KR20240014713A - Polycarbonate copolymer and method for preparing the same - Google Patents

Abstract

The present invention relates to a polycarbonate copolymer with improved hardness while maintaining impact strength. The polycarbonate copolymer containing a specific ester repeating unit according to the present invention has the characteristic of excellent surface hardness while maintaining the inherent physical properties of basic polycarbonate.

Description

Polycarbonate copolymer and method for preparing the same}

The present invention is to provide a polycarbonate copolymer with excellent impact strength and hardness.

Polycarbonate resin is manufactured by condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene, and has excellent impact strength, dimensional stability, heat resistance, and transparency, and is used as exterior materials for electrical and electronic products, automobile parts, building materials, and optical components. Applies to a wide range of fields.

Recently, in order to apply this polycarbonate resin to a wider range of fields, many studies have been attempted to obtain desired physical properties by copolymerizing two or more types of aromatic diol compounds with different structures and introducing units with different structures into the main chain of polycarbonate. . In particular, as the demand for glass-replacement plastics has increased recently, research on polycarbonate with suitable physical properties is needed in order to use polycarbonate as an interior and exterior material.

Meanwhile, the existing high-hardness polycarbonate has excellent hardness, but has limitations in its application as an interior and exterior material due to its low impact strength. Therefore, there is a need for the development of polycarbonate with improved surface hardness while maintaining the inherent properties of polycarbonate, such as room temperature impact resistance and transparency.

Accordingly, the present inventors completed the present invention by confirming that a polycarbonate copolymer obtained by copolymerizing an ester repeating unit derived from an aromatic diol with an existing polycarbonate satisfies the above requirements, as will be described later.

The present invention is to provide a polycarbonate copolymer with excellent surface hardness while maintaining the physical properties of existing polycarbonate and a method for producing the same.

In order to solve the above problems, the present invention provides a polycarbonate copolymer containing repeating units represented by the following formulas 1 to 4:

[Formula 1]

In Formula 1,

R ₁ to R ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,

Z is C _1-10 alkylene unsubstituted or substituted with phenyl, C _3-15 cycloalkylene unsubstituted or substituted with C _1-10 alkyl, O, S, SO, SO ₂ , or CO,

[Formula 2]

[Formula 3]

[Formula 4]

In Formula 4 above,

X is substituted or unsubstituted C _1-10 alkylene, or substituted or unsubstituted C _2-10 heteroarylene containing at least one heteroatom selected from the group consisting of N, O and S.

In addition, the present invention includes the steps of preparing an oligomer containing repeating units represented by Formulas 2 to 4 (Step 1); and copolymerizing the oligomer containing the repeating units represented by Formulas 2 to 4 with the repeating units represented by Formula 1 (Step 2).

Polycarbonate is manufactured by condensation polymerization of aromatic diol compounds such as bisphenol A and carbonate precursors such as phosgene. It has excellent impact strength, dimensional stability, heat resistance, and transparency, and is used as exterior materials for electrical and electronic products, automobile parts, building materials, and optics. It is applied to a wide range of fields including parts. However, existing high-hardness polycarbonate had the problem of reduced impact strength.

Accordingly, in the present invention, by introducing an ester repeating unit into polycarbonate and simultaneously including the existing polycarbonate and the ester repeating unit, surface hardness can be improved while maintaining the physical properties of polycarbonate.

Hereinafter, the present invention will be described in detail.

polycarbonate copolymer

The polycarbonate copolymer according to the present invention refers to a polymer copolymerized with polycarbonate and ester repeating units, and specifically includes repeating units represented by Formulas 1 to 4 above.

The polycarbonate is formed by reacting an aromatic diol compound and a carbonate precursor, and specifically refers to a repeating unit represented by Formula 1 above.

