KR20230097858A - Polyester oligomer and method for preparing the same, and polyester-polycarbonate block copolymer comprising the oligomer with improved scratch resistance and high refractive index and method for preparing the same - Google Patents

Abstract

The present invention relates to a polyester oligomer and a producing method thereof, and a polyester-polycarbonate block copolymer containing the oligomer and a producing method thereof. More specifically, the present invention relates to a polyester oligomer containing a polymerization unit having a structure derived from a diallyl bisphenol compound and a polymerization unit having a structure derived from a fluorene diol compound, and a producing method thereof, and a high refractive index polyester-polycarbonate copolymer including a block formed from the polyester oligomer and a polycarbonate block as a repeating unit, having improved scratch resistance compared to conventional linear polycarbonate and a polycarbonate copolymer, and maintaining excellent impact resistance, and a producing method thereof. Provided is the polyester oligomer which comprises: a polymerization unit having a structure represented by chemical formula I; and a polymerization unit having a structure represented by chemical formula II.

Description

Polyester oligomer and method for preparing the same, polyester-polycarbonate block copolymer comprising the oligomer and having improved scratch resistance and high refractive index, and method for preparing the same COPOLYMER COMPRISING THE OLIGOMER WITH IMPROVED SCRATCH RESISTANCE AND HIGH REFRACTIVE INDEX AND METHOD FOR PREPARING THE SAME}

The present invention relates to a polyester oligomer and a method for preparing the same, and a polyester-polycarbonate block copolymer containing the oligomer and a method for producing the same, and more particularly, to a polymerized unit having a structure derived from a diallyl bisphenol-based compound and A polyester oligomer comprising a polymerized unit having a structure derived from a fluorene-based diol compound and a method for producing the same, and a block formed from the polyester oligomer and a polycarbonate block as repeating units, and conventional linear polycarbonate and polycarbonate air It relates to a high refractive index polyester-polycarbonate copolymer having improved scratch resistance compared to composites and excellent impact resistance, and a manufacturing method thereof.

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 entails 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 having a high refractive index with improved scratch resistance while maintaining transparency and impact resistance, which are inherent properties of polycarbonate.

The present invention is intended to solve the problems of the prior art as described above, and has improved scratch resistance compared to conventional linear polycarbonate and conventional polycarbonate copolymers, while maintaining excellent impact resistance and transparency. It is a technical task to provide a polyester oligomer capable of producing an ester-polycarbonate block copolymer, a method for producing the same, and a polyester-polycarbonate block copolymer having a high refractive index and a method for producing the same.

In order to solve the above technical problem, one aspect of the present invention, a polymerized unit having a structure represented by the following formula (I); And a polymer unit having a structure represented by Formula II below;

[Formula I]

[Formula II]

In Formulas I and II above,

P is a divalent organic group derived from a substituted or unsubstituted diallyl bisphenol-based compound,

Q is a divalent organic group derived from a substituted or unsubstituted fluorene-based diol compound,

A is a substituted or unsubstituted, aliphatic or aromatic monocyclic, polycyclic or fused cyclic group; or a substituted or unsubstituted monoheterocyclic, polyheterocyclic or fused heterocyclic group containing at least one atom selected from N, O and S,

* indicates the point of attachment to adjacent polymerized units.

According to one embodiment of the present invention, the polyester oligomer may have a structure represented by Formula III below:

[Formula III]

In Formula III,

P, Q and A are as defined in Formulas I and II above;

a and b represent the relative mole fractions of the corresponding structures, respectively, where a is a positive number from 0.05 to 0.95, b is a positive number from 0.05 to 0.95, and a+b is 1.

Another aspect of the present invention is a substituted or unsubstituted diallyl bisphenol-based compound; A substituted or unsubstituted fluorene-based diol compound; And a compound represented by Formula IV;

[Formula IV]

In Formula IV, A is as defined in Formulas I and II, and Y each independently represents a halogen atom, a hydroxyl group, or an alkoxy group.

According to another aspect of the present invention, the compound represented by Formula IV; a compound represented by the following formula (V); And a compound represented by Formula VI below; a method for producing the polyester oligomer comprising the step of reacting is provided:

[Formula V]

[Formula VI]

In Formulas V and VI above, P, Q and A are as defined in Formulas I and II above.

According to one preferred embodiment of the present invention, the polyester oligomer is a polymerization unit having a structure represented by the following formula (1); And a polymer unit having a structure represented by Formula 2 below; may include:

[Formula 1]

In Formula 1,

R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms;

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

m and n each independently represents an integer from 0 to 3;

* indicates the point of attachment to adjacent polymerized units;

[Formula 2]

In Formula 2,

R ₃ and R ₄ are each independently a hydrogen atom; an alkyl group having 1 to 30 carbon atoms; Cycloalkyl group having 3 to 30 carbon atoms; Or represents an aryl group having 6 to 30 carbon atoms,

A ₁ is as defined in Formula 1 above,

o and p each independently represents an integer from 0 to 4;

* indicates the point of attachment to adjacent polymerized units.

According to a preferred embodiment of the present invention, the polyester oligomer may have a structure represented by Formula 3 below:

[Formula 3]

In Formula 3,

R ₁ , R ₂ , A ₁ , m and n are as defined in Formula 1 above,

R ₃ , R ₄ , o and p are as defined in Formula 2 above,

a and b represent the relative mole fractions of the corresponding structures, respectively, where a is a positive number from 0.05 to 0.95, b is a positive number from 0.05 to 0.95, and a+b is 1.

