WO2021133048A1

WO2021133048A1 - Polycarbonate copolymer comprising units derived from anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol, method for producing same, and molded article comprising same

Info

Publication number: WO2021133048A1
Application number: PCT/KR2020/018967
Authority: WO
Inventors: 유승현; 류훈; 임준섭; 강민구; 손용재; 장민정; 박상현
Original assignee: 주식회사 삼양사
Priority date: 2019-12-24
Filing date: 2020-12-23
Publication date: 2021-07-01
Also published as: KR102303199B1; KR20210082290A

Abstract

The present invention relates to a polycarbonate copolymer, a method for producing same, and a molded article comprising same, and more specifically, to: a polycarbonate copolymer exhibiting remarkably improved physical properties (in particular, tensile strength and elongation) compared to a conventional polycarbonate copolymer, by including repeating units derived from a diol component and a carbonic acid diester component containing an anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol in a specific content ratio; a method for producing same; and a molded article comprising same.

Description

Polycarbonate copolymer containing units derived from anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol, method for preparing same, and molded article comprising same

The present invention relates to a polycarbonate copolymer, a method for producing the same, and a molded article comprising the same, and more particularly, to a diol component comprising anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol in a specific content ratio and a diester carbonate By including repeating units derived from the component, a polycarbonate copolymer exhibiting significantly improved physical properties (in particular, tensile strength and elongation) compared to a conventional polycarbonate copolymer, and a method for preparing the same, and including the same It is related to the molded article.

Polycarbonate resin is a general-purpose thermoplastic engineering plastic having a glass transition temperature of around 150° C., and has excellent mechanical properties such as tensile strength and impact strength, and has numerical stability, heat resistance, and optical transparency.

Polycarbonate is usually manufactured by polycondensation of bisphenol A and phosgene, which are petroleum-based raw materials. For this reason, a method for partially or completely replacing polycarbonate manufacturing raw materials with environmentally friendly components has been requested.

Anhydrosugar alcohol is an eco-friendly material derived from a natural product, and can be prepared by dehydrating a hydrogenated sugar (eg, hexitol) derived from a natural product such as starch. Hydrogenated sugar (also referred to as “sugar alcohol”) refers to a compound obtained by adding hydrogen to a reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer of 2 to 5) ), and is classified into tetritol, pentitol, hexitol and heptitol (with 4, 5, 6 and 7 carbon atoms, respectively) according to the number of carbon atoms. Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, and the like, and sorbitol and mannitol are particularly effective substances. Such anhydrosugar alcohol has attracted a lot of attention due to its various application possibilities, and its use in actual industry is also gradually increasing.

A technology for producing polycarbonate using anhydrosugar alcohol has been proposed. For example, Korean Patent Application Laid-Open No. 10-2009-0018788 discloses a technique for preparing a polycarbonate copolymer using isosorbide, an anhydrosugar alcohol, and a cyclic diol compound as a diol component, and Korean Patent Registration No. 10- 1080669 discloses a technique for preparing a polycarbonate copolymer using isosorbide and a linear diol compound as a diol component.

However, the polycarbonate copolymer prepared by the above prior art has poor mechanical properties (particularly, tensile strength and/or elongation) in spite of the improvement of eco-friendliness, so it is difficult to be practically utilized for engineering plastics.

Therefore, by using anhydrosugar alcohol as a raw material to improve eco-friendliness and at the same time significantly improve mechanical properties such as tensile strength and elongation compared to the prior art, development of a technology capable of producing a polycarbonate copolymer that can be actually used for engineering plastics This is being requested.

An object of the present invention, including units derived from anhydrosugar alcohol and its derivatives, is excellent in environmental friendliness, and at the same time, mechanical properties such as tensile strength and elongation are significantly improved compared to existing anhydrosugar alcohol-containing polycarbonate resins. To provide a coalescence, a method for manufacturing the same, and a molded article including the same.

In order to solve the above technical problem, the present invention provides a repeating unit derived from a diol component; and a repeating unit derived from a carbonic acid diester component, wherein the diol component comprises (a) 69 to 99 mol% of anhydrosugar alcohol and (b) anhydrosugar alcohol-alkylene glycol based on 100 mol% of the total diol component. 1 to 31 mole % of the polycarbonate copolymer.

According to another aspect of the present invention, it comprises the step of reacting a mixture comprising a diol component and a carbonic acid diester component in the presence of a polymerization catalyst, wherein the diol component is based on a total of 100 mol% of the diol component, (a) anhydrosugar alcohol 69 to 99 mol% and (b) anhydrosugar alcohol-alkylene glycol 1 to 31 mol%, a method for preparing a polycarbonate copolymer is provided.

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

The polycarbonate copolymer according to the present invention is prepared by using anhydrosugar alcohol and its derivative anhydrosugar alcohol-alkylene glycol as a raw material, so it is excellent in eco-friendliness and isosorbide and a cyclic or linear diol compound as a diol component It shows significantly improved mechanical properties (particularly, tensile strength and elongation) compared to the existing polycarbonate copolymer prepared using

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

The polycarbonate copolymer of the present invention is prepared from a diol component comprising (a) 69 to 99 mol% of anhydrosugar alcohol and (b) 1 to 31 mol% of anhydrosugar alcohol-alkylene glycol based on 100 mol% of the total diol component. derived repeat units; and a repeating unit derived from a carbonic acid diester component.

In the present invention, the anhydrosugar alcohol may be mono-anhydrosugar alcohol, dianhydrosugar alcohol, or a mixture thereof, which may be obtained in the process of preparing anhydrosugar alcohol by dehydrating hydrogenated sugar. Hydrogenated sugar (also referred to as “sugar alcohol”) refers to a compound obtained by adding hydrogen to a reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer of 2 to 5) ), and is classified into tetritol, pentitol, hexitol and heptitol (with 4, 5, 6 and 7 carbon atoms, respectively) according to the number of carbon atoms. Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, and the like.

The monoanhydrosugar alcohol is an anhydrosugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetraol form having four hydroxyl groups in the molecule. The type of mono-anhydrosugar alcohol that can be used in the present invention is not particularly limited, but may preferably be mono-anhydrosugar hexitol, and more specifically, 1,4-anhydrohexitol, 3,6-anhydrohexitol, 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more thereof.