In addition to containing the repeating unit represented by Formula 1, the polycarbonate copolymer of the present invention includes ester repeating units represented by Formulas 2 to 4. In the case of polycarbonate made from bisphenol A, its use was limited due to its low surface hardness. The present inventors were able to confirm that by introducing repeating units represented by Formulas 2 to 4 into the structure of a polycarbonate copolymer, improved surface hardness can be achieved while maintaining the excellent intrinsic properties of existing polycarbonate.

The repeating units represented by Formulas 2 to 4 are ester repeating units manufactured through a production method described later. Specifically, the repeating units represented by Formulas 2 to 4 include structures derived from aromatic diols and phthalate-based compounds or dicarbonyl-based compounds.

Preferably, it includes an oligomer in which the repeating unit represented by Formula 1 and the repeating units represented by Formulas 2 to 4 are randomly copolymerized. The repeating units represented by Formulas 2 to 4 are randomly reacted with the aromatic diol and the phthalate-based compound or dicarbonyl-based compound to form each repeating unit, and these are copolymerized again to form the repeating units represented by Formulas 2 to 4 at random. Forms copolymerized oligomers. That is, the polycarbonate copolymer of the present invention may be a copolymer of the above oligomer and polycarbonate containing a repeating unit represented by Formula 1.

Preferably, the weight average molecular weight of the oligomer is 1,000 to 30,000 g/mol. More preferably, the weight average molecular weight of the oligomer is at least 4,000 g/mol, at least 7,000 g/mol, or at least 10,000 g/mol, and at most 27,000 g/mol, at most 25,000 g/mol, or at most 20,000 g/mol. am. If the weight average molecular weight of the oligomer is less than 1,000 g/mol, there may be problems in realizing physical properties, and if it is more than 30,000 g/mol, the molecular weight of polycarbonate may become too high during copolymerization or there may be problems in polymerization.

Meanwhile, in Formula 1, preferably, R ₁ to R ₄ are each independently hydrogen, methyl, chloro, or bromo.

Also preferably, Z is straight or branched C _1-10 alkylene that is unsubstituted or substituted with phenyl, more preferably methylene, ethane-1,1-diyl, propane-2,2-diyl, butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Also preferably, Z is cyclohexane-1,1-diyl, O, S, SO, SO ₂ , or CO.

Preferably, the repeating unit represented by Formula 1 is 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, 2,2-bis (4-hydroxyphenyl) Propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z), 2,2-bis(4-hydroxy- 3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C), 2,2-bis(4-hydroxy- It may be derived from any one or more aromatic diol compounds selected from the group consisting of 3,5-dimethylphenyl)propane and 1,1-bis(4-hydroxyphenyl)-1-phenylethane.

The meaning of ‘derived from an aromatic diol compound’ means that the hydroxyl group of the aromatic diol compound and the carbonate precursor react to form a repeating unit represented by Formula 1.

For example, when bisphenol A, an aromatic diol compound, and triphosgene, a carbonate precursor, are polymerized, the repeating unit represented by Formula 1 is represented by Formula 1-1 below.

[Formula 1-1]

The carbonate precursors include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis(chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate, One or more types selected from the group consisting of bis(diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate may be used. Preferably, triphosgene or phosgene can be used.

Meanwhile, in Formula 4, preferably, X is furandiyl, thiophenediyl, or n-octylene. More preferably, Formula 4 is represented by any one selected from the group consisting of the following Formulas 4-1 to 4-3:

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

Preferably, the repeating unit represented by Formulas 2 to 4 is included in an amount of 5 to 50 parts by weight based on 100 parts by weight of the polycarbonate copolymer. More preferably, based on 100 parts by weight of the polycarbonate copolymer, the repeating unit represented by Formulas 2 to 4 is contained in an amount of 7 parts by weight or more, 9 parts by weight or more, 10 parts by weight or more, 12 parts by weight or more, or 15 parts by weight. or more, and includes 48 parts by weight or less, 46 parts by weight or less, 45 parts by weight or less, 43 parts by weight or less, or 40 parts by weight or less. When the repeating units represented by Formulas 2 to 4 are included in the above range, there is an advantage that desired physical properties can be achieved and copolymerization is easy.

