KR101608411B1 - [poly(isosorbide carbonate-aromatic carbonate)]-[polycarbonate] block copolymer and method for preparing the same - Google Patents

Abstract

The present invention relates to [poly (isosorbide carbonate-aromatic carbonate)] - [polycarbonate] block copolymer and a process for producing the same, and more particularly, to a process for producing a poly (isosorbide carbonate- aromatic carbonate) ) Oligomer and a polycarbonate oligomer and is excellent in color, molding processability, heat resistance and impact resistance while having a high content of a biomass-derived material, and a process for producing the same.

Description

[POLY (ISOSORBIDE CARBONATE-AROMATIC CARBONATE)] - [POLYCARBONATE] BLOCK COPOLYMER AND METHOD FOR PREPARING THE SAME [0002]

The present invention relates to [poly (isosorbide carbonate-aromatic carbonate)] - [polycarbonate] block copolymer and a process for producing the same, and more particularly, to a process for producing a poly (isosorbide carbonate- aromatic carbonate) ) Oligomer and a polycarbonate oligomer and is excellent in color, molding processability, heat resistance and impact resistance while having a high content of a biomass-derived material, and a process for producing the same.

Aromatic bisphenol-based polycarbonates are excellent in mechanical properties such as tensile strength and impact resistance, and are excellent in dimensional stability, heat resistance and optical transparency, and thus are widely used in industrial applications. However, since conventional polycarbonate is produced mainly by using raw materials obtained from petroleum resources, production and use of such polycarbonate are restricted due to depletion of petroleum resources. Therefore, there is a demand for the production of polycarbonate using a raw material (biomass-derived material) obtained from renewable resources such as plants.

From this point of view, a technique for producing polycarbonate by melt polymerization using isosorbide among plant-derived materials has been proposed (WO09 / 050682). However, the isosorbide homopolycarbonate synthesized by melt polymerization has a high boiling point and has a disadvantage in that the melt viscosity is significantly increased due to the rigid structure of isosobide, which makes molding processing difficult.

Also, in the case of isosorbide-based carbonates, it is difficult to obtain a high-molecular-weight polymer by the interfacial polymerization method, and therefore, it is commercially produced by a melt polymerization method. However, the isosorbide-based polycarbonate obtained by melt polymerization at a high temperature has a disadvantage in that the impact resistance is poor and the mechanical properties are not excellent. In addition, the suitable temperature for the polymerization of isosorbide polycarbonate during the melt polymerization is 210 to 240 ° C., whereas the aromatic polycarbonate is sufficiently reacted at the polymerization temperature of 250 to 300 ° C., so that the isocyanide polycarbonate and the aromatic polycarbonate When melt polymerization is carried out at a high temperature of 250 to 300 ° C, the isosorbide is discolored by heat and the YI value is increased.

Therefore, it is required to develop a technique capable of producing a polycarbonate copolymer excellent in various physical properties such as color, molding processability, heat resistance and impact resistance, while having a high content of a biomass-derived material.

Disclosure of the Invention The present invention has been made to solve the above problems of the prior art, and it is an object of the present invention to provide a biodegradable resin composition which is excellent in physical properties such as color, molding processability, heat resistance and impact resistance )] - [polycarbonate] block copolymer, and a method capable of producing the copolymer at a lower temperature and easily controlling the molecular weight thereof.

In order to solve the above-mentioned technical problems, the present invention relates to a hydroxy-terminated (isosorbide carbonate-aromatic carbonate) oligomer having a viscosity-average molecular weight of 1,000 to 20,000, (Isocyanide carbonate-aromatic carbonate)] - [polycarbonate] block copolymer, which has a viscosity average molecular weight (Mv) of from 10,000 to 70,000, as a repeating unit, and a polycarbonate block :

[Chemical Formula 1]

In Formula 1,

X represents a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms substituted or unsubstituted with an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom, or nitro; n represents an integer of 1 to 110; m represents an integer of 1 to 20;

According to another aspect of the present invention, there is provided a process for producing a polyurethane elastomer comprising the steps of (1) melt polymerization of isosorbide, carbonic acid diester and aromatic diol to obtain a hydroxy terminal having a viscosity average molecular weight of 1,000 to 20,000, Isosorbide carbonate-aromatic carbonate) oligomer; And (2) surface-polymerizing the hydroxyl-terminated (isosorbide carbonate-aromatic carbonate) oligomer prepared above and a polycarbonate oligomer prepared separately therefrom to obtain a copolymer having a viscosity average molecular weight (Mv) of 10,000 to 70,000 (Polycarbonate) block copolymer, comprising the steps of: (a) preparing a poly (isobornyl carbonate-aromatic carbonate) - [polycarbonate] block copolymer.

According to another aspect of the present invention, there is provided a molded article comprising the above-mentioned [poly (isosorbide carbonate-aromatic carbonate)] - [polycarbonate] block copolymer.

