KR101722741B1 - Copolymeric polycarbonate resin and molded product of the same - Google Patents

Abstract

The present invention relates to an aliphatic polycarbonate repeating unit having a chain structure; Aromatic polyester repeating units; And an aliphatic polyester repeating unit having a chain structure, and having a glass transition temperature of -50 占 폚 to 0 占 폚, and a process for producing the copolymer.

Description

TECHNICAL FIELD [0001] The present invention relates to a copolymerized polycarbonate resin,

The present invention relates to a copolymerized polycarbonate resin and a process for producing the same. More particularly, the present invention relates to a copolymerized polycarbonate resin having an appropriate level of biodegradation rate, high molecular weight, excellent processability, and improved heat resistance, and a method for producing the same.

Aliphatic polycarbonate resins are known as biodegradable resins and have been applied in various fields such as films, garbage bags, sheets, food containers, automobile interior materials and the like. In general, the carbonate functional group contained in the aliphatic polycarbonate resin has biodegradability. However, when decomposed by microorganisms in nature or decomposed by itself in the natural world, the decomposition rate is considerably slow and biodegradation takes a long time. In addition, when the aromatic monomer is added to secure the structural stability of the aliphatic polycarbonate resin and to increase the molecular weight, the aliphatic polycarbonate resin has a limit of lowering the rate of biodegradation.

On the other hand, the aliphatic polyester resin has been extensively used in terms of excellent biodegradability and excellent processability, but has a limit in that the life of the product is shortened due to the biodegradability.

In addition, the aliphatic polycarbonate resin and the aliphatic polyester resin themselves have insufficient mechanical properties and thus have a limited application in products.

Accordingly, there has been a demand for development of a copolymerized polycarbonate resin having a proper level of biodegradation rate by incorporating a carbonate group and an ester group together in the polymer chain and having a high molecular weight, an excellent processability, and an improved heat resistance, and a production method thereof.

The present invention is to provide a copolymerized polycarbonate resin which is structurally stable, has an appropriate level of biodegradation rate, is high in molecular weight, is excellent in workability, and has improved heat resistance.

The present invention also provides a process for producing a copolymerized polycarbonate resin which proceeds in a simple and quick reaction under mild conditions and exhibits a high yield.

In the present specification, an aliphatic polycarbonate repeating unit having a chain structure; Aromatic polyester repeating units; And an aliphatic polyester repeating unit having a chain structure, wherein the copolymerized polycarbonate resin has a glass transition temperature of -50 ° C to 0 ° C.

The present invention also relates to a process for esterifying a mixture of an aliphatic diol, an aliphatic carbonate compound, an aromatic ester compound and an aliphatic ester compound having a chain structure in a chain structure; And subjecting the esterification reaction product to a polycondensation reaction. The present invention also provides a process for producing a copolymerized polycarbonate resin.

BEST MODE FOR CARRYING OUT THE INVENTION The copolymer polycarbonate resin according to a specific embodiment of the present invention will be described in detail below.

In the present specification, alkyl (Alkyl) means a monovalent functional group derived from an alkane, and aryl means a monovalent functional group derived from arene.

Also, in the present specification, alkylene means a divalent functional group derived from an alkane, and arylene means a divalent functional group derived from arene.

According to an embodiment of the present invention, there is provided a resin composition comprising: an aliphatic polycarbonate repeating unit having a chain structure; Aromatic polyester repeating units; And an aliphatic polyester repeating unit having a chain structure, and having a glass transition temperature of -50 占 폚 to 0 占 폚.

The inventors of the present invention have found that when the above-mentioned specific copolymer polycarbonate resin is used, mechanical strength and molecular weight can be improved through the structural stability of the copolymerized polycarbonate resin as the aromatic polyester repeating unit is included, And that the biodegradation rate of the copolymerized polycarbonate resin can be improved to an appropriate level by including the aliphatic polyester repeating unit having the chain structure.

Particularly, the copolymerized polycarbonate resin has an aliphatic polycarbonate repeating unit having a chain structure; Aromatic polyester repeating units; And an aliphatic polyester repeating unit having a chain structure. As the copolymerized polycarbonate resin includes the above-mentioned random copolymer, a copolymerized polycarbonate resin having improved physical properties such as mechanical strength, molecular weight and molding processability can be realized.

Further, the glass transition temperature of the copolymerized polycarbonate resin may be -50 캜 to 0 캜, or -40 캜 to -5 캜. The glass transition temperature means a temperature at which amorphous solid changes from a loose state such as glass to a viscous state. For example, the copolymerized polycarbonate resin is annealed in a differential scanning calorimeter (DSC) at 300 DEG C for 5 minutes, cooled to room temperature, and then cooled to room temperature. And a method of re-scanning at a heating rate of 10 DEG C / min can be used.

