KR20220058742A - Polyester oligomer and method for preparing the same, and polyester-polycarbonate block copolymer comprising the oligomer with improved surface scratch resistance and method for preparing the same - Google Patents

Abstract

The present invention relates to a polyester oligomer and a method for preparing the same, and a polyester-polycarbonate block copolymer including the oligomer and having improved surface scratch resistance and a method for preparing the same. Particularly, the present invention relates to a polyester oligomer including a polymerization unit having a binaphthyl structure and a method for preparing the same, and a polyester-polycarbonate copolymer including a block formed from the polyester oligomer and a polycarbonate block as repeating units and having improved surface resistance as compared to the conventional linear polycarbonate and polycarbonate copolymer, while maintaining excellent impact strength, and a method for preparing the same.

Description

Polyester oligomer and method for producing the same, and polyester-polycarbonate block copolymer with improved scratch resistance including the oligomer, and method for producing the same OLIGOMER WITH IMPROVED SURFACE SCRATCH RESISTANCE AND METHOD FOR PREPARING THE SAME}

The present invention relates to a polyester oligomer and a method for producing the same, and to a polyester-polycarbonate block copolymer with improved scratch resistance and a method for producing the same comprising the oligomer, and more particularly, to binaphthyl A polyester oligomer including a polymer unit having a structure and a method for producing the same, and a block formed from the polyester oligomer and a polycarbonate block as repeating units, improved surface scratch resistance compared to conventional linear polycarbonate and polycarbonate copolymer The present invention relates to a polyester-polycarbonate copolymer having excellent impact strength while having properties, and a method for producing the same.

Polycarbonate has excellent mechanical properties such as tensile strength and impact resistance, and has excellent dimensional stability, heat resistance and optical transparency, so it is widely used for industrial purposes. Research on various copolymers is continued in order to improve the physical properties of polycarbonate, for example, 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 terminal group, and a new type of polymer can be prepared by using a method of activating hydroxyl groups of both terminal groups. In this case, polymerization may be performed in an aqueous solution, at an interface, or in a non-aqueous solution.

However, especially polycarbonates made from bisphenol A have limited scratch resistance. Therefore, in order to prevent or minimize the scratch damage, it is necessary to apply a hard coat as a surface modification, which is accompanied by an additional process and cost, and has disadvantages of poor durability.

Korean Patent No. 10-1815930 discloses a polycarbonate copolymer having improved scratch resistance and antifogging properties, and the polycarbonate copolymer disclosed herein exhibits excellent antifogging properties, but scratch resistance needs further improvement.

Therefore, there is a demand for the development of a polycarbonate copolymer with improved surface scratch resistance while maintaining excellent transparency and impact strength, which are the intrinsic properties of polycarbonate.

The present invention is intended to solve the problems of the prior art as described above, and has improved surface scratch resistance compared to conventional linear polycarbonate and conventional polycarbonate copolymer, while maintaining excellent impact strength polyester-polycarbonate It is a technical task to provide a polyester oligomer capable of producing a copolymer, a method for producing the same, and such a polyester-polycarbonate copolymer and a method for producing the same.

In order to solve the above technical problem, the present invention provides a polyester oligomer comprising a polymerization unit having a structure represented by the following formula (1):

[Formula 1]

In Formula 1,

A is a divalent group derived from a substituted or unsubstituted binaphthyl diol,

R ¹ is a substituted or unsubstituted aliphatic group having 5 to 30 carbon atoms or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 30 carbon atoms; or a substituted or unsubstituted divalent monoheterocyclic, polyheterocyclic or fused heterocyclic group containing at least one atom selected from N, O and S,

* indicates the point of attachment to an adjacent polymerized unit.

According to one embodiment of the present invention, the polyester oligomer may further include a polymerization unit having a structure represented by the following Chemical Formula 2:

[Formula 2]

In Formula 2,

B is a divalent group derived from diallyl bisphenol A,

R ¹ is as defined in Formula 1 above,

* indicates the point of attachment to adjacent polymerized units.

In addition, according to one embodiment of the present invention, the polyester oligomer may have a structure represented by the following Chemical Formula 3:

[Formula 3]

In Formula 3,

R ¹ and A are as defined in Formula 1 above,

B is as defined in Formula 2 above,

* indicates the point of attachment to an adjacent polymerized unit,

a and b each represent a relative mole fraction of the structure, a is a positive number from 0.03 to 1, b is a positive number from 0 to 0.97, but a+b is 1.