[Poly (isosorbide carbonate-aromatic carbonate)] - [polycarbonate] block copolymer according to the present invention is excellent in various physical properties such as color, molding processability, heat resistance, and impact resistance, while having a high content of biomass- It can be suitably used for molded articles such as materials for electric / electronic parts such as TVs and cellular phones, materials for automobile parts such as lamps and lenses, and the like. Further, according to the process for producing a copolymer of the present invention, such a copolymer can be produced at a lower temperature than the prior art, its molecular weight can be easily controlled, and a high molecular weight A polycarbonate copolymer containing a sulfobis carbonate block can be obtained.

As used herein, the term " reaction product " means a material in which two or more reactants are formed by reaction.

In addition, although the terms "first", "second" and the like are used herein to describe a polymerization catalyst, the polymerization catalyst is not limited by these terms. These terms are merely used to distinguish polymerization catalysts from each other. For example, the first polymerization catalyst and the second polymerization catalyst may be the same kind of catalyst or different kinds of catalysts.

The letter "R" used to represent hydrogen, a halogen atom and / or a hydrocarbon group in the formulas described in the present specification has a subscript indicated by a numeral, but the letter "R" But is not limited thereto. The "R" represents, independently of each other, hydrogen, a halogen atom and / or a hydrocarbon group. For example, the "R" s may represent the same hydrocarbon group or may represent other hydrocarbon groups, irrespective of whether two or more "R" have the same or different numbers of subscripts.

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

(A) Hydroxy  End ( Isosobaid Carbonate - Aromatics Carbonate ) Oligomer

The hydroxyl-terminated (isosorbide carbonate-aromatic carbonate) oligomer contained in the polycarbonate block copolymer of the present invention as a repeating unit has a structure represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

X represents a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms substituted or unsubstituted with an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom, or nitro; n represents an integer of 1 to 110; m represents an integer of 1 to 20;

For example, the alkyl group is an alkyl group having 1 to 20 carbon atoms (more specifically, an alkyl group having 1 to 13 carbon atoms such as methyl, ethyl or propyl), the cycloalkyl group is a cycloalkyl group having 3 to 10 carbon atoms (more specifically, An alkenyl group having 2 to 20 carbon atoms (more specifically, an alkenyl group having 2 to 13 carbon atoms); the alkoxy group is an alkoxy group having 1 to 20 carbon atoms (more specifically, a carbon number An alkoxy group of 1 to 13, such as methoxy, ethoxy or propoxy), and the halogen atom may be Cl or Br.

For example, X may be a substituted or unsubstituted arylene group derived from bisphenol A, resorcinol, hydroquinone or diphenyl phenol, For example, they may be represented by the following formulas (1a) to (1h).

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

[Formula 1g]

[Chemical Formula 1h]

The hydroxyl-terminated (isosorbide carbonate-aromatic carbonate) oligomer of Formula 1 has a viscosity average molecular weight (Mv) of 1,000 to 20,000, and more preferably a viscosity average molecular weight (Mv) of 5,000 to 15,000. If the viscosity average molecular weight is less than 1,000, there is a limit to increase the content of isosorbide in the oligomer, so that the effect including the biologically-derived material may be insufficient. When the viscosity exceeds 20,000, the reactivity becomes poor, have.

The hydroxy-terminated (isosorbide carbonate-aromatic carbonate) oligomer of Formula 1 may be prepared by melt polymerization of isosorbide, carbonic acid diester and aromatic diol.

The isosorbide is a diol-free anhydrosugar alcohol obtained by dehydration of sorbitol, which is an alcohol per C ₆ . In the present invention, isosorbide derived from plants (i.e., isosorbide obtained by dehydration of sorbitol derived from starch) is preferably used.

As the carbonic acid diester, for example, a diorganocarbonate having two organic groups selected from an alkyl group, an aryl group and an aralkyl group can be used, and those represented by the following formula 2 can be preferably used.

(2)

In Formula 2, A and A 'are each independently selected from an unsubstituted or halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 25 carbon atoms.

More specifically, the carbonic acid diester may be selected from diphenyl carbonate, bischlorophenyl carbonate, dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate and mixtures thereof, more preferably diphenyl Carbonate can be used.

As the aromatic diol, a substituted or unsubstituted monocyclic or polycyclic aromatic diol may be used. The aromatic diol may be unsubstituted or substituted with at least one selected from an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom and a nitro group.

More specifically, as the aromatic diol, bisphenol A, naphthalene diol, biphenol or a mixture thereof may be used, and more preferably, bisphenol A may be used.

The amount of isosorbide used is preferably from 70 mol% to 98 mol%, more preferably from 80 mol% to 95 mol%, based on 100 mol% of the total amount of the isosorbide and the aromatic diol. If the amount of isosorbide used is too small, there may be a problem that the use of the biologically-derived raw material in the final polymer is not matched with the object of increasing the utilization of the raw material. If the isosorbide is excessively large, Can be.