More specifically, the polyester oligomer may have a structure represented by Formula 3-1 below:

[Formula 3-1]

In Formula 3-1, a and b are as defined in Formula 3 above.

According to a preferred embodiment of the present invention, a compound represented by Formula 4; A compound represented by Formula 5 below; And a compound represented by Formula 6; a method for producing the polyester oligomer comprising the step of reacting is provided:

[Formula 4]

In Formula 4, R ₁ , R ₂ , m and n are as defined in Formula 1 above;

[Formula 5]

In Formula 5, R ₃ , R ₄ , o and p are as defined in Formula 2;

[Formula 6]

In Formula 6, A ₁ is as defined in Formula 1, and Y each independently represents a halogen atom, a hydroxyl group, or an alkoxy group.

According to a preferred embodiment of the present invention, the compound represented by the formula (6); A compound represented by Formula 7 below; And a compound represented by Formula 8; a method for producing the polyester oligomer comprising the step of reacting is provided:

[Formula 7]

In Formula 7, R ₁ , R ₂ , A ₁ , m and n are as defined in Formula 1 above;

[Formula 8]

In Formula 8, R ₃ , R ₄ , A ₁ , o and p are as defined in Formula 2 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, there is provided a method for producing a polyester-polycarbonate block copolymer comprising the step of copolymerizing a polyester oligomer and a polycarbonate oligomer according to the present invention in the presence of a catalyst.

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

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

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

polyester oligomer

The polyester oligomer of the present invention has a polymer unit having a structure represented by the following formula (I); and a polymerized unit having a structure represented by Formula II below:

[Formula I]

[Formula II]

In Formulas I and II above,

P is a divalent organic group derived from a substituted or unsubstituted diallyl bisphenol-based compound,

Q is a divalent organic group derived from a substituted or unsubstituted fluorene-based diol compound,

A is a substituted or unsubstituted, aliphatic or aromatic monocyclic, polycyclic or fused cyclic group; or a substituted or unsubstituted monoheterocyclic, polyheterocyclic or fused heterocyclic group containing at least one atom selected from N, O and S,

* indicates the point of attachment to adjacent polymerized units.

More specifically, in Formulas I and II, A is a substituted or unsubstituted aliphatic group having 5 to 30 total carbon atoms or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 30 total carbon atoms; or a substituted or unsubstituted divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic group of 5 to 30 total ring atoms containing at least one atom selected from N, O and S; More specifically, A is an aliphatic group having 5 to 20 total carbon atoms or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 20 total carbon atoms; or a substituted or unsubstituted divalent monoheterocyclic, polyheterocyclic or fused heterocyclic group of 5 to 20 total ring atoms containing at least one atom selected from N, O and S; Even more specifically, A is a substituted or unsubstituted, aliphatic group having 5 to 10 total carbon atoms or aromatic monocyclic, polycyclic or fused cyclic group having 6 to 12 total carbon atoms; or a substituted or unsubstituted divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic group of 5 to 12 total ring atoms containing at least one atom selected from N, O and S.

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), alkoxy group (eg, 1 to 10 carbon atoms or 1 to 6 carbon atoms alkoxy group), cycloalkyl group (eg, 3 to 10 carbon atoms or 3 to 6 carbon atoms cycloalkyl group), aryl group ( For example, an aryl group having 6 to 12 carbon atoms or 6 carbon atoms) or a combination thereof.

In the present specification, a diallyl bisphenol-based compound refers to a compound containing at least one “bisphenol” structure and having allyl groups at two phenol sites in the bisphenol structure, and the diallyl bisphenol-based compound may be substituted or unsubstituted. there is.

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

According to one embodiment of the present invention, in the polyester oligomer, the mole ratio of the substituted or unsubstituted repeating unit derived from the fluorene-based diol compound per 1 mole of the repeating unit derived from the substituted or unsubstituted diallyl bisphenol-based compound is, for example, It may be more than 0.1 mol, 0.11 mol or more, 0.13 mol or more, 0.15 mol or more, 0.17 mol or more, 0.19 mol or more, 0.2 mol or more, or 0.22 mol or more, and also less than 10 mol, 9.9 mol or less, 9 mol or less, 8 mol or less. . mole, 0.2 to 9 moles or 0.22 to 4.5 moles. When the molar ratio of the substituted or unsubstituted repeating unit derived from the fluorene-based diol compound per 1 mole of the repeating unit derived from the substituted or unsubstituted diallyl bisphenol compound is less than the above level, the scratch resistance of the copolymer prepared using the oligomer is The refractive index may be deteriorated or the refractive index may be lowered, and conversely, when the molar ratio exceeds the above level, the impact resistance of the copolymer may be lowered.

In a preferred embodiment of the present invention, the polyester oligomer is a polymer unit having a structure represented by Formula 1 below; and a polymerized unit having a structure represented by Formula 2 below:

[Formula 1]

In Formula 1,

R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms;

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

m and n each independently represents an integer from 0 to 3;

* indicates the point of attachment to adjacent polymerized units;

[Formula 2]

In Formula 2,

R ₃ and R ₄ are each independently a hydrogen atom; an alkyl group having 1 to 30 carbon atoms; Cycloalkyl group having 3 to 30 carbon atoms; Or represents an aryl group having 6 to 30 carbon atoms,

A ₁ is as defined in Formula 1 above,

o and p each independently represents an integer from 0 to 4;

* indicates the point of attachment to adjacent polymerized units.

More specifically, in Formula 1,

R ₁ and R ₂ are each independently a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; or an aryl group having 6 to 20 carbon atoms, more specifically, a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; Cycloalkyl group having 3 to 10 carbon atoms; Or represents an aryl group having 6 to 12 carbon atoms,

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

More specifically, in Formula 2, A ₁ is as defined in the specific examples of Formula 1 above.

