KR102293310B1 - Polycarbonate and method for preparing the same - Google Patents

Abstract

The present invention provides a polycarbonate having a novel structure, which exhibits excellent weather resistance, and a method for manufacturing the same.

Description

Polycarbonate and its manufacturing method

The present invention relates to polycarbonate and a method for preparing the same. More specifically, it relates to a polycarbonate having a novel structure having excellent weather resistance and a method for manufacturing the same.

Polycarbonate resin is a polymer material that is used in various fields such as exterior materials for electrical and electronic products, automobile parts, building materials, and optical parts due to its excellent impact strength, dimensional stability, heat resistance and transparency.

However, polycarbonate exhibits a high absorption rate up to 380 nm in the ultraviolet region, but has a disadvantage in that the structure is deformed, so that physical properties are easily weakened and the coloration phenomenon is easily caused, so that the weather resistance is weak.

Accordingly, research is being attempted to obtain desired physical properties by introducing units having different structures into the main chain of polycarbonate by copolymerizing two or more types of aromatic diols having different structures, or by changing the terminal terminator, but most techniques When the production cost is high and the weather resistance and impact strength are increased, the transparency is lowered on the contrary, and when the transparency is improved, there are limitations such as lowering the chemical resistance and impact strength.

Recently, as the outdoor market grows, the demand from customers for materials with excellent weather resistance while maintaining the high impact properties of polycarbonate resins is increasing.

Accordingly, studies such as introducing an end terminator having excellent weather resistance have been conducted, but polycarbonate having sufficiently excellent weather resistance has not yet been developed.

An object of the present invention is to provide a polycarbonate having excellent weather resistance and a method for manufacturing the same.

The present invention provides a polycarbonate comprising a functional group derived from a first terminal terminator represented by Formula 1 and a functional group derived from a second terminal terminator represented by Formula 2 as a polymer of an aromatic diol and a carbonate precursor.

In addition, the present invention provides a method for producing a polycarbonate, comprising polymerizing a composition comprising an aromatic diol, a carbonate precursor, a first terminal terminator represented by Formula 4, and a second terminal terminator represented by Formula 5 provides

In addition, the present invention provides a molded article made of the polycarbonate.

Hereinafter, a polycarbonate according to a specific embodiment of the present invention, a manufacturing method and a molded article thereof, and a terminal terminator useful for preparing the polycarbonate will be described in more detail.

According to one embodiment of the invention, as a polymer of an aromatic diol and a carbonate precursor, a polycarbonate comprising a functional group derived from a first terminal terminator represented by the following Chemical Formula 1 and a functional group derived from a second terminal terminator represented by the following Chemical Formula 2 is prepared. to provide.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

R ₁ to R ₃ are each independently C _1-10 alkyl, C _1-10 alkoxy, or halogen,

R _{4 is C 1-30} alkyl unsubstituted or substituted with phenyl;

a to c are each independently an integer of 0 to 3,

d is an integer from 1 to 4,

n is an integer from 1 to 100,

An asterisk (*) means a bonding point.

The polycarbonate includes a functional group derived from the first terminal terminator of the oligomeric type represented by Chemical Formula 1 and a functional group derived from the second terminal terminator in the form of a monomolecular compound represented by Chemical Formula 2, thereby providing excellent results of conventional polycarbonate. It is possible to exhibit improved weather resistance while maintaining mechanical properties.

Specifically, the functional group derived from the first terminal terminator of the oligomeric type represented by Chemical Formula 1 can be changed in structure by Fries-rearrangement of the ester group located between the benzene structures, and as a result, excellent weather resistance improvement effect may be exhibited.

Accordingly, the effect of improving the weather resistance of polycarbonate can be further increased by controlling the content (n) of the repeating structure included in the functional group derived from the first terminal terminator. Specifically, in Formula 1, n is 1 or more, 2 It is an integer greater than or equal to 3 or greater, and may be an integer of 50 or less, 45 or less, or 40 or less. When it is within the above range, it is possible to exhibit improved weather resistance while maintaining excellent mechanical properties.