According to another aspect of the present invention, there is provided a method for preparing the polyester oligomer, comprising reacting a substituted or unsubstituted binaphthyl diol with a compound represented by the following Chemical Formula 4:

[Formula 4]

In Formula 4,

R ¹ is as defined in Formula 1 above,

Y each independently represents a halogen atom, a hydroxy group or an alkoxy group.

According to another aspect of the present invention, there is provided a method for preparing the polyester oligomer, comprising reacting a substituted or unsubstituted binaphthyl diol, diallyl bisphenol A, and a compound represented by Formula 4 above.

According to another aspect of the present invention, as a repeating unit, a block formed from the polyester oligomer according to the present invention; and a polycarbonate block; containing, a polyester-polycarbonate block copolymer is provided.

According to another aspect of the present invention, copolymerizing the polyester oligomer and the polycarbonate oligomer according to the present invention in the presence of a catalyst; comprising, a polyester-a method for producing a polycarbonate block copolymer is provided.

According to another aspect of the present invention, there is provided a molded article comprising the polyester-polycarbonate block copolymer according to the present invention.

The polyester-polycarbonate block copolymer according to the present invention exhibits improved surface scratch resistance while maintaining excellent impact strength and transparency, and thus molded articles (eg, films, sheets, lenses, cover glasses, interior and exterior materials, etc.) ) can be used very suitably for optical applications and material lightweight substitutes in various industries.

As used herein, that any group or structure is “substituted” means that the group or structure is a halogen atom (eg, F, Cl or Br), a hydroxy group, an alkyl group (eg, having 1 to 10 carbon atoms, or 1 to 6 carbon atoms). alkyl group), an alkoxy group (eg, an alkoxy group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms), a cycloalkyl group (eg, a cycloalkyl group having 3 to 10 carbon atoms or 3 to 6 carbon atoms), an aryl group (eg, 6 carbon atoms) to 12, or an aryl group having 6 carbon atoms) or a combination thereof means substituted by one or more functional groups selected from the group consisting of.

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

polyester oligomer

The polyester oligomer of the present invention includes a polymerization unit having a structure represented by the following formula (1):

[Formula 1]

In Formula 1,

A is a divalent group derived from a substituted or unsubstituted binaphthyl diol,

R ¹ is a substituted or unsubstituted aliphatic group having 5 to 30 carbon atoms or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 30 carbon atoms; or a substituted or unsubstituted divalent monoheterocyclic, polyheterocyclic or fused heterocyclic group containing at least one atom selected from N, O and S,

* indicates the point of attachment to an adjacent polymerized unit.

According to one embodiment of the present invention, the binaphthyl diol and a divalent group derived therefrom (ie, A) may each have the following structures:

(Where * indicates the point of attachment to the adjacent oxygen.)

More specifically, the binaphthyl diol and a divalent group derived therefrom (ie, A) may each have the following structures:

(Where * indicates the point of attachment to the adjacent oxygen.)

According to one embodiment of the present invention, in Formula 1, R ¹ is a substituted or unsubstituted, aliphatic group having 5 to 20 carbon atoms or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 20 carbon atoms. ; or a substituted or unsubstituted divalent monoheterocyclic, polyheterocyclic or fused heterocyclic group comprising at least one atom selected from N, O and S, and having a total number of ring atoms of 5 to 20; Specifically, a substituted or unsubstituted aliphatic group having 5 to 10 carbon atoms or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 12 carbon atoms in total; or a substituted or unsubstituted divalent monoheterocyclic, polyheterocyclic or fused heterocyclic group containing at least one atom selected from N, O and S, having 5 to 12 total ring atoms.

According to one embodiment of the present invention, the polyester oligomer may further include a polymerization unit having a structure represented by the following Chemical Formula 2:

[Formula 2]

In Formula 2,

B is a divalent group derived from diallyl bisphenol A,

R ¹ is as defined in Formula 1 above,

* indicates the point of attachment to adjacent polymerized units.

According to one embodiment of the present invention, the diallyl bisphenol A and a divalent group derived therefrom (ie, B) may each have the following structures:

(Where * indicates the point of attachment to the adjacent oxygen.)