The dianhydrosugar alcohol is an anhydrosugar alcohol formed by removing two water molecules from the inside of a hydrogenated sugar, has a diol form having two hydroxyl groups in the molecule, and can be prepared by using hexitol derived from starch. Since dianhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, research on its manufacturing method has been conducted with a lot of interest from a long time ago. Among these dianhydrosugar alcohols, isosorbide prepared from sorbitol has the widest current industrial application range. The type of dianhydrosugar alcohol that can be used in the present invention is not particularly limited, but preferably dianhydrosugar hexitol, and more specifically 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol is isosorbide (1,4:3,6-dianhydrosorbitol), isomannide (1,4:3,6-dianhydromannitol), isoi Died (1,4:3,6-dianhydroiditol) or a mixture of two or more thereof, more preferably isosorbide.

In the present invention, the anhydrosugar alcohol-alkylene glycol may be obtained by reacting anhydrosugar alcohol and alkylene oxide.

In one embodiment, the alkylene oxide may be a linear or branched alkylene oxide having 2 to 18 carbon atoms or a branched alkylene oxide having 3 to 18 carbon atoms, and more specifically, ethylene oxide, propylene oxide, or a combination thereof.

In the present invention, “anhydrosugar alcohol-alkylene glycol” refers to a terminal (eg, one or more terminals) of a mono-anhydrosugar alcohol or a dianhydrosugar alcohol, a hydroxyl group and an alkylene oxide (eg, C2-C18 alkylene oxide, more specifically is an adduct obtained by reacting ethylene oxide, propylene oxide, or a mixture thereof), wherein the hydrogen of the hydroxy group at the terminal (eg, at least one terminal) of the monoanhydride alcohol or the dianhydrosugar alcohol is a hydroxy group in the ring-opened form of the alkylene oxide It refers to a compound substituted with an alkyl group.

In one embodiment, the anhydrosugar alcohol-alkylene glycol may be a compound represented by the following formula (A).

[Formula A]

In the above formula (A),

R ₁ is each independently hydrogen or alkyl, more specifically hydrogen or alkyl having 1 to 18 carbon atoms,

m and n are each independently an integer from 0 to 15, and m+n is an integer from 1 to 25.

In another embodiment, the anhydrosugar alcohol-alkylene glycol may be a compound represented by the following Chemical Formula B.

[Formula B]

In Formula B, R ¹ and R ² each independently represent a linear or branched alkylene group having 2 to 18 carbon atoms or a branched alkylene group having 3 to 18 carbon atoms, and m and n each independently represent an integer of 0 to 15, provided that m+n represents the integer of 1-30 or the integer of 1-25.

More specifically, in Formula B, R ¹ and R ² each independently represent an ethylene group, a propylene group, or an isopropylene group, and even more specifically, R ¹ and R ² are the same as each other, and m and n are Each independently represents an integer of 0 to 14, provided that m+n represents an integer of 1 to 25 or an integer of 2 to 15.

In one embodiment, as the anhydrosugar alcohol-alkylene glycol, the following isosorbide-propylene glycol, isosorbide-ethylene glycol, or a mixture thereof may be used.

[Isosorbide-Propylene Glycol]

In the above formula, a and b each independently represent an integer from 0 to 15, provided that a+b is an integer from 1 to 30 or an integer from 1 to 25, and more specifically, a and b are each independently An integer of 0 to 14 is represented, with the proviso that a+b may be an integer of 1 to 25 or an integer of 2 to 15.

[Isosorbide-ethylene glycol]

In the above formula, c and d each independently represent an integer of 0 to 15, with the proviso that c+d may be an integer of 1 to 30 or an integer of 1 to 25, and more specifically, c and d are each independently represents an integer from 0 to 14, with the proviso that c+d may be an integer from 1 to 25 or an integer from 2 to 15.

The diol component included as a repeating unit in the polycarbonate copolymer of the present invention is, based on 100 mol% of the total diol component, (a) 69 to 99 mol% of anhydrosugar alcohol and (b) anhydrosugar alcohol-alkylene glycol 1 to 31 mole %.

If the anhydrosugar alcohol content in the diol component is less than 69 mol% based on 100 mol% of the total diol component, the tensile strength of the copolymer is poor, and conversely, when it exceeds 99 mol%, the elongation of the copolymer is poor.

If the content of anhydrosugar alcohol-alkylene glycol in the diol component is less than 1 mol% based on 100 mol% of the total diol component, the elongation of the copolymer is poor, and conversely, if it exceeds 31 mol%, the tensile strength of the copolymer is decreased get worse

In one embodiment, the anhydrosugar alcohol content in the diol component is 70 mol% or more, 71 mol% or more, 72 mol% or more, 73 mol% or more, 74 mol% or more, 75 based on 100 mol% of the total diol component. mol% or more, 76 mol% or more, 77 mol% or more, 78 mol% or more, 79 mol% or more, or 80 mol% or more, and also 98 mol% or less, 97 mol% or less, 96 mol% or less, 95 mol% or more or less, 94 mol% or less, 93 mol% or less, 92 mol% or less, 91 mol% or less, or 90 mol% or less.

In one embodiment, the content of anhydrosugar alcohol-alkylene glycol in the diol component is 2 mol% or more, 3 mol% or more, 4 mol% or more, 5 mol% or more, 6 mol% based on 100 mol% of the total diol component. % or more, 7 mol% or more, 8 mol% or more, 9 mol% or more, or 10 mol% or more, and also 30 mol% or less, 29 mol% or less, 28 mol% or less, 27 mol% or less, 26 mol% or less , 25 mol% or less, 24 mol% or less, 23 mol% or less, 22 mol% or less, 21 mol% or less, or 20 mol% or less.

In one embodiment, the diol component may further include an additional diol selected from (c) an aliphatic diol, an anhydrosugar alcohol and an alicyclic diol other than an anhydrosugar alcohol-alkylene glycol, an aromatic diol, or a mixture thereof. have.

