KR102200882B1 - Manufacturing method of polyester-carbonate resin with improved heat resistance and impact strength - Google Patents

Abstract

Disclosed are a polyester-carbonate copolymer having excellent heat resistance of polyarylate and excellent in impact strength, and a method for preparing a polyester-carbonate copolymer capable of alleviating existing harsh reaction conditions and reducing reaction time. The present invention comprises the steps of: (a) esterifying a monomer mixture including a compound represented by Chemical Formula 3 and a compound represented by Chemical Formula 4 to polymerize to a form represented by Chemical Formula 5; And (b) adding and reacting a compound represented by Formula 4 and a monomer represented by Formula 6 to produce an oligomer in the form represented by Formula 7 and condensation polymerization; a method for producing a polyester-carbonate copolymer comprising to provide.

Description

Manufacturing method of polyester-carbonate resin with improved heat resistance and impact strength}

The present invention relates to a method for producing a polyester-carbonate copolymer, and more particularly, to a method for producing a polyester-carbonate copolymer having improved heat resistance and impact strength.

Polyarylate (PAR) resin is generally produced by interfacial polymerization of bisphenol A and terephthaloyl chloride (TPC), and has excellent heat resistance and is transparent. However, due to its high heat resistance, processability is very inferior to other engineering plastic resins.

In order to improve the processing performance of such polyarylate resins, transparent engineering plastic resins having excellent processing performance such as polycarbonate (PC) are blended in a compound form and used. However, since the refractive indices of polycarbonate and polyarylate are similar but not the same, optical performances such as transmittance and haze when used in combination are lower than those of the original resins, and polycarbonate and polyarylate are synthesized respectively. After that, it must go through a two-step process of blending at a certain ratio.

Korean Patent Publication No. 2013-0136777 discloses a polyester resin comprising a residue of a dicarboxylic acid component including terephthalic acid, and a residue of a diol component including isosorbide, cyclohexanedimethanol, and other diol compounds. Although it is disclosed, severe reaction conditions of high temperature and high pressure are required, the esterification reaction time is prolonged, and when the heat resistance using isosorbide is strengthened, the impact resistance is weakened, and the heat resistance and impact resistance performance can be simultaneously achieved above a certain level. There is an impossible problem.

In addition, Non-Patent Document 1 (H. Eliot Edling, Polymer, 2018, 120-130) compares the tensile strength and gas permeability of PET resins and copolyesters with biphenyl functional groups, while comparing dimethyl terephthalate (DMT) and dimethyl bisulfide. A technology using phenyl dicarboxylate (DMBP) or the like has been disclosed, but the polymerization reaction conditions, methods, and properties of expression for application of secondary alcohols such as isosorbide are not mentioned.

In addition, non-patent document 2 (Qian Li, Polymer chemistry, 2013, 1387-1397) relates to the production of copolycarbonate using isosorbide (ISB) and dimethyl carbonate (DMC), ISB-DMC, primary aliphatic alcohol- Each DMC is subjected to an ester (ES) reaction, and a technology for producing a block copolymerized polycarbonate by combining the two reactants is disclosed, but the production of a polycarbonate that does not contain an aromatic component and does not use ester monomers (TPA and DMT) It is about.

The present invention is a method for preparing a polyester-carbonate copolymer capable of reducing the existing harsh reaction conditions and reducing reaction time in the preparation of a polyester-carbonate copolymer having excellent heat resistance and excellent impact strength of a polyarylate. Want to provide.

In order to solve the above problems, the present invention comprises the steps of: (a) ester-reacting a monomer mixture including a compound represented by the following formula (3) and a compound represented by the following formula (4) to polymerize into a form represented by the following formula (5); And (b) adding and reacting a compound represented by the following Formula 4 and a monomer represented by the following Formula 6 to generate and condensate an oligomer in the form represented by the following Formula 7; polyester-carbonate copolymer comprising Provides a manufacturing method.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Formulas 3 to 7, R is each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and A is a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms or a carbon number 6 to 40 arylene group, substituted or unsubstituted C 1 to C 40 heteroalkylene group or C 2 to C 40 hetero arylene group, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements or metal elements are included in the structure And B is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, or a heteroarylene group having 2 to 20 carbon atoms, , Some of the repeating units include a biphenyl moiety, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements, or metal elements may be included in the structure.

