KR102510028B1 - Preparing method of polycarbonate using carbon dioxide, polycarbonate prepared using the same, and a molded article comprising the same - Google Patents

Abstract

The present invention relates to a method for producing polycarbonate using carbon dioxide, a polycarbonate produced using the same, and a molded article including the same. polycarbonate can be provided.

Description

Method for producing polycarbonate using carbon dioxide, polycarbonate manufactured using the same, and molded body including the same

The present invention relates to a method for producing polycarbonate using carbon dioxide, a polycarbonate produced using the same, and a molded body including the same, and more particularly, to a method for producing a polycarbonate having a graft structure using carbon dioxide as a raw material and an organic catalyst. It relates to a method, a polycarbonate prepared using the same, and a molded article including the same.

Polycarbonate resin is a thermoplastic resin put into practical use and is a polycarbonate ester compound of bisphenol A. It is transparent and has excellent mechanical properties, especially shock resistance, heat resistance, cold resistance, and electrical properties in a well-balanced, and is non-toxic and self-extinguishing. It is used for parts and mechanical parts such as various fans, helmets, and fire extinguisher covers.

Methods for producing polycarbonate resin include interfacial polymerization (solvent method) and transesterification (dissolution method), and conventional methods mainly depend on interfacial polymerization (solvent method). In the case of the interfacial polymerization method (solvent method), bisphenol A in an aqueous solution substituted with sodium and phosgene contained in a chlorine-based organic solvent are used as raw materials and vigorously mixed to produce a polycarbonate resin by polymerization at the interface between the aqueous solution and the organic solvent do. Therefore, since phosgene, the raw material used above, shows very strong toxicity, and chlorine-based organic solution is a volatile pollutant and is the main cause of environmental pollution and working environment, water or wastewater after use is treated with activated sludge or adsorbed with activated carbon , ozone treatment, etc. to decompose, remove, and discharge bisphenol A. In addition, in order to remove salts and reaction residues remaining in the polycarbonate resin thus prepared, it had to be washed and dried using a large amount of water.

In addition, in the case of the interfacial polymerization method (solvent method) as described above, despite the use of various types of catalysts, there is a disadvantage that the reaction time is long, so efforts to improve this are required. Microwaves are known to dramatically increase the rate of organic and inorganic synthesis reactions, and thus, patents related thereto are greatly increasing. Choi et al. (K.Y. Choi et al.: U.S. Pat. No. 6,525,169, Korean Registered Patent Publication No. 10-0364496) is a polycarbonate that performs solid-state polymerization by crystallizing a prepolymer polymerized from an aromatic dihydroxy compound and diaryl carbonate. Microwaves were applied to the production of resins to develop a high-molecular-weight polycarbonate production technology in a short time.

On the other hand, as part of preparations for the recent movement to regulate substances that cause global warming, such as the conclusion of the Kyoto Protocol, we have secured an independent process technology to utilize carbon dioxide as an industrial resource, and at the same time reduce environmental pollutants generated in existing chemical processes. It is time to actively promote research to replace the process with an environmentally friendly process.

From this point of view, the development of chemical processes that can utilize carbon dioxide is being developed by other advanced companies in various ways. Various efforts are being made to convert to a non-phosgene carbon dioxide process.

Therefore, the present invention, as a way to solve the above problems, developed a method for producing polycarbonate using carbon dioxide as a raw material and an organic catalyst, and confirmed the characteristics of the polycarbonate produced using the method to complete the present invention. .

Republic of Korea Patent Registration No. 10-0364496 (2002.12.12. Notice)

An object of the present invention is to provide a method for producing polycarbonate using carbon dioxide, a polycarbonate prepared using the same, and a molded body including the same.

Another object of the present invention is to provide a method for producing polycarbonate that does not contain heavy metals by using an organic catalyst, a polycarbonate prepared using the same, and a molded article including the same.

Another object of the present invention is to provide a method for producing a polycarbonate having a graft structure, a polycarbonate prepared using the same, and a molded article including the same.

The problem to be solved by the present invention is not limited to the above-mentioned problem (s), and another problem (s) not mentioned will be clearly understood by those skilled in the art from the following description.

