copolymer and can be prepared using a polymerization method widely known to those skilled in the art. For example, it can manufacture using the melt polymerization method by transesterification or the phosgene polymerization method.

Therefore, according to another aspect of the present invention, a diol component containing a substituted or unsubstituted acenaphthoquinone-based diol compound; And a carbonic acid diester compound or a carbonate precursor; a method for producing a polycarbonate copolymer comprising the step of copolymerizing is provided.

In a preferred embodiment of the present invention, the method for preparing the copolymer includes a diol component including the compound represented by Formula 1; And a carbonic acid diester compound or a carbonate precursor; It includes the step of copolymerizing.

According to one embodiment of the present invention, the diol component further includes a diol compound (“additional diol compound”) other than the substituted or unsubstituted acenaphthoquinone-based diol compound (more specifically, the compound of Formula 1) can do.

A substituted or unsubstituted acenaphthoquinone-based diol compound (more specifically, a compound of Formula 1), an additional diol compound (more specifically, a compound of Formula 3) usable in the method for preparing a copolymer according to the present invention, The specific types and amounts of the carbonic acid diester compound and the carbonate precursor are as described above.

Conditions for the copolymerization reaction are not particularly limited, and may be carried out at room temperature (eg, 20-30 °C) or elevated temperature (eg, 150-250 °C), but are not limited thereto.

In one embodiment, the preparation method of the copolymer may be performed in the presence of a catalyst.

As the catalyst, a polymerization catalyst and/or a phase transfer catalyst may be used. As the polymerization catalyst, for example, a base catalyst, more specifically, an organic amine catalyst such as triethylamine (TEA) may be used, and as a phase transfer catalyst, for example, a compound represented by Formula 5 may be used. .

[Formula 5]

(R ₇ ) ₄ Q ⁺ Z ^-

In Formula 5, R ₇ represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and Z represents a halogen atom or -OR ₈ . Here, R ₈ 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 NZ, [CH ₃ (CH ₂ ) ₃ ] ₄ PZ, [CH ₃ (CH ₂ ) ₅ ] ₄ NZ, [CH ₃ (CH ₂ ) ₆ ] ₄ NZ, [CH ₃ (CH ₂ ) ₄ ] ₄ NZ, CH ₃ [CH ₃ (CH ₂ ) ₃ ] ₃ NZ or CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NZ there is. In the above formulas, Z represents Cl, Br or -OR ₈ , where R ₈ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. When using a phase transfer catalyst, its content is preferably 0.01% by weight or more in terms of transparency of the resulting copolymer, but is not limited thereto.

In one embodiment, a molecular weight modifier may be used in the method for preparing the copolymer.

As the molecular weight modifier, a monofunctional compound similar to a monomer used in preparing polycarbonate may be used. The monofunctional substances are, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol and p-isononyl. It may be a derivative based on phenol, such as phenol, or an aliphatic alcohol. Preferably, p-tert-butylphenol (PTBP) may be used.

In one embodiment, the method for preparing the copolymer may further include extracting an organic phase from the resultant mixture after the copolymerization reaction is completed.

According to one embodiment, after preparing the copolymer, the organic phase dispersed in methylene chloride is washed with alkali and then separated. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution and then washed with distilled water 2 to 3 times repeatedly. When the washing is completed, the concentration of the organic phase dispersed in methylene chloride is constantly adjusted, and granulation is performed using a certain amount of pure water in the range of 30 to 100 ° C., preferably in the range of 60 to 80 ° C. If the temperature of the pure water is less than 30 ° C, the assembly speed may be slowed and the assembly time may be very long. When the assembly is completed, it is preferable to dry at 100 to 120 ° C for 5 to 10 hours, more preferably first at 100 to 110 ° C for 5 to 10 hours, and secondly at 110 to 120 ° C for 5 to 10 hours. .

Since the polycarbonate copolymer of the present invention exhibits improved heat resistance and scratch resistance while maintaining excellent transparency and fluidity, molded articles including the same (eg, film, sheet, lens, cover glass, interior and exterior materials, etc.) are used in various industries. It can be used very suitably for optical use and for use as a substitute for lightweight materials.

Accordingly, according to another aspect of the present invention, a molded article comprising the polycarbonate copolymer of the present invention is provided. In the present invention, 'molded article' means a molded article by extrusion, injection, or other processing.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereby.