The amount of the carbonic acid diester component to be used is preferably 1.02 to 0.98 in a molar ratio with respect to 1 mole of the total amount of the isosorbide and the aromatic diol. If the molar ratio of the carbonic acid diester component exceeds 1.02, it may be difficult to obtain an oligomer having a sufficient molecular weight because the carbonic ester residue functions as a terminal stopper. On the other hand, if the molar ratio is less than 0.98, the diol component functions as a terminal stopper, It may be difficult to obtain an oligomer having a molecular weight.

The isosorbide, the carbonic acid diester and the aromatic diol may be melt polymerized in the presence of a polymerization catalyst.

Examples of the polymerization catalyst include alkali metal salt compounds such as sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, cesium carbonate and the like; Alkaline earth metal salt compounds such as calcium hydroxide, barium oxide, and magnesium oxide; Nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, triethylamine and the like; These may be used singly or in combination of two or more kinds. Among them, it is more preferable to use a combination of a nitrogen-containing basic compound and an alkali metal salt compound. The amount of the polymerization catalyst to be used is preferably 1 * 10 ^-9 to 1 * 10 ^-3 equivalents, more preferably 1 * 10 ^-8 to 5 * 10 ^-4 equivalents, per 1 mole of the carbonic acid diester .

The melt polymerization can be carried out under elevated temperature conditions, for example, 180 ° C to 240 ° C (more specifically, 200 ° C to 220 ° C), at normal pressure or reduced pressure (for example, from 0.1 torr to 50 torr). According to one embodiment of the present invention, the melt polymerization process comprises mixing and heating an isosorbide, a carbonic acid diester and a polymerization catalyst at normal pressure and reacting at a temperature of 180 to 240 캜 (e.g., 200 캜); Followed by removal of phenol, the minor reactant, at a temperature of 180 ° C to 240 ° C under reduced pressure to 50 torr or less (eg, up to 0.1 torr) and reacting; And returning it to atmospheric pressure and then introducing an aromatic diol thereto and again reacting at a temperature of 180 ° C to 240 ° C (for example, 220 ° C) under reduced pressure to 50 torr or less (for example, up to 0.1 torr) .

(B) Polycarbonate block

The polycarbonate block contained as a repeating unit in the copolymer of the present invention may preferably be an aromatic polycarbonate block having a unit structure represented by the following formula (3).

 (3)

In Formula 3, Y represents a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms, which is substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group.

For example, the halogen atom may be Cl or Br, the alkyl group may be an alkyl group having 1 to 20 carbon atoms (more specifically, an alkyl group having 1 to 13 carbon atoms such as methyl, ethyl or propyl), the alkoxy group having 1 to 20 carbon atoms An alkoxy group (more specifically, an alkoxy group having 1 to 13 carbon atoms such as methoxy, ethoxy or propoxy), and the aryl group may be an aryl group having 6 to 10 carbon atoms (e.g., phenyl, chlorophenyl or tolyl) .

For example, Y may be a substituted or unsubstituted arylene group derived from bisphenol A, resorcinol, hydroquinone or diphenyl phenol. For example, Y may be derived from a divalent phenol compound having the structure of formula (3a).

[Chemical Formula 3]

In the above formula (3a)

L represents an alkylene group, a linear, branched or cyclic alkylene group having no functional group, or a linear, branched or cyclic alkylene group containing a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, Lt; / RTI > Preferably, L may be a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms and 3 to 6 carbon atoms. R ₆ and R ₇ may independently represent a hydrogen atom, a halogen atom, or an alkyl group, for example, a linear, branched or cyclic alkyl group having from 1 to 20 carbon atoms and having from 3 to 20 carbon atoms, preferably from 3 to 6 carbon atoms. a and b independently represent an integer of 0 to 4;

The compound of formula (3a) is, for example, selected from the group consisting of bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis ) - (4-isobutylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1- Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2- Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, Bis (4-hydroxyphenyl) propane, bis (3-methyl-4-hydroxyphenyl) propane, 2,2- , 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) Resorcinol, Hydroquine, 4,4'-dihydroxyphenyl ether [bis (4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-di Dihydroxy-3,3'-dichlorodiphenyl ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dichloro- Hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p, Dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5- (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, 1,1- Bis (4-hydroxyphenyl) propane, 1,4-bis (4- (4-hydroxyphenyl) butane, 2,2-bis (3-chloro-4-hydroxyphenyl) Bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 2,2- Bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis -Bis (4-hydroxyphenyl) sulfone], bis (3,5-dimethyl-4-hydroxyphenyl) Sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis , Bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone, ', 5,5'-tetramethyl-4,4'-dihydroxybenzophe , 4,4'-dihydroxy-diphenyl, methyl may be a hydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxy naphthalene, but is not limited thereto. Representative examples include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). Other functional dihydric phenols can be found in US Pat. Nos. US 2,999,835, US 3,028,365, US 3,153,008 and US 3,334,154, and the dihydric phenols may be used singly or in combination of two or more. Can be used.

In the case of the carbonate precursor, as other monomers of the polycarbonate resin, for example, carbonyl chloride (phosgene), carbonyl bromide, bishaloformate, diphenyl carbonate or dimethyl carbonate can be used.