In addition, the phenyl group in the functional group derived from the first terminal terminator is a functional group of R ₁ , R ₂ or R _{3 , specifically, a linear or branched C 1-10} alkyl such as methyl, ethyl, isopropyl, or the like; _{C 1-10} alkoxy such as methoxy, ethoxy or propoxy; Alternatively, it may be substituted with a halogen group such as chloro or bromo, or unsubstituted, that is, each of a to c in Formula 1 may be 0. When substituted with the above functional groups, since electrons are abundantly present, the Fries potential properties of the aforementioned polycarbonate can be further increased, and when unsubstituted, the flow properties and heat resistance properties of the polycarbonate are further improved. can do it

The functional group derived from the first terminal terminator of the oligomeric structure having the above structure, specifically, has a weight average molecular weight (Mw) of 500 g/mol or more, 5,000 g/mol or more, and 15,000 g/mol or less, 10,000 g/mol or less. It may be derived from a terminal terminator. When the first terminal terminator has a weight average molecular weight within the above range, the weather resistance can be further improved due to the presence of abundant ester groups and increased fluidity of the terminal groups.

More specifically, the functional group derived from the first terminal terminator of Formula 1 may be a functional group having a structure represented by Formula 1a or 1b below:

[Formula 1a]

[Formula 1b]

In Formulas 1a and 1b, R ₁ to R ₃ , a to c are as defined above, n ₁ and n ₂ are each independently an integer of 1 or more, 2 or more, or 3 or more, and 50 or less, 45 or less, or 40 It may be an integer of the following.

On the other hand, in order to control the molecular weight of the polycarbonate, a terminal terminator should be introduced in a certain amount. However, when a high molecular weight oligomeric type terminator is introduced, it is difficult to replace the same equivalent with an oligomeric type terminator. Accordingly, the polycarbonate according to an embodiment of the present invention may contain only the functional group derived from the first terminal terminator by using the above-described oligomeric first terminator alone as a terminator during the preparation thereof, but a single molecule The second end terminator in the form of may be used in combination with the first terminator in the oligomeric form. Accordingly, the polycarbonate according to an embodiment of the present invention includes a functional group derived from the second terminal terminator represented by Formula 2 together with the functional group derived from the first terminal terminator in the oligomeric form.

The functional group derived from the second terminal terminator is a functional group derived from an alkylphenol-based terminator to be described later, has a structure in which hydrogen is separated from the hydroxy group included in _{C 1-20 alkylphenol, and is bonded to one end of the polycarbonate.} It serves to control the molecular weight of the polycarbonate together with the functional group derived from the terminal terminator of Formula 1 above.

Specifically, the phenyl group in the functional group derived from the second terminal terminator _{may be substituted with a functional group of R 4} or unsubstituted, that is, d may be 0 in Formula 2 above. When the phenyl group is substituted with the functional _{group of R 4 , R 4} is specifically methyl, ethyl, isopropyl, tert-butyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, or straight-chain or branched C _1-30 alkyl or C _4-30 alkyl such as triacontyl; Or it may be a straight-chain or branched C _{1-30 alkyl substituted with phenyl.}

More specifically, the functional group derived from the second terminal terminator is p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosyl. It may be a functional group derived from the second terminal terminator selected from the group consisting of phenol and triacontylphenol.

The polycarbonate according to an embodiment of the present invention can control the molecular weight and further enhance the effect of improving weather resistance by controlling the mixing ratio of the first terminal terminator and the second terminal terminator during the preparation thereof. Accordingly, in consideration of the weight average molecular weight and weather resistance improvement effect of the polycarbonate finally manufactured, the first terminal terminator and the second terminal terminator are 1:100 or more, 1:99 or more, or 20:80 or more, and 100:1 or less, or 99:1 or less, or 80:20 or less, may be mixed and used, and as a result, polycarbonate is derived from the first terminal terminator and the second terminal terminator in a weight ratio corresponding to the above mixed weight ratio. It may contain functional groups.