According to one aspect of the present invention, the present invention comprises (a) preparing an initiator represented by Formula 1; (b) reacting carbon dioxide, an epoxy compound and triethylborane with the initiator of step (a); and (c) reacting the compound obtained in step (b) with carboxylic acid to prepare a compound represented by Formula 2; It provides a method for producing polycarbonate, including:

[Formula 1]

[Formula 2]

In the above formula,

R ₁ represents an alkyl ester having 1 to 18 carbon atoms, an alkylamide having 1 to 18 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and The heteroaryl group may be substituted with a substituent selected from halogen, cyano, hydroxy, thiol, amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl groups. there is,

R ₂ represents hydrogen or a methyl group;

R ₃ is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms;

R ₄ is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and the alkyl group, aryl group and heteroaryl group are halogen, cyano, hydroxy, thiol may be substituted with a substituent selected from amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl groups,

m is an integer from 0 to 500, n is an integer from 1 to 200, x is an integer from 1 to 1000, and y is an integer from 0 to 10.

The initiator of step (a) may be obtained through a free radical polymerization reaction.

The initiator of step (a) may be a compound represented by Formula 3 below.

[Formula 3]

In the above formula, m is an integer from 0 to 500, and n is an integer from 1 to 200.

The epoxy compound may be selected from the group consisting of alkylene oxides having 1 to 20 carbon atoms, cycloalkene oxides having 4 to 20 carbon atoms, and styrene oxides having 8 to 20 carbon atoms.

Step (b) may be performed at 40 to 80 °C.

The carbon dioxide in step (b) may be applied at a pressure of 10 bar or more.

According to another aspect of the present invention, the present invention provides a polycarbonate prepared by the above-described method and represented by the following formula (2):

[Formula 2]

R ₁ represents an alkyl ester having 1 to 18 carbon atoms, an alkylamide having 1 to 18 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and The heteroaryl group may be substituted with a substituent selected from halogen, cyano, hydroxy, thiol, amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl groups. there is,

R ₂ represents hydrogen or a methyl group;

R ₃ is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms;

R ₄ is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and the alkyl group, aryl group and heteroaryl group are halogen, cyano, hydroxy, thiol may be substituted with a substituent selected from amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl groups,

m is an integer from 0 to 500, n is an integer from 1 to 200, x is an integer from 1 to 1000, and y is an integer from 0 to 10.

The number average molecular weight ( M _n ) of the polycarbonate may exceed 56,000 g/mol.

The polycarbonate may contain carbon dioxide in an amount of 30% by weight or more of the total weight of the polycarbonate.

The polycarbonate may not contain heavy metals.

The polycarbonate may be a graft polymer.

According to another aspect of the present invention, the present invention provides a molded article comprising a polycarbonate represented by the following formula (2):

[Formula 2]

In the above formula,

R ₁ represents an alkyl ester having 1 to 18 carbon atoms, an alkylamide having 1 to 18 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and The heteroaryl group may be substituted with a substituent selected from halogen, cyano, hydroxy, thiol, amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl groups. there is,

R ₂ represents hydrogen or a methyl group;

R ₃ is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms;

R ₄ is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and the alkyl group, aryl group and heteroaryl group are halogen, cyano, hydroxy, thiol may be substituted with a substituent selected from amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl groups,

m is an integer from 0 to 500, n is an integer from 1 to 200, x is an integer from 1 to 1000, and y is an integer from 0 to 10.

According to the present invention, since carbon dioxide is used as a raw material, there is an environmentally friendly effect of reducing carbon dioxide.

In addition, according to the present invention, there is an advantage of providing polycarbonate that does not contain heavy metals by using an organic catalyst.

In addition, according to the present invention, there is an advantage that can provide a polycarbonate having a graft structure.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the detailed description of the present invention or the configuration of the invention described in the claims.

1 is a process flow diagram of a polycarbonate manufacturing method according to an embodiment of the present invention.
2 shows a GPC (Gel Permeation Chromatography) graph of an initiator according to an embodiment of the present invention.