In one embodiment, the aliphatic diol is ethylene glycol, propanediol (eg, 1,2-propanediol and 1,3-propanediol, etc.), butanediol (eg, 1,2-butanediol, 1,3) -butanediol and 1,4-butanediol, etc.), pentanediol (eg, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol and 1,5-pentanediol, etc.), hexanediol (For example, 1,2-hexanetanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, etc.), diethylene glycol, triethylene glycol , tetraethylene glycol or a mixture thereof may be selected, but is not limited thereto.

In one embodiment, the alicyclic diol other than the anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol is cyclohexanedimethanol (eg, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, etc.), 2-methyl-1,4-cyclohexanediol, decalindimethanol (e.g., 2,6-decalindimethanol, 1,5-decalindimethanol and 2,3 -decalin dimethanol, etc.), norbornane dimethanol (for example, 2,3-norbornane dimethanol and 2,5-norbornane dimethanol, etc.), adamantanediol (for example, 1,2-a damantanediol, 1,3-adamantanediol, 1,4-adamantanediol, etc.) or a mixture thereof, but is not limited thereto.

In one embodiment, the aromatic diol is 2,2-bis(4-hydroxyphenyl)propane [hereinafter referred to as bisphenol A], 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane , 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4'-dihydroxy-diphenylmethane, bis (4-hydroxy Phenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1- Bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-di Hydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether, 9,9-bis ( 4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy-2-methyl)phenyl)fluorene, 9,9-bis(4-hydroxy It may be selected from phenyl)fluorene, 9,9-bis(4-hydroxy-2-methylphenyl)fluorene, or a mixture thereof, but is not limited thereto.

The (c) additional diol compound used in the present invention is not limited to the above examples, and one type of the additional diol compound may be used alone, or two or more types may be mixed and used.

In one embodiment, the (c) additional diol content in the diol component is 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, 5 mol% based on 100 mol% of the total diol component. % or more, 6 mol% or more, 7 mol% or more, 8 mol% or more, 9 mol% or more, or 10 mol% or more, and also 30 mol% or less, 29 mol% or less, 28 mol% or less, 27 mol% or less , 26 mol% or less, 25 mol% or less, 24 mol% or less, 23 mol% or less, 22 mol% or less, 21 mol% or less, or 20 mol% or less.

In one embodiment, when the diol component further comprises the (c) additional diol, based on 100 mol% of the total diol component, (a) the content of anhydrosugar alcohol may be 69 to 98 mol%, ( b) The content of the anhydrosugar alcohol-alkylene glycol may be 1 to 30 mol%, and the content of the (c) additional diol may be 1 to 30 mol%.

In the present invention, the type of the carbonate diester component is not limited as long as the effect of the present invention is not lost, but, for example, it may be selected from dialkyl carbonate, diaryl carbonate, alkylene carbonate, or a combination thereof. .

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

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

In one embodiment, the carbonic acid diester component may be selected from compounds represented by the following formula (C).

[Formula C]

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

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

In preparing the polycarbonate copolymer of the present invention, the carbonic acid diester component may be used in a molar equivalent of 0.90 to 1.10, preferably in a molar equivalent of 0.96 to 1.04, based on 1 molar equivalent of the total diol component. have. If the molar equivalent of the carbonic acid diester component is less than 0.90 with respect to 1 molar equivalent of the total diol component, the OH group at the end of the prepared polycarbonate copolymer is increased, and the thermal stability of the polycarbonate copolymer is deteriorated, or a high molecular weight of a desired level cannot be obtained, and if the molar equivalent of the carbonic acid diester component is more than 1.10, the rate of the transesterification reaction is reduced under the same conditions, or it is not possible to obtain a high molecular weight of a desired level, but also the residual carbonic acid in the prepared polycarbonate copolymer The amount of diester is increased, and due to such residual diester carbonate, an odor is generated during molding using the polycarbonate copolymer, or it is a cause of bad smell of the molded article, which is not preferable.

In one embodiment, the polycarbonate copolymer of the present invention includes a repeating unit having a structure of Formula 1 below; and a repeating unit having the structure of Formula 2 below.

[Formula 1]

[Formula 2]

In Formula 2,

Also, in one embodiment, the polycarbonate copolymer of the present invention may further include a repeating unit having a structure of Formula 3 below.

[Formula 3]

In Formula 3,

R is an alkylene group having 2 to 12 carbon atoms, a cycloalkylene group having 3 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, or a combination thereof.

The present invention also comprises the step of reacting a mixture comprising a diol component and a carbonic acid diester component in the presence of a polymerization catalyst, wherein the diol component is based on a total of 100 mol% of the diol component, (a) anhydrosugar alcohol 69 to 99 It provides a method for preparing a polycarbonate copolymer, comprising 1 to 31 mol% of anhydrosugar alcohol-alkylene glycol and (b) anhydrous sugar alcohol.

In one embodiment, the diol component used in the method for preparing the polycarbonate copolymer is (c) an aliphatic diol, an anhydrosugar alcohol and an anhydrosugar alcohol- an alicyclic diol other than an alkylene glycol, or a mixture thereof. It may further include a diol of.

The types and amounts of anhydrosugar alcohol, anhydrosugar alcohol-alkylene glycol, additional diol and diester carbonate components usable in the method for producing the polycarbonate copolymer of the present invention are as described above.

In the polycarbonate copolymer manufacturing method of the present invention, a transesterification catalyst may be used as the polymerization catalyst, and for example, an alkali metal salt compound, an alkaline earth metal salt compound, or a mixture thereof may be used.

In one embodiment, together with a polymerization catalyst selected from an alkali metal salt compound, an alkaline earth metal salt compound, or a mixture thereof, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, an amine compound, or a mixture thereof. Although it is also possible to use the compounds together, it is preferable to use the polymerization catalyst alone without the auxiliary basic compound used.

In one embodiment, the alkali metal salt compound used as the polymerization catalyst includes, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, Potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, hydride Cesium boron, sodium boron phenylide, potassium boron phenylide, lithium boron phenylide, cesium boron phenylide, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, lithium hydrogen phosphate, Cesium hydrogen phosphate, disodium hydrogen phosphite, potassium hydrogen phosphite, lithium hydrogen phosphite, 2 cesium hydrogen phosphite, disodium phenyl phosphate, dipotassium phenyl phosphate, dilithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, lithium, alcoholate, phenolate of cesium, disodium salt, dipotassium salt, dilithium salt, or dicesium salt of bisphenol A; and the like.