According to one embodiment of the present invention, the polyester oligomer may have a structure represented by the following Chemical Formula 3:

[Formula 3]

In Formula 3,

R ¹ and A are as defined in Formula 1 above,

B is as defined in Formula 2 above,

* indicates the point of attachment to an adjacent polymerized unit,

a and b each represent a relative mole fraction of the structure, a is a positive number from 0.03 to 1, b is a positive number from 0 to 0.97, but a+b is 1.

According to one embodiment of the present invention, in Formula 3, a may be 0.05 or more, 0.1 or more, 0.12 or more, or 0.15 or more, and may be 0.97 or less, 0.95 or less, 0.9 or less, 0.88 or less, or 0.85 or less, and b is It may be 0.03 or more, 0.05 or more, 0.1 or more, 0.12 or more, or 0.15 or more, and may be 0.95 or less, 0.9 or less, 0.88 or less, or 0.85 or less, but is not limited thereto, with the proviso that a+b is 1.

According to one embodiment of the present invention, the number average molecular weight (Mn) of the polyester oligomer of the present invention may be 800 to 20,000, more specifically, may be 900 to 18,000, and even more specifically, 1,000 to 16,000 days. However, the present invention is not limited thereto.

According to another aspect of the present invention, there is provided a method for preparing a polyester oligomer of the present invention, comprising reacting a substituted or unsubstituted binaphthyl diol and a compound represented by the following formula (4):

[Formula 4]

In Formula 4,

R ¹ is as defined in Formula 1 above,

Y each independently represents a halogen atom, a hydroxy group or an alkoxy group.

According to one embodiment of the present invention, in Formula 4, Y is each independently a halogen atom (eg, a fluorine atom, a bromine atom or a chlorine atom, more specifically a chlorine atom), a hydroxy group or an alkoxy group (eg, carbon number) 1 to 10, or an alkoxy group having 1 to 6 carbon atoms).

In addition, according to one embodiment of the present invention, in the method for producing the polyester oligomer, the amount of the compound of Formula 4 per 1 mol of binaphthyl diol may be 0.3 mol or more, 0.4 mol or more, or 0.5 mol or more, and 1.1 moles or less, 1.05 moles or less, or 1 mole or less.

There is no particular limitation on the reaction conditions of binaphthyl diol and the compound of Formula 4, for example, at room temperature (ie, 20-30°C) or at elevated temperature (eg 200-250°C) under a catalyst (eg, a base catalyst, more specifically As an organic amine catalyst such as triethylamine) may be carried out in the presence, but is not limited thereto.

According to another aspect of the present invention, there is provided a method for preparing a polyester oligomer of the present invention, comprising reacting a substituted or unsubstituted binaphthyl diol, diallyl bisphenol A, and a compound represented by Formula 4 this is provided

According to one embodiment of the present invention, the amount of the compound of Formula 4 used per 1 mol of the total of binaphthyl diol and diallyl bisphenol A may be 0.3 mol or more, 0.4 mol or more, or 0.5 mol or more, and also 1.1 mol or less, 1.05 mol or more mol or less, or 1 mol or less.

There is no particular limitation on the reaction conditions of the binaphthyl diol, diallyl bisphenol A, and the compounds of Formula 4, for example, at room temperature (ie, 20-30° C.) or at elevated temperature (eg, 200-250° C.) under a catalyst (eg, It may be carried out in the presence of a base catalyst, more specifically an organic amine catalyst such as triethylamine), but is not limited thereto.

Polyester-Polycarbonate Block Copolymer

The polyester-polycarbonate block copolymer of the present invention comprises, as a repeating unit, a block formed from the above-described polyester oligomer of the present invention (hereinafter also referred to as a polyester oligomer block); and a polycarbonate block.

In one embodiment, the polyester oligomer block content in the polyester-polycarbonate block copolymer of the present invention may be greater than 10% by weight to less than 60% by weight, based on 100% by weight of the total copolymer. More specifically, the polyester oligomer block content in the copolymer is, based on 100% by weight of the total copolymer, 11% by weight or more, 12% by weight or more, 13% by weight or more, 14% by weight or more, 15% by weight or more, or 20 It may be more than or equal to 59 wt%, and may be less than or equal to 59 wt%, less than or equal to 58 wt%, less than or equal to 57 wt%, less than or equal to 56 wt%, less than or equal to 55 wt% or less than or equal to 50 wt%. If the content of the polyester oligomer block in the copolymer is excessively less than the above level, the surface scratch resistance of the copolymer may be poor, and on the contrary, if it is excessively greater than the above level, the impact resistance of the copolymer may be reduced.