[Example]

Preparation Example 1: Preparation of acenaphthoquinone-based derivative diol compound

After adding 3 g (16.5 mmol) of acenaphthoquinone, 9.29 g (98.7 mmol) of phenol, and 2 mL of 1-dodecanethiol to a 250 mL one-neck reactor, dichloro 50 mL of ethane (dichloroethane) was added. Thereafter, 2 mL of methanesulfonic acid was added to the reactor under a nitrogen atmosphere and stirred under reflux conditions for 3 hours. Thereafter, the reaction-completed solution is cooled to room temperature, and the precipitate is filtered and washed with dichloromethane (3 X 100 mL) and water (2 X 100 mL). Then, the mixture was air-dried for 8 hours to obtain 5.11 g (14.5 mmol) of an acenaphthoquinone-based derivative diol compound represented by Formula A as a white solid.

[Formula A]

<Preparation of Copolymer>

Example 1: Preparation of copolymer using phosgene polymerization

177.61 g of bisphenol A (0.65 mol based on 1 mol of total diols) and 147.63 g of the compound of Formula A (0.35 mol based on 1 mol of total diols) obtained in Preparation Example 1 were 5.6 wt% hydroxylated in a 3L three-necked reactor After dissolving in 900 mL of aqueous sodium solution, 118.40 g of phosgene was collected in methylene chloride and reacted while being slowly introduced through a Teflon tube (5 mm). The external temperature was maintained at 0°C. The reactants passing through the tubular reactor were subjected to an interfacial reaction for about 10 minutes under a nitrogen atmosphere. After the reaction was completed, 1 L of the reaction product was mixed with 2.98 g of p-tert-butylphenol (PTBP) and 0.24 mL of a trimethylamine catalyst, followed by interfacial reaction for 1 hour. After layer separation, the organic phase was taken, and an aqueous solution of sodium hydroxide prepared by dissolving 14 g of sodium hydroxide in 140 g of distilled water was mixed with 255 g of methylene chloride, and 250 µl of triethylamine was added to react for 1 hour and 30 minutes. After the reaction was finished, distilled water was added to alkali wash, and only the organic phase was separated. The organic phase was washed with 0.1 N hydrochloric acid solution and then washed with distilled water three times repeatedly. After washing was completed, the concentration of the organic phase was kept constant, and then granulated using a certain amount of distilled water at 80 °C. After assembly was completed, a copolymer was obtained by drying at 105° C. for 12 hours.

Example 2: Preparation of copolymer using phosgene polymerization

The content of bisphenol A was changed from 177.61 g to 46.83 g (0.20 mol based on 1 mol of total diol total), and the content of the compound of formula A obtained in Preparation Example 1 was changed from 147.63 g to 289.12 g (total total of diol 1 A copolymer was obtained in the same manner as in Example 1, except for changing to 0.80 mol based on mol).

Example 3: Preparation of copolymer using phosgene polymerization

The content of bisphenol A was changed from 177.61 g to 271.09 g (0.90 mol based on 1 mol of total diol total), and the content of the compound of formula A obtained in Preparation Example 1 was changed from 147.63 g to 46.50 g (total total of diol 1 A copolymer was obtained in the same manner as in Example 1, except for changing to 0.10 mol based on mol).

Example 4: Preparation of Copolymer Using Melt Polymerization

In a 2L three-necked condensation reactor, 246.69 g of diphenyl carbonate, 157.74 g of bisphenol A (0.6 mol based on 1 mol of the total diol total), and 162.32 g of the compound of formula A obtained in Preparation Example 1 (0.4 g based on 1 mol of the total diol total) mol), and 0.0001 g of cesium carbonate, and stirred while slowly raising the temperature to 180° C. under a nitrogen gas atmosphere. Then, over 1 hour, the pressure was gradually lowered to 50 torr, and the temperature of the reactor was raised to 260° C. to continue the reaction while removing phenol as a side reactant. A copolymer was obtained by removing a residual amount of phenol while lowering the pressure to 0.1 torr for an additional hour and terminating the reaction.

Comparative Example 1: Preparation of thermoplastic aromatic polycarbonate (linear polycarbonate) resin

A linear polycarbonate having a viscosity average molecular weight of 21,000 was prepared by a conventional interfacial polymerization method.

=25mm 인 이축 용융 혼합 압출기를 사용하여 용융 및 혼련시켰다. 그 후 압출 다이를 통해 나온 용융물을 냉각하여 성형용 펠렛을 제조하였다. 상기 제조된 성형용 펠렛을 90~100℃의 온도에서 4 시간 이상 열풍 건조 후, 280~320℃의 온도에서 사출 성형하여 시편을 제조하였다. 상기 제조된 시편에 대한 물성들을 측정 및 평가하였고, 그 결과를 하기 표 1에 나타내었다.The polycarbonate copolymer prepared in Examples 1 to 4 and the linear polycarbonate prepared in Comparative Example 1, respectively, L / D = 40

=25 mm was melted and kneaded using a twin screw melt mixing extruder. Thereafter, the melt coming out through the extrusion die was cooled to prepare pellets for molding. The prepared pellets for molding were dried in hot air for 4 hours or more at a temperature of 90 to 100 ° C., and then injection molded at a temperature of 280 to 320 ° C. to prepare a specimen. The physical properties of the prepared specimens were measured and evaluated, and the results are shown in Table 1 below.

