KR20200062633A - Manufacturing method of polyester-carbonate resin with improved heat resistance and impact strength - Google Patents

Abstract

Disclosed in the present invention is a method for preparing a polyester-carbonate copolymer with excellent heat resistance of polyacrylate and excellent impact strength, as well as a polyester-carbonate copolymer capable of relieving existing stress reaction conditions and shortening a reaction time. The present invention provides a method for preparing a polyester-carbonate copolymer, comprising the steps of: (a) esterifying a monomer mixture including a compound represented by the formula 3 and a compound represented by the formula 4 to be polymerized into a form represented by the formula 5; and (b) adding a compound represented by the formula 4 and a monomer represented by the formula 6 and reacting the same to produce and condensation-polymerize an oligomer having a form represented by the formula 7.

Description

Manufacturing method of polyester-carbonate copolymer with improved heat resistance and impact strength {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 preparing a polyester-carbonate copolymer having improved heat resistance and impact strength.

Polyarylate (PAR) resins are generally produced by interfacial polymerization of bisphenol A and terephthaloyl chloride (TPC), and have excellent heat resistance and transparency. However, processability is very poor compared to other engineering plastic resins due to its high heat resistance.

In order to improve the processing performance of the polyarylate resin, it is used by blending in a compound form with transparent engineering plastic resins having excellent processing performance such as polycarbonate (PC). However, the refractive index of polycarbonate and polyarylate is similar, but is not the same, so when mixed, optical performances such as transmittance and cloudiness appear to be lower than those of the original resins, and polycarbonate and polyarylate are synthesized respectively. After that, you have to go through a two-step process of blending at a certain rate.

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

In addition, in Non-Patent Document 1 (H. Eliot Edling, Polymer, 2018, 120-130), while comparing the tensile strength and gas permeability of copolyester introduced with PET resin and biphenyl functional group, dimethyl terephthalate (DMT), dimethyl bi Although it discloses a technique using phenyl dicarboxylate (DMBP) or the like, it does not mention polymerization reaction conditions, methods, expression properties, etc. for the application of secondary alcohol such as isosorbide.

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 technique of preparing a block copolymerized polycarbonate by combining two reactants is disclosed, but an aromatic component is not included, and polycarbonate is produced without using ester monomers (TPA and DMT). It is about.

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

In order to solve the above problems, the present invention comprises: (a) polymerizing a monomer mixture comprising a compound represented by the following formula (3) and a compound represented by the following formula (4) into a form represented by the following formula (5); And (b) reacting by adding a compound represented by the following formula (4) and a monomer represented by the following formula (6) to produce and condensate an oligomer in the form represented by the following formula (7): polyester-carbonate copolymer comprising Provide 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 carbon number. It is an arylene group of 6 to 40, a substituted or unsubstituted heteroalkylene group of 1 to 40 carbon atoms or a heteroarylene group of 2 to 40 carbon atoms, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements or metal elements are included in the structure. B may be 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 contain biphenyl residues, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements or metal elements may be included in the structure.

In addition, the compound represented by Chemical 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 the 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'-isopropylidene dicyclohexanol, 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'-dihydroxydiphenyl 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-hydroxye Methoxy-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 member selected from the group consisting of 4-cyclohexanedimethanol.

In addition, the compound represented by the formula (6) is dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, dimethyl 4,4-biscyclohexane carboxylate, dimethyl propanedioate, dimethyl butanedioate, dimethyl pentanedioate, dimethyl hexanedioate Eight, dimethyl heptanedioate, dimethyl octanedioate, dimethyl nonanedioate, dimethyl decanedioate and dimethyl biphenylcarboxylate compounds are selected from the group consisting of at least one selected from the group consisting of polyester-carbonate copolymer production method Gives

In addition, in the 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 in that.

In addition, it provides a method for producing a polyester-carbonate copolymer 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 has a glass transition temperature (Tg) of 100 ~ 200 ℃, IZOD impact strength (ASTM D256, 23 ℃) provides a method for producing a polyester-carbonate copolymer characterized in that more than 100 J / m .

According to the present invention, it is prepared by reacting a specific monomer mixture, but introduces a continuous aromatic structure (biphenyl) to increase the aromatic content to enhance heat resistance, as well as to the polymer chain (flipping, reverting structure) By providing the can provide a method for producing a polyester-carbonate copolymer having improved impact resistance.