Polycarbonate block included as a repeating unit in the polyester-polycarbonate block copolymer of the present invention may have a repeating unit represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5,

R ² is an alkyl group having 1 to 20 carbon atoms (eg, an alkyl group having 1 to 13 carbon atoms), a cycloalkyl group (eg, a cycloalkyl group having 3 to 6 carbon atoms), an alkenyl group (eg, an alkenyl group having 2 to 13 carbon atoms), an alkoxy group (For example, an alkoxy group having 1 to 13 carbon atoms), a halogen atom or a nitro-substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms.

In one embodiment, the polycarbonate block may be formed from oligomeric polycarbonate, and the viscosity average molecular weight of the oligomeric polycarbonate may be 800 to 20,000, more specifically 800 to 15,000 or 1,000 to 12,000. there is.

In one embodiment, the oligomeric polycarbonate may be prepared by adding a dihydroxy compound to an aqueous alkali solution to form a phenol salt, and then reacting the phenols in the salt state into dichloromethane injected with phosgene gas. For preparing the oligomer, it is preferred to maintain the molar ratio of phosgene to dihydroxy compound in the range of about 1:1 to 1.5:1, more preferably about 1:1 to 1.2:1. If the molar ratio of phosgene to the dihydroxy compound is less than 1, the reactivity may decrease, and if the molar ratio of phosgene to the dihydroxy compound exceeds 1.5, processability may be reduced due to an excessive increase in molecular weight.

The oligomer formation reaction may be generally performed at a temperature in the range of about 15 to 60° C., and an alkali metal hydroxide (eg, sodium hydroxide) may be used to adjust the pH of the reaction mixture.

The dihydroxy compound is, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4-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-hydroxy Phenyl) 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-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-hydro Roxyphenyl)isobutane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxy Phenyl) 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'-dihydroxydiphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, isosorbide, isomannide, isoidide or these It may be a combination of, but is not limited thereto. Representative of these are 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) and isosorbide. Other functional dihydroxy compounds may refer to US Pat. Nos. 2,999,835, US 3,028,365, US 3,153,008, and US 3,334,154, and the like, and the dihydroxy compounds may be used alone or in combination of two or more. .

In one embodiment, the polyester-polycarbonate block copolymer of the present invention may have a viscosity average molecular weight of 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 reduced, and if it is excessively greater than the above level, moldability may decrease.

The polyester-polycarbonate block copolymer of the present invention can be prepared using a polymerization method widely known to those of ordinary skill in the art. For example, it can manufacture using the melt polymerization method by transesterification or the phosgene polymerization method.

Accordingly, according to another aspect of the present invention, copolymerizing the polyester oligomer and the polycarbonate oligomer according to the present invention in the presence of a catalyst; comprising, a polyester-a method for producing a polycarbonate block copolymer is provided.

In one embodiment, the method for preparing the polyester-polycarbonate block copolymer may further include extracting the organic phase from the resulting mixture after the polymerization reaction of the polyester oligomer and the polycarbonate oligomer is completed.

In one embodiment, the polyester-polycarbonate block copolymer of the present invention may be prepared by adding the polyester oligomer to an organic phase-aqueous mixture containing polycarbonate, and gradually adding a molecular weight modifier and a catalyst.

As the molecular weight control agent, a monofunctional compound similar to a monomer used for preparing polycarbonate may be used. The monofunctional substances include, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol and p-isononyl. phenol-based derivatives such as phenol, or aliphatic alcohols. Preferably, p-tert-butylphenol (PTBP) can be used.

A polymerization catalyst and/or a phase transfer catalyst may be used as the catalyst. As the polymerization catalyst, for example, triethylamine (TEA) may be used, and as the phase transfer catalyst, for example, a compound of Formula 6 below may be used.

[Formula 6]

(R ³ ) ₄ Q ⁺ Z ^-

In Formula 6, R ³ represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and Z represents a halogen atom or —OR ⁴ . Here, R ⁴ 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 day can In the above formulas, Z represents Cl, Br or -OR ⁴ , wherein R ⁴ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. When the phase transfer catalyst is used, the content thereof is preferably 0.01 wt% or more in terms of transparency of the resulting copolymer, but is not limited thereto.