The polycarbonate block contained in the copolymer of the present invention as a repeating unit can be prepared by interfacially polymerizing a separately prepared polycarbonate oligomer with the hydroxyl end (isosorbide carbonate-aromatic carbonate) oligomer of the above formula (1) .

The viscosity average molecular weight (Mv) of the polycarbonate oligomer is preferably 3,000 to 20,000, more preferably 4,000 to 15,000. If the viscosity average molecular weight of the polycarbonate oligomer is less than 3,000, the molecular weight distribution of the final product copolymer may be widened and the physical properties may be deteriorated. If the viscosity average molecular weight is more than 20,000, the reactivity may be excessively decreased during the production of the copolymer.

There is no particular limitation on the method for producing the polycarbonate oligomer. According to one embodiment of the present invention, the divalent phenol compound of formula (3a) is added to an aqueous alkaline solution to form a phenol salt state, and then the salt phenol is dissolved in methylene chloride (MC) or dichloromethane And then reacted to prepare a polycarbonate oligomer. For oligomer preparation, the molar ratio of phosgene to bifunctional phenolic compounds is preferably maintained in the range of about 1: 1 to 1.5: 1, more preferably about 1: 1 to 1.2: 1. If the molar ratio of phosgene to 1 mol of the divalent phenol compound is less than 1, the reactivity may be lowered. If the molar ratio exceeds 1.5, the workability may be lowered due to an excessive molecular weight increase.

For example, triethylamine (TEA) may be used as a reaction catalyst in the formation of the polycarbonate oligomer, but it is not limited thereto. As the molecular weight regulator, a monofunctional compound similar to the monomer used in the production of the polycarbonate may be used. The monofunctional material may be, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumyl phenol, p- Phenol-based derivatives such as phenol, or aliphatic alcohols. Preferably, p-tert-butylphenol (PTBP) is used.

The polycarbonate oligomerization reaction is suitably carried out at a pH in the range of from 6 to 8 and at a temperature in the range of from 15 to 40 ° C, and an alkali metal hydroxide (for example, sodium hydroxide) may be used to adjust the pH of the reaction mixture. If the pH of the reaction mixture is less than 6, the reactivity may deteriorate and the molecular weight increase may decrease or the reaction time may become longer. If the pH of the reaction mixture exceeds 8, the molecular weight distribution of oligomers becomes larger, The problem may become larger.

In one embodiment of the present invention, the intermediate liquid containing the polycarbonate oligomer thus prepared is extracted and separated from the reaction mixture and used in the next step, the copolymer preparation step.

(C) [poly ( Isosobaid Carbonate - aromatic carbonate)] - [polycarbonate] block copolymer

[Poly (isosorbide carbonate-aromatic carbonate)] - [polycarbonate] block copolymer of the present invention is obtained by reacting the hydroxy terminal (isosorbide carbonate-aromatic carbonate) oligomer of the above-described formula 1 and the polycarbonate block As a repeat unit.

The viscosity average molecular weight (Mv) of the copolymer of the present invention is 10,000 to 70,000, preferably 15,000 to 50,000, and more preferably 18,000 to 30,000. If the viscosity average molecular weight of the copolymer is less than 10,000, there is a problem in realizing sufficient mechanical properties. If the copolymer has a molecular weight exceeding 70,000, the copolymer has a too high molecular weight, resulting in poor melt characteristics and difficult processing.

In addition, the copolymer of the present invention preferably contains 10 to 60% by weight, based on the total weight of the copolymer, of the hydroxyl end (isosorbide carbonate-aromatic carbonate) oligomer of formula (1) % To 50% by weight. If the oligomer content of the formula (1) is less than 10% by weight, the content of the plant may be lowered. If the content of the oligomer is more than 60% by weight, the melting temperature may increase.

In the copolymer of the present invention, the isosorbide content based on the total weight of the copolymer is preferably 5% by weight to 50% by weight, more preferably 7% by weight to 40% by weight. If the content of isosorbide is less than 5% by weight, the content of the plant may be lowered. If the content of isosorbide is more than 50% by weight, the melting temperature may be increased and there may be a problem in processing.

Such a copolymer of the present invention can be prepared by surface-polymerizing a hydroxy terminal (isosorbide carbonate-aromatic carbonate) oligomer of formula (1) and a polycarbonate oligomer prepared separately.

The interfacial polymerization reaction may be carried out under an interfacial reaction condition comprising an aqueous alkali solution and an organic phase.

According to one embodiment of the present invention, a polycarbonate oligomer having a viscosity-average molecular weight adjusted to a specific level is prepared first, and then a hydroxyl-terminated (isosorbide carbonate-aromatic carbonate) oligomer of Formula 1 is added thereto, To form a copolymer.

The mixture of the polycarbonate oligomer and the oligomer of Formula 1 for the interfacial reaction may further contain a molecular weight regulator, a first polymerization catalyst, a phase transfer catalyst, a pH adjuster (e.g., NaOH), methylene chloride (MC) Specifically, the copolymer of the present invention can be prepared by adding an oligomer of the formula (1) to an organic phase-water mixture containing a polycarbonate oligomer and gradually adding a molecular weight regulator, a catalyst and the like.