Preferably, the repeating unit represented by Formula 4 is contained in an amount of 0.1 to 5 mol% relative to the total number of moles of repeating units represented by Formulas 2 to 4, more preferably 0.2 mol% or more, 0.3 mole. % or more, 0.4 mol% or more, 0.5 mol% or more, 0.6 mol% or more, 0.7 mol% or more, 0.8 mol% or more, 0.9 mol% or more, or 1.0 mol% or more, but 0.4 mol% or less, 3 mol% or less, Included is 2 mol% or less, 1.5 mol% or less, or 1.2 mol% or less. When the repeating unit represented by Chemical Formula 4 is included in the above range, there is an advantage of exhibiting superior impact resistance compared to conventional high-hardness polycarbonate.

Preferably, the weight average molecular weight of the polycarbonate copolymer is 10,000 to 100,000 g/mol, more preferably 15,000 to 85,000 g/mol. More preferably, the weight average molecular weight is at least 20,000 g/mol, at least 25,000 g/mol, at least 30,000 g/mol, at least 35,000 g/mol, at least 40,000 g/mol, at least 45,000 g/mol, or at least 50,000 g/mol. It is more than mol. Additionally, the weight average molecular weight is 80,000 g/mol or less, 75,000 g/mol or less, or 70,000 g/mol or less.

Preferably, the room temperature impact strength of the polycarbonate copolymer according to the present invention measured at 23°C according to ASTM D256 (1/8 inch, Notched Izod) is 500 J/m to 1,000 J/m. More preferably, the room temperature impact strength is 550 J/m or more, 575 J/m or more, or 6000 J/m or more. In addition, the room temperature impact strength is better as the value increases, so there is no upper limit, but for example, it may be 990 J/m or less, 980 J/m or less, or 970 J/m or less.

Preferably, the pencil hardness of the polycarbonate copolymer according to the present invention measured according to ASTM D3363 is HB or higher.

Polycarbonate copolymer manufacturing method

The method for producing a polycarbonate copolymer according to the present invention includes preparing an oligomer containing repeating units represented by Formulas 2 to 4 (step 1); and copolymerizing the oligomer containing the repeating units represented by Formulas 2 to 4 with the repeating units represented by Formula 1 (Step 2). As described above, the repeating unit represented by Formula 1 refers to polycarbonate.

According to one embodiment of the present invention, Step 1 includes polymerizing bisphenol C and a compound represented by the following Chemical Formulas 5-1 to 5-3:

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

In Formulas 5-1 to 5-3,

X is as defined in paragraph 1,

Y is halogen.

More preferably, Y is bromo or chloro.

The repeating units represented by Formulas 2 to 4 of the present invention are manufactured by reacting an aromatic diol compound with three or more types of polyfunctional acyl halide compounds. Specifically, aromatic diols and polyfunctional acyl halides are produced through an esterification reaction, and by using three or more types of acyl halides, it has a structure in which repeating units represented by Formulas 2 to 4 are randomly repeated.

Preferably, the compounds represented by Formula 5-1 and Formula 5-2 are used in an amount of 0.1 to 1 mole part, respectively, based on 100 mole parts of bisphenol C. More preferably, it is used in an amount of 0.15 equivalents or more, 0.2 equivalents or more, 0.3 equivalents or more, and 0.95 equivalents or less, 0.9 equivalents or less, and 0.85 equivalents or less. If the amount of the compounds represented by Formula 5-1 and Formula 5-2 is less than 0.1 equivalent or more than 1 equivalent, respectively, compared to the equivalent weight of bisphenol C, a problem may occur in which oligomers are not formed.