Before describing the present invention in detail, the terms or words used in this specification should not be construed as unconditionally limited in a conventional or dictionary sense, and in order for the inventor of the present invention to explain his/her invention in the best way It should be noted that concepts of various terms may be appropriately defined and used, and furthermore, these terms or words should be interpreted as meanings and concepts corresponding to the technical idea of the present invention.

That is, the terms used in this specification are only used to describe preferred embodiments of the present invention, and are not intended to specifically limit the contents of the present invention, and these terms represent various possibilities of the present invention. It should be noted that it is a defined term.

In addition, in this specification, it should be noted that singular expressions may include plural expressions unless the context clearly indicates otherwise, and similarly, even if they are expressed in plural numbers, they may include singular meanings. do.

Throughout this specification, when a component is described as "including" another component, it does not exclude any other component, but further includes any other component, unless otherwise stated. It can mean you can do it.

In addition, in the following description of the present invention, a detailed description of a configuration that is determined to unnecessarily obscure the subject matter of the present invention, for example, the known technology including the prior art, may be omitted.

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

Manufacturing method of polycarbonate

The polycarbonate manufacturing method of the present invention comprises the steps of (a) preparing an initiator represented by Formula 1; (b) reacting carbon dioxide, an epoxy compound and triethylborane with the initiator of step (a); and (c) reacting the compound obtained in step (b) with carboxylic acid to prepare a compound represented by Formula 2; includes

Hereinafter, it will be described with reference to the process flow diagram of the polycarbonate manufacturing method according to the present invention of FIG.

First, an initiator represented by Chemical Formula 1 is prepared (S10).

[Formula 1]

In the above formula,

R ₁ represents an alkyl ester having 1 to 18 carbon atoms, an alkylamide having 1 to 18 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and The heteroaryl group may be substituted with a substituent selected from halogen, cyano, hydroxy, thiol, amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl groups. there is,

R ₂ represents hydrogen or a methyl group;

R ₃ is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms;

m is an integer from 0 to 500, n is an integer from 1 to 200, x is an integer from 1 to 1000, and y is an integer from 0 to 10.

The initiator may be a macroinitiator obtained through a free radical polymerization reaction. For example, a macroinitiator obtained by radical copolymerization of methyl methacrylate and 2-diethylaminoethyl methacrylate [2-(diethylamino)ethyl methacrylate, DEAEMA] may be used.

The initiator may be a compound represented by Formula 3 obtained by free radical polymerization.

[Formula 3]

In the above formula, m is an integer from 0 to 500, and n is an integer from 1 to 200.

Next, carbon dioxide, an epoxy compound, and triethylborane are reacted with the initiator of step (S10) (S20).

[Scheme 1]

Referring to Scheme 1, in this step, compound (2) is produced by reacting carbon dioxide, an epoxy compound, and triethylborane with compound (1) of step S10. R ₁ , R ₂ , R ₃ , m, n, x, and y in Scheme 1 are the same as those defined in S10 above.

Conventionally, heavy metal catalysts were mainly used in the production of polycarbonate, but in the present invention, triethylborane (TEB or Et ₃ B), which is an organic catalyst, is characterized in that it is used.

The epoxy compound may be selected from the group consisting of alkylene oxides having 1 to 20 carbon atoms, cycloalkene oxides having 4 to 20 carbon atoms, and styrene oxides having 8 to 20 carbon atoms.

This step is preferably performed at 40 to 60 °C. If it is out of the above range, there may be a problem in that by-products such as pentagonal cyclic carbonate are generated instead of the polymer compound.

Also, in this step, carbon dioxide (CO ₂ ) is preferably applied at a pressure of 10 bar or more. At a carbon dioxide pressure of 10 bar or less, y of compound (2) increases, and thus the carbon dioxide weight of the polymer may decrease.

According to the production method of the present invention, 30% by weight or more of the polymer is composed of carbon dioxide introduced in this step, so that the strength of the polycarbonate can be increased. Also, for example, when m = 0, n = 200, x = 200, y = 0, carbon dioxide may be included up to 42% by weight of the polymer.

Then, the compound represented by Chemical Formula 2 is prepared by reacting the compound obtained in step (S20) with carboxylic acid (S30).