In addition, the compound represented by Formula 3 is at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate, dicyclohexyl carbonate, and diphenyl carbonate. And, the compound represented by Formula 4 is ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptane Diol, 1,6-hexanediol, 4,4'-isopropylidenedicyclohexanol, diethylene glycol, triethylene glycol, tetraethylene glycol, 2,2-bis(4-hydroxyphenyl)propane (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-hydroxyphenyl)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'-dihydroxy Diphenylsulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxy-3,3'-dichlorodiphenylether, 4,4' -Dihydroxy-2,5-diethoxydiphenylether, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxye) Oxy-2-methyl)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-2-methylphenyl)fluorene, isosorbide and 1, It provides a method for producing a polyester-carbonate copolymer, characterized in that at least one selected from the group consisting of 4-cyclohexanedimethanol.

In addition, the compound represented by Formula 6 is dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, dimethyl 4,4-biscyclohexane carboxylate, dimethyl propanedioate, dimethyl butanedioate, dimethyl pentanedioate, dimethyl hexanedioate. Eate, dimethyl heptanedioate, dimethyl octanedioate, dimethyl nonanedioate, dimethyl decanedioate and dimethyl biphenylcarboxylate compound, characterized in that at least one selected from the group consisting of a polyester-carbonate copolymer production method Provides.

In addition, in step (a), the content of the carbonate residue by the compound represented by Formula 3 is 2 to 10% by weight, and the content of the diol residue by the compound represented by Formula 4 is 5 to 23% by weight. It provides a method for producing a polyester-carbonate copolymer characterized by.

In addition, it provides a polyester-carbonate copolymer production method, characterized in that the content of the biphenyl residue by the compound represented by the formula (6) in step (b) is 5 to 20% by weight.

In addition, the copolymer provides a polyester-carbonate copolymer production method, characterized in that the glass transition temperature (Tg) is 100 ~ 200 ℃, IZOD impact strength (ASTM D256, 23 ℃) is 100 J / m or more. .

According to the present invention, it is prepared by reacting a specific monomer mixture, but by introducing a continuous type of aromatic structure (biphenyl), the aromatic content is increased to enhance heat resistance, as well as activity (flipping, structure regaining) in the polymer chain. It is possible to provide a method for producing a polyester-carbonate copolymer having enhanced impact resistance by having a

In addition, in the production of polyester-carbonate copolymer, a specific monomer is used, but the polymerization process is separated to alleviate the existing harsh reaction conditions, and the reaction time is reduced, while the production of a polyester-carbonate copolymer excellent in heat resistance and impact resistance. Can provide a way.

Hereinafter, a preferred embodiment of the present invention will be described in detail. In describing the present invention, when it is determined that a detailed description of a related known technology may obscure the subject matter of the present invention, a detailed description thereof will be omitted. Throughout the specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components, unless otherwise stated.

In order to prepare a polyester-carbonate copolymer having excellent heat resistance and excellent impact strength of a conventional polyarylate, the present inventors have been working on preparing a polyester-carbonate copolymer that can alleviate the harsh reaction conditions and shorten the reaction time. As a result of repeated research, it was discovered that it was prepared by reacting a specific monomer mixture, but by introducing an aromatic structure (biphenyl) in a continuous form, it was found that heat resistance as well as impact resistance can be dramatically improved. .

The polyester-carbonate copolymer prepared according to the present invention includes a repeating unit represented by the following formula (1); And a repeating unit represented by Formula 2 below.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, A is a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms or an arylene group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 40 carbon atoms, or a heteroaryl having 2 to 40 carbon atoms. Is a ene group, nitrogen, oxygen, phosphorus, sulfur, silicon, a halogen element or a metal element may be included in the structure, and B is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, substituted or It is an unsubstituted C1-C20 heteroalkyl group or a C2-C20 heteroarylene group, but some of the repeating units contain a biphenyl residue, and nitrogen, oxygen, phosphorus, sulfur, silicon, a halogen element or a metal in the structure Elements may be included.

Hereinafter, it will be described in detail through the manufacturing process of the polyester-carbonate copolymer according to the present invention.