Preferably, the compound represented by Formula 5-3 can be used in an amount of 0.1 to 5 mole parts based on 100 mole parts of bisphenol C, more preferably, 0.2 mole part or more, 0.3 mole part or more, 0.4 mole part or more, 0.5 mole part or more, 0.6 mole part or more, 0.7 mole part or more, 0.8 mole part or more, 0.9 mole part or more, or 1.0 mole part or more; It can be used in amounts of 4.5 mole parts or less, 4.0 mole parts or less, 3.5 mole parts or less, 3.0 mole parts or less, 2.5 mole parts or less, 2.0 mole parts or less, or 1.5 mole parts or less. When the compound represented by Formula 5-3 is used in the above range, it has the effect of exhibiting superior impact resistance than conventional high hardness polycarbonate.

For example, the aromatic diol used to prepare the repeating unit represented by Formulas 2 to 4 may be bisphenol C (BPC), and the polyfunctional acyl halide may be isophthaloyl chloride (IPCl), terephthaloyl chloride (TPCl), or furan. It may be -2,5-dicarbonyl dichloride (FDCl) or a mixture thereof.

In addition, the method for producing a polycarbonate copolymer according to the present invention includes the step of copolymerizing an oligomer containing the repeating units represented by Formulas 2 to 4 and the repeating unit represented by Formula 1.

The copolymerization is preferably performed by interfacial polymerization. During interfacial polymerization, the polymerization reaction is possible at normal pressure and low temperature, and the molecular weight is easy to control. In addition, the interfacial polymerization may include, for example, the step of adding a coupling agent after pre-polymerization and then polymerizing again. In this case, a high molecular weight polycarbonate copolymer can be obtained.

The polymerization temperature is preferably 0°C to 40°C, and the reaction time is preferably 10 minutes to 5 hours. Additionally, it is desirable to maintain the pH at 9 or more or 11 or more during the reaction.

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

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

Additionally, in order to control the molecular weight of the polycarbonate copolymer during the polymerization, it is preferable to polymerize in the presence of a molecular weight regulator. C _1-20 alkylphenol can be used as the molecular weight regulator, and specific examples thereof include p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, and eico. Examples include sylphenol, docosylphenol, or triacontylphenol. The molecular weight regulator may be added before the start of polymerization, during the start of polymerization, or after the start of polymerization. For example, the molecular weight regulator is included in an amount of 0.01 parts by weight or more, 0.1 parts by weight or more, or 1 part by weight or less, and 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less, based on 100 parts by weight of the aromatic diol compound. and the desired molecular weight can be obtained within this range.

In addition, in order to promote the polymerization reaction, reactions such as tertiary amine compounds such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compounds, quaternary phosphonium compounds, etc. Additional accelerators may be used.

Additionally, the present invention provides an article comprising the polycarbonate copolymer described above. As described above, the polycarbonate copolymer according to the present invention contains an ester repeating unit, and thus has excellent surface hardness while maintaining the impact strength and transparency of existing polycarbonate, and has a wide range of applications.

Preferably, the article is injection molded. In addition, the product further contains, for example, one or more selected from the group consisting of antioxidants, heat stabilizers, light stabilizers, plasticizers, antistatic agents, nucleating agents, lubricants, impact modifiers, fluorescent whitening agents, ultraviolet absorbers, pigments and dyes. can do.

The manufacturing method of the product includes mixing the polycarbonate copolymer according to the present invention and additives such as antioxidants using a mixer, extruding the mixture with an extruder to produce pellets, drying the pellets, and then extruding the mixture. It may include the step of injection into a molding machine.

As discussed above, the polycarbonate copolymer containing a specific ester repeating unit according to the present invention is characterized by excellent hardness while maintaining the basic physical properties of polycarbonate.

Below, preferred embodiments are presented to aid understanding of the invention. However, the following examples are only for illustrating the present invention and do not limit the present invention to these only.