[Scheme 2]

Referring to Reaction Scheme 2, in this step, compound (3) represented by Formula 2 is prepared by reacting carboxylic acid with compound (2) obtained in step S20.

R ₁ , R ₂ , R ₃ , m, n, x, and y in Scheme 2 are the same as those defined in S10 above.

R ₄ of the carboxylic acid is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and the alkyl group, aryl group and heteroaryl group are halogen, cyano , hydroxy, thiol, amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl group.

polycarbonate

The present invention provides a polycarbonate prepared by the above-described method and represented by the following formula (2):

[Formula 2]

In the above formula,

R ₁ represents an alkyl ester having 1 to 18 carbon atoms, an alkylamide having 1 to 18 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and The heteroaryl group may be substituted with a substituent selected from halogen, cyano, hydroxy, thiol, amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl groups. there is,

R ₂ represents hydrogen or a methyl group;

R ₃ is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms;

R ₄ is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and the alkyl group, aryl group and heteroaryl group are halogen, cyano, hydroxy, thiol may be substituted with a substituent selected from amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl groups,

m is an integer from 0 to 500, n is an integer from 1 to 200, x is an integer from 1 to 1000, and y is an integer from 0 to 10.

The number average molecular weight ( M _n ) of the polycarbonate may exceed 56,000 g/mol. Referring to Table 2, the number average molecular weight ( M _n ) of the polycarbonate prepared by the production method of the polycarbonate of the present invention exceeds 56,000 g / mol, and the weight average molecular weight ( M _w ) exceeds 85,000 g / mol confirmed that

The polycarbonate may contain carbon dioxide in an amount of 30% by weight or more of the total weight of the polycarbonate. When carbon dioxide is less than 30% by weight, the strength of polycarbonate may be weak.

The polycarbonate may not contain heavy metals. In the present invention, triethylborane, an organic catalyst, was used instead of heavy metal, which was used in the conventional polycarbonate manufacturing method, as a catalyst. Therefore, the polycarbonate according to the manufacturing method of the present invention has the advantage of not containing heavy metals.

The polycarbonate may be a graft polymer. The polycarbonate prepared according to the production method of the present invention is a polymer having a graft structure as shown in Chemical Formula 2 above.

The polycarbonate has various physical properties depending on the initiator used. For example, it can be used for elastomer or plastic applications.

Molded body containing polycarbonate

The present invention provides a molded body comprising polycarbonate represented by Formula 2.

[Formula 2]

In the above formula,

R ₁ represents an alkyl ester having 1 to 18 carbon atoms, an alkylamide having 1 to 18 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and The heteroaryl group may be substituted with a substituent selected from halogen, cyano, hydroxy, thiol, amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl groups. there is,

R ₂ represents hydrogen or a methyl group;

R ₃ is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms;

R ₄ is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and the alkyl group, aryl group and heteroaryl group are halogen, cyano, hydroxy, thiol may be substituted with a substituent selected from amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl groups,

m is an integer from 0 to 500, n is an integer from 1 to 200, x is an integer from 1 to 1000, and y is an integer from 0 to 10.

The molded body includes all types of molded bodies commonly manufactured in the art.

Example

Hereinafter, examples will be described in detail to explain the present invention in detail. However, the embodiments according to the present invention can be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

<Material>

99.99% pure CO ₂ was obtained commercially without further purification. (±) Propylene oxide (>99.5%, Acros) and 1,2-Epoxychclohexane (98%, TCI) were distilled once with CaH ₂ and used. Methyl methacrylate (with 30 ppm MEHQ, Aldrich) and Butyl Acrylate (with 30 ppm MEHQ, TCI), 2-(diethylamino)ethyl methacrylate (with 1500 ppm MEHQ, Aldrich), Styrene (with 4-tert-butylcatechol, Aldrich) are Stabilizers (MEHQ and 4-tert-butylcatechol) were removed through an alumina and silica filter before use. α,α′-Azobis(isobutyronitrile) (AIBN) was purchased from JUNSEI and used as received without further purification.