In one embodiment, after preparing the polyester-polycarbonate block copolymer, the organic phase dispersed in methylene chloride is washed with alkali and then separated. Subsequently, the organic phase is washed with a 0.1N hydrochloric acid solution, and then washed with distilled water 2 to 3 times. When washing is complete, the concentration of the organic phase dispersed in methylene chloride is constantly adjusted, and granulation is performed using a certain amount of 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 ℃, the assembly speed is slow, the assembly time may be very long, and if the temperature of the pure water exceeds 100 ℃, it may be difficult to obtain the shape of the polycarbonate in a certain size. When the assembly is completed, it is preferably dried at 100 to 120 ° C. for 5 to 10 hours, more preferably firstly at 100 to 110 ° C. for 5 to 10 hours, secondly at 110 to 120 ° C. for 5 to 10 hours. .

Since the polyester-polycarbonate block copolymer of the present invention exhibits improved surface scratch resistance while maintaining excellent impact strength and transparency, molded articles including the same (eg, film, sheet, lens, cover glass, interior and exterior materials, etc.) can be used well for optical applications and material lightweight substitutes in various industries.

Accordingly, according to another aspect of the present invention, there is provided a molded article comprising the polyester-polycarbonate block copolymer of the present invention. 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 binaphthyl diol

After adding 200 mL of water (H ₂ O) to a 1L three-necked reactor, 3 g of 2-naphthol and 5 g of iron (III) chloride hexahydrate (Ferric chloride hexahydrate) were put into the reactor and stirred. . Afterwards, the mixture was reacted at 100° C. for 3 hours. After the temperature of the reaction solution was cooled to room temperature, ethyl acetate was added to separate the reaction solution into a water layer and an organic layer. The solvent of the separated organic layer was evaporated and recrystallized using n-heptane and ethyl acetate. By drying the obtained crystals in an oven at 80° C. for 24 hours, binaphthyl diol represented by the following formula (A) was obtained.

[Formula A]

Preparation Example 2: Preparation of polycarbonate oligomer

In a 10L four-necked flask, 600 g (2.63 mol) of bisphenol A was dissolved in 3,300 ml (184.6 g, 4.62 mol) of a 5.6 wt% aqueous sodium hydroxide solution, and then 260 g (2.63 mol) of phosgene was collected in methylene chloride and a Teflon tube (20 mm) through the slowly inputted reaction. The external temperature was maintained at 0°C. An oligomeric polycarbonate having a viscosity average molecular weight of about 1,000 was prepared by subjecting the reactants passing through the tubular reactor to an interfacial reaction under a nitrogen atmosphere for about 10 minutes. From the mixture containing the prepared oligomeric polycarbonate, 2,150 mL of the organic phase and 3,220 mL of the aqueous phase were collected, and 13.83 g of p-tert-butylphenol (PTBP) (92.1 mmol, 3.5 mol% with respect to bisphenol A), tetrabutylammonium Chloride (tetrabutyl ammonium chloride, TBACl) 7.31 g (26.3 mmol, 1 mol % with respect to bisphenol A) and 15 wt % tri-ethylamine (TEA) aqueous solution 1 mL were mixed and reacted for 30 minutes, the viscosity A polycarbonate oligomer solution having an average molecular weight of about 4,000 was prepared.

<Production of polyester oligomer>

Example A1: Preparation of polyester oligomer using compound of formula A

A solution prepared by dissolving 30.06 g (1.1 mol) of Formula A obtained in Preparation Example 1 in 250 g of methylene chloride was put into a 1 L three-necked reactor, followed by 20.30 g of terephthaloyl chloride of Formula B A solution prepared by dissolving 150 g of methylene chloride was introduced into the three-necked reactor. Then, 20.24 g of triethylamine was added to the three-necked reactor while dropping for 30 minutes. After completion of the dropwise addition, the reaction solution was stirred for 320 minutes, and then salts were removed by filtration, 100 ml of 1N hydrochloric acid aqueous solution and 400 ml of distilled water were added to the filtrate, followed by stirring for 30 minutes. After standing at room temperature for more than 12 hours, filtration was performed in a mixed solution of ethanol and distilled water (weight ratio of ethanol and distilled water = 10:1) to obtain a precipitate. Thereafter, a polyester oligomer (number average molecular weight: about 5,800) was obtained by drying the precipitate in an oven at 110° C. for 24 hours.