<Example>

Preparation Example 1: Preparation of oligomer (BPCIPTPFD, 10,000 g/mol)

Bisphenol C (BPC, 24.23 g, 0.094 mol) was dissolved in a mixed solution of 19 g of 40% NaOH solution and 120 g of water to prepare an aqueous BPC solution. Afterwards, terephthaloyl chloride (TPCl, 10 g, 0.049 mol), isophthaloyl chloride (IPCl, 10 g, 0.049 mol), and furan-2,5-dicarbonyl dichloride (FDCl, 0.2 g, 0.001 mol) were dispersed/dissolved in methylene chloride. After doing so, it was added dropwise to the BPC aqueous solution. Afterwards, 0.093 g of tetraethylammonium chloride was added and stirred for 40 minutes. After the reaction was terminated using 1N HCl, the stirred reactant was washed several times with distilled water using a separatory funnel. Afterwards, the solvent was removed using a rotary reduced pressure evaporator and dried at 120°C overnight to obtain a solid. The molecular weight of the obtained oligomer containing the ester repeating unit (BPCIPTPFD) was 10,000 g/mol.

Preparation Example 2: Preparation of oligomer (BPCIPTPFD, 20,000 g/mol)

An oligomer containing an ester repeating unit was prepared in the same manner as Preparation Example 1, except that 24 g of BPC, 9.5 g of TPCl, 9.5 g of IPCl, and 0.19 g of FDCl were used. The molecular weight of the obtained oligomer (BPCIPTPFD) was 20,000 g/mol.

Preparation Example 3: Preparation of oligomer (BPCIPTPTD, 10,000 g/mol)

An oligomer containing an ester repeating unit was prepared in the same manner as in Preparation Example 1, except that thiophene-2,5-dicarbonyl dichloride (TDCl, 0.2 g) was used instead of furan-2,5-dicarbonyl dichloride (FDCl). did. The molecular weight of the obtained oligomer (BPCIPTPTD) was 10,000 g/mol.

Comparative Preparation Example 1: Preparation of oligomer (BPAIPTP, 10,000 g/mol)

Bisphenol A (BPA, 23.5 g, 0.103 mol) was dissolved in a mixed solution of 19 g of 40% NaOH solution and 120 g of water to prepare an aqueous BPA solution. Afterwards, terephthaloyl chloride (TPCl, 11 g, 0.054 mol) and isophthaloyl chloride (IPCl, 11 g, 0.054 mol) were dispersed/dissolved in methylene chloride and then added dropwise to the BPA aqueous solution. Afterwards, 0.093 g of tetraethylammonium chloride was added and stirred for 40 minutes. After the reaction was terminated using 1N HCl, the stirred reactant was washed several times with distilled water using a separatory funnel. Afterwards, the solvent was removed using a rotary reduced pressure evaporator and dried at 120°C overnight to obtain a solid. The molecular weight of the obtained oligomer (BPAIPTP) containing the ester repeating unit was 10,000 g/mol.

Comparative Preparation Example 2: Preparation of oligomer (ResorcinolIPTP, 8,000 g/mol)

ResorcinolPTP was prepared in the same manner as Step 1 of Preparation Example 1, except that Resorcinol (11.3 g, 0.103 mol) was used instead of BPA. The molecular weight of the obtained oligomer (ResorcinolIPTP) was 8,000 g/mol.

Example 1

Water (619.33 g), bisphenol A (BPA, 115.78 g), and BPCIPTPFD (22.5 g, 10,000 g/mol), 40% by weight NaOH aqueous solution (102.5 g), and dichloromethane (200 ml) were added and stirred for several minutes.

Stop nitrogen purging, add triphosgene (62.81 g) and MeCl ₂ (120 ml) to a 1 L round bottom flask, dissolve triphosgene, and then slowly add the dissolved triphosgene solution into the main reactor. When the addition is complete, PTBP (p-tert-butylphenol, 3.04 g) was added and stirred for about 10 minutes. After stirring was completed, a 40% by weight NaOH aqueous solution (99.8 g) was added, and then TEA (triethylamine, 1.5 ml) was added as a coupling agent. At this time, the reaction pH was maintained between 11 and 13. To allow sufficient time for the reaction to occur, HCl was added to terminate the reaction, lowering the pH to 3-4. Then, stirring was stopped to separate the polymer layer from the water layer, and then the water layer was removed, pure H ₂ O was added again, and the washing process was repeated 3 to 5 times. Once the water washing was complete, only the polymer layer was extracted and a polycarbonate copolymer was obtained by reprecipitation using a non-solvent such as methanol and H ₂ O.