In addition, under the condition that the mixing weight ratio range is satisfied, the total content of the functional groups derived from the first terminal terminator and the functional group derived from the second terminal terminator is 5% by weight or more, or 8% by weight or more, based on the total weight of the polycarbonate; or 12% by weight or more, 45% by weight or less, or 35% by weight or less, or 20% by weight or less. When included in the above content range, the polycarbonate may have an appropriate molecular weight to exhibit excellent impact resistance.

Furthermore, within the range satisfying the above content conditions, the functional group derived from the first terminal terminator is 4 wt% or more, or 10 wt% or more, or 15 wt% or more, and 40 wt% or less, based on the total weight of the polycarbonate. , or 30% by weight or less, or 20% by weight or less.

On the other hand, in the present invention, the content of the functional group derived from the first or second terminal terminator in the polycarbonate, and the content of the repeating unit of a specific structure, ^{after 1} H NMR analysis of the polycarbonate, from the result to a conventional method can be calculated accordingly.

In addition, in the polycarbonate according to an embodiment of the present invention, the aromatic diol-derived repeating unit may be a repeating unit specifically represented by the following formula (3).

[Formula 3]

In Formula 3,

R ₅ to R ₈ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,

Z is an unsubstituted or beach, or a phenyl C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, CO or substituted.

More specifically, in Formula 3, R ₅ to R ₈ may be each independently hydrogen or C _1-4 alkyl, and more specifically, R ₅ to R ₈ are each independently hydrogen, methyl , chloro, or bromo.

In addition, in Formula 3, Z may be more specifically unsubstituted or phenyl-substituted straight-chain or branched C _1-10 alkylene, more specifically methylene, ethane-1,1-diyl, propane- 2,2-diyl, butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene.

The repeating unit represented by the formula (3) has excellent transparency and impact resistance, and it is possible to prepare a polycarbonate having desired physical properties by controlling the content thereof. Specifically, the aromatic diol-derived repeating unit represented by Formula 3 is 10 wt% or more, 20 wt% or more, or 50 wt% or more, and 99 wt% or less, 90 wt% or less, or 85 wt% based on the total weight of the polycarbonate. % or less. When included within the above content range, excellent impact resistance may be exhibited.

The weight average molecular weight (Mw) of the polycarbonate containing the structural unit and functional group can be appropriately adjusted according to the purpose and use, and is 30,000 g/mol or more, or 40,000 g/mol or more, or 45,000 g/mol or more, 65,000 g/mol or less, or 55,000 g/mol or less, or 50,000 g/mol or less.

In the present invention, the weight average molecular weight (Mw) of the polycarbonate can be measured by gel permeation chromatography (GPC) using a polystyrene standard (PS standard) using an Agilent 1200 series. Specifically, it can be measured using an Agilent 1200 series instrument using a Polymer Laboratories PLgel MIX-B 300 mm long column, and the measurement temperature is 40° C., the solvent used is tetrahydrofuran, and the flow rate is 1 mL/min. The sample was prepared at a concentration of 10 mg/10 mL, then supplied in an amount of 200 μL, and Mw values were derived using a calibration curve formed using a polystyrene standard. The molecular weight (g/mol) of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

In addition, the melt index (melt index) measured according to ASTM D1238 (300 ℃, 1.2 kg conditions) of the polycarbonate can be appropriately adjusted according to the purpose and use, 3 g / 10 min or more, or 5 g / 10 min or more, or 10 g /10min or more, or 13g/10min or more, and 120g/10min or less, or 45g/10min or less, or 30g/10min or less, or 15g/10min or less.

In addition, the polycarbonate of the present invention may have a weather resistance (ΔE) calculated according to Equation 1 below, 14 or less, or 12 or less, preferably 4 to 12.

[Equation 1]

(In Equation 1, L, a, and b are values measured by the ASTM D7869 method for a 1/8 inch thick specimen, and L', a' and b' are measured again after leaving the specimen in a 2250 hr weather resistance condition. one value.)

Meanwhile, according to another embodiment of the present invention, a composition comprising an aromatic diol, a carbonate precursor, a first terminal terminator represented by the following Chemical Formula 4 and a second terminal terminator represented by the following Chemical Formula 5 is polymerized. A method for producing the polycarbonate may be provided, wherein:

[Formula 4]

[Formula 5]

In Formulas 4 and 5, R ₁ to R ₄ , a to d, and n are as defined above.