In addition, in preparing the polyester-carbonate copolymer, a specific monomer is used, but the process of the polymerization reaction is separated to alleviate the existing severe reaction conditions, and the reaction time is reduced while the polyester-carbonate copolymer is excellent in heat resistance and impact resistance. You can provide a method.

Hereinafter, preferred embodiments of the present invention will be described in detail. In the description of the present invention, when it is determined that a detailed description of related known technologies may obscure the subject matter of the present invention, the detailed description will be omitted. Throughout the specification, when a part “includes” a certain component, this means that other components may be further included instead of excluding other components, unless specifically stated to the contrary.

The present inventors are preparing a polyester-carbonate copolymer capable of alleviating the existing severe reaction conditions and reducing the reaction time for the production of a polyester-carbonate copolymer having excellent heat resistance and excellent heat resistance of a conventional polyarylate. As a result of repeated research on the present invention, it has been found that a specific monomer mixture is reacted to produce a continuous aromatic structure (biphenyl), thereby enhancing heat resistance and dramatically improving impact resistance. .

The polyester-carbonate copolymer prepared according to the present invention includes a repeating unit represented by the following Chemical 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 heteroaryl having 2 to 40 carbon atoms. A alkylene group, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements or metal elements 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 heteroalkyl group having 1 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms, and some of the repeating units contain biphenyl residues, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements or metals in the structure Element may be included.

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

The method for preparing the polyester-carbonate copolymer according to the present invention is (a) esterified to a monomer mixture comprising a compound represented by the following formula (3) and a compound represented by the following formula (4) to polymerize to a form represented by the following formula (5) step; And (b) reacting by adding a compound represented by the following formula (4) and a monomer represented by the following formula (6) to produce and condensate polymerize in the form represented by the following formula (7).

[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 carbon number. It is an arylene group of 6 to 40, a substituted or unsubstituted heteroalkylene group of 1 to 40 carbon atoms or a heteroarylene group of 2 to 40 carbon atoms, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements or metal elements are included in the structure. B may be 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 contain biphenyl residues, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements or metal elements may be included in the structure.

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

In addition, the compound represented by the 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'-isopropylidene dicyclohexanol, 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-hydroxy Hydroxyphenyl)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-diethoxydiphenyl ether, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxy Hydroxyethoxy-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 the 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 biphenyl carboxylate compound.

On the other hand, when considering the heat resistance and impact resistance of the polyester carbonate copolymer to be finally produced, the content of carbonate residues 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 to be 5 to 23% by weight, and the content of the biphenyl residue by the compound represented by the formula (6) in step (b) is 5 to 20% by weight.

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

In the step (a), for example, a compound represented by Chemical Formula 3, a compound represented by Chemical Formula 4, and an ester reaction catalyst are mixed in a 2 L volume reactor, and the reactor temperature is 70 to 110° C. under 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 performed by reacting by maintaining the operating conditions for 10 to 100 minutes, preferably 40 to 80 minutes.

In addition, in 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). With stirring and adding, the reaction temperature is raised to 220 to 260°C, preferably to 230 to 250°C for 10 to 100 minutes, preferably 20 to 60 minutes, after reaching the temperature for 10 to 100 minutes, preferably 40 to 80 It can be performed by maintaining the reaction conditions for a minute to react.

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

The polyester-carbonate copolymer prepared through the reaction is, for example, a compound represented by Formula 3 as dimethyl carbonate, a compound represented by Formula 4 as isosorbide, 1,4-cyclohexanedimethanol and 1,3- As a propane diol, when the compound represented by the formula (6) is applied to dimethyl terephthalate and dimethyl biphenyl carboxylate, it has a structure as in the 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 B's

When the aromatic content by the component is high, the heat resistance is high, but it has a disadvantage that it may have crystallinity, thus lowering the impact strength and making processing impossible. Specifically, the content of the compound having a biphenyl residue based on 100 mol% of the compounds represented by Chemical Formulas 3 and 6 is 40 mol% (theoretically, the content of the biphenyl residue in the final polyester-carbonate copolymer is 20 wt% ), crystallization may occur during the reaction, and the reaction may not proceed.

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

Conversely, when the content of the 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 directly proportional.

In the present invention, in the esterification reaction of the diol monomer in the form of a secondary alcohol represented by Formula 4 and the carbonate monomer represented by Formula 3, 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 or cesium hydroxide 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 alkali metal catalyst is used in an amount of 1×10 ^-1 to 1×10 ^-8 equivalents, preferably 1×10 ^-2 to 1×10 ^-7 equivalents, and more preferably 1×10 ^-3 per mole of carbonate monomer. To 1×10 ^-6 equivalents.