In one embodiment, the alkaline earth metal salt compound used as the polymerization catalyst includes, for example, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate. , barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, or strontium stearate.

The alkali metal salt compound and alkaline earth metal salt compound mentioned above may be used individually by 1 type, and may use 2 or more types together.

In one embodiment, examples of the basic boron compound used in combination with the polymerization catalyst described above include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethyl Sodium salts, potassium salts, lithium salts such as boron, triethylbenzylboron, triethylphenylboron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron and butyltriphenylboron , calcium salt, barium salt, magnesium salt, or strontium salt.

In one embodiment, examples of basic phosphorus compounds include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, or A quaternary phosphonium salt etc. are mentioned.

In one embodiment, examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium Hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide , tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, or butyltriphenylammonium hydroxide.

In one embodiment, examples of the amine-based compound include 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxy and pyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole or aminoquinoline.

The above-mentioned basic compound used together with a polymerization catalyst may be used individually by 1 type, and may use 2 or more types together.

When the polycarbonate copolymer according to the present invention is used, the physical properties are significantly improved compared to the existing polycarbonate copolymer prepared by using isosorbide and a cyclic or linear diol compound as a diol component while being excellent in eco-friendliness, especially , it is possible to obtain a molded article exhibiting improved tensile strength and elongation at the same time.

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

The molded article may be manufactured by extrusion or injection molding of the polycarbonate copolymer of the present invention.

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 thereto.

[실시예][Example]

Example 1

513.2 mmol of isosorbide, ethylene oxide of isosorbide in a 250 ml 4-necked reactor including a stirrer, a thermometer and a heater that a nitrogen tube, a trap for removing by-products and a vacuum pump for pressure reduction are connected, and the stirring torque can be checked 57.0 mmol of the 1 mol adduct, 570.2 mmol of diphenyl carbonate, and magnesium acetate tetrahydrate (100 ppm of the total amount of diol used) were added, and the temperature was raised to 100° C. under a nitrogen atmosphere, and the reaction raw materials were dissolved with stirring as necessary. After dissolving the reaction raw material, the reactor temperature was raised to 160° C. and reacted for 1 hour, and then phenol, a by-product, was partially removed while the pressure was reduced from normal pressure to a level of 20 torr.

Then, the temperature of the reactor was raised to 240° C. and the pressure was reduced to a pressure of 5 torr or less, and an additional reaction was performed for 1 hour. After the stirring torque of the stirrer reached a predetermined stirring torque, the reaction was terminated. As a result of the reaction, about 99 g of a transparent polycarbonate copolymer having a number average molecular weight of 29,600 g/mol, a polydispersity index (PDI) of 2.0, and a glass transition temperature of 152° C. was obtained.

Five identical tensile specimens were prepared according to ASTM D638 using the obtained polycarbonate resin, and the tensile strength and elongation of the five tensile specimens were measured using a universal testing machine (UTM). As a result, five tensile strengths The average tensile strength of the measured values was 97 MPa, and the average elongation of the five measured values of elongation was 18%, and the results are shown in Table 1 below.

Example 2

Change the content of isosorbide from 513.2 mmol to 479.0 mmol of isosorbide, change the content of diphenyl carbonate from 570.2 mmol to 532.2 mmol, and 57.0 mmol of the ethylene oxide 1 mole adduct of isosorbide with isosorbide Poly with a number average molecular weight of 30,800 g/mol, a PDI of 2.2, and a glass transition temperature of 142° C. was carried out in the same manner as in Example 1, except that 53.2 mmol of the 5 mol adduct of sorbide was used. 101 g of carbonate copolymer was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 94 MPa and the average elongation was 22%, and the results are shown in Table 1 below.

Example 3

The content of isosorbide was changed from 513.2 mmol to 479.0 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 532.2 mmol, and 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide was replaced with ethylene of isosorbide. 112 g of polycarbonate copolymer having a number average molecular weight of 30,900 g/mol, a PDI of 3.2, and a glass transition temperature of 132° C. in the same manner as in Example 1, except that 53.2 mmol of the oxide 10 mol adduct was used. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 89 MPa and the average elongation was 26%, and the results are shown in Table 1 below.

Example 4

The content of isosorbide was changed from 513.2 mmol to 479.0 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 532.2 mmol, and 57.0 mmol of the ethylene oxide 1 mole adduct of isosorbide was replaced with propylene of isosorbide. 103 g of a polycarbonate copolymer having a number average molecular weight of 30,500 g/mol, a PDI of 2.3, and a glass transition temperature of 145° C. in the same manner as in Example 1, except that 53.2 mmol of the oxide 5 mol adduct was used. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 95 MPa and the average elongation was 24%, and the results are shown in Table 1 below.

Example 5

The content of isosorbide was changed from 513.2 mmol to 376.4 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 418.2 mmol, and 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide was replaced with propylene of isosorbide. 126 g of a polycarbonate copolymer having a number average molecular weight of 31,800 g/mol, a PDI of 3.9, and a glass transition temperature of 125° C. in the same manner as in Example 1, except that 41.8 mmol of the oxide 25 mol adduct was used. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 83 MPa and the average elongation was 35%, and the results are shown in Table 1 below.

Example 6

The content of isosorbide was changed from 513.2 mmol to 342.1 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 488.8 mmol, and 57.0 mmol of the ethylene oxide 1 mole adduct of isosorbide was replaced with ethylene of isosorbide. 112 g of a polycarbonate copolymer having a number average molecular weight of 30,000 g/mol, a PDI of 2.2, and a glass transition temperature of 113° C. in the same manner as in Example 1, except that 146.6 mmol of the oxide 5 mol adduct was used. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 86 MPa and the average elongation was 29%, and the results are shown in Table 1 below.

Example 7

The content of isosorbide is changed from 513.2 mmol to 205.3 mmol, the content of diphenyl carbonate is changed from 570.2 mmol to 293.3 mmol, and 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide is replaced with ethylene of isosorbide. 140 g of polycarbonate copolymer having a number average molecular weight of 31,300 g/mol, a PDI of 3.6, and a glass transition temperature of 60° C. in the same manner as in Example 1, except that 88.0 mmol of the oxide 25 mol adduct was used. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 80 MPa and the average elongation was 42%, and the results are shown in Table 1 below.