Examples 2 to 5, and Comparative Examples 1 to 5

A polycarbonate copolymer was prepared in the same manner as in Example 1, except that the type and content of the oligomer copolymerized with bisphenol A were used as shown in Table 1 below.

The content and molecular weight of the copolymerized oligomers used in Examples 1 to 4 and Comparative Examples 1 to 5 are shown in Table 1 below. In Table 1 below, the content refers to the weight of each repeating unit based on the total polycarbonate copolymer weight.

Types of copolymer oligomers Copolymer oligomer content (%) Copolymer oligomer molecular weight (g/mol) Example 1 BPCIPTPFD 15 10,000 Example 2 BPCIPTPFD 40 10,000 Example 3 BPCIPTPFD 15 20,000 Example 4 BPCIPTPFD 40 20,000 Example 5 BPCIPTPTD 15 10,000 Comparative Example 1 - - - Comparative Example 2 B.P.C. 15 - Comparative Example 3 B.P.C. 40 - Comparative Example 4 BPAIPTP 15 10,000 Comparative Example 5 Resorcinol IPTP 15 8,000

<Experimental example>

Preparation of specimens

For 1 part by weight of each polycarbonate copolymer prepared in the above examples and comparative examples, 0.050 parts by weight of tris(2,4-di-tert-butylphenyl)phosphite, octadecyl-3-(3,5- 0.010 parts by weight of di-tert-butyl-4-hydroxyphenyl)propionate and 0.030 parts by weight of pentaerythritol tetrastearate were added, pelletized using a Φ30 mm twin-screw extruder with a vent, and then extruded into JSW Co., Ltd. ) The specimen was manufactured by injection molding at a cylinder temperature of 300°C and a mold temperature of 80°C using an N-20C injection molding machine.

The properties of the specimen were measured by the following method, and the results are shown in Table 2 below.

(1) Weight average molecular weight

200 mg of polymer resin was diluted in 200 ml Tetrahydrofuran (THF) solvent to prepare a sample of about 1000 ppm, and the molecular weight was measured through an RI detector using an Agilent 1200 series GPC device at a flow of 1 ml/min. The standard for calculating the molecular weight of the sample was to measure 8 types of standard PS standards, create a calibration curve, and calculate the molecular weight of the sample based on this.

(2) Pencil hardness

Pencil hardness was measured according to ASTM D 3363. Specifically, after fixing the angle of the pencil at 45°, the surface of the specimen was scratched about 6.5 mm to evaluate whether scratches were observed with the naked eye, and the test was repeated by changing the strength of the pencil.

(3) Impact strength

Each was measured at 23°C according to ASTM D256 (1/8 inch, Notched Izod).

(4) Transmittance

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

Weight average molecular weight (g/mol) pencil hardness Impact strength (J/m) Transmittance (3T, %) Example 1 54,000 HB 750 89 Example 2 54,000 H 620 88 Example 3 54,000 HB 770 89 Example 4 54,000 H 640 88 Example 5 54,000 HB 740 88 Comparative Example 1 54,000 2B 800 89 Comparative Example 2 54,000 HB 130 88 Comparative Example 3 54,000 H 90 88 Comparative Example 4 54,000 2B 650 89 Comparative Example 5 54,000 2B 680 88

As can be seen in Table 2, it was confirmed that the polycarbonate copolymer according to the present invention had similar room temperature impact strength and permeability compared to the existing polycarbonate composition, and had excellent pencil hardness.