As the molecular weight regulator, a monofunctional compound similar to the monomers used in the polycarbonate production as mentioned above may be used.

As the catalyst, a polymerization catalyst and / or a phase transfer catalyst may be used. As the polymerization catalyst, for example, triethylamine (TEA) can be used. As the phase transfer catalyst, for example, a compound of the following formula (4) can be used.

[Chemical Formula 4]

(R ₂ ) ₄ Q ⁺ X ^-

In Formula 4, R ₂ represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and X represents a halogen atom or -OR ₃ . Here, R ₃ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.

Specifically, the phase-transfer catalyst, for example, _{[CH 3 (CH 2) 3} ] 4 NX, [CH 3 (CH 2) 3] 4 PX, [CH 3 (CH 2) 5] 4 NX, [CH 3 _{(CH 2) 6] 4 NX} , [CH 3 (CH 2) 4] 4 NX, CH 3 [CH 3 (CH 2) 3] 3 NX, CH 3 [CH 3 (CH 2) 2] can be a ₃ NX have. In the above formulas, X represents Cl, Br or -OR ₃ , wherein R ₃ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.

The content of the phase transfer catalyst is preferably about 0.01 to 10% by weight, more preferably 0.1 to 10% by weight based on the total weight of the mixture of the polycarbonate oligomer and the compound of the formula (1). If the content is less than 0.01% by weight, the reactivity may be deteriorated. If the content is more than 10% by weight, precipitates may precipitate or the transparency may be deteriorated.

In one preferred embodiment, the polymerization of the polycarbonate oligomer and the oligomer of formula (I) is carried out stepwise, first and secondarily. Specifically, one step of polymerizing is carried out from a mixture of oligomers of the formula (I), a first polymerization catalyst, a phase transfer catalyst, a molecular weight regulator, a pH regulator (for example, NaOH), methylene chloride (MC) and the like into a polycarbonate oligomer, The second polymerization catalyst is charged to perform the second polymerization step. Here, the two steps of polymerisation can be carried out by providing a second polymerization catalyst to the resulting mixture after the first polymerization step is completed.

In one embodiment, the copolymer is prepared as described above, and then the organic phase dispersed in methylene chloride is alkaline cleaned and then separated. Subsequently, the organic phase is washed with 0.1N hydrochloric acid solution and then washed repeatedly with distilled water two to three times. When the washing is completed, the concentration of the organic phase dispersed in methylene chloride is adjusted to a constant level, and granulation is performed using a predetermined amount of pure water in the range of 30 to 100 ° C, preferably 60 to 80 ° C. If the pure water temperature is less than 30 ° C, the assembling speed is decreased and the assembling time may become very long. When the pure water temperature exceeds 100 ° C, it may become difficult to obtain the polycarbonate shape to a certain size. When the assembly is completed, drying is preferably performed at 100 to 120 ° C for 5 to 10 hours, more preferably at 100 to 110 ° C for 5 to 10 hours, and further at 110 to 120 ° C for 5 to 10 hours .

[Poly (isosorbide carbonate-aromatic carbonate)] - [polycarbonate] block copolymer according to the present invention is excellent in various physical properties such as color, molding processability, heat resistance and impact resistance, while having a high content of biomass- Therefore, it can be suitably used, for example, in molded articles such as materials for electric / electronic parts such as mobile phones and TVs and materials for automobile parts such as lamps and lenses.

Therefore, according to another aspect of the present invention, there is provided a molded article comprising the [poly (isosorbide carbonate-aromatic carbonate)] - [polycarbonate] block copolymer of the present invention.

The method of molding the copolymer of the present invention into a molded article is not particularly limited, and a molded article can be produced by a method generally used in the plastic molding field.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.

[ Example ]

Example  One

< Hydroxy  End ( Isosobaid Carbonate - Aromatics Carbonate ) Oligomeric  Manufacturing>

235 g of diphenyl carbonate, 155 g of isosorbide and 0.0001 g of cesium carbonate (cesium carbonate) were placed in a 2L three-neck condenser, and the mixture was slowly heated at 200 占 폚 under a nitrogen gas atmosphere. The pressure was gradually reduced to 0.1 torr over 1 hour to remove phenol as a byproduct in the reduced pressure state. After the decompression was released, 25 g of bisphenol A was further added, and the reaction was allowed to proceed for 30 minutes under reduced pressure at a temperature of 220 ° C lowered to 0.1 torr. As a result, a hydroxyl-terminated (isosorbide carbonate-aromatic carbonate) oligomer having a viscosity average molecular weight (Mv) of 6,020 was obtained.

[Chemical Formula 5]

<[Poly ( Isosobaid Carbonate - Aromatics Carbonate )] - [polycarbonate] &lt; / RTI &gt; &lt; RTI ID =

Bisphenol A in an aqueous solution and phosgene gas were interfacially reacted in the presence of methylene chloride to prepare 400 mL of a polycarbonate oligomer having a viscosity average molecular weight of about 1,000.