More specifically, the first terminal terminator may be a compound represented by the following Chemical Formula 4a or 4b:

[Formula 4a]

[Formula 4b]

In Formulas 4a and 4b, R ₁ to R ₃ , a to c, n ₁ and n ₂ are as defined above.

The types of the first and second end terminators are as described above, and the amounts of the first and second end terminators are also adjusted to satisfy the content conditions of functional groups derived from each end terminator in the polycarbonate described above. It can be added in quantity.

The first and second terminal terminators may be added before, during, or after polymerization, and may be added in an amount to satisfy the content of functional groups derived from the terminal terminator in the polycarbonate as described above. .

In addition, the aromatic diol may be a compound represented by the following formula (6):

[Formula 6]

In Formula 6, R ₅ to R ₈ , and Z are as defined above.

Specific examples of the aromatic diol compound represented by Formula 6 include bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, and bis(4-hydroxyphenyl). )sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl) Propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z), 2,2-bis(4-hydroxy- 3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5- and at least one compound selected from the group consisting of dimethylphenyl)propane and 1,1-bis(4-hydroxyphenyl)-1-phenylethane.

As described above, the aromatic diol may be added in an amount to satisfy the content range of the aromatic diol-derived repeating unit in the polycarbonate, specifically, the aromatic diol, the carbonate precursor, and the first and second terminal terminators. Based on 100% by weight of the total weight, 10% by weight or more, 20% by weight or more, or 50% by weight or more, and may be added in an amount of 99% by weight or less, 90% by weight or less, or 85% by weight or less.

In addition, the carbonate precursor serves to connect the aromatic diol, and specific examples thereof include phosgene, triphosgene, diphosgene, bromophosgene, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate or bishaloformate, and any one or a mixture of two or more thereof this can be used

The carbonate precursor is at least 3 wt%, at least 5 wt%, or at least 10 wt%, based on 100 wt% of the total weight of the aromatic diol, carbonate precursor, first and second end terminators, and 40 wt% or less, 35% by weight or less, or 30% by weight or less.

In this case, the polymerization is preferably carried out by interfacial polymerization, and the polymerization reaction is possible at normal pressure and low temperature during interfacial polymerization, and molecular weight control is easy.

The polymerization temperature is preferably 0°C to 40°C, and the reaction time is preferably 10 minutes to 5 hours. In addition, the pH during the reaction is preferably maintained at 9 or more or 11 to 13. In addition, upon completion of the reaction, it is preferable to lower the pH to 3 to 4, and at this time, if necessary, hydrochloric acid or the like may be additionally added.

The solvent that can be used for the polymerization is not particularly limited as long as it is a solvent used for polymerization of polycarbonate in the art, and for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene may be used.

In addition, the polymerization is preferably performed in the presence of an acid binder, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine may be used as the acid binder.

In addition, in order to promote the polymerization reaction, a reaction such as a tertiary amine compound such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound Accelerators may additionally be used.

According to another embodiment of the invention, a molded article made of the polycarbonate may be provided. As described above, the polycarbonate including the functional group derived from the first terminal terminator represented by Formula 1 together with the functional group derived from the second terminal terminator represented by Formula 2 has excellent mechanical properties and fluidity, and weather resistance is also improved. Compared to the molded products made of polycarbonate used in the past, the field of application is wide. In addition, by adjusting the molar ratio of the functional group derived from the first terminal terminator represented by Formula 1, the functional group derived from the second terminal terminator represented by Formula 2, and the repeating unit derived from an aromatic diol, a polycarbonate having desired physical properties can be prepared. have.

In addition to the polycarbonate according to the present invention, the molded article may contain at least one selected from the group consisting of antioxidants, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, optical brighteners, UV absorbers, pigments and dyes, if necessary may additionally include.

As an example of the method for manufacturing the molded article, the polycarbonate and other additives according to the present invention are mixed well using a mixer, extrusion-molded with an extruder to produce pellets, and the pellets are dried and then injected with an injection molding machine. may include.