Example 8

The content of isosorbide was changed from 513.2 mmol to 376.4 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 537.6 mmol, and 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide was replaced with propylene of isosorbide. 98 g of a polycarbonate copolymer having a number average molecular weight of 30,100 g/mol, a PDI of 2.1, and a glass transition temperature of 134° C. in the same manner as in Example 1, except that 161.3 mmol of the oxide 1 mole adduct was used. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 92 MPa and the average elongation was 20%, and the results are shown in Table 1 below.

Example 9

The content of isosorbide was changed from 513.2 mmol to 342.1 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 488.8 mmol, and 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide was replaced with propylene of isosorbide. 120 g of a polycarbonate copolymer having a number average molecular weight of 30,300 g/mol, a PDI of 2.4, and a glass transition temperature of 110° C. in the same manner as in Example 1, except that 146.6 mmol of the oxide 5 mol adduct was used. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 87 MPa and the average elongation was 31%, and the results are shown in Table 1 below.

Example 10

The content of isosorbide was changed from 513.2 mmol to 273.7 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 391.0 mmol, and 57.0 mmol of the ethylene oxide 1 mole adduct of isosorbide was replaced with propylene of isosorbide. 130 g of a polycarbonate copolymer having a number average molecular weight of 30,200 g/mol, a PDI of 3.3, and a glass transition temperature of 82° C. in the same manner as in Example 1, except that 117.3 mmol of the oxide 10 mol adduct was used. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 84 MPa and the average elongation was 35%, and the results are shown in Table 1 below.

Example 11

Same as Example 1, except that 28.5 mmol of ethylene oxide 5 mol adduct of isosorbide and 28.5 mmol of 1,4-cyclohexanedimethanol were used instead of 57.0 mmol of 1 mol adduct of ethylene oxide of isosorbide 100 g of a polycarbonate copolymer having a number average molecular weight of 30,000 g/mol, a PDI of 2.0, and a glass transition temperature of 135° C. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 95 MPa and the average elongation was 19%, and the results are shown in Table 1 below.

Example 12

A number average was carried out in the same manner as in Example 1, except that 28.5 mmol of an ethylene oxide 5 mole adduct of isosorbide and 28.5 mmol of ethylene glycol were used instead of 57.0 mmol of an ethylene oxide 1 mole adduct of isosorbide. 98 g of a polycarbonate copolymer having a molecular weight of 30,500 g/mol, a PDI of 2.1, and a glass transition temperature of 140°C was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 94 MPa and the average elongation was 16%, and the results are shown in Table 1 below.

Example 13

It was carried out in the same manner as in Example 1, except that 28.5 mmol of an ethylene oxide 5-mol adduct of isosorbide and 28.5 mmol of 1,4-butanediol were used instead of 57.0 mmol of an ethylene oxide 1-mol adduct of isosorbide Thus, 99 g of a polycarbonate copolymer having a number average molecular weight of 30,400 g/mol, a PDI of 2.0, and a glass transition temperature of 130° C. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 89 MPa and the average elongation was 20%, and the results are shown in Table 1 below.

Example 14

In the same manner as in Example 1, except that 28.5 mmol of ethylene oxide 5 mol adduct of isosorbide and 28.5 mmol of 1,6-hexanediol were used instead of 57.0 mmol of 1 mol adduct of ethylene oxide of isosorbide 99 g of a polycarbonate copolymer having a number average molecular weight of 31,000 g/mol, a PDI of 2.2, and a glass transition temperature of 122° C. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 90 MPa and the average elongation was 25%, and the results are shown in Table 1 below.

Example 15

The content of isosorbide was changed from 513.2 mmol to 376.4 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 537.6 mmol, and 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide was replaced with propylene of isosorbide. A number average molecular weight of 30,600 g/mol, a PDI of 2.3, and a glass transition were carried out in the same manner as in Example 1, except that 53.8 mmol of the oxide 5 mol adduct and 107.5 mmol of 1,4-cyclodimethanol were used. 103 g of a polycarbonate copolymer having a temperature of 114°C was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 88 MPa and the average elongation was 28%, and the results are shown in Table 1 below.

Example 16

The content of isosorbide was changed from 513.2 mmol to 376.4 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 537.6 mmol, and 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide was replaced with propylene of isosorbide. A number average molecular weight of 30,200 g/mol, a PDI of 2.4, and a glass transition temperature of 105° C. was carried out in the same manner as in Example 1, except that 53.8 mmol of an oxide 5 mol adduct and 107.5 mmol of ethylene glycol were used. 95 g of a polycarbonate copolymer was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 85 MPa and the average elongation was 22%, and the results are shown in Table 1 below.

Example 17

The content of isosorbide was changed from 513.2 mmol to 376.4 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 537.6 mmol, and 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide was replaced with propylene of isosorbide. A number average molecular weight of 30,100 g/mol, a PDI of 2.2, and a glass transition temperature were carried out in the same manner as in Example 1 except that 53.8 mmol of the oxide 5 mol adduct and 107.5 mmol of 1,4-butanediol were used. 99 g of a polycarbonate copolymer at 110° C. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 86 MPa and the average elongation was 27%, and the results are shown in Table 1 below.

Example 18

The content of isosorbide was changed from 513.2 mmol to 376.4 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 537.6 mmol, and 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide was replaced with propylene of isosorbide. A number average molecular weight of 30,600 g/mol, a PDI of 2.2, and a glass transition temperature were carried out in the same manner as in Example 1, except that 53.8 mmol of the oxide 5 mol adduct and 107.5 mmol of 1,6-hexanediol were used. 102 g of a polycarbonate copolymer having a value of 88°C was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 85 MPa and the average elongation was 30%, and the results are shown in Table 1 below.