According to one embodiment of the present invention, the polyester oligomer may have a structure represented by Formula III below:

[Formula III]

In Formula III,

P, Q and A are as defined in Formulas I and II above;

a and b represent the relative mole fractions of the corresponding structures, respectively, where a is a positive number from 0.05 to 0.95, b is a positive number from 0.05 to 0.95, and a+b is 1.

More specifically, in Formula III, a may be 0.05 to 0.5, b may be 0.5 to 0.95, provided that a+b is 1.

In a preferred embodiment of the present invention, the polyester oligomer may have a structure represented by Formula 3 below:

[Formula 3]

In Formula 3,

R ₁ , R ₂ , A ₁ , m and n are as defined in Formula 1 above,

R ₃ , R ₄ , o and p are as defined in Formula 2 above,

a and b represent the relative mole fractions of the corresponding structures, respectively, where a is a positive number from 0.05 to 0.95, b is a positive number from 0.05 to 0.95, and a+b is 1.

More specifically, in Formula 3, a may be 0.05 to 0.5, b may be 0.5 to 0.95, provided that a+b is 1.

If the content of the unit containing the structure derived from the diallyl bisphenol-based compound present in the polyester oligomer of the present invention (that is, the polymerized unit having the structure represented by Formula I (more specifically, Formula 1)) is too small, (For example, if a is less than the above level in Formula III (more specifically, Formula 3)), scratch resistance or impact resistance of a copolymer prepared using the oligomer may be deteriorated, and conversely, the content thereof may be reduced. If it is too large (for example, if a exceeds the above level in Formula III (more specifically, Formula 3)), the scratch resistance of the copolymer may deteriorate or the refractive index may decrease.

More specifically, the polyester oligomer may have a structure represented by Formula 3-1 below:

[Formula 3-1]

In Formula 3-1, a and b are as defined in Formula 3 above.

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 900 to 18,000, and more specifically 1,000 to 16,000 days It may, but is not limited thereto.

According to another aspect of the present invention, a substituted or unsubstituted diallyl bisphenol-based compound; A substituted or unsubstituted fluorene-based diol compound; And a compound represented by the following formula (IV); a method for producing a polyester oligomer comprising the step of reacting is provided:

[Formula IV]

In Formula IV, A is as defined in Formulas I and II, and Y is each independently a halogen atom (eg, a fluorine atom, a bromine atom, or a chlorine atom, more specifically a chlorine atom), a hydroxyl group, or an alkoxy group. (For example, an alkoxy group having 1 to 10 carbon atoms or 1 to 6 carbon atoms).

In one preferred embodiment of the present invention, the method for producing the polyester oligomer is a compound represented by Formula 4; A compound represented by Formula 5 below; and reacting a compound represented by Formula 6 below:

[Formula 4]

In Formula 4, R ₁ , R ₂ , m and n are as defined in Formula 1 above;

[Formula 5]

In Formula 5, R ₃ , R ₄ , o and p are as defined in Formula 2;

[Formula 6]

In Formula 6, A ₁ is as defined in Formula 1, and Y is each independently a halogen atom (eg, a fluorine atom, a bromine atom or a chlorine atom, more specifically a chlorine atom), a hydroxyl group, or an alkoxy group ( For example, an alkoxy group having 1 to 10 carbon atoms or 1 to 6 carbon atoms).

According to one embodiment of the present invention, in the method for producing the polyester oligomer, a substituted or unsubstituted fluorene-based compound per mole of the substituted or unsubstituted diallyl bisphenol-based compound (more specifically, the compound of Formula 4) structure and having hydroxyl groups at both ends (more specifically, the compound of Formula 5) used is, for example, greater than 0.1 mole, 0.11 mole or more, 0.13 mole or more, 0.15 mole or more, 0.17 mole or more, 0.19 mole or more. It may be 0.2 mol or more, 0.2 mol or more, or 0.22 mol or more, and may be less than 10 mol, 9.9 mol or less, 9 mol or less, 8 mol or less, 7 mol or less, 6 mol or less, 5 mol or less, or 4.5 mol or less. As, it may be greater than 0.1 moles and less than 10 moles, and more specifically, may be 0.11 moles to 9.9 moles, 0.15 moles to 9 moles, 0.2 moles to 9 moles, or 0.22 moles to 4.5 moles. For example, if the amount of the compound of Formula 5 per 1 mole of the compound of Formula 4 is less than the above level, the scratch resistance or refractive index of a copolymer prepared using the oligomer may be deteriorated. If it exceeds, the impact resistance of the copolymer may be lowered.

In addition, according to one embodiment of the present invention, in the method for producing the polyester oligomer, a compound containing a substituted or unsubstituted fluorene-based structure and having a hydroxyl group at both ends (more specifically, of Formula 5) compound) and the substituted or unsubstituted diallyl bisphenol-based compound (more specifically, the compound of Formula 4), the amount of the compound of Formula IV (more specifically, the compound of Formula 6) used is 0.3 mol or more, It may be 0.4 mole or more, or 0.5 mole or more, and may be 1.1 mole or less, 1.05 mole or less, or 1 mole or less.

The reaction conditions of the above compounds (eg, compounds of Formulas 4 to 6) are not particularly limited. a base catalyst, more specifically, an organic amine catalyst such as triethylamine), but is not limited thereto.