Advantageous Effects of Invention According to the present invention, it is possible to provide a polycarbonate having a novel structure with improved weather resistance and excellent mechanical properties and fluidity, and a method for manufacturing the same.

^{1 is a 1} H-NMR graph of phenyl-4-hydroxybenzoate (oligomer) prepared in Example 1.
^{2 is a 1} H-NMR graph of phenyl-3-hydroxybenzoate (oligomer) prepared in Example 4.

The invention is described in more detail in the following examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

Example 1: Preparation of polycarbonate

(1) Preparation of phenyl-4-hydroxybenzoate (oligomer)

0.5 g of phenol was added dropwise to 200 ml of methylene chloride solvent in a round flask, and 29.4 g of 1,4-hydroxybenzoic acid was added dropwise. After that, 26.9 g of oxalyl chloride and 0.01 g of DMF were added dropwise at room temperature, stirred at room temperature for about 4 hours, and the solvent was removed through a vacuum rotary evaporator to form oligomeric phenyl-4-hydroxybenzoate (phenyl-4-hydroxybenzoate). (oligomer)) was obtained. Then, the obtained phenyl-4-hydroxybenzoate (oligomer) is subjected to an acid-base worked up process through 1N NaOH, 1N HCl aqueous solution and methylene chloride solvent, and phenyl-4-hydroxybenzoate (oligomer) without any other purification process was obtained in a crude yield of 90%.

For the phenyl-4-hydroxybenzoate (oligomer) prepared above, using the Agilent 1200 series, the weight average molecular weight measured by GPC using PS standard was about 5,000 mol/g (n1 value = 40 in Formula 4a) .

^{In addition, 1} H NMR (in Acetone-d6) analysis was performed on the prepared phenyl-4-hydroxybenzoate (oligomer), and the results are shown in FIG. 1 .

(2) Preparation of polycarbonate resin

In a 2L main reactor equipped with a nitrogen purge and a condenser and capable of maintaining room temperature with a circulator, 620 g of water, 116.47 g of 2,2-bis(4-hydroxyphenyl)propane (BPA), 40 wt% NaOH aqueous solution 102.5 g, and _{200 ml of methylene dichloride (MeCl 2} ) were added and stirred for several minutes.

Stop nitrogen purging, put 62 g of triphosgene and _{120 g of MeCl 2} into a 1L round-bottom flask, dissolve triphosgene, and then slowly put the dissolved triphosgene solution into the main reactor in which the BPA solution is dissolved, and when the input is completed (1) 6 g of phenyl-4-hydroxybenzoate (oligomer) prepared in , and 2.48 g of p-tert-butylphenol (PTBP) were added and stirred for 10 minutes. After stirring was completed, 97 g of a 40 wt% NaOH aqueous solution was added, and then 1.16 g of TEA as a coupling agent was added. At this time, the reaction pH was maintained at 11-13. To complete the reaction with sufficient time to complete the reaction, HCl was added to drop the pH to 3-4. Then, the stirring was stopped to separate the polymer layer and the water layer, the water layer was removed, and _{the process of washing with water by adding pure H 2} O again was repeated 3 to 5 times. After washing with water, only the polymer layer was extracted, and polymer crystals were obtained _{by reprecipitation using methanol and H 2 O.}

^{As a} result of 1 H NMR analysis, the content of functional groups derived from the first and second terminal terminators in the total weight of the prepared polycarbonate resin was 5 wt% and 3 wt%, respectively.

Example 2: Preparation of polycarbonate

A polycarbonate resin was prepared in the same manner as in Example 1, except that 12 g of phenyl-4-hydroxybenzoate (oligomer) and 2.3 g of PTBP were used in Example 1.

^{As a} result of 1 H NMR analysis, the content of functional groups derived from the first and second terminal terminators in the total weight of the prepared polycarbonate resin was 10 wt% and 2 wt%, respectively.

Example 3: Preparation of polycarbonate

A polycarbonate resin was prepared in the same manner as in Example 1, except that 36 g of phenyl-4-hydroxybenzoate (oligomer) and 1.58 g of PTBP were used in Example 1.