Example 19

The content of isosorbide is changed from 513.2 mmol to 581.6 mmol, the content of diphenyl carbonate is changed from 570.2 mmol to 587.5 mmol, and 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide is replaced with isosorbide A polycarbonate copolymer having a number average molecular weight of 30,000 g/mol, a PDI of 1.9, and a glass transition temperature of 158° C. was carried out in the same manner as in Example 1, except that 5.9 mmol of the 5 mol adduct of ethylene oxide was used. 100 g were obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 105 MPa and the average elongation was 14%, and the results are shown in Table 1 below.

Example 20

The content of isosorbide is changed from 513.2 mmol to 581.6 mmol of isosorbide, the content of diphenyl carbonate is changed from 570.2 mmol to 587.5 mmol, and 57.0 mmol of ethylene oxide 1 mole adduct of isosorbide is replaced with isosorbide. Poly with a number average molecular weight of 30,100 g/mol, a PDI of 1.9, and a glass transition temperature of 160° C. was carried out in the same manner as in Example 1, except that 5.9 mmol of a 5 mol adduct of sorbide was used. 100 g of carbonate copolymer was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 106 MPa and the average elongation was 13%, and the results are shown in Table 1 below.

Example 21

The content of isosorbide was changed from 513.2 mmol to 444.8 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 556.0 mmol, and the content of 1 mole adduct of ethylene oxide of isosorbide was changed from 57.0 mmol to 111.2 mmol 97 g of a polycarbonate copolymer having a number average molecular weight of 30,000 g/mol, a PDI of 2.0, and a glass transition temperature of 146° C. was obtained in the same manner as in Example 1, except for that. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 95 MPa and the average elongation was 22%, and the results are shown in Table 1 below.

Example 22

The content of isosorbide was changed from 513.2 mmol to 410.6 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 513.2 mmol, and 57.0 mmol of the ethylene oxide 1 mole adduct of isosorbide was replaced with ethylene of isosorbide. 107 g of polycarbonate copolymer having a number average molecular weight of 30,300 g/mol, a PDI of 2.4, and a glass transition temperature of 125° C. in the same manner as in Example 1, except that 102.6 mmol of the oxide 5 mol adduct was used. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 91 MPa and the average elongation was 28%, and the results are shown in Table 1 below.

Example 23

The content of isosorbide was changed from 513.2 mmol to 342.1 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 427.7 mmol, and 57.0 mmol of the ethylene oxide 1 mole adduct of isosorbide was replaced with propylene of isosorbide. 119 g of a polycarbonate copolymer having a number average molecular weight of 30,400 g/mol, a PDI of 3.0, and a glass transition temperature of 104° C. in the same manner as in Example 1, except that 85.5 mmol of the oxide 10 mol adduct was used. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 85 MPa and the average elongation was 26%, and the results are shown in Table 1 below.

Example 24

The content of isosorbide was changed from 513.2 mmol to 239.5 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 299.4 mmol, and 57.0 mmol of the ethylene oxide 1 mole adduct of isosorbide was replaced with propylene of isosorbide. 135 g of a polycarbonate copolymer having a number average molecular weight of 30,800 g/mol, a PDI of 3.5, and a glass transition temperature of 81° C. in the same manner as in Example 1, except that 59.9 mmol of the oxide 25 mol adduct was used. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 82 MPa and the average elongation was 32%, and the results are shown in Table 1 below.

[비교예][Comparative example]

Comparative Example 1

A number average molecular weight of 30,300 g/mol was carried out in the same manner as in Example 1, except that 57.0 mmol of 1,4-cyclohexanedimethanol was used instead of 57.0 mmol of the 1 mol adduct of ethylene oxide of isosorbide. , PDI is 2.2, and a glass transition temperature of 94 g of a polycarbonate copolymer of 156 ℃ was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 82 MPa and the average elongation was 8%, and the results are shown in Table 2 below.

Comparative Example 2

In the same manner as in Example 1, except that 57.0 mmol of ethylene glycol was used instead of 57.0 mmol of 1 mol adduct of ethylene oxide of isosorbide, the number average molecular weight was 30,200 g/mol, the PDI was 2.1, 90 g of a polycarbonate copolymer having a glass transition temperature of 158° C. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 77 MPa and the average elongation was 3%, and the results are shown in Table 2 below.

Comparative Example 3

In the same manner as in Example 1, except that 57.0 mmol of 1,4-butanediol was used instead of 57.0 mmol of 1 mol adduct of ethylene oxide of isosorbide, the number average molecular weight was 30,400 g/mol, and PDI was 2.1, and 92 g of a polycarbonate copolymer having a glass transition temperature of 157° C. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 67 MPa and the average elongation was 2%, and the results are shown in Table 2 below.

Comparative Example 4

It was carried out in the same manner as in Example 1, except that 57.0 mmol of 1,6-hexanediol was used instead of 57.0 mmol of 1 mol adduct of ethylene oxide of isosorbide, and the number average molecular weight was 31,000 g/mol, PDI is 2.3, and 93 g of a polycarbonate copolymer having a glass transition temperature of 147° C. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 59 MPa and the average elongation was 2%, and the results are shown in Table 2 below.

Comparative Example 5

The content of isosorbide is changed from 513.2 mmol to 410.6 mmol, the content of diphenyl carbonate is changed from 570.2 mmol to 586.5 mmol, and 1,4-cyclo is replaced by 57.0 mmol of 1 mole adduct of ethylene oxide of isosorbide. 96 g of a polycarbonate copolymer having a number average molecular weight of 30,100 g/mol, a PDI of 2.1, and a glass transition temperature of 130° C. was obtained in the same manner as in Example 1, except that 176.0 mmol of hexanedimethanol was used. did. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 80 MPa and the average elongation was 10%, and the results are shown in Table 2 below.

Comparative Example 6

The content of isosorbide was changed from 513.2 mmol to 444.8 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 635.4 mmol, and 190.6 mmol of ethylene glycol was added instead of 57.0 mmol of the ethylene oxide 1 mole adduct of isosorbide. Except for that, it was carried out in the same manner as in Example 1 to obtain 90 g of a polycarbonate copolymer having a number average molecular weight of 29,500 g/mol, a PDI of 2.2, and a glass transition temperature of 124°C. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 72 MPa and the average elongation was 5%, and the results are shown in Table 2 below.