[How to measure physical properties]

(1) Viscosity average molecular weight

The viscosity of the methylene chloride solution was measured at 20° C. using an Ubbelohde Viscometer, and the intrinsic viscosity [η] was calculated by the following equation.

[η]=1.23 X 10 ^-5 Mv ^0.83

(2) Pencil hardness (scratch resistance)

YASUDA SEIKI's No. The pencil hardness of each specimen prepared in Examples and Comparative Examples was measured using a 553-M1 pencil hardness tester. Specifically, the coating film of the specimen was scratched at an angle of 45 °, and the hardest pencil density symbol immediately before the coating film was ruptured and scratched was indicated as the pencil hardness value.

The pencil hardness is in the order of 9H (highest)-8H-7H-6H-5H-4H-3H-2H-H-F-HB-B-2B-3B-4B-5B-6B-7B-8B-9B (least). hardness decreases with

(3) Glass transition temperature (heat resistance)

The glass transition temperature was measured using a differential scanning calorimeter (DSC-7 & Robotic from Perkin-Elmer).

[Table 1]

As shown in Table 1, in the case of the copolymers of Examples 1 to 4 according to the present invention, the pencil hardness is superior to HB or higher, and the glass transition temperature is excellently maintained at 176 ° C. or higher, resulting in scratch resistance and heat resistance. was able to secure the balanced physical properties of On the other hand, in the case of Comparative Example 1, which is a linear polycarbonate resin, the pencil hardness was 2B, which was poor in scratch resistance, and the glass transition temperature was 148°C, which was very poor in heat resistance.

Claims (13)

Repeating units derived from substituted or unsubstituted acenaphthoquinone-based diol compounds; and
Polycarbonate repeating unit; including,
polycarbonate copolymer. The method of claim 1, wherein the repeating unit is derived from a compound represented by Formula 1; And a polycarbonate repeating unit; containing, a polycarbonate copolymer:
[Formula 1]

In Formula 1,
R and R' each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. The polycarbonate copolymer according to claim 1, wherein the acenaphthoquinone-based diol compound has a structure represented by Formula 2 below:
[Formula 2]

The polycarbonate copolymer according to claim 1, further comprising a repeating unit derived from an additional diol compound that is a diol compound other than a substituted or unsubstituted acenaphthoquinone-based diol compound. 5. The polycarbonate copolymer according to claim 4, wherein the further diol compound is a dihydric phenolic compound. The polycarbonate copolymer according to claim 5, wherein the dihydric phenolic compound is a compound having a structure represented by the following formula (3):
[Formula 3]

In Formula 3,
A is a straight, branched or cyclic alkylene group having no functional group; Or a straight, branched or cyclic alkylene group containing at least one functional group selected from the group consisting of a sulfide group, an ether group, a sulfoxide group, a sulfone group, a ketone group, a phenyl group, an isobutylphenyl group or a naphthyl group,
R ₁ and R ₂ are each independently a halogen atom; or represents a straight, branched or cyclic alkyl group;
m and n each independently represents an integer of 0 to 4; The polycarbonate copolymer according to claim 1, wherein the molar ratio of the repeating units derived from the substituted or unsubstituted acenaphthoquinone-based diol compound per 1 mole of repeating units derived from all diol components is 0.05 to 0.9. The polycarbonate copolymer of claim 1, wherein the polycarbonate repeating units are derived from a carbonic acid diester compound or a carbonate precursor. 9. The polycarbonate copolymer of claim 8, wherein the carbonic acid diester compound is selected from dialkyl carbonates, diaryl carbonates, alkylene carbonates, or combinations thereof. 9. The polycarbonate copolymer of claim 8, wherein the carbonate precursor is selected from the group consisting of phosgene (carbonyl chloride), carbonyl bromide, bishalo formate, diphenyl carbonate, dimethyl carbonate, or combinations thereof. a diol component including a substituted or unsubstituted acenaphthoquinone-based diol compound; And a carbonic acid diester compound or a carbonate precursor; comprising the step of copolymerizing, a method for producing a polycarbonate copolymer. The method of claim 11, wherein the diol component including a compound represented by the formula (1); and copolymerizing a carbonic acid diester compound or carbonate precursor;
[Formula 1]

In Formula 1,
R and R' each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. A molded article comprising the polycarbonate copolymer according to any one of claims 1 to 10.