Claims (16)

Containing repeating units represented by the following formulas 1 to 4,
Polycarbonate copolymer:
[Formula 1]

In Formula 1,
R ₁ to R ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,
Z is C _1-10 alkylene unsubstituted or substituted with phenyl, C _3-15 cycloalkylene unsubstituted or substituted with C _1-10 alkyl, O, S, SO, SO ₂ , or CO,
[Formula 2]

[Formula 3]

[Formula 4]

In Formula 4 above,
X is substituted or unsubstituted C _1-10 alkylene, or substituted or unsubstituted C _2-10 heteroarylene containing at least one heteroatom selected from the group consisting of N, O and S.
According to paragraph 1,
A repeating unit represented by Formula 1 above, and
Containing an oligomer in which the repeating units represented by Formulas 2 to 4 are randomly copolymerized,
Polycarbonate copolymer.
According to paragraph 2,
The weight average molecular weight of the oligomer is 1,000 to 30,000 g/mol,
Polycarbonate copolymer.
According to paragraph 1,
The repeating unit represented by Formula 1 is bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, and bis(4-hydroxyphenyl)sulfoxide. , bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z), 2,2-bis(4-hydroxy-3,5 -Dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2 -bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C), 2,2-bis(4-hydroxy-3,5 -Dimethylphenyl)propane and 1,1-bis(4-hydroxyphenyl)-1-phenylethane, characterized in that it is derived from any one or more aromatic diol compounds selected from the group consisting of
Polycarbonate copolymer.
According to paragraph 1,
The repeating unit represented by Formula 1 is represented by Formula 1-1 below,
Polycarbonate copolymer:
[Formula 1-1]

According to paragraph 1,
X is furandiyl, thiophenediyl, or n-octylene,
Polycarbonate copolymer.
According to paragraph 1,
Formula 4 is represented by any one selected from the group consisting of the following formulas 4-1 to 4-3,
Polycarbonate copolymer:
[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

According to paragraph 1,
For 100 parts by weight of polycarbonate copolymer,
Containing 5 to 50 parts by weight of repeating units represented by Formulas 2 to 4,
Polycarbonate copolymer.
According to paragraph 1,
The repeating unit represented by Formula 4 is,
Contained in an amount of 0.1 to 5 mol% relative to the total number of moles of repeating units represented by Formulas 2 to 4,
Polycarbonate copolymer.
According to paragraph 1,
The weight average molecular weight of the polycarbonate copolymer is 10,000 to 100,000 g/mol,
Polycarbonate copolymer.
According to paragraph 1,
The Izod room temperature impact strength measured at 23°C based on ASTM D256 (1/8 inch, Notched Izod) of the polycarbonate copolymer is 500 to 1,000 J/m,
Polycarbonate copolymer.
According to paragraph 1,
The pencil hardness of the polycarbonate copolymer measured according to ASTM D3363 is HB or higher,
Polycarbonate copolymer.
Preparing an oligomer containing repeating units represented by Formulas 2 to 4 (Step 1); and
Comprising the step (step 2) of copolymerizing an oligomer containing repeating units represented by Formulas 2 to 4 with repeating units represented by Formula 1,
Method for producing polycarbonate copolymer.
According to clause 13,
Step 1 includes polymerizing bisphenol C and compounds represented by the following formulas 5-1 to 5-3,
Method for producing polycarbonate copolymer:
[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

In Formulas 5-1 to 5-3,
X is as defined in paragraph 1,
Y is halogen.
According to clause 14,
The compounds represented by Formula 5-1 and Formula 5-2 are used in an amount of 0.1 to 1 mole parts, respectively, based on 100 mole parts of bisphenol C.
Method for producing polycarbonate copolymer.
According to clause 14,
The compound represented by Formula 5-3 is used in an amount of 0.1 to 5 mole parts based on 100 mole parts of bisphenol C,
Method for producing polycarbonate copolymer.