The method for preparing a polyester-carbonate copolymer according to the present invention includes (a) esterifying a monomer mixture including a compound represented by the following formula (3) and a compound represented by the following formula (4) to polymerize into a form represented by the following formula (5). step; And (b) adding and reacting a compound represented by the following Formula 4 and a monomer represented by the following Formula 6 to generate an oligomer in the form represented by the following Formula 7 and condensation polymerization.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Formulas 3 to 7, R is each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and A is a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms or a carbon number 6 to 40 arylene group, substituted or unsubstituted C 1 to C 40 heteroalkylene group or C 2 to C 40 hetero arylene group, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements or metal elements are included in the structure And B is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, or a heteroarylene group having 2 to 20 carbon atoms, , Some of the repeating units include a biphenyl moiety, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements, or metal elements may be included in the structure.

Here, the compound represented by Formula 3 is, for example, 1 selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate, dicyclohexyl carbonate, and diphenyl carbonate. It may be more than one species, preferably dimethyl carbonate.

In addition, the compound represented by Formula 4 is, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5 -Heptanediol, 1,6-hexanediol, 4,4'-isopropylidenedicyclohexanol, diethylene glycol, triethylene glycol, tetraethylene glycol, 2,2-bis(4-hydroxyphenyl)propane ( 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-hydroxy Phenyl) pentane, 2,4'-dihydroxy-diphenylmethane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane, 1,1-bis(4-hydroxyl) Roxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-di Hydroxy diphenylsulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4, 4'-dihydroxy-2,5-diethoxydiphenylether, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxy) Oxyethoxy-2-methyl)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-2-methylphenyl)fluorene, isosorbide and It may be one or more selected from the group consisting of 1,4-cyclohexanedimethanol, preferably isosorbide, 1,4-cyclohexanedimethanol, and 1,3-propanediol.

In addition, the compound represented by Formula 6 is, for example, dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, dimethyl 4,4-biscyclohexane carboxylate, dimethyl propanedioate, dimethyl butanedioate, dimethyl pentanedioate, dimethyl hexane It may be one or more selected from the group consisting of dioate, dimethyl heptanedioate, dimethyl octanedioate, dimethyl nonanedioate, dimethyl decanedioate and dimethyl biphenylcarboxylate compounds, preferably dimethyl terephthalate and dimethyl It may be a biphenylcarboxylate compound.

On the other hand, when considering the heat resistance and impact resistance of the finally prepared polyester carbonate copolymer, the content of the carbonate residue by the compound represented by Formula 3 in step (a) is 2 to 10% by weight, represented by Formula 4 It is preferable that the content of the diol residue by the compound is 5 to 23% by weight, and the content of the biphenyl residue by the compound represented by Formula 6 in step (b) is preferably 5 to 20% by weight.

In the present invention, each unit in the structure represented by Formula 7 is irregularly bonded, and each component of A and B is also irregularly bonded in the repeating unit.

In the step (a), for example, the compound represented by Chemical Formula 3, the compound represented by Chemical Formula 4, and the ester reaction catalyst are added to and mixed in a reactor having a volume of 2 L, and the temperature of the reaction tank is set at 70 to 110°C in a nitrogen atmosphere. Preferably, the raw material is melted while heating and stirring at 80 to 100° C., and the temperature is raised to 160 to 200° C., preferably 170 to 190° C. for 10 to 100 minutes, preferably 40 to 80 minutes under normal pressure, After reaching the target temperature, it may be carried out by reacting by maintaining the operating conditions for 10 to 100 minutes, preferably 40 to 80 minutes.

In addition, in the step (b), a compound represented by Formula 4, a compound represented by Formula 6, and a titanium-based catalyst 10 to 100 ppm, preferably 30 to 70 ppm are added to the reaction product of step (a). While adding and stirring, the reaction temperature is increased to 220 to 260°C, preferably from 230 to 250°C for 10 to 100 minutes, preferably for 20 to 60 minutes, and after reaching the temperature for 10 to 100 minutes, preferably 40 to 80 It can be carried out by reacting by maintaining the reaction conditions for a minute.

Thereafter, when the esterification reaction is complete, and when 80% or more of the by-product flows out of the reactor, the condensation polymerization reaction proceeds in a vacuum of 1 Torr or less and at 260 to 280°C, and the reaction is terminated when the target viscosity is reached. It can be carried out in the order of collecting the final polymer.