In addition, a titanium (Ti)-based metal catalyst may be used in the esterification reaction and condensation polymerization reaction of the carbonate-diol compound with the dimethyl ester monomer represented by Chemical Formula 6, and the diol monomer represented by Chemical Formula 4. Any combination of salt-forming compounds is applicable. The amount of the titanium metal catalyst used may be selected from 1×10 ^-2 to 1×10 ^-8 equivalents, preferably 1×10 ^-3 to 1×10 ^-6 equivalents, per 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 aromatic structure (biphenyl), increasing the aromatic content to enhance heat resistance, as well as improving the polymer chain's activity ( Impact resistance is enhanced by having flipping, a phenomenon in which the structure is reverted).

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. Transition temperature (Tg) is 110 ~ 150 ℃, IZOD impact strength (ASTM D256, 23 ℃) may be more than 150 J / m.

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 into other forms of energy that are not harmful to the polymer, or inhibits the photoreaction of the polymer, particularly the photolysis initiation reaction, to the polymer resin composition. Components or compounds that can be used can be used without great limitation.

Specific examples of the ultraviolet absorber, 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-benzooxazin-4-one) or 2 of these And mixtures of species or more.

The ultraviolet absorber may be included in 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 above embodiment may further include a release agent to increase productivity and reduce defect rates during extrusion and injection.

The release agents 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, natural coal waxes such as montan wax, And olefinic waxes, silicone oils, organopolysiloxanes, 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 deterioration in color 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, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite Phyt, monodecyldiphenylphosphite, monooctyldiphenylphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 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 mixtures 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 a stabilizer with the above content, it is possible to prevent a decrease in molecular weight or discoloration of the resin without causing bleeding of additives and the like.

In addition, the polyester-carbonate resin composition of the above 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 -Diethyl ester, 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, And 10-tetraoxaspiro(5,5)undecane or mixtures 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.

Meanwhile, the polyester-carbonate resin composition of the embodiment may further include other polymer resins other than the polyester-carbonate resin for the purpose of further improving and adjusting the molding processability and various physical properties.

Specifically, the polyester-carbonate resin composition of the embodiment may further include at least one other polymer resin selected from the group consisting of polyester-based resins, polyethers, polyamides, polyolefins, and polymethylmethacrylates. At this time, the other polymer resin may be further included in a content of 1 to 50 parts by weight based on 100 parts by weight of the polyester-carbonate resin.

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

That is, the polyester-carbonate resin composition of the embodiment may be prepared by melt-kneading each component included therein. A Banbury mixer, a kneading roll, an extruder, etc. are mentioned as an apparatus used for the said melt kneading. 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.

The resin composition obtained as described above may be used in the manufacture of various products by injection molding after being produced in the form of pellets. In such injection molding, as well as a conventional molding method, depending on the purpose, injection compression molding, injection press molding, gas assist injection molding, foam molding (including injection of supercritical fluid), insert molding, and in-molding Molded products can be obtained using injection molding methods such as de-coating, insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-fast injection molding. Molding can be selected from either a cold runner method or a hot runner method.

In addition, the resin composition may be used in the form of various molded extrusion molded articles, sheets, films, etc. by extrusion molding. In addition, an inflation method, a calendering method, a casting method, or the like can be used to form the sheet or film. It is also possible to form as a heat shrink tube by applying a specific stretching operation.

Moreover, it is also possible to make the said resin composition into a molded article by rotational molding, blow molding, etc. Through the molding process, a molded article having transparency and excellent designability can be obtained.

Meanwhile, 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 means an article obtained by molding the polyester-carbonate resin composition of the above-described embodiment.

The resin molded article is preferably transparent depending on the characteristics required in the field to be used. The transparency of the 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 visible light total transmittance is high. Specifically, the resin molded article of the embodiment may have a visible light transmittance of 50% or more or 50 to 99% at a thickness of 3 mm.

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

Hereinafter, a specific embodiment according to the present invention will be described. The symbol and source of the compound 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 (Sigma Aldrich)

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

-EG: Ethylene glycol (Sigma Aldrich)

Examples 1-3, Comparative Examples 6 and 7

(a) As a step process, DMC, ISB and lithium acetylacetonate (ester reaction catalyst) are added and mixed in a 2 L volume reactor in the amount shown in Table 1 below, and the reaction vessel temperature is heated to 90° C. under a nitrogen atmosphere and stirred while stirring. Melted. After confirming that the mixture was completely melted, the temperature was raised to 180° C. for 60 minutes under normal pressure, and the reaction condition was maintained for 60 minutes after reaching the target temperature.