^{As a} result of 1 H NMR analysis, the content of functional groups derived from the first and second terminal terminators in the total weight of the prepared polycarbonate resin was 30 wt% and 1 wt%, respectively.

Example 4: Preparation of polycarbonate

(1) Preparation of phenyl-3-hydroxybenzoate (oligomer)

0.5 g of phenol was added dropwise to 200 ml of methylene chloride solvent in a round flask, and 29.4 g of 1,3-hydroxybenzoic acid was added dropwise. After that, 26.9 g of oxalyl chloride and 0.01 g of DMF were added dropwise at room temperature, stirred at room temperature for about 4 hours, and the solvent was removed through a vacuum rotary evaporator to obtain phenyl-3-hydroxybenzoate (oligomer). Then, the obtained phenyl-3-hydroxybenzoate (oligomer) is subjected to an acid-base worked up process through 1N NaOH, 1N HCl aqueous solution, and a methylene chloride solvent, and phenyl-3-hydroxybenzoate (oligomer) without another purification process. was obtained in a crude yield of 93%.

For the phenyl-3-hydroxybenzoate (oligomer) prepared above, using the Agilent 1200 series, the weight average molecular weight measured by GPC using PS standard was about 5,000 mol/g (n ₂ value in Formula 4b = 40).

^{In addition, 1} H NMR (in CDCl ₃ ) analysis was performed on the prepared phenyl-3-hydroxybenzoate (oligomer), and the results are shown in FIG. 2 .

(2) Preparation of polycarbonate resin

It was carried out in the same manner as in Example 1, except that in Example 1, phenyl-3-hydroxybenzoate (oligomer) prepared above was used instead of phenyl-4-hydroxybenzoate (oligomer). to prepare a polycarbonate resin.

^{As a} result of 1 H NMR analysis, the content of functional groups derived from the first and second terminal terminators in the total weight of the prepared polycarbonate resin was 5 wt% and 3 wt%, respectively.

Example 5: Preparation of polycarbonate

In the same manner as in Example 2, except that phenyl-3-hydroxybenzoate (oligomer) prepared above was used instead of phenyl-4-hydroxybenzoate (oligomer) in Example 2 to prepare a polycarbonate resin.

^{As a} result of 1 H NMR analysis, the content of functional groups derived from the first and second terminal terminators in the total weight of the prepared polycarbonate resin was 10 wt% and 2 wt%, respectively.

Example 6: Preparation of polycarbonate

In the same manner as in Example 3, except that phenyl-3-hydroxybenzoate (oligomer) prepared above was used instead of phenyl-4-hydroxybenzoate (oligomer) in Example 3 to prepare a polycarbonate resin.

^{As a} result of 1 H NMR analysis, the content of functional groups derived from the first and second terminal terminators in the total weight of the prepared polycarbonate resin was 30 wt% and 1 wt%, respectively.

Example 7: Preparation of polycarbonate

A polycarbonate resin was prepared in the same manner as in Example 4, except that 82.3 g of phenyl-3-hydroxybenzoate (oligomer) and 0.4 g of PTBP were used in Example 4.

^{As a} result of 1 H NMR analysis, the content of the functional groups derived from the first and second terminal terminators in the total weight of the prepared polycarbonate resin was 40% by weight and 0.4% by weight, respectively.

Comparative Example 1: Preparation of polycarbonate

_{620g of water, 116g of BPA, 102.5g of 40 wt% NaOH aqueous solution, and 200ml of MeCl 2} were put into a 2L main reactor equipped with a nitrogen purge and condenser, and maintained at room temperature with a circulator, and stirred for several minutes.

_{Stop purging with nitrogen and put 62 g of triphosgene and 120 g of MeCl 2} in a 1L round bottom flask to dissolve triphosgene, and then slowly put the dissolved triphosgene solution into the main reactor in which the BPA solution is dissolved, and when the input is complete, PTBP 2.66 g was added and stirred for 10 minutes. After stirring was completed, 97 g of a 40 wt% NaOH aqueous solution was added, and then 1.16 g of TEA as a coupling agent was added. At this time, the reaction pH was maintained at 11-13. In order to complete the reaction with sufficient time to complete the reaction, HCl was added to drop the pH to 3-4. Then, after stopping the stirring to separate the polymer layer and the water layer, the process of removing the water layer and _{adding pure H 2} O again to wash with water was repeated 3 to 5 times. After completion of washing with water, only the polymer layer was extracted, and polymer crystals were obtained _{by reprecipitation using methanol and H 2 O.}

^{As a} result of 1 H NMR analysis, the content of PTBP-derived functional groups in the total weight of the prepared polycarbonate resin was 2.5 wt %.