To the obtained polycarbonate oligomer was added 20% by weight (based on 100% by weight of the polycarbonate oligomer) of the hydroxy terminal (isosorbide carbonate-aromatic carbonate) oligomer of Formula 5 dissolved in methylene chloride, 20% by weight of tetrabutylammonium chloride 2.8 g of p-tert-butylphenol (PTBP) and 275 μL of triethylamine (TEA, 15 wt% aqueous solution) were mixed and reacted for 30 minutes. As a result of the reaction, the mixture was allowed to stand to separate layers, and then only the organic phase was taken, and 170 g of aqueous sodium hydroxide solution, 360 g of methylene chloride and 300 μL of a 15 wt% aqueous solution of triethylamine were mixed and reacted for 2 hours. After separating the layers, the organic phase with increased viscosity was washed with alkali and separated. Subsequently, the organic phase was washed with 0.1 N hydrochloric acid solution and then washed repeatedly with distilled water two to three times. After the cleaning was completed, a certain amount of pure water was used to assemble at 76 ° C. After the assembly was completed, it was dried at 110 ° C for 8 hours and then at 120 ° C for 10 hours. The physical properties of the prepared [poly (isosorbide carbonate-aromatic carbonate)] - [polycarbonate] block copolymer were measured and described in Table 1 below.

Example  2

< Hydroxy  End ( Isosobaid Carbonate - Aromatics Carbonate ) Oligomeric  Manufacturing>

(Isosorbide carbonate-aromatic carbonate) oligomer having a viscosity average molecular weight of 12,250 was obtained in the same manner as in Example 1, using 240 g of diphenyl carbonate, 160 g of isosorbide and 18 g of bisphenol A. [

<[Poly ( Isosobaid Carbonate - Aromatics Carbonate )] - [polycarbonate] &lt; / RTI &gt; &lt; RTI ID =

Using the obtained hydroxy terminal (isosorbide carbonate-aromatic carbonate) oligomer 10% by weight (based on 100% by weight of polycarbonate oligomer), [poly (isosorbide carbonate- aromatic carbonate )] - [polycarbonate] block copolymer was prepared, and physical properties thereof were measured and described in Table 1 below.

Example  3

< Hydroxy  End ( Isosobaid Carbonate - Aromatics Carbonate ) Oligomeric  Manufacturing>

(Isosorbide carbonate-aromatic carbonate) oligomer having a viscosity average molecular weight of 11,500 was obtained in the same manner as in Example 1, using 250 g of diphenyl carbonate, 165 g of isosorbide and 23 g of bisphenol A.

<[Poly ( Isosobaid Carbonate - Aromatics Carbonate )] - [polycarbonate] &lt; / RTI &gt; &lt; RTI ID =

(P-tert-butylphenol (PTBP) was obtained in the same manner as in Example 1, except that 50% by weight of the obtained hydroxy terminal (isosorbide carbonate-aromatic carbonate) oligomer (based on 100% by weight of polycarbonate oligomer) ) Was used to prepare a poly (isosorbide carbonate-aromatic carbonate)] - [polycarbonate] block copolymer, and physical properties thereof were measured and described in Table 1 below.

Comparative Example  One

A mixture of 488 g of diphenyl carbonate, 320 g of isosorbide and 23 g of bisphenol A was subjected to the same procedure as in Example 1 (using 0.0002 g of the catalyst) with a hydroxy terminal having a viscosity average molecular weight of 18,500 (isosorbide carbonate-aromatic carbonate ) Oligomers were prepared, and physical properties thereof were measured and described in Table 1 below. (I.e., no copolymerization with the polycarbonate oligomer through the interfacial reaction is performed)

Comparative Example  2

Was prepared in the same manner as in Example 1 using 30 weight% (based on 100 weight% of polycarbonate oligomer) of the hydroxy terminal (isosorbide carbonate-aromatic carbonate) oligomer (viscosity average molecular weight: 6,020) obtained in Example 1 Except that 4.57 g of p-tert-butylphenol (PTBP) was used) to prepare [poly (isosorbide carbonate-aromatic carbonate)] - [polycarbonate] block copolymer, Respectively.

Comparative Example  3

< Hydroxy  End ( Isosobaid Carbonate - Aromatics Carbonate ) Oligomeric  Manufacturing>

(Isosorbide carbonate-aromatic carbonate) oligomer having a viscosity average molecular weight of 35,040 was obtained in the same manner as in Example 1, using 255 g of diphenyl carbonate, 172 g of isosorbide and 18 g of bisphenol A. [

<[Poly ( Isosobaid Carbonate - Aromatics Carbonate )] - [polycarbonate] &lt; / RTI &gt; &lt; RTI ID =

(P-tert-butylphenol (PTBP) was obtained in the same manner as in Example 1, except that 20 weight% of the obtained hydroxy terminal (isosorbide carbonate-aromatic carbonate) oligomer (based on 100 weight% of polycarbonate oligomer) ) [Poly (isosorbide carbonate-aromatic carbonate)] - [polycarbonate] block copolymer was prepared and its properties were measured and described in Table 1 below.