According to another aspect of the present invention, the compound represented by Formula IV; a compound represented by the following formula (V); And a compound represented by Formula VI below; a method for producing the polyester oligomer comprising the step of reacting is provided:

[Formula V]

[Formula VI]

In Formulas V and VI above, P, Q and A are as defined in Formulas I and II above.

In a preferred embodiment of the present invention, the method for preparing the polyester oligomer comprises a compound represented by Formula 6; A compound represented by Formula 7 below; and reacting a compound represented by Formula 8 below:

[Formula 7]

In Formula 7, R ₁ , R ₂ , A ₁ , m and n are as defined in Formula 1 above;

[Formula 8]

In Formula 8, R ₃ , R ₄ , A ₁ , o and p are as defined in Formula 2 above.

According to one embodiment of the present invention, in the method for producing the polyester oligomer, the compound of formula VI (more specifically, the compound of formula 8) per mole of the compound of formula V (more specifically, the compound of formula 7) The amount used may be, for example, greater than 0.1 mol, 0.11 mol or more, 0.13 mol or more, 0.15 mol or more, 0.17 mol or more, 0.19 mol or more, 0.2 mol or more, or 0.22 mol or more, and may also be less than 10 mol, 9.9 mol or less, 9 mol or more. It may be 8 moles or less, 7 moles or less, 6 moles or less, 5 moles or less, or 4.5 moles or less, more specifically, greater than 0.1 moles and less than 10 moles, and more specifically, 0.11 moles to 9.9 moles. , 0.15 to 9 moles, 0.2 to 9 moles or 0.22 to 4.5 moles.

In addition, according to one embodiment of the present invention, the compound of formula IV (more specifically, the compound of formula 7) per mole of the total of the compound of formula V (more specifically, the compound of formula 7) and the compound of formula VI (more specifically, the compound of formula 8) Specifically, the amount of the compound of Formula 6) used may be 0.3 mol or more, 0.4 mol or more, or 0.5 mol or more, and may also be 1.1 mol or less, 1.05 mol or less, or 1 mol or less.

There is no particular limitation on the reaction conditions of the above compounds (eg, compounds of Formula 6, Formula 7, and Formula 8), for example, room temperature (ie, 20 to 30 ° C.) or elevated temperature (eg, 200 to 230 ° C.) of the catalyst. (eg, a base catalyst, more specifically, an organic amine catalyst such as triethylamine), but is not limited thereto.

In one embodiment, the compound of Formula V (more specifically, the compound of Formula 7) is a substituted or unsubstituted diallyl bisphenol-based compound (more specifically, the compound of Formula 4) and the compound of Formula IV (more specifically, the compound of Formula 4). It can be prepared by reacting the compound of Formula 6). At this time, For example, the amount of the compound of Formula 6 used per 1 mole of the compound of Formula 4 may be 0.5 mol or more, 0.6 mol or more, or 0.7 mol or more, and may be 1 mol or less, 0.99 mol or less, or 0.95 mol or less, and the reaction is carried out at room temperature. (ie, 20 ~ 30 ℃) or an elevated temperature (eg, 200 ~ 300 ℃) may be carried out in the presence of a catalyst (eg, a base catalyst, more specifically, an organic amine catalyst such as triethylamine), but is not limited thereto. don't

In one embodiment, the compound of Formula VI (more specifically, the compound of Formula 8) contains a substituted or unsubstituted fluorene-based structure and has a hydroxyl group at both ends (more specifically, a compound of Formula 5). ) and a compound of formula IV (more specifically, a compound of formula 6). At this time, for example, per 1 mole of the compound of Formula 5 The amount of the compound of Formula 6 used may be 0.5 mol or more, 0.6 mol or more, or 0.7 mol or more, and may also be 1 mol or less, 0.99 mol or less, or 0.95 mol or less, and the reaction is carried out at room temperature (ie, 20 to 30 ° C.) Alternatively, it may be performed in the presence of a catalyst (eg, a base catalyst, more specifically, an organic amine catalyst such as triethylamine) under elevated temperature (eg, 200 to 300° C.), but is not limited thereto.

Polyester-polycarbonate block copolymer

The polyester-polycarbonate block copolymer of the present invention includes, 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 5% by weight and less than 55% by weight based on 100% by weight of the copolymer. More specifically, the polyester oligomer block content in the copolymer is greater than 5% by weight, greater than 6% by weight, greater than 7% by weight, greater than 8% by weight, greater than 9% by weight, or greater than 10% by weight, based on 100% by weight of the total copolymer. It may be more than 55 wt%, 54 wt% or less, 53 wt% or less, 52 wt% or less, 51 wt% or less, or 50 wt% or less. If the content of the polyester oligomer block in the copolymer is too less than the above level, the scratch resistance of the copolymer may be deteriorated and the refractive index may be reduced. can

The polycarbonate block included as a repeating unit in the polyester-polycarbonate block copolymer of the present invention may have a repeating unit represented by Formula 9 below.

[Formula 9]

In Formula 9,

R ₆ 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), or an alkoxy group. (For example, an alkoxy group having 1 to 13 carbon atoms), an aromatic hydrocarbon group having 6 to 30 carbon atoms, unsubstituted or substituted with a halogen atom or a nitro group.

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, and 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 make a phenol salt state, and then reacting the salt state phenol in dichloromethane injected with phosgene gas. For oligomer production, 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 in the range of about 1:1 to 1.2:1. If the molar ratio of phosgene to dihydroxy compound is less than 1, reactivity may be reduced, and if the molar ratio of phosgene to dihydroxy compound exceeds 1.5, processability may be deteriorated due to an excessive increase in molecular weight.