[Formula B]

Example A2: Preparation of a polyester oligomer using a compound of formula A and a compound of formula C

A solution prepared by dissolving 22.91 g (0.8 mol) of Formula A obtained in Preparation Example 1 and 9.25 g (0.3 mol) of diallyl bisphenol A of the following Formula C in 250 g of methylene chloride was put into a 1L three-necked reactor, A solution prepared by dissolving 20.30 g of terephthaloyl chloride of Formula B in 150 g of methylene chloride was introduced into the three-neck reactor. Then, 20.24 g of triethylamine was added to the three-necked reactor while dropping for 30 minutes. Then, in the same manner as in Example A1, a polyester oligomer (number average molecular weight: about 4,900) was obtained.

[Formula C]

Comparative Example A3: Preparation of polyester oligomer using the compound of formula C

A solution prepared by dissolving 32.38 g (1.1 mol) of diallyl bisphenol A of Formula C in 250 g of methylene chloride was put into a 1 L three-necked reactor, and 20.30 g of terephthaloyl chloride of Formula B was added to methylene A solution prepared by dissolving 150 g of chloride was introduced into the three-necked reactor. Then, 20.24 g of triethylamine was added to the three-necked reactor while dropping for 30 minutes. Then, in the same manner as in Example A1, a polyester oligomer (number average molecular weight: about 7,100) was obtained.

<Preparation of polyester-polycarbonate block copolymer>

Example B1: Preparation of polyester-polycarbonate block copolymer

429 g of the compound obtained in Example A1 (25% by weight based on the total amount of monomer compounds constituting the copolymer) was added to the polycarbonate oligomer solution prepared in Preparation Example 2, methylene chloride (2990 g), 1.1N hydroxylated 1570 mL of sodium aqueous solution (20% by volume with respect to the total mixture) and 234 μL of 15% by weight of triethylamine were mixed and reacted for 1 hour, and then 2600 μL of 15% by weight of triethylamine was added to react for 1 hour more. After layer separation, pure water was added to the organic phase with increased viscosity, washed with alkali, and then separated. Subsequently, the organic phase was washed with a 0.1N hydrochloric acid solution, followed by repeated washing with distilled water 2 to 3 times. After washing was completed and the concentration of the organic phase was constant, it was assembled using a predetermined amount of secondary distilled water at 76°C. After the assembly was completed, the polycarbonate block copolymer was prepared by drying the first at 110° C. for 8 hours and second at 120° C. for 10 hours.

Example B2: Preparation of polyester-polycarbonate block copolymer

Polyester-polycarbonate in the same manner as in Example B1, except that 143 g of the polyester oligomer obtained in Example A1 (10% by weight based on the total weight of the monomer compound constituting the copolymer) was added. A block copolymer was prepared.

Example B3: Preparation of polyester-polycarbonate block copolymer

Polyester-polycarbonate in the same manner as in Example B1, except that 1270 g of the polyester oligomer obtained in Example A1 (50% by weight based on the total weight of the monomer compound constituting the copolymer) was added A block copolymer was prepared.

Example B4: Preparation of polyester-polycarbonate block copolymer

A polyester-polycarbonate block copolymer was prepared in the same manner as in Example B1, except that the polyester oligomer obtained in Example A2 was added instead of the polyester oligomer obtained in Example A1. did

Example B5: Preparation of polyester-polycarbonate block copolymer

A polyester-polycarbonate block copolymer was prepared in the same manner as in Example B2, except that the polyester oligomer obtained in Example A2 was added instead of the polyester oligomer obtained in Example A1. did

Example B6: Preparation of polyester-polycarbonate block copolymer

A polyester-polycarbonate block copolymer was prepared in the same manner as in Example B3, except that the polyester oligomer obtained in Example A2 was added instead of the polyester oligomer obtained in Example A1. did

Comparative Example B1: 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.

Comparative Example B2: Preparation of thermoplastic aromatic polycarbonate (linear polycarbonate) resin

A linear polycarbonate having a viscosity average molecular weight of 30,000 was prepared by a conventional interfacial polymerization method.