Comparative Example 2: Preparation of polycarbonate

In Example 1, 4.6 g of phenyl-4-hydroxybenzoate (i) having the following structure was used instead of phenyl-4-hydroxybenzoate (oligomer), and PTBP was not used. It was carried out in the same manner as in Example 1 to obtain a polycarbonate resin.

^{As a} result of 1 H NMR analysis, the content of functional groups derived from phenyl-4-hydroxybenzoate in the total weight of the prepared polycarbonate resin was 4.5 wt%.

(i)

(i)

Comparative Example 3: Preparation of polycarbonate

In Example 1, 4.6 g of phenyl-3-hydroxybenzoate (ii) having the following structure was used instead of phenyl-4-hydroxybenzoate (oligomer), and PTBP was not used. It was carried out in the same manner as in Example 1 to obtain a polycarbonate resin.

^{As a} result of 1 H NMR analysis, the content of functional groups derived from phenyl-3-hydroxybenzoate in the total weight of the prepared polycarbonate resin was 4.5 wt%.

(ii)

(ii)

Experimental Example: Evaluation of physical properties of polycarbonate

The properties of the polycarbonate injection specimens prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 1.

* Weight average molecular weight (g/mol): Measured by GPC using PS standard using Agilent 1200 series. Specifically, it was measured using an Agilent 1200 series instrument using a Polymer Laboratories PLgel MIX-B 300 mm long column, and the measurement temperature was 40° C., the solvent used was tetrahydrofuran, and the flow rate was 1 mL/min. The sample was prepared at a concentration of 10 mg/10 mL, then supplied in an amount of 200 μL, and Mw values were derived using a calibration curve formed using a polystyrene standard. The molecular weight (g/mol) of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

* Melt index (MI): Melt index was measured according to ASTM D1238 (300℃, 1.2 kg condition), and the fluidity was evaluated from the result.

* Glass transition temperature (Tg, ℃): Differential Scanning Calorimetry (DSC)

* Weather resistance (ΔE): After measuring L, a, and b values by ASTM D7869 on a 1/8 inch thick specimen, the specimen was left in weathering conditions for 2250 hr using a Weather-Ometer® (Ci 5000) machine. The L, a and b values were measured again. From this, the weather resistance ΔE was calculated according to Equation 1 below.

[Equation 1]

(In Equation 1, L, a, and b are values measured by the ASTM D7869 method for a 1/8 inch thick specimen, and L', a' and b' are measured again after leaving the specimen in a 2250 hr weather resistance condition. one value.)

The specimen used for the measurement of weather resistance was prepared according to the following method.

<Production of injection specimen>

Based on 1 part by weight of each of the polycarbonates prepared in Examples and Comparative Examples, 0.050 parts by weight of tris(2,4-di-tert-butylphenyl)phosphite and 0.030 parts by weight of pentaerythritol tetrastearate were added, After pelletizing using a vented Φ30mm twin-screw extruder, a 1/8 inch thick film specimen was injection molded at a cylinder temperature of 300°C and a mold temperature of 80°C using a JSW N-20C injection molding machine.

weight average molecular weight
(g/mol) MI
(g/10min) weather resistance
(ΔE) Example 1 48,000 13.5 12 Example 2 50,000 13 8.5 Example 3 48,000 15 7.8 Example 4 48,500 15 11.7 Example 5 48,000 15 8.8 Example 6 49,000 14 7.3 Example 7 49,000 13 12 Comparative Example 1 48,000 15 32 Comparative Example 2 48,000 14 15.5 Comparative Example 3 48,500 15 14.9

As a result of the experiment, the polycarbonates of Examples 1 to 7 and Comparative Examples 1 to 3 had the same weight average molecular weight and melt index, but the polycarbonates of Examples 1 to 7 including the functional group derived from the terminal terminator represented by Formula 1 Polycarbonate showed better weather resistance than Comparative Examples 1 to 3.