The oligomer formation reaction may be generally carried out 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-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3-chloro-4-hydroxyphenyl) 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'-dihydroxydiphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, isosorb It may be a bead, isomannide, isoidide or a combination thereof, but is not limited thereto. Representative of these are 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) and isosorbide. Other functional dihydroxy compounds 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 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 deteriorated, and conversely, if it is excessively greater than the above level, moldability may be deteriorated.

The polyester-polycarbonate block copolymer of the present invention 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 method for preparing a polyester-polycarbonate block copolymer comprising the step of copolymerizing a polyester oligomer and a polycarbonate oligomer according to the present invention in the presence of a catalyst is provided.

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

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

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.

As the catalyst, a polymerization catalyst and/or a phase transfer catalyst may be used. As the polymerization catalyst, for example, triethylamine (TEA) may be used, and as the phase transfer catalyst, for example, a compound represented by Chemical Formula 10 may be used.

[Formula 10]

(R ₇ ) ₄ Q ⁺ Z ^-

In Formula 10, 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 allyl 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 can 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 allyl 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, 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 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 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. can be dried during

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

Accordingly, according to another aspect of the present invention, a molded article comprising the polyester-polycarbonate block 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 polycarbonate oligomer

In a 10 L 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% by weight aqueous sodium hydroxide solution, and then 260 g (2.63 mol) of phosgene was collected in methylene chloride and placed in a Teflon tube (20 mm) and reacted while slowly introducing it. The external temperature was maintained at 0°C. An oligomeric polycarbonate having a viscosity average molecular weight of about 1,000 was prepared by interfacially reacting the reactant passing through the tubular reactor for about 10 minutes under a nitrogen atmosphere. Of the mixture containing the oligomeric polycarbonate prepared above, 2,150 mL of the organic phase and 3,220 mL of the aqueous phase were collected, and 13.83 g (92.1 mmol, 3.5 mol% of bisphenol A) of p-tert-butylphenol (PTBP), tetrabutylammonium After mixing 7.31 g (26.3 mmol, 1 mol% of bisphenol A) of chloride (tetrabutyl ammonium chloride, TBACl) and 1 mL of a 15 wt% aqueous solution of triethylamine (TEA) and reacting for 30 minutes, the viscosity average molecular weight About 4,000 polycarbonate oligomer solutions were prepared.

<Preparation of polyester oligomer>

Example A1: Preparation of polyester oligomer using diallyl bisphenol-based compound and fluorene-based diol compound [molar ratio of diallyl bisphenol A: fluorene-based diol compound = 1:1)

141.44 g (0.46 mol) of diallyl bisphenol A as a diallyl bisphenol-based compound and 9,9-bis (4-hydroxyphenyl) fluorene as a fluorene-based diol compound [9,9-Bis (4-hydroxyphenyl) fluorene] A solution prepared by dissolving 161.2 g (0.46 mol) in 2,300 g of methylene chloride was introduced into a 5 L three-necked reactor, and then 175.67 g of terephthaloyl chloride of formula A was dissolved in 1,400 g of methylene chloride. The prepared solution was introduced into the three-necked reactor. Thereafter, 175.12 g of triethylamine was added to the three-necked reactor while being dropped for 120 minutes. After completion of dropping, the reaction solution was stirred for 240 minutes, and then salt was removed through filtration, and 160 ml of 1N hydrochloric acid aqueous solution and 1,000 ml of distilled water were added to the filtrate and stirred for 30 minutes. Then, after standing at room temperature for 12 hours or more, the filtrate was precipitated in ethanol and washed with distilled water. Thereafter, a polyester oligomer (number average molecular weight: about 6,900 g/mol) was obtained by drying the filtrate from which the precipitate was removed in an oven at 110° C. for 24 hours.

[Formula A]

Example A2: Preparation of polyester oligomer using diallyl bisphenol-based compound and fluorene-based diol compound [molar ratio of diallyl bisphenol A: fluorene-based diol compound = 1:0.22]

231.31 g (0.75 mol) of diallyl bisphenol A as a diallyl bisphenol-based compound and 9,9-bis (4-hydroxyphenyl) fluorene [9,9-Bis (4-hydroxyphenyl) fluorene] as a fluorene-based diol compound A solution prepared by dissolving 59.57g (0.17 mol) in 2,330g of methylene chloride was introduced into a 5L three-necked reactor, and then a solution prepared by dissolving 169.79g of terephthaloyl chloride in 1,360g of methylene chloride was added to the three-necked reactor. was put into. Thereafter, 169.26 g of triethylamine was added to the three-necked reactor while being dropped for 120 minutes. Then, in the same manner as in Example A1, a polyester oligomer (number average molecular weight: about 4,800 g/mol) was obtained.

Example A3: Preparation of polyester oligomer using diallyl bisphenol-based compound and fluorene-based diol compound [molar ratio of diallyl bisphenol A: fluorene-based diol compound = 1:4.5]

52.43 g (0.17 mol) of diallyl bisphenol A as a diallyl bisphenol-based compound and 9,9-bis (4-hydroxyphenyl) fluorene [9,9-Bis (4-hydroxyphenyl) fluorene] as a fluorene-based diol compound A solution prepared by dissolving 266.31 g (0.76 mol) in 2,300 g of methylene chloride was introduced into a 5 L three-neck reactor, and then a solution prepared by dissolving 172.29 g of terephthaloyl chloride in 1,380 g of methylene chloride was added to the three-neck reactor. was put into. Thereafter, 171.75 g of triethylamine was added to the three-necked reactor while being dropped for 120 minutes. Then, in the same manner as in Example A1, a polyester oligomer (number average molecular weight: about 4,700 g/mol) was obtained.