<Analysis method>

¹ H- and ¹³ C-nuclear magnetic resonance (NMR) spectra were recorded on a Bruker Biospin AVANCE DPX-400 spectrometer and a Bruker AVANCE III HD500 using deuterated solvents and corrected using residual non-hydrogenated solvents. A Fourier transform infrared (FT-IR) transmission spectrum of the compound was obtained in the range of 4000 to 550 cm ^-1 using a Bio-RAD FTS165 spectrometer.

Two types of size exclusion chromatography (SEC) were used to calculate the molecular weight (M _n ), weight average molecular weight (M _w ) and polydispersity index (PDI) of the obtained polymer. A FUTECS SD-500 equipped with Shodex KD-804, KD-803 and KD-802 column sets was used with a DMF system (5 mM LiBr, 0.8 mL/min) at 50 °C. A poly(ethylene oxide) standard sample was used for calibration of the column.

<Example 1> Preparation of macroinitiator (6)

For the preparation of the macroinitiator (6), the molecular weight and the composition ratio of m and n were adjusted according to the composition ratio of compound (4) and compound (5), AIBN or the concentration of the solvent.

<Example 1-1>

After dissolving 1.1 mL (10 equivalents) of compound (4) and 0.2 g (1 equivalent) of compound (5) in 1 mL of 1,4-dioxane (10 M), 16 mg (0.1 equivalents) of AIBN was added. The mixture was stirred for 18 hours in a nitrogen atmosphere at 65 °C. After cooling to room temperature, the reactant was precipitated in 50 mL of MeOH. After filtering the reactant, it was dried under reduced pressure to obtain 0.8 g (yield 68%) of compound (6).

<Example 1-2>

Compound (4) (2 mL) and compound (5) (0.34 g) were the same as in Example 1-1, and heated to 65° C. using 6.3 mL of 1,4-dioxane (3 M) and 0.5 equivalent of AIBN. It was stirred for 2 hours in a nitrogen atmosphere. After cooling to room temperature, the reactant was precipitated in 50 mL of MeOH. After filtering the reactant, it was dried under reduced pressure to obtain 0.97 g (yield 44%) of compound (6).

<Example 1-3>

Compound (4) (2 mL) and compound (5) (0.34 g) were the same as in Example 1, using 27 mL of 1,4-dioxane (0.7 M) and 0.05 equivalent of AIBN in a nitrogen atmosphere at 65 ° C. was stirred for 6 hours. After cooling to room temperature, the reactant is precipitated in 50 mL of MeOH. The reactant was filtered and dried under reduced pressure to obtain 1.71 g (yield: 77%) of compound (6).

The GPC graphs for the macroinitiators (6) obtained in Examples 1-1 to 1-3 are shown in FIG. 2, and the number average molecular weight ( M _n ), weight average molecular weight ( M _w ) and polydispersity shown in the GPC graphs The index (PDI) is shown in Table 1.

<Example 2> Preparation of polycarbonate compound (10)

For the preparation of the polycarbonate compound (10), the macroinitiator (6) of Example 1-1 or 1-2 was used, and the molecular weight was adjusted by adjusting the reaction temperature.

<Example 2-1>

After drying the 80 mL autoclave in an oven at 100 ° C. for 24 hours and vacuum drying for 1 hour in a glove box, 0.15 g (1 equivalent) of the macroinitiator (6) obtained in Example 1-1 was added. After dissolving in 0.5 mL of THF, adding propylene oxide (2 mL, 200 equivalents) and 0.28 mL of TEB (1 M solution in THF), it was sealed and taken out of the glove box. After putting 20 bar of CO ₂ in an autoclave, the mixture was stirred at 40 °C for 6 hours. After cooling to room temperature, remaining CO ₂ was slowly removed and dried under reduced pressure to obtain compound (9). After dissolving compound (9) in 1.5 mL CHCl ₃ , 0.17 g (10 equivalents) of benzoic acid was added, and the mixture was stirred at 50 °C for 3 hours. After cooling to room temperature, the reactant is precipitated in 60 mL of normal hexane. After filtering the reactant, it was dried under reduced pressure to obtain 0.2 g (yield 10%) of compound (10).

<Example 2-2>

Example 2-1 was performed except that the macroinitiator (6) obtained in Example 1-2 was used.