Comparative Example  4

< Hydroxy  End ( Isosobaid Carbonate - Aromatics Carbonate ) Oligomeric  Manufacturing>

(Isosorbide carbonate-aromatic carbonate) oligomer having a viscosity average molecular weight of 12,250 was obtained in the same manner as in Example 1, using 240 g of diphenyl carbonate, 160 g of isosorbide and 18 g of bisphenol A. [

<[Poly ( Isosobaid Carbonate - Aromatics Carbonate )] - [polycarbonate] &lt; / RTI &gt; &lt; RTI ID =

Using the same procedure as in Example 1 except that 3 wt% of the obtained hydroxy terminal (isosorbide carbonate-aromatic carbonate) oligomer (based on 100 wt% of polycarbonate oligomer) was used (provided that p-tert-butylphenol (PTBP ) [Poly (isosorbide carbonate-aromatic carbonate)] - [polycarbonate] block copolymer was prepared and its properties were measured and described in Table 1 below.

Comparative Example  5

An aromatic polycarbonate was prepared by an interfacial polymerization method without a separate hydroxy terminal oligomer preparation process.

&Lt; Preparation of aromatic polycarbonate >

Bisphenol A in an aqueous solution and phosgene gas were interfacially reacted in the presence of methylene chloride to prepare 400 mL of a polycarbonate oligomer having a viscosity average molecular weight of about 1,000.

1.8 mL of tetrabutyl ammonium chloride (TBACl), 2.65 g of p-tert-butylphenol (PTBP), and 2.65 g of triethylamine (TEA, 15 wt%) dissolved in methylene chloride were added to the obtained polycarbonate oligomer. Aqueous solution) were mixed and reacted for 30 minutes. As a result of the reaction, the mixture was allowed to stand to separate layers, and then only the organic phase was taken, and 170 g of aqueous sodium hydroxide solution, 360 g of methylene chloride and 300 μL of a 15 wt% aqueous solution of triethylamine were mixed and reacted for 2 hours. After separating the layers, the organic phase with increased viscosity was washed with alkali and separated. Subsequently, the organic phase was washed with 0.1 N hydrochloric acid solution and then washed repeatedly with distilled water two to three times. After the cleaning was completed, a certain amount of pure water was used to assemble at 76 ° C. After the assembly was completed, it was dried at 110 ° C for 8 hours and then at 120 ° C for 10 hours. The properties of the prepared aromatic polycarbonate were measured and reported in Table 1 below.

(a) Viscosity average molecular weight (Mv): The viscosity of the methylene chloride solution was measured at 20 占 폚 using a Ubbelohde Viscometer, from which the intrinsic viscosity [?] was calculated from the following formula:

^{[η] = 1.23x10 -5 Mv 0} .83

(b) Impact strength: A notch cut specimen was prepared according to ASTM D256 method, and the impact strength was measured using an impact tester (CEAST, IT-98).

(c) Glass transition temperature (Tg): Using a differential scanning calorimeter (DSC Q100, TA Instrument), the temperature was raised from 20 ° C to 200 ° C at a heating rate of 10 ° C / min, And the temperature was raised to 200 ° C.

(d) YI (Yellowness Index): The YI value was obtained by measuring a reflection mode using a color meter (CM-3700D).

(e) Molding processability: injection molding was carried out, and the shape of a 2 mm molded plate was visually evaluated (mold temperature: 80 to 110 deg. C, molding temperature: 250 to 290 deg. The evaluation criteria are as follows.

O: HAZE, silver phenomenon due to shrinkage and decomposition (water, air, or plastic particles in the form of pellet-like silver-white lines in the flow direction of the resin due to disintegrated plastic particles) are not seen.

X: HAZE, shrinkage, and silver phenomenon due to decomposition.

Unformed: lack of flowability prevents molding within the processing temperature range.

As shown in Table 1, the [poly (isosorbide carbonate-aromatic carbonate)] - [polycarbonate] block copolymers prepared in the examples of the present invention were the same as the isosorbide carbonate homopolymer (I.e. excellent heat resistance), high impact strength and excellent molding processability as compared with the low molecular weight copolymer prepared in Comparative Example 2, exhibiting high impact strength, excellent color characteristics and excellent molding processability . On the other hand, the copolymer of Comparative Example 2 showed decomposition at the processing temperature during molding, and the copolymer of Comparative Examples 3 and 4 was too high in molecular weight to form. In addition, the copolymers of Comparative Examples 4 and 5 had a low content of the plant-derived material (i.e., isosorbide) of 3 wt% and 0 wt%, respectively, and the raw materials obtained from natural resources (i.e., biomass- ), But did not meet the purpose of increasing utilization.