Comparative Example B3: Preparation of polyester-polycarbonate block copolymer

A polyester-polycarbonate block copolymer was prepared in the same manner as in Example B1, except that the polyester oligomer obtained in Comparative Example A3 was added instead of the polyester oligomer obtained in Example A1. prepared.

[Method of measuring physical properties]

(1) 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 pencil hardness value was expressed as the pencil hardness value indicating the hardness of the pencil just before the coating film was ruptured and scratched by scratching the coating film of the specimen at a 45° angle.

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 (lowest) to lower the hardness.

(2) Impact strength (impact resistance) (Kgf cm/cm)

Based on ASTM D256, each specimen of Examples and Comparative Examples was evaluated by taking a notch, and the final test result was performed 10 times for each specimen, and the average value of the 10 test results was calculated.

The physical property values of each of the polymers prepared in Examples B1 to B6 and Comparative Examples B1 to B3 are shown in Table 1 below.

[Table 1]

As shown in Table 1, in the case of the copolymers of the examples according to the present invention, the pencil hardness is excellent at F or more, and at the same time, the impact strength is maintained excellently at 35 kgf cm/cm or more, and the scratch resistance and impact resistance are excellent. It is possible to demonstrate eco-friendliness while securing balanced physical properties. On the other hand, in the case of the polymers of Comparative Examples, the pencil hardness was relatively poor compared to the Examples, and in particular, in the case of Comparative Examples B1 and B2, which are linear polycarbonate resins, the pencil hardness was very poor as 2B.

Claims (10)

A polyester oligomer comprising a polymerization unit having a structure represented by the following formula (1):
[Formula 1]

In Formula 1,
A is a divalent group derived from a substituted or unsubstituted binaphthyl diol,
R ¹ is a substituted or unsubstituted aliphatic group having 5 to 30 carbon atoms or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 30 carbon atoms; or a substituted or unsubstituted divalent monoheterocyclic, polyheterocyclic or fused heterocyclic group containing at least one atom selected from N, O and S,
* indicates the point of attachment to an adjacent polymerized unit. The polyester oligomer according to claim 1, wherein A has the structure:

Here, * indicates the point of attachment to the adjacent oxygen. According to claim 1, Polyester oligomer further comprising a polymerization unit having a structure represented by the following formula (2):
[Formula 2]

In Formula 2,
B is a divalent group derived from diallyl bisphenol A,
R ¹ is as defined in Formula 1 of claim 1,
* indicates the point of attachment to adjacent polymerized units. 4. The polyester oligomer according to claim 3, wherein B has the structure:

Here, * indicates the point of attachment to the adjacent oxygen. The polyester oligomer according to claim 1, having a structure represented by the following formula (3):
[Formula 3]

In Formula 3,
R ¹ and A are as defined in Formula 1 of claim 1,
B is a divalent group derived from diallyl bisphenol A,
* indicates the point of attachment to an adjacent polymerized unit,
a and b each represent a relative mole fraction of the structure, a is a positive number from 0.03 to 1, b is a positive number from 0 to 0.97, but a+b is 1. As a method for producing the polyester oligomer according to claim 1,
A method comprising reacting a substituted or unsubstituted binaphthyl diol and a compound represented by the following formula (4):
[Formula 4]

In Formula 4,
R ¹ is as defined in Formula 1 of claim 1,
Y each independently represents a halogen atom, a hydroxy group or an alkoxy group. A method for producing the polyester oligomer according to claim 3,
A method comprising reacting a substituted or unsubstituted binaphthyl diol, diallyl bisphenol A, and a compound represented by the following formula (4):
[Formula 4]

In Formula 4,
R ¹ is as defined in Formula 1 of claim 1,
Y each independently represents a halogen atom, a hydroxy group, or an alkoxy group. 6. A repeating unit comprising: a block formed from the polyester oligomer according to any one of claims 1 to 5; and a polycarbonate block; containing, a polyester-polycarbonate block copolymer. According to any one of claims 1 to 5, copolymerizing the polyester oligomer and the polycarbonate oligomer according to any one of claims 1 to 5 in the presence of a catalyst; Containing, a method for producing a polyester-polycarbonate block copolymer. A molded article comprising the polyester-polycarbonate block copolymer according to claim 8.