Claims (13)

A polymer of an aromatic diol and a carbonate precursor, comprising:
A polycarbonate comprising a functional group derived from a first terminal terminator represented by the following Chemical Formula 1 and a functional group derived from a second terminator represented by the following Chemical Formula 2:
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
R ₁ to R ₃ are each independently C _1-10 alkyl, C _1-10 alkoxy, or halogen,
R ₄ is a C _{1 -30} alkyl substituted by unsubstituted or phenyl Beach,
a to c are each independently an integer of 0 to 3,
d is an integer from 1 to 4,
n is an integer from 1 to 100,
An asterisk (*) means a bonding point.
According to claim 1,
The functional group derived from the first terminal terminator and the functional group derived from the second terminal terminator are included in a weight ratio of 1:100 to 100:1.
According to claim 1,
The content of the functional group derived from the first terminal terminator is 4 to 40% by weight based on the total weight of the polycarbonate.
According to claim 1,
The first end terminator has a weight average molecular weight of 500 to 15,000 g / mol, polycarbonate.
According to claim 1,
The functional group derived from the first terminal terminator is a functional group represented by the following Chemical Formula 1a or 1b, polycarbonate.
[Formula 1a]

[Formula 1b]

In Formulas 1a and 1b, R ₁ to R ₃ , a to c are as defined in claim 1, and n ₁ and n ₂ are each independently an integer of 1 or more and 50 or less.
According to claim 1,
The second terminal terminator is p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol. A polycarbonate comprising at least one compound selected from the group consisting of.
According to claim 1,
The polycarbonate is a polycarbonate comprising a repeating unit represented by the following formula (3) as a repeating unit derived from the aromatic diol:
[Formula 3]

In Formula 3,
R ₅ to R ₈ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,
Z is an unsubstituted or beach, or a phenyl C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, CO or substituted.
8. The method of claim 7,
The aromatic diol is bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, and bis(4-hydroxyphenyl)sulfoxide. Hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis( 4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) Propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane and 1,1-bis(4-hydroxyphenyl) ) A polycarbonate comprising at least one compound selected from the group consisting of -1-phenylethane.
According to claim 1,
The polycarbonate has a weight average molecular weight of 30,000 to 65,000 g / mol, and a melt index measured according to ASTM D1238 (300 ° C., 1.2 kg condition) is 3 to 120 g / 10 min, and is calculated according to the following Equation 1 A polycarbonate having a weather resistance (ΔE) of 14 or less:
[Equation 1]

(In Equation 1, L, a, and b are values measured by the ASTM D7869 method for a 1/8 inch thick specimen, and L', a' and b' are measured again after leaving the specimen in a 2250 hr weather resistance condition. one value)
A method for producing the polycarbonate of claim 1, comprising polymerizing a composition comprising an aromatic diol, a carbonate precursor, a first terminal terminator represented by the following Chemical Formula 4, and a second terminal terminator represented by the following Chemical Formula 5:
[Formula 4]

[Formula 5]

In Formulas 4 and 5,
R ₁ to R ₃ are each independently C _1-10 alkyl, C _1-10 alkoxy, or halogen,
R ₄ is a C _{1 -30} alkyl substituted by unsubstituted or phenyl Beach
a to c are each independently an integer of 0 to 3,
d is an integer from 1 to 4,
n is an integer from 1 to 100;
11. The method of claim 10,
The first and second terminal terminators are added in a weight ratio of 1:100 to 100:1, a method for producing polycarbonate.
11. The method of claim 10,
The aromatic diol is a method for producing a polycarbonate comprising a compound represented by the following formula (6):
[Formula 6]

In Formula 6,
R ₅ to R ₈ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,
Z is an unsubstituted or beach, or a phenyl C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, CO or substituted.
A molded article comprising the polycarbonate of any one of claims 1 to 9.

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