Example A4: Preparation of polyester oligomer using diallyl bisphenol-based compound and fluorene-based diol compound [molar ratio of diallyl bisphenol A: fluorene-based diol compound = 1:9]

24.67 g (0.08 mol) of diallyl bisphenol A as a diallyl bisphenol-based compound and 9,9-bis (4-hydroxyphenyl) fluorene as a fluorene-based diol compound [9,9-Bis (4-hydroxyphenyl) fluorene] A solution prepared by dissolving 252.30 g (0.72 mol) in 2,300 g of methylene chloride was introduced into a 5 L three-neck reactor, and then a solution prepared by dissolving 155.92 g of terephthaloyl chloride in 1,380 g of methylene chloride was added to the three-neck reactor. was put into. Thereafter, 171.75 g of triethylamine was added to the three-necked reactor while being dropped for 120 minutes. Then, in the same manner as in Example A1, a polyester oligomer (number average molecular weight: about 4,500 g/mol) was obtained.

Example A5: Preparation of polyester oligomer using diallyl bisphenol-based compound and fluorene-based diol compound [molar ratio of diallyl bisphenol A: fluorene-based diol compound = 1:1]

123.36 g (0.40 mol) of diallyl bisphenol A as a diallyl bisphenol-based compound, 9,9-bis (4-hydroxyphenyl) fluorene [9,9-Bis (4-hydroxyphenyl) fluorene] as a fluorene-based diol compound 140.17 g (0.40 mol) and 147.02 g of dimethyl terephthalate were put into a 1 L reactor, 700 ppm of triethylamine based on the weight of dimethyl terephthalate was added to the reactor, and then the reactor temperature was raised to 230 ° C. It was reacted while raising the temperature. Methanol produced as a by-product was removed, and after reaction for 3 hours, a polyester oligomer (number average molecular weight: about 6,600 g/mol) was obtained.

Comparative Example A1: Preparation of Polyester Oligomer Using Diallyl Bisphenol-based Compound

As a diallyl bisphenol-based compound, a solution prepared by dissolving 283.74 g (0.92 mol) of diallyl bisphenol A in 2,330 g of methylene chloride was introduced into a 5L three-necked reactor, and then 168.51 g (0.83 mol) of terephthaloyl chloride was added to methylene chloride. A solution prepared by dissolving in 1,350 g of chloride was introduced into the three-necked reactor. Thereafter, 168.56 g of triethylamine was added to the three-necked reactor while being dropped for 120 minutes. Then, in the same manner as in Example A1, a polyester oligomer (number average molecular weight: about 4,800 g/mol) of Formula B was obtained.

[Formula B]

Comparative Example A2: Preparation of polyester oligomer using fluorene-based diol compound

A solution prepared by dissolving 322.39 g (0.92 mol) of 9,9-bis (4-hydroxyphenyl) fluorene [9,9-Bis (4-hydroxyphenyl) fluorene] as a fluorene-based diol compound in 2,330 g of methylene chloride was introduced into a 5L three-neck reactor, and a solution prepared by dissolving 168.51 g (0.83 mol) of terephthaloyl chloride in 1,350 g of methylene chloride was introduced into the three-neck reactor. Thereafter, 168.56 g of triethylamine was added to the three-necked reactor while being dropped for 120 minutes. Then, in the same manner as in Example A1, a polyester oligomer of Formula C (number average molecular weight: about 4,700 g/mol) was obtained.

[Formula C]

Comparative Example A3: Preparation of polyester oligomer using diallyl bisphenol-based compound and fluorene-based diol compound [molar ratio of diallyl bisphenol A: fluorene-based diol compound = 1: 0.1]

255.98 g (0.83 mol) of diallyl bisphenol A as a diallyl bisphenol-based compound and 9,9-bis (4-hydroxyphenyl) fluorene [9,9-Bis (4-hydroxyphenyl) fluorene] as a fluorene-based diol compound A solution prepared by dissolving 28.03 g (0.08 mol) in 2,330 g of methylene chloride was introduced into a 5 L three-neck reactor, and then a solution prepared by dissolving 177.36 g of terephthaloyl chloride in 1,360 g of methylene chloride was added to the three-neck reactor. was put into. Thereafter, 168.91 g of triethylamine was added to the three-necked reactor while being dropped for 120 minutes. Then, in the same manner as in Example A1, a polyester oligomer (number average molecular weight: about 4,800 g/mol) was obtained.

Comparative Example A4: Preparation of polyester oligomer using diallyl bisphenol-based compound and fluorene-based diol compound [molar ratio of diallyl bisphenol A: fluorene-based diol compound = 1:10]

27.76 g (0.09 mol) of diallyl bisphenol A as a diallyl bisphenol-based compound and 9,9-bis (4-hydroxyphenyl) fluorene as a fluorene-based diol compound [9,9-Bis (4-hydroxyphenyl) fluorene] A solution prepared by dissolving 297.86g (0.85 mol) in 2,320g of methylene chloride was introduced into a 5L three-necked reactor, and then a solution prepared by dissolving 172.65g of terephthaloyl chloride in 1,380g of methylene chloride was added to the three-necked reactor. was put into. Thereafter, 172.11 g of triethylamine was added to the three-necked reactor while being dropped for 120 minutes. Then, in the same manner as in Example A1, a polyester oligomer (number average molecular weight: about 4,700 g/mol) was obtained.