The polyester-carbonate copolymer prepared through the above reaction is, for example, a compound represented by Formula 3 as dimethyl carbonate, and a compound represented by Formula 4 as isosorbide, 1,4-cyclohexanedimethanol, and 1,3- When propanediol, the compound represented by Formula 6, is applied as dimethyl terephthalate and dimethyl biphenyl carboxylate, it has a structure as shown in Formula 7.

[Formula 7]

성분에 의한 방향족 함량이 높아지면 내열도는 높아지지만, 결정성을 갖게 되어 충격강도가 낮아지고, 가공이 불가능해질 수 있는 단점이 있다. 구체적으로, 상기 화학식 3 및 6으로 표시되는 화합물 총 100 몰%를 기준으로 바이페닐 잔기를 가지는 화합물 함량이 40 몰%(이론적으로 최종 폴리에스터-카보네이트 공중합체 중 바이페닐 잔기 함량 20 중량%에 상응)를 초과할 경우에는 반응도중 결정화되어 반응이 더 이상 진행되지 않을 수 있다.Where, of B

When the aromatic content of the component increases, the heat resistance increases, but there is a disadvantage that the impact strength decreases due to crystallinity and processing becomes impossible. Specifically, the content of the compound having a biphenyl residue is 40 mol% based on the total 100 mol% of the compounds represented by Formulas 3 and 6 (in theory, the content of the biphenyl residue in the final polyester-carbonate copolymer corresponds to 20% by weight If it exceeds ), it may crystallize during the reaction and the reaction may no longer proceed.

In addition, even when the isosorbide content is high, the heat resistance increases, but the impact strength may be weakened. Specifically, if the isosorbide monomer exceeds 45 mol% based on the total 100 mol% of the compound represented by Chemical Formula 4, impact resistance may be greatly reduced.

Conversely, when the content of an aliphatic diol component such as 1,4-cyclohexanedimethanol increases, the heat resistance rapidly decreases and the impact strength may increase, but the level of increase is not largely proportional.

In the present invention, in the esterification reaction of the carbonate monomer represented by Formula 3 and the diol monomer in the form of a secondary alcohol represented by Formula 4, a catalyst may be used to speed up the reaction rate. As the polymerization catalyst, an alkali metal salt of a hydroxyl group such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, etc. may be used, and even if it is not a hydroxyl group, any component capable of forming a salt with an alkali metal may be used. The amount of alkali metal catalyst used is 1×10 ^-1 to 1×10 ^-8 equivalent, preferably 1×10 ^-2 to 1×10 ^-7 equivalent, more preferably 1×10 ^{-3 based} on 1 mol of carbonate monomer. To 1×10 ^-6 equivalents.

In addition, in the esterification and condensation reaction of the carbonate-diol compound, the dimethyl ester monomer represented by Formula 6, and the diol monomer represented by Formula 4, a titanium (Ti)-based metal catalyst may be used. Any combination of compounds forming a salt with a salt can be applied. The amount of the titanium metal catalyst used may be selected in the range of 1×10 ^-2 to 1×10 ^-8 equivalent, preferably 1×10 ^-3 to 1×10 ^-6 equivalent, based on 1 mole of the ester monomer.

The polyester-carbonate copolymer prepared according to the above method is prepared by reacting a specific monomer mixture, but by introducing a continuous type of aromatic structure (biphenyl), the aromatic content is increased to enhance heat resistance as well as activity in the polymer chain ( The impact resistance performance is reinforced by having flipping, the phenomenon that the structure is rebound).

Specifically, the polyester-carbonate copolymer according to the present invention may have a glass transition temperature (Tg) of 100 to 200°C and an IZOD impact strength (ASTM D256, 23°C) of 100 J/m or more, preferably glass The transition temperature (Tg) may be 110 to 150°C, and the IZOD impact strength (ASTM D256, 23°C) may be 150 J/m or more.

Meanwhile, a resin composition further comprising an ultraviolet absorber in the polyester-carbonate copolymer according to the present invention may be considered as an embodiment of the present invention. The ultraviolet absorber refers to a compound that blocks ultraviolet energy or selectively absorbs ultraviolet energy and releases it as another form of energy that does not harm the polymer, or inhibits the photoreaction of the polymer, especially the photolysis initiation reaction. Components or compounds that can be used may be used without great limitation.