<Example 2-3>

Example 2-2 was performed except that 70 equivalents of propylene oxide were used.

Table 2 shows the number average molecular weight ( M _n ), weight average molecular weight ( M _w ), and polydispersity index (PDI) of the polycarbonate compound (10) obtained in Examples 2-1 to 2-3.

So far, the method for producing polycarbonate using carbon dioxide according to the present invention, the polycarbonate produced using the same, and specific examples of a molded body including the same have been described, but various implementations are carried out without departing from the scope of the present invention. It is obvious that variations are possible.

Therefore, the scope of the present invention should not be limited to the described embodiments and should not be defined, and should be defined by not only the claims to be described later, but also those equivalent to these claims.

That is, it should be understood that the above-described embodiments are illustrative in all respects and not restrictive, and the scope of the present invention is indicated by the claims to be described later rather than the detailed description, and the meaning and scope of the claims and All changes or modified forms derived from the equivalent concept should be construed as being included in the scope of the present invention.

Claims (12)

(a) preparing a macroinitiator represented by Compound 6 using Compounds 4 and 5 and α,α'-Azobis (isobutyronitrile) (AIBN);
(b) reacting the macroinitiator of step (a) with carbon dioxide, an epoxy compound, and triethylborane as an organic catalyst; and
(c) preparing a polycarbonate represented by Compound 10 by reacting the compound obtained in step (b) with carboxylic acid; including,
Manufacturing method of polycarbonate:
[Compound 4]

[Compound 5]

[Compound 6]

[Compound 10]

In the above formula,
R ₄ is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and the alkyl group, aryl group and heteroaryl group are halogen, cyano, hydroxy, thiol may be substituted with a substituent selected from amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl groups,
m is an integer from 0 to 500, n is an integer from 1 to 200, x is an integer from 1 to 1000, and y is an integer from 0 to 10.
According to claim 1,
The macroinitiator of step (a) is
Characterized in that obtained through a free radical polymerization reaction,
Manufacturing method of polycarbonate.
delete According to claim 1,
The epoxy compound is
Characterized in that it is selected from the group consisting of alkylene oxides having 1 to 20 carbon atoms, cycloalkene oxides having 4 to 20 carbon atoms, and styrene oxides having 8 to 20 carbon atoms,
Manufacturing method of polycarbonate.
According to claim 1,
The step (b) is characterized in that carried out at 40 ~ 80 ℃,
Manufacturing method of polycarbonate.
According to claim 1,
Characterized in that the carbon dioxide in step (b) is applied at a pressure of 10 bar or more,
Manufacturing method of polycarbonate.
It is prepared by the method of claim 1,
Represented by compound 10 below,
Polycarbonate:
[Compound 10]

In the above formula,
R ₄ is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and the alkyl group, aryl group and heteroaryl group are halogen, cyano, hydroxy, thiol may be substituted with a substituent selected from amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl groups,
m is an integer from 0 to 500, n is an integer from 1 to 200, x is an integer from 1 to 1000, and y is an integer from 0 to 10.
According to claim 7,
Characterized in that the number average molecular weight ( M _n ) is greater than 56,000 g/mol,
polycarbonate.
According to claim 7,
Characterized in that it contains carbon dioxide at least 30% by weight of the total polycarbonate,
polycarbonate.
According to claim 7,
Characterized in that it does not contain heavy metals,
polycarbonate.
According to claim 7,
Characterized in that it is a graft polymer,
polycarbonate.
It is prepared by the method of claim 1,
A molded article comprising a polycarbonate represented by the following compound 10:
[Compound 10]

In the above formula,
R ₄ is a substitutable hydrocarbon group, and represents an alkyl group having 1 to 10 carbon atoms, an aryl group or a heteroaryl group having 3 to 10 ring atoms, and the alkyl group, aryl group and heteroaryl group are halogen, cyano, hydroxy, thiol may be substituted with a substituent selected from amino, alkyl, alkyloxy, alkylamino, dialkylamino, aryl, aryloxy, arylamino, diarylamino or heteroaryl groups,
m is an integer from 0 to 500, n is an integer from 1 to 200, x is an integer from 1 to 1000, and y is an integer from 0 to 10.

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