Comparative Example 7

The content of isosorbide was changed from 513.2 mmol to 410.6 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 586.5 mmol, and 1,4-butanediol was replaced by 57.0 mmol of the 1 mole adduct of ethylene oxide of isosorbide. 89 g of a polycarbonate copolymer having a number average molecular weight of 30,400 g/mol, a PDI of 2.2, and a glass transition temperature of 119° C. was obtained in the same manner as in Example 1, except that 176.0 mmol was used. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 65 MPa and the average elongation was 4%, and the results are shown in Table 2 below.

Comparative Example 8

The content of isosorbide is changed from 513.2 mmol to 410.6 mmol, the content of diphenyl carbonate is changed from 570.2 mmol to 586.5 mmol, and 1,6-hexane is replaced with 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide. 92 g of a polycarbonate copolymer having a number average molecular weight of 31,100 g/mol, a PDI of 2.1, and a glass transition temperature of 96° C. was obtained in the same manner as in Example 1, except that 176.0 mmol of the diol was used. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 52 MPa and the average elongation was 7%, and the results are shown in Table 2 below.

Comparative Example 9

Change the content of isosorbide from 513.2 mmol to 479.0 mmol, and change the content of diphenyl carbonate from 570.2 mmol to 598.7 mmol, 1,4- in place of 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide 92 g of a polycarbonate copolymer having a number average molecular weight of 29,400 g/mol, a PDI of 2.0, and a glass transition temperature of 138° C. was obtained in the same manner as in Example 1, except that 119.8 mmol of butanediol was used. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 74 MPa and the average elongation was 6%, and the results are shown in Table 2 below.

Comparative Example 10

The content of isosorbide is changed from 513.2 mmol to 479.0 mmol, the content of diphenyl carbonate is changed from 570.2 mmol to 598.7 mmol, and 1,6-hexane is replaced with 57.0 mmol of the 1 mole adduct of ethylene oxide of isosorbide. 96 g of a polycarbonate copolymer having a number average molecular weight of 30,200 g/mol, a PDI of 1.9, and a glass transition temperature of 123° C. was obtained in the same manner as in Example 1, except that 119.8 mmol of the diol was used. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 63 MPa and the average elongation was 5%, and the results are shown in Table 2 below.

Comparative Example 11

The content of isosorbide was changed from 513.2 mmol to 615.9 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 618.9 mmol, and 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide was replaced with ethylene of isosorbide. 104 g of a polycarbonate copolymer having a number average molecular weight of 29,900 g/mol, a PDI of 1.8, and a glass transition temperature of 160° C. in the same manner as in Example 1, except that 3.1 mmol of the oxide 5 mol adduct was used. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 81 MPa and the average elongation was 3%, and the results are shown in Table 2 below.

Comparative Example 12

The content of isosorbide was changed from 513.2 mmol to 615.9 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 618.9 mmol, and 57.0 mmol of the ethylene oxide 1 mole adduct of isosorbide was replaced with isosorbide. A polycarbonate copolymer having a number average molecular weight of 30,100 g/mol, a PDI of 1.9, and a glass transition temperature of 160° C. was carried out in the same manner as in Example 1, except that 3.1 mmol of the 5 mol adduct of propylene oxide was used. 105 g of coalescence was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 82 MPa and the average elongation was 2%, and the results are shown in Table 2 below.

Comparative Example 13

The content of isosorbide was changed from 513.2 mmol to 342.1 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 503.1 mmol, and 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide was replaced with ethylene of isosorbide. 117 g of polycarbonate copolymer having a number average molecular weight of 30,200 g/mol, a PDI of 2.3, and a glass transition temperature of 112° C. in the same manner as in Example 1, except that 161.0 mmol of the oxide 5 mol adduct was used. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 71 MPa and the average elongation was 11%, and the results are shown in Table 2 below.

Comparative Example 14

The content of isosorbide was changed from 513.2 mmol to 342.1 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 503.1 mmol, and 57.0 mmol of the ethylene oxide 1 mole adduct of isosorbide was replaced with propylene of isosorbide. 130 g of a polycarbonate copolymer having a number average molecular weight of 30,000 g/mol, a PDI of 2.4, and a glass transition temperature of 115° C. in the same manner as in Example 1, except that 161.0 mmol of the oxide 5 mol adduct was used. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 70 MPa and the average elongation was 10%, and the results are shown in Table 2 below.

Comparative Example 15

The content of isosorbide was changed from 513.2 mmol to 307.9 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 473.7 mmol, and 57.0 mmol of the ethylene oxide 1 molar adduct of isosorbide was replaced with propylene of isosorbide. It was carried out in the same manner as in Example 1, except that 94.8 mmol of the oxide 5 mol adduct and 71.1 mmol of 1,4-cyclohexanedimethanol were used, the number average molecular weight was 30,000 g/mol, the PDI was 2.3, and the free 105 g of a polycarbonate copolymer having a transition temperature of 127° C. was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 76 MPa and the average elongation was 12%, and the results are shown in Table 2 below.

Comparative Example 16

The content of isosorbide was changed from 513.2 mmol to 307.9 mmol, the content of diphenyl carbonate was changed from 570.2 mmol to 473.7 mmol, and propylene oxide of isosorbide was replaced by 57.0 mmol of the 1 mole adduct of ethylene oxide of isosorbide. A number average molecular weight of 29,600 g/mol, a PDI of 2.2, and a glass transition temperature of 120 was carried out in the same manner as in Example 1, except that 94.8 mmol of the 5-mol adduct and 71.1 mmol of 1,4-butanediol were used. 100 g of a polycarbonate copolymer having a temperature of ℃ was obtained. As a result of measuring the tensile strength and elongation of the obtained polycarbonate copolymer in the same manner as in Example 1, the average tensile strength was 72 MPa and the average elongation was 9%, and the results are shown in Table 2 below.