The mole ratio of the aromatic polyester repeating unit and the chain structure aliphatic polyester repeating unit may be 1: 1 to 5: 1, or 1: 1 to 3: 1, or 1: 1 to 2: 1. When the molar ratio of the aliphatic polyester repeating units in the chain structure is too large, the polymerizability of the copolymerized polycarbonate resin may be decreased, and the molecular weight of the copolymerized polycarbonate resin due to the decrease in the aromatic polyester repeating unit content And the mechanical properties can be reduced. In addition, when the molar ratio of the chain structure aliphatic polyester repeating units is too small, the biodegradability of the copolymerized polycarbonate resin may be decreased.

The mole ratio of the aromatic polyester repeating unit and the chain structure aliphatic polyester repeating unit to the chain structure aliphatic polycarbonate repeating unit is 1: 1 to 1: 5, or 1: 1.1 to 1: 3, or 1: 1.1 To 1: 2. As described above, since the ratio of the polyester-based repeating units to the polycarbonate-based repeating units is satisfied, the biodegradable rate of the copolymerized polycarbonate resin is higher than the biodegradable rate of the relatively slow polycarbonate- And the biodegradable rate of the ester-based repeating unit.

The copolymerized polycarbonate resin may have a weight average molecular weight of 60,000 g / mol to 150,000 g / mol, or 61,000 g / mol to 140,000 g / mol. Specifically, by the aromatic polyester repeating unit contained in the copolymerized polycarbonate resin, the copolymerized polycarbonate resin can exhibit the weight average molecular weight described above. If the weight average molecular weight of the copolymerized polycarbonate resin is less than 60,000 g / mol, the moldability and processability of the copolymerized polycarbonate resin may be reduced.

On the other hand, the copolymerized polycarbonate resin may include an aliphatic polycarbonate repeating unit having a chain structure. Specifically, the aliphatic polycarbonate repeating unit of the chain structure may include a repeating unit represented by the following formula (1).

[Chemical Formula 1]

In the formula (1), R ₁ is a linear or branched alkylene of 3 to 30 carbon atoms; Or straight or branched chain C3-C30 heteroalkylene.

The 'heteroalkylene' may mean an alkylene compound having at least one heteroatom in the molecule. The hetero atom may be a carbon or a non-hydrogen atom, for example, a nitrogen atom, an oxygen atom, or the like.

Examples of the linear or branched alkylene having 3 to 30 carbon atoms include, but are not limited to, linear or branched alkylene having 3 to 10 carbon atoms, specifically, n-butylene, 2,2-di Methyl propylene and the like can be used, and n-butylene can be preferably used.

Examples of the linear or branched C3-C30 heteroalkylene include, but are not limited to, compounds represented by the following general formula (11) or (22).

(11)

In Formula 11, a is an integer of 1 to 10.

[Chemical Formula 12]

In Formula (12), b is an integer of 1 to 7.

Further, the copolymerized polycarbonate resin may include an aromatic polyester repeating unit. Specifically, the aromatic polyester repeating unit may include a repeating unit represented by the following formula (2).

(2)

In Formula 2, R ₂ is a substituted or unsubstituted arylene having 5 to 20 carbon atoms; Or substituted or unsubstituted heteroarylene having 5 to 20 carbon atoms,

R ₃ is a linear or branched alkylene of 3 to 30 carbon atoms; Or straight or branched chain C3-C30 heteroalkylene.

The 'heteroarylene' may mean an arylene compound containing at least one heteroatom in the molecule. The hetero atom may be a carbon or a non-hydrogen atom, for example, a nitrogen atom, an oxygen atom, or the like.

Examples of the substituted or unsubstituted arylene having 5 to 20 carbon atoms include, but are not limited to, compounds represented by the following general formulas (21) to (23), preferably compounds represented by general formula .

[Chemical Formula 21]

[Chemical Formula 22]

(23)

Examples of the linear or branched alkylene having 3 to 30 carbon atoms include, but are not limited to, linear or branched alkylene having 3 to 10 carbon atoms, specifically, n-butylene, 2,2-di Methyl propylene and the like can be used, and n-butylene can be preferably used.

Examples of the linear or branched C3-C30 heteroalkylene include, but not limited to, the compounds represented by Formula 11 or Formula 12.

In addition, the copolymerized polycarbonate resin may contain an aliphatic polyester repeating unit having a chain structure. Specifically, the aliphatic polyester repeating unit of the chain structure may include a repeating unit represented by the following formula (3).