<Preparation of polyester-polycarbonate block copolymer>

Example B1: Preparation of a polyester-polycarbonate block copolymer using the polyester oligomer of Example A1 (25% by weight based on the total weight of the block copolymer)

5,120 g of the polycarbonate oligomer solution obtained in Preparation Example 1 was placed in a 5L reactor, and 430 g of the polyester oligomer obtained in Example A1 (25% by weight based on the total weight of the block copolymer) was dissolved in 2,990 g of methylene chloride. 1,570mL of 1.1N sodium hydroxide aqueous solution (20% by volume based on the total mixture) and 234 μL of 15% by weight triethylamine were added to the reactor, reacted for 1 hour, and then added 15% by weight of triethylamine. 2,600 μL of amine was added and further reacted for 1 hour. After layer separation, pure water was added to the organic phase with increased viscosity to wash with alkali, and then only the organic phase was separated. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution and then washed with distilled water 2 to 3 times repeatedly. After washing was completed and the concentration of the organic phase was made constant, it was assembled using a certain amount of secondary distilled water at 76 °C. After assembly was completed, a polyester-polycarbonate block copolymer was prepared by firstly drying at 110° C. for 8 hours and secondarily drying at 120° C. for 10 hours.

Example B2: Preparation of a polyester-polycarbonate block copolymer using the polyester oligomer of Example A2 (50% by weight based on the total weight of the block copolymer)

Example B1 and A polyester-polycarbonate block copolymer was prepared in the same manner.

Example B3: Preparation of a polyester-polycarbonate block copolymer using the polyester oligomer of Example A3 (10% by weight based on the total weight of the block copolymer)

Same as Example B1, except that 143 g (10% by weight based on the total weight of the block copolymer) of the polyester oligomer obtained in Example A3 was added instead of the polyester oligomer obtained in Example A1. A polyester-polycarbonate block copolymer was prepared by performing the method.

Example B4: Preparation of a polyester-polycarbonate block copolymer using the polyester oligomer of Example A4 (50% by weight based on the total weight of the block copolymer)

Example B1 and A polyester-polycarbonate block copolymer was prepared in the same manner.

Example B5: Preparation of a polyester-polycarbonate block copolymer using the polyester oligomer of Example A5 (25% by weight based on the total weight of the block copolymer)

Same as Example B1, except that 430 g (25% by weight based on the total weight of the block copolymer) of the polyester oligomer obtained in Example A5 was added instead of the polyester oligomer obtained in Example A1. A polyester-polycarbonate block copolymer was prepared by performing the method.

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 a polyester-polycarbonate block copolymer using the polyester oligomer of Comparative Example A1 (25% by weight based on the total weight of the block copolymer)

Same as Example B1, except that 430 g (25% by weight based on the total weight of the block copolymer) of the polyester oligomer obtained in Comparative Example A1 was added instead of the polyester oligomer obtained in Example A1. A polyester-polycarbonate block copolymer was prepared by performing the method.

Comparative Example B3: Preparation of a polyester-polycarbonate block copolymer using the polyester oligomer of Comparative Example A2 (25% by weight based on the total weight of the block copolymer)

Same as Example B1, except that 430 g (25% by weight based on the total weight of the block copolymer) of the polyester oligomer obtained in Comparative Example A2 was added instead of the polyester oligomer obtained in Example A1. A polyester-polycarbonate block copolymer was prepared by performing the method.

[How to measure physical properties]

(1) Pencil hardness (scratch resistance)

YASUDA SEIKI's No. The pencil hardness of each specimen of 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

(2) Impact strength (impact resistance)

In accordance with ASTM D256, each specimen of Examples and Comparative Examples was evaluated by notching, and as a final test result, 10 measurement values for each specimen were obtained and the average value thereof was calculated.

(3) refractive index

Using an ellipsometer (model name: Elli-SE, manufacturer: Ellipsotechnology) equipment, the refractive index (wavelength: 470 nm) of each specimen of Examples and Comparative Examples was measured.

As shown in Table 1, in the case of Examples B1 to B5 according to the present invention, the pencil hardness is excellent at F or higher, the impact strength is maintained at 20 kgf cm/cm or higher, and the refractive index is 1.59 or higher. Since it has high refractive index, it was possible to secure balanced physical properties of scratch resistance, impact resistance, and high refractive index.

On the other hand, in the case of Comparative Example 1, which is a conventional linear polycarbonate resin, the pencil hardness was 2B and the refractive index was less than 1.59, so the scratch resistance was very poor and the refractive index was also low. In addition, in the case of Comparative Example 2 in which the fluorene-based diol compound was not used as the diol compound, the pencil hardness was B and the scratch resistance was very poor, the refractive index was also low at less than 1.59, and the diallyl bisphenol-based compound was used as the diol compound Even in the case of Comparative Example 3, which was not performed, the pencil hardness was HB, which was poor in scratch resistance, and the impact strength was also poor at less than 20 kgf cm/cm.