Specific examples of the ultraviolet absorber include 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5 -Chlorobenzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzo Triazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one) or 2 thereof Mixtures of more than one kind are mentioned.

The ultraviolet absorber may be included in an amount of 0.0005 to 1 part by weight based on 100 parts by weight of the polyester-carbonate resin. When the content of the ultraviolet absorber is within the above range, it is possible to improve the weather resistance of the resin composition and the molded article without causing bleeding of the ultraviolet absorber to the surface of the molded article and deterioration of mechanical properties of various molded articles.

In addition, the polyester-carbonate resin composition of the embodiment may further include a release agent to increase productivity during extrusion and injection and to reduce defect rates.

Examples of the release agent include higher fatty acids, higher fatty acid esters of monohydric or polyhydric alcohols, natural animal waxes such as beeswax, natural plant waxes such as carnauba wax, natural petroleum waxes such as paraffin wax, and natural coal-based waxes such as montan wax, Olefin wax, silicone oil, organopolysiloxane, or mixtures of two or more thereof.

The release agent may be used in an amount of 0.0001 to 0.01 parts by weight based on 100 parts by weight of the polyester-carbonate resin.

In addition, the polyester-carbonate resin composition of the embodiment may further include a heat stabilizer to prevent a decrease in molecular weight or color deterioration of the resin molded article.

Examples of the heat stabilizer include phosphorous acid, phosphoric acid, aphosphonic acid, phosphonic acid, and esters thereof, and specifically, triphenylphosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert -Butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite Pite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite, 2,2-methylenebis(4,6-di -tert-butylphenyl) octylphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tri Butyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4'-biphenylenediphosphinic acid tetrakis (2 ,4-di-tert-butylphenyl), dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, or a mixture of two or more thereof.

The heat stabilizer may be used in an amount of 0.0001 to 1 part by weight based on 100 parts by weight of the polyester-carbonate resin. By using the stabilizer in the above amount, it is possible to prevent the molecular weight decrease or discoloration of the resin without causing bleeding of the additive.

In addition, the polyester-carbonate resin composition of the embodiment may further include a commonly known antioxidant.

Specific examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, tri Ethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl -4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl )Benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate -Diethylester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis (2,4-di-tert- Butylphenyl), 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8, 10-tetraoxaspiro(5,5)undecane or a mixture of two or more thereof.

The antioxidant may be used in an amount of 0.0001 to 1 part by weight based on 100 parts by weight of the polyester-carbonate resin.

On the other hand, the polyester-carbonate resin composition of the embodiment may further include a polymer resin other than the polyester-carbonate resin for the purpose of further improvement and adjustment of molding processability or various physical properties.

Specifically, the polyester-carbonate resin composition of the embodiment may further include one or more other polymer resins selected from the group consisting of polyester-based resins, polyethers, polyamides, polyolefins and polymethyl methacrylate. In this case, the other polymer resin may be further included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polyester-carbonate resin.

The preparation of the polyester-carbonate resin composition according to the present invention is not particularly limited, and a method or apparatus commonly used for manufacturing a polymer resin, etc. may be used without any other limitation, but a melt polymerization method may be preferably used. .

That is, the polyester-carbonate resin composition of the embodiment may be prepared by melt-kneading each component contained therein. As an apparatus used for the melt-kneading, a Banbury mixer, a kneading roll, an extruder, and the like can be mentioned. Among them, an extruder is preferable from the viewpoint of kneading efficiency, and a multi-screw extruder such as a twin-screw extruder is preferable.

After the resin composition obtained as described above is manufactured in the form of pellets, it can be used for manufacturing various products by injection molding. In such injection molding, not only the usual molding method, but also injection compression molding, injection press molding, gas assisted injection molding, foam molding (including those by injection of supercritical fluid), insert molding, in-mold depending on the purpose as appropriate. Molded products can be obtained using injection molding methods such as de-coating molding, thermal insulation mold molding, rapid heating cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. For molding, either a cold runner method or a hot runner method can be selected.