(3)

In Formula 3, R ₄ and R ₅ are the same or different from each other and each independently represents a linear or branched alkylene group having 3 to 30 carbon atoms; Or straight or branched chain C3-C30 heteroalkylene.

Examples of the linear or branched alkylene having 3 to 30 carbon atoms include, but are not limited to, linear or branched alkylene having 3 to 10 carbon atoms, specifically, n-butylene, 2,2-di Methyl propylene and the like can be used, and n-butylene can be preferably used.

Examples of the linear or branched C3-C30 heteroalkylene include, but not limited to, the compounds represented by Formula 11 or Formula 12.

The random copolymer may further include repeating units represented by the following general formulas (4), (5) and (6). Since the random copolymer further includes the repeating units represented by the following general formulas (4), (5) and (6), the copolymeric polycarbonate resin is changed into amorphous, so that transparency is improved and heat resistance is improved. It can be varied. The term 'amorphous' means that the arrangement of atoms or molecules does not have regularity and thus does not have a constant shape.

[Chemical Formula 4]

In Formula 4, R ₆ is a substituted or unsubstituted cycloalkylene having 4 to 30 carbon atoms; Or substituted or unsubstituted heterocycloalkylene;

[Chemical Formula 5]

In Formula 5, R ₇ is substituted or unsubstituted arylene having 5 to 20 carbon atoms; Or substituted or unsubstituted heteroarylene having 5 to 20 carbon atoms,

R ₈ is substituted or unsubstituted cycloalkylene having 4 to 30 carbon atoms; Or substituted or unsubstituted heterocycloalkylene;

[Chemical Formula 6]

In Formula 4, R ₉ represents a linear or branched alkylene group having 3 to 30 carbon atoms; Or straight or branched chain C3-C30 heteroalkylene;

R ₁₀ is a substituted or unsubstituted cycloalkylene having 4 to 30 carbon atoms; Or substituted or unsubstituted heterocycloalkylene.

Examples of the substituted or unsubstituted cycloalkylene having 4 to 30 carbon atoms are not particularly limited. For example, compounds represented by the following formulas (31) to (34), preferably compounds represented by the following formula (31) can be used.

(31)

(32)

(33)

(34)

Examples of the substituted or unsubstituted heterocycloalkylene include, but are not limited to, compounds represented by the following general formula (35).

(35)

The substituted or unsubstituted arylene having 5 to 20 carbon atoms; Or a substituted or unsubstituted heteroarylene having 5 to 20 carbon atoms includes the above-mentioned contents.

The straight or branched chain alkylene having 3 to 30 carbon atoms may be further exemplified. Or a straight chain or branched chain alkyl group having 3 to 30 carbon atoms.

Examples of the use of the copolymerized polycarbonate resin are not limited, but can be used, for example, in films, vinyls, and rubbers.

According to another embodiment of the present invention, there is provided a process for producing a polyester resin composition, comprising the steps of: esterifying a mixture of an aliphatic diol, an aliphatic carbonate compound, an aromatic ester compound and an aliphatic ester compound having a chain structure; And a step of subjecting the esterification reaction product to a polycondensation reaction, and a method for producing the copolymerized polycarbonate resin. The inventors of the present invention have confirmed through experimentation that a simple and quick reaction can be carried out under mild conditions and a high yield can be obtained by using the above-mentioned method for producing a specific copolymerized polycarbonate resin, and the inventors have completed the invention.

Specifically, the method for producing the copolymerized polycarbonate resin may include esterifying a mixture of a chain-like aliphatic diol, an aliphatic carbonate compound, an aromatic ester compound, and a chain-like aliphatic ester compound. The process for producing the copolymerized polycarbonate resin is simple in that the reaction process is simple by simultaneously mixing an aliphatic diol having a chain structure, an aliphatic carbonate compound, an aromatic ester compound and an aliphatic ester compound having a chain structure and esterifying the mixture.

The molar ratio of the aromatic ester compound and the aliphatic ester compound having a chain structure may be 10: 1 to 1:10, or 5: 1 to 1: 5, or 4.5: 1 to 1: 4.

The molar ratio of the aromatic ester compound and the chain structure aliphatic ester compound to the aliphatic carbonate compound may be from 10: 1 to 1: 1, or from 5: 1 to 1.5: 1, or from 4.5: 1 to 1.8: 1.

1 to 1: 5, or 1: 1.2 to 1: 3, or 1: 1.4 to 1: 3, based on the weight of the aliphatic carbonate compound, the aromatic ester compound and the aliphatic ester compound having a chain structure, : May be two.