[성분 설명][Ingredient Description]

ISB: isosorbide

EI 1: 1 mole adduct of ethylene oxide of isosorbide

EI 5: Ethylene oxide 5 molar adduct of isosorbide

EI 10: 10 mole adduct of ethylene oxide of isosorbide

EI 25: 25 mole adduct of ethylene oxide of isosorbide

PI 1: 1 mole adduct of propylene oxide of isosorbide

PI 5: Propylene oxide 5 molar adduct of isosorbide

PI 10: 10 molar adduct of propylene oxide of isosorbide

PI 25: 25 mole adduct of propylene oxide of isosorbide

1,4-CHDM: 1,4-cyclohexanedimethanol

EG: ethylene glycol

1,4-BD: 1,4-butanediol

1,6-HD: 1,6-hexanediol

DPC: diphenyl carbonate

Mg(Ac) ₂ .4H ₂ O: magnesium acetate tetrahydrate

[물성 측정 방법][Method of measuring physical properties]

- Number average molecular weight (Mn) and polydispersity index (PDI): Each of the polycarbonate copolymers prepared in Examples and Comparative Examples was dissolved in chloroform in an amount of 1 to 3% by weight, followed by gel permeation chromatography (Gel Permeation) A number average molecular weight (Mn) and a polydispersity index (PDI) were measured using a Chromatography, GPC) apparatus (Agilent, Inc.). The column used at this time was PLgel 5μm MIXED-D 300 x 7.5mm (Agilent, Inc.), the column temperature was 35°C, and the developing solvent used was chloroform, which was flowed at 0.5 mL/min, and the standard material was polystyrene ( Aldrich Co.) was used.

-Glass transition temperature (Tg): Differential scanning calorimetry (DSC Q100, TA Instrument) was used, and specifically, the temperature was raised from 20 °C to 300 °C at a temperature increase rate of 10 °C min, and then rapidly cooled to 20 °C, then 300 again The glass transition temperature was measured by raising the temperature to ℃.

- Tensile strength and elongation: According to ASTM D638, tensile strength and elongation were measured at a rate of 5 mm/min using UTM (Instron, Instron 5967). Specifically, a total of five tensile strength and elongation were measured for each specimen prepared in Examples and Comparative Examples, and the average value of the five measurement results of each specimen was calculated.

As shown in Table 1, the polycarbonate copolymers of Examples 1 to 24 according to the present invention all exhibited a high average tensile strength of 80 MPa or more and a high average elongation of 13% or more.

On the other hand, as shown in Table 2, in the case of the polycarbonate copolymers of Comparative Examples 1 to 10, the average elongation was 10% or less, which was poor compared to the polycarbonate copolymer of the Example, and the average tensile strength was also up to 82 MPa. It was inferior to the polycarbonate copolymer. In addition, in the case of the polycarbonate copolymers of Comparative Examples 11 and 12, the average elongation was very poor at 3% or less, and in the case of the polycarbonate copolymers of Comparative Examples 13 to 16, the average tensile strength was poor at 76 MPa or less.

Claims

repeating units derived from a diol component; and a repeating unit derived from a carbonic acid diester component;

The diol component comprises (a) 69 to 99 mol% of anhydrosugar alcohol and (b) 1 to 31 mol% of anhydrosugar alcohol-alkylene glycol based on 100 mol% of the total diol component,

polycarbonate copolymer.
According to claim 1, wherein the anhydrosugar alcohol is isosorbide (1,4:3,6-dianhydrosorbitol), isomannide (1,4:3,6-dianhydromannitol), isoidide (1,4) : 3,6-dianhydroiditol) or a mixture thereof, a polycarbonate copolymer.
The polycarbonate copolymer according to claim 1, wherein the anhydrosugar alcohol-alkylene glycol is obtained by reacting anhydrosugar alcohol and alkylene oxide.
The polycarbonate copolymer according to claim 3, wherein the alkylene oxide is a linear or branched alkylene oxide having 2 to 18 carbon atoms or 3 to 18 carbon atoms.
The poly according to claim 1, wherein the diol component further comprises (c) an additional diol selected from aliphatic diols, cycloaliphatic diols other than anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol, aromatic diol or mixtures thereof. carbonate copolymer.
According to claim 5, wherein the diol component, based on 100 mol% of the total diol component, (a) 69 to 98 mol% of anhydrosugar alcohol, (b) 1 to 30 mol% of anhydrosugar alcohol-alkylene glycol, and (c) ) further from 1 to 30 mole % of a diol.
The polycarbonate copolymer of claim 1 , wherein the carbonic acid diester component is selected from dialkyl carbonates, diaryl carbonates, alkylene carbonates, or combinations thereof.
The polycarbonate copolymer according to claim 1, wherein the carbonic acid diester component is selected from compounds represented by the following formula (C):

[Formula C]

In the formula (C), A and A' are each independently selected from an unsubstituted or halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 25 carbon atoms, A and A' is the same as or different from each other.
According to claim 1, wherein the repeating unit having the structure of the formula (1); And a repeating unit having a structure of Formula 2; Containing, polycarbonate copolymer:

[Formula 1]

[Formula 2]

In Formula 2,

R 1 is each independently hydrogen or alkyl,

m and n are each independently an integer from 0 to 15, and m+n is an integer from 1 to 25.
The polycarbonate copolymer according to claim 9, further comprising a repeating unit having a structure of the following formula (3):

[Formula 3]

In Formula 3,

R is an alkylene group having 2 to 12 carbon atoms, a cycloalkylene group having 3 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, or a combination thereof.
A step of reacting a mixture comprising a diol component and a carbonic acid diester component in the presence of a polymerization catalyst,

The diol component comprises (a) 69 to 99 mol% of anhydrosugar alcohol and (b) 1 to 31 mol% of anhydrosugar alcohol-alkylene glycol based on 100 mol% of the total diol component,

A method for producing a polycarbonate copolymer.
12. The poly according to claim 11, wherein the diol component further comprises (c) an additional diol selected from aliphatic diols, cycloaliphatic diols other than anhydrosugar alcohol and anhydrosugar alcohol-alkylene glycol, aromatic diol or mixtures thereof. A method for preparing a carbonate copolymer.
The method according to claim 12, wherein the diol component comprises (a) 69 to 98 mol% of anhydrosugar alcohol, (b) 1 to 30 mol% of anhydrosugar alcohol-alkylene glycol, and (c) based on 100 mol% of the total diol component. ) further comprising 1 to 30 mole % of a diol.
A molded article comprising the polycarbonate copolymer of any one of claims 1 to 10.