In addition, the resin composition may be used in the form of various release extrusion molded products, sheets, films, etc. by extrusion molding. In addition, an inflation method, a calender method, a casting method, or the like can be used for forming a sheet or film. Further, it is also possible to form a heat-shrinkable tube by applying a specific stretching operation.

Further, it is also possible to make the resin composition into a molded article by rotational molding or blow molding. By the above molding process, a molded article having transparency and excellent designability can be obtained.

On the other hand, according to another embodiment of the present invention, a resin molded article comprising the prepared polyester-carbonate resin composition may be provided. The resin molded article refers to an article obtained by molding the polyester-carbonate resin composition of the embodiment described above.

It is preferable that the resin molded article is transparent depending on the properties required in the field to be used. The transparency of such a resin molded article can be evaluated by the total light transmittance in the visible light region of the resin molded article, and it is preferable that the total light transmittance of visible light is high. Specifically, the resin molded article of the embodiment may have a total visible light transmittance of 50% or more, or 50 to 99% at a thickness of 3 mm.

The specific use of the resin molded product is not limited, and the use of lenses such as transparent films, sheets, bottles and containers, camera lenses, and finder lenses, retardation films for displays, diffusion sheets, polarizing films, optical disks, optical materials, optical parts , It can be used as a window member for construction.

Hereinafter, a specific example according to the present invention will be described. The symbols and sources of the compounds used in the description of the examples are as follows.

-DMC: dimethyl carbonate (Sigma-Aldrich)

-DMT: dimethyl terephthalate (Sigma-Aldrich)

-DMBP: dimethyl bipheyl-4,4'-dicarboxylate (Sigma-Aldrich)

-ISB: isosorbide (rocket)

-CHDM: 1,4-cyclohexanedimethanol (1,4-cyclohexanedimethanol, Sigma-Aldrich)

-PDO: 1,3-propanediol (1,3-propanediol, Sigma-Aldrich)

-EG: ethylene glycol (Sigma-Aldrich)

Examples 1 to 3, Comparative Examples 6 and 7

(a) As a step process, DMC, ISB, and lithium acetylacetonate (ester reaction catalyst) were added and mixed in the contents of Table 1 in a 2L reactor, and the reaction tank temperature was heated to 90°C in a nitrogen atmosphere and stirred while raw materials Was melted. After confirming that it was completely melted, the temperature was raised to 180° C. for 60 minutes under normal pressure, and the reaction was carried out by maintaining the operating conditions for 60 minutes after reaching the target temperature.

(b) As a step process, DMT, DMBP, CHDM, PDO, and titanium isopropoxide (Ti(O-iC ₃ H ₇ ) ₄ ) 50 ppm of catalyst were additionally added to the reaction product of step (a) as shown in Table 1 below. And while stirring, the reaction temperature was raised to 240° C. for 40 minutes. After reaching the temperature, the reaction conditions were maintained for 60.

When the esterification reaction was completed and the by-products flowed out of the reactor by 80% or more, the condensation polymerization reaction proceeded under a vacuum of 1 Torr or less and 270°C conditions, and when the target viscosity was reached, the reaction was terminated and a polymer was collected. .

Comparative Examples 1 to 5

The results of the experiment in Korean Patent Publication No. 2013-0136777 were referenced, and the resin product of the patent applicant (SK Chemical), which was manufactured and sold with the same composition for injection specimens and physical properties, was purchased, molded and measured. In the case of Comparative Examples 1 and 2, commercial products, PET and PET-G, were purchased, formed, and measured.

Test example

The glass transition temperature and IZOD impact strength were measured by the following method for resins prepared or prepared according to the above Examples and Comparative Examples, and the results are shown in Table 1 below.

(1) Glass transition temperature (Tig)

Using about 10 mg of a sample in a differential scanning calorimeter (Q200, TA Instrumnets), measured by heating at a heating rate of 10°C/min, and in accordance with ASTM D3418, a straight line extending from the low temperature side to the high temperature side, The extrapolated glass transition initiation temperature Tig, which is the temperature at the intersection of the drawn broken lines, was obtained at the point where the gradient of the curve at the stepwise change portion of the glass transition became maximum.