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

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

Comparative Examples 1 to 5

Reference was made to the experimental results of Korean Patent Publication No. 2013-0136777, and injection specimens and physical properties were purchased and molded and measured by purchasing resin products of the patent applicant (SK Chemicals) that are manufactured and sold with the same composition. In Comparative Examples 1 and 2, commercial products PET and PET-G were purchased and molded and measured, respectively.

Test example

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

(1) Glass transition temperature (Tig)

A differential scanning calorimeter (Q200, TA Instrumnets) using a sample of about 10 mg, measured by heating at a heating rate of 10° C./min, and in accordance with ASTM D3418, a straight line extending the low-temperature base line to the high-temperature side, The extrapolated glass transition initiation temperature Tig, which is the temperature of the intersection point of the broken line, was determined at the point where the gradient of the curve of the stair-step change portion of the glass transition becomes maximum.

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

A test piece was formed by using a 25 ton injection molding machine from Dongshin Hydraulic Co., Ltd. to inject a test piece with a length of 64 mm, a width of 12.7 mm, and a thickness of 3.2 mm at a temperature of 210°C to 260°C to form a notch with a depth of 2.54 mm. The Izod impact strength at which a notch was formed at 23°C was measured using a CAT NO.612 ambient temperature Izod impact tester manufactured by Toyoseiki. The larger this value is, the greater the impact strength is, and the more difficult it is to break.

Referring to Table 1, a specific monomer according to the present invention is prepared by reacting stepwise, but a continuous form of aromatic structure (biphenyl) is introduced to prepare a polyester-carbonate copolymer (Examples 1 to 3). It can be seen that the heat resistance was enhanced by increasing the content, and the impact resistance performance was strengthened by having activity (flipping, the phenomenon in which the structure was reverted) in the polymer chain.

In addition, it was found that the reaction of the secondary alcohol, which is difficult to react with the carboxylic acid residue, was facilitated in a more relaxed condition in a similar form using an alkali metal catalyst and a carbonate base, and the reaction time was also shortened.

The preferred embodiments of the present invention have been described above in detail. The description of the present invention is for illustrative purposes, and those skilled in the art to which the present invention pertains will appreciate 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, which will be described later, rather than by the detailed description, and all the changed or modified forms derived from the meaning, scope, and equivalent concepts of the claims are included in the scope of the present invention. Should be interpreted.

Claims (6)

(a) ester-reacting a monomer mixture comprising a compound represented by the following formula (3) and a compound represented by the following formula (4) to polymerize to a form represented by the following formula (5); And
(b) reacting by adding a compound represented by the following formula (4) and a monomer represented by the following formula (6) to produce and condensate polymerize in the form represented by the following formula (7);
Method for producing a polyester-carbonate copolymer 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 carbon number. It is an arylene group of 6 to 40, a substituted or unsubstituted heteroalkylene group of 1 to 40 carbon atoms or a heteroarylene group of 2 to 40 carbon atoms, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements or metal elements are included in the structure. B may be 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 contain biphenyl residues, and nitrogen, oxygen, phosphorus, sulfur, silicon, halogen elements or metal elements may be included in the structure. According to claim 1,
The compound represented by Chemical 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 Chemical 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'-isopropylidene dicyclohexanol, 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 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 diphenyl Sulfone, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 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- Method for producing a polyester-carbonate copolymer, characterized in that at least one member selected from the group consisting of cyclohexanedimethanol. According to claim 1,
The compound represented by Chemical Formula 6 is dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, dimethyl 4,4-biscyclohexane carboxylate, dimethyl propanedioate, dimethyl butanedioate, dimethyl pentanedioate, dimethyl hexanedioate, Method for producing a polyester-carbonate copolymer, characterized in that at least one selected from the group consisting of dimethyl heptanedioate, dimethyl octanedioate, dimethyl nonanedioate, dimethyl decanedioate and dimethyl biphenylcarboxylate compounds. According to claim 1,
In the 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. Polyester-carbonate copolymer manufacturing method. According to claim 1,
Method of producing a polyester-carbonate copolymer 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. The method according to any one of claims 1 to 5,
The copolymer has a glass transition temperature (Tg) of 100 ~ 200 ℃, IZOD impact strength (ASTM D256, 23 ℃) is a polyester-carbonate copolymer manufacturing method characterized in that more than 100 J / m.