Claims (14)

A hydroxy-terminated (isosorbide carbonate-aromatic carbonate) oligomer having a viscosity average molecular weight of 1,000 to 20,000, represented by the following formula (1); And an aromatic polycarbonate block having a unit structure represented by the following formula (3) as repeating units,
Wherein the copolymer has a viscosity average molecular weight (Mv) of 10,000 to 70,000,
[Poly (isosorbide carbonate-aromatic carbonate)] - [aromatic polycarbonate] block copolymer:
[Chemical Formula 1]

In Formula 1, X represents a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms substituted or unsubstituted with an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom, or nitro; n represents an integer of 1 to 110; m represents an integer of 1 to 20,
(3)

In Formula 3, Y represents a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms, which is substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group. The process according to claim 1, wherein the hydroxy-terminated (isosorbide carbonate-aromatic carbonate) oligomer is prepared by melt polymerization of isosorbide, carbonic acid diester and aromatic diol [polyisocyanate carbonate-aromatic carbonate )] - [aromatic polycarbonate] block copolymer. 3. The poly (isosorbide carbonate-aromatic carbonate) - [aromatic polycarbonate] block copolymer according to claim 2, wherein the carbonic acid diester is represented by the following formula 2:
(2)

In Formula 2, A and A 'are each independently selected from an unsubstituted or halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 25 carbon atoms. The [poly (isosorbide carbonate-aromatic carbonate)] - [aromatic polycarbonate] block copolymer according to claim 2, wherein the aromatic diol is a substituted or unsubstituted monocyclic or polycyclic aromatic diol. delete The aromatic polycarbonate block according to claim 1, wherein the aromatic polycarbonate block is formed from an aromatic polycarbonate oligomer having a viscosity average molecular weight of from 3,000 to 20,000. [Poly (isosorbide carbonate-aromatic carbonate)] - [aromatic polycarbonate] Copolymer. The poly (isosorbide carbonate-aromatic carbonate) oligomer according to claim 1, which contains 10 to 60 wt% of a hydroxyl end (isosorbide carbonate-aromatic carbonate) oligomer, based on the total weight of the copolymer. ] - [aromatic polycarbonate] block copolymer. The composition according to claim 1, wherein the content of isosorbide based on the total weight of the copolymer is from 5% to 50% by weight. [Poly (isosorbide carbonate-aromatic carbonate)] - [Aromatic polycarbonate] coalescence. (1) A process for producing a hydroxyl-terminated (isosorbide carbonate-aromatic carbonate) oligomer having a viscosity-average molecular weight of 1,000 to 20,000 represented by the following formula (1) by melt polymerization of isosorbide, carbonic acid diester and aromatic diol step; And
(2) an aromatic polycarbonate oligomer prepared separately from the above-prepared hydroxy terminal (isosorbide carbonate-aromatic carbonate) oligomer and having a unit structure represented by the following formula (3) Wherein the copolymer has a number average molecular weight of from 10,000 to 70,000.
[Preparation of poly (isosorbide carbonate-aromatic carbonate)] - [aromatic polycarbonate] block copolymer:
[Chemical Formula 1]

In Formula 1, X represents a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms substituted or unsubstituted with an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom, or nitro; n represents an integer of 1 to 110; m represents an integer of 1 to 20,
(3)

In Formula 3, Y represents a monocyclic or polycyclic arylene group having 6 to 30 carbon atoms, which is substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group. The method according to claim 9, wherein the molten polymerization of step (1) is carried out in the presence of a polymerization catalyst which is an alkali metal salt compound, an alkaline earth metal salt compound, a nitrogen-containing basic compound, (Aromatic carbonate - aromatic carbonate)] - [aromatic polycarbonate] block copolymer. 11. The method according to claim 10, wherein the molten polymerization of step (1) comprises mixing and heating the isosorbide, the carbonic acid diester and the polymerization catalyst at normal pressure and heating to react at a temperature of from 180 DEG C to 240 DEG C; Removing phenol as a byproduct at a temperature of 180 ° C to 240 ° C under a reduced pressure of 50 torr or less; And returning to normal pressure and then introducing an aromatic diol thereto, and further reacting at a temperature of 180 ° C to 240 ° C under a reduced pressure of 50 torr or less. Isosorbide carbonate-aromatic carbonate)] - [aromatic polycarbonate] block copolymer. The method according to claim 9, wherein the interfacial polymerization in step (1) is carried out under an interfacial reaction condition comprising an aqueous alkali solution and an organic phase, wherein the poly (isosorbide carbonate- aromatic carbonate) - [aromatic polycarbonate] &Lt; / RTI &gt; The method according to claim 9, wherein an aromatic polycarbonate oligomer is first prepared, and then a hydroxyl end (isosorbide carbonate-aromatic carbonate) oligomer is added thereto and subjected to an interfacial reaction [poly (isosorbide carbonate-aromatic Carbonate)] - [aromatic polycarbonate] block copolymer. A molded article comprising the poly (isosorbide carbonate-aromatic carbonate) - [aromatic polycarbonate] block copolymer according to any one of claims 1 to 4 and 6 to 8.