(2) Izod impact strength (ASTM D256, 23℃)

A test piece of 64 mm in length, 12.7 mm in width, and 3.2 mm in thickness was injected at a temperature of 210°C to 260°C using a 25-ton injection molding machine of Dongshin Hydraulic Co., and a notch having a depth of 2.54 mm was formed by a notching machine to obtain a test piece. With respect to this test piece, a CAT NO.612 room temperature Izod impact tester manufactured by Toyoseiki was used to measure the Izod impact strength in which a notch was formed at 23°C. The larger this value is, the greater the impact resistance is, and the harder it is to break.

Referring to Table 1, in the case of preparing a polyester-carbonate copolymer by stepwise reaction of a specific monomer according to the present invention, but introducing a continuous aromatic structure (biphenyl) (Examples 1 to 3) It can be seen that the content is increased, the heat resistance is enhanced, and the impact resistance is enhanced by giving the polymer chain activity (flipping, structure rebound).

In addition, it can be seen that the reaction of the carboxylic acid residue and the secondary alcohol, which is difficult to react, was facilitated in a similar form using an alkali metal catalyst and a carbonate substrate under more relaxed conditions, and the reaction time was also shortened.

The preferred embodiments of the present invention have been described in detail above. The description of the present invention is for illustration only, and those of ordinary skill in the art to which the present invention pertains will be able to understand that other specific forms can be easily modified without changing the technical spirit or essential features of the present invention.

Therefore, the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and all changes or modified forms derived from the meaning, scope, and equivalent concepts of the claims are included in the scope of the present invention. It must be interpreted.

Claims (6)

(a) esterifying a monomer mixture including a compound represented by the following formula (3) and a compound represented by the following formula (4) to perform an ester reaction to polymerize to a form represented by the following formula (5); And
(b) adding and reacting a compound represented by the following formula (4) and a monomer represented by the following formula (6) to produce an oligomer in a form represented by the following formula (7) and condensation polymerization;
Polyester-carbonate copolymer preparation method comprising:
[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Formulas 3 to 7, R is each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and A is a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms or a carbon number 6 to 40 arylene group, substituted or unsubstituted C 1 to C 40 heteroalkylene group or C 2 to C 40 hetero arylene group, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements or metal elements are included in the structure And B is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, or a heteroarylene group having 2 to 20 carbon atoms, , Some of the repeating units include a biphenyl moiety, and nitrogen, oxygen, phosphorus, sulfur, silicon, a halogen element or a metal element may be included in the structure. The method of claim 1,
The compound represented by Formula 3 is at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate, dicyclohexyl carbonate and diphenyl carbonate, The compound represented by Formula 4 is ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexanediol, 4,4'-isopropylidenedicyclohexanol, diethylene glycol, triethylene glycol, tetraethylene glycol, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxyl Roxy-(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-hydroxyphenyl)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'-dihydroxy diphenyl Sulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxy-3,3'-dichlorodiphenylether, 4,4'-di Hydroxy-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-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-2-methylphenyl)fluorene, isosorbide and 1,4- A method for producing a polyester-carbonate copolymer, characterized in that at least one selected from the group consisting of cyclohexanedimethanol. The method of claim 1,
The compound represented by Formula 6 is dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, dimethyl 4,4-biscyclohexane carboxylate, dimethyl propanedioate, dimethyl butanedioate, dimethyl pentanedioate, dimethyl hexanedioate, A method for producing a polyester-carbonate copolymer, characterized in that it is at least one selected from the group consisting of dimethyl heptanedioate, dimethyl octanedioate, dimethyl nonanedioate, dimethyl decanedioate and dimethyl biphenylcarboxylate compounds. The method of claim 1,
Based on 100% by weight of the polyester-carbonate copolymer, the content of the carbonate residue by the compound represented by Formula 3 in the step (a) is 2 to 10% by weight, and the diol by the compound represented by Formula 4 Polyester-carbonate copolymer production method, characterized in that the content of the residue is 5 to 23% by weight. The method of claim 1,
Polyester-carbonate copolymer, characterized in that the content of the biphenyl residue by the compound represented by Formula 6 in step (b) is 5 to 20% by weight based on 100% by weight of the polyester-carbonate copolymer Manufacturing method. The method according to any one of claims 1 to 5,
The copolymer has a glass transition temperature (Tg) of 100 to 200° C., and an IZOD impact strength (ASTM D256, 23° C.) of 100 J/m or more.