Claims (16)

A polymerized unit having a structure represented by the following formula (I); and
A polymerized unit having a structure represented by Formula II below;
Polyester oligomers:
[Formula I]

[Formula II]

In Formulas I and II above,
P is a divalent organic group derived from a substituted or unsubstituted diallyl bisphenol-based compound,
Q is a divalent organic group derived from a substituted or unsubstituted fluorene-based diol compound,
A is a substituted or unsubstituted, aliphatic or aromatic monocyclic, polycyclic or fused cyclic group; or a substituted or unsubstituted monoheterocyclic, polyheterocyclic or fused heterocyclic group containing at least one atom selected from N, O and S,
* indicates the point of attachment to adjacent polymerized units. The polyester oligomer according to claim 1, wherein the polyester oligomer has a structure represented by Formula III:
[Formula III]

In Formula III,
P, Q and A are as defined in formulas I and II of claim 1,
a and b represent the relative mole fractions of the corresponding structures, respectively, where a is a positive number from 0.05 to 0.95, b is a positive number from 0.05 to 0.95, and a+b is 1. According to claim 1, Polymerized unit having a structure represented by the following formula (1); And a polymeric unit having a structure represented by Formula 2 below; polyester oligomer containing:
[Formula 1]

In Formula 1,
R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms;
A ₁ is a substituted or unsubstituted, aliphatic group having 5 to 30 total carbon atoms or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 30 total carbon atoms; or a substituted or unsubstituted divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic group of 5 to 30 total ring atoms containing at least one atom selected from N, O and S,
m and n each independently represents an integer from 0 to 3;
* indicates the point of attachment to adjacent polymerized units;
[Formula 2]

In Formula 2,
R ₃ and R ₄ are each independently a hydrogen atom; an alkyl group having 1 to 30 carbon atoms; Cycloalkyl group having 3 to 30 carbon atoms; Or represents an aryl group having 6 to 30 carbon atoms,
A ₁ is a substituted or unsubstituted, aliphatic group having 5 to 30 total carbon atoms or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 30 total carbon atoms; or a substituted or unsubstituted divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic group of 5 to 30 total ring atoms containing at least one atom selected from N, O and S,
o and p each independently represents an integer from 0 to 4;
* indicates the point of attachment to adjacent polymerized units. The polyester oligomer according to claim 3, wherein the polyester oligomer has a structure represented by Formula 3 below:
[Formula 3]

In Formula 3,
R ₁ , R ₂ , A ₁ , m and n are as defined in Formula 1 of claim 3,
R ₃ , R ₄ , o and p are as defined in Formula 2 of claim 3,
a and b represent the relative mole fractions of the corresponding structures, respectively, where a is a positive number from 0.05 to 0.95, b is a positive number from 0.05 to 0.95, and a+b is 1. The polyester oligomer according to claim 4, wherein a is from 0.05 to 0.5, b is from 0.5 to 0.95, and a+b is 1. The polyester oligomer according to claim 4, wherein the polyester oligomer has a structure represented by Formula 3-1:
[Formula 3-1]

In Formula 3-1, a and b are as defined in Formula 3 of claim 4. The polyester oligomer according to claim 1, wherein the mole ratio of the substituted or unsubstituted repeating unit derived from the fluorene-based diol compound per mole of the repeating unit derived from the substituted or unsubstituted diallyl bisphenol compound is greater than 0.1 mole and less than 10 mole. A method for producing the polyester oligomer according to claim 1 or 2,
A substituted or unsubstituted diallyl bisphenol-based compound; A substituted or unsubstituted fluorene-based diol compound; And a compound represented by Formula IV; a method comprising the step of reacting:
[Formula IV]

In the above formula IV, A is as defined in formulas I and II of claim 1, and Y each independently represents a halogen atom, a hydroxyl group or an alkoxy group. A method for producing the polyester oligomer according to any one of claims 3 to 6,
A compound represented by Formula 4 below; A compound represented by Formula 5 below; And a compound represented by Formula 6; comprising the step of reacting, a method:
[Formula 4]

In Formula 4, R ₁ , R _{2 ,} m and n are as defined in Formula 1 of claim 3;
[Formula 5]

In Formula 5, R ₃ , R ₄ , o and p are as defined in Formula 2 of claim 3;
[Formula 6]

In Formula 6, A ₁ is as defined in Formula 1 of claim 3, and Y each independently represents a halogen atom, a hydroxy group, or an alkoxy group. The method according to claim 9, wherein the amount of the compound of formula 5 used per mole of the compound of formula 4 is greater than 0.1 mole and less than 10 moles. A method for producing the polyester oligomer according to claim 1 or 2,
a compound represented by the following formula (IV); a compound represented by the following formula (V); And a compound represented by Formula VI below; a method comprising the step of reacting:
[Formula IV]

[Formula V]

[Formula VI]

In Formulas IV, V and VI above, P, Q and A is as defined in formulas I and II of claim 1, and Y each independently represents a halogen atom, a hydroxy group or an alkoxy group. A method for producing the polyester oligomer according to any one of claims 3 to 6,
A compound represented by Formula 6 below; A compound represented by Formula 7 below; And a compound represented by Formula 8; comprising the step of reacting, a method:
[Formula 6]

In Formula 6, A ₁ is as defined in Formula 1 of claim 3, and Y each independently represents a halogen atom, a hydroxyl group, or an alkoxy group;
[Formula 7]

In Formula 7, R ₁ , R _{2 ,} A ₁ , m and n are as defined in Formula 1 of claim 3;
[Formula 8]

In Formula 8, R ₃ , R ₄ , A ₁ , o and p are as defined in Formula 2 of claim 3. As the repeating unit, a block formed from the polyester oligomer according to any one of claims 1 to 7; And a polycarbonate block; comprising a polyester-polycarbonate block copolymer. 14. The polyester-polycarbonate block copolymer according to claim 13, wherein the content of blocks formed from the polyester oligomer is greater than 5% by weight and less than 55% by weight, based on 100% by weight of the total copolymer. A method for producing a polyester-polycarbonate block copolymer comprising: copolymerizing the polyester oligomer and the polycarbonate oligomer according to any one of claims 1 to 7 in the presence of a catalyst. A molded article comprising the polyester-polycarbonate block copolymer according to claim 13.