The aliphatic diol, the aliphatic carbonate compound, the aromatic ester compound, and the chain structure of the chain structure of the aliphatic diol, the aliphatic carbonate compound, the aromatic ester compound, Of the aliphatic ester compound proceeds efficiently in the esterification reaction, so that the copolymerized polycarbonate resin in one embodiment can be produced with high yield.

Examples of the aliphatic diol having such a chain structure are not limited, but 1,4-butanediol; 2,2-dimethylpropane-1,3-diol; Diethylene glycol; And the like can be used, and 1,4-butanediol can be preferably used.

Although examples of the aliphatic carbonate compound are not limited to a great extent, for example, dialkyl carbonate can be used. In the above dialkyl carbonate, examples of the alkyl group are not limited to a great degree, but straight chain or branched alkyl groups having 1 to 10 carbon atoms can be used, and a methyl group can be preferably used.

Examples of the aromatic ester compound are not particularly limited, but for example, a dialkyl phthalate can be used. In the above-mentioned dialkyl phthalate, examples of the alkyl group are not limited to a great degree. For example, a straight or branched alkyl group having 1 to 10 carbon atoms can be used, and a methyl group can be preferably used. Examples of the positions of the two alkyl groups in the dialkyl phthalate are not particularly limited, and examples thereof include 1,4-dialkyl phthalate, 1,3-dialkyl phthalate, 1,2-dialkyl phthalate and the like. 1,4-dialkyl phthalate, among which 1,4-dimethyl phthalate can be used.

Examples of the aliphatic ester compound having a chain structure include, but not limited to, an aliphatic ester compound having a chain structure of 6 to 20 carbon atoms. Examples of the above-mentioned aliphatic ester compound having a chain structure of 6 to 20 carbon atoms are not particularly limited, but dialkyl succinate, dialkyl adipate and the like can be used, and a dialkyl adipate can be preferably used. Examples of the alkyl group include a straight chain or branched alkyl group having 1 to 10 carbon atoms, preferably a methyl group.

The esterification reaction may be carried out at a temperature of from 110 DEG C to 150 DEG C, or from 120 DEG C to 140 DEG C and at normal pressure for from 60 minutes to 120 minutes, or from 70 minutes to 115 minutes, or from 75 minutes to 110 minutes. The esterification reaction may be carried out batchwise or continuously, and the reactants may be introduced separately or in a mixture, but may be introduced in the form of a slurry in which the reactants are mixed together.

In addition, the method for producing the copolymerized polycarbonate resin may include polycondensation reaction of an esterification reaction product of a mixture of a chain-like aliphatic diol, an aliphatic carbonate compound, an aromatic ester compound and a chain-like aliphatic ester compound . The method for producing the copolymerized polycarbonate resin comprises simultaneously mixing an aliphatic diol having a chain structure, an aliphatic carbonate compound, an aromatic ester compound and an aliphatic ester compound having a chain structure, subjecting the mixture to an esterification reaction, By subjecting the repeating units of one embodiment to a polycondensation reaction, a random copolymer containing the repeating unit can be prepared.

The polycondensation reaction may be carried out at a temperature of 200 ° C to 250 ° C, or 205 ° C to 220 ° C, and a pressure of 0.1 mmHg to 100 mmHg for 200 minutes to 500 minutes, or 250 minutes to 450 minutes, or 300 minutes to 440 minutes . As a result, only the by-products generated during the reaction can be sufficiently removed from the reaction system to improve the yield of the copolymerized polycarbonate resin. The polycondensation reaction may be carried out at a pressure of 0.1 mmHg to 100 mmHg, specifically, a pressure of 100 mmHg to a pressure of 0.1 mmHg continuously.

If the temperature of the polycondensation reaction is less than 200 ° C, the polycondensation reaction time becomes longer, a copolymerized polycarbonate resin having a lower molecular weight is produced, and yellowing of the copolymerized polycarbonate resin may occur due to a long reaction time . If the temperature of the polycondensation reaction is more than 250 ° C, tetrahedrofuran may be produced as a by-product.

Also, if the polycondensation reaction time is too short to be less than 200 minutes, a monomolecular or oligomer material having a small molecular weight may be discharged to the outside to reduce the yield of the copolymerized polycarbonate resin, and the polycondensation reaction time may be 500 minutes If it is excessively long, energy consumption is high and reaction efficiency may be reduced.

The mixture of the aliphatic diol, the aliphatic carbonate compound, the aromatic ester compound and the chain-like aliphatic ester compound of the chain structure may further include a cyclic aliphatic diol.

Examples of the cyclic aliphatic diol include, but are not limited to, 2,2,4,4-tetramethylcyclobutane-1 , 3-diol]; 1,4-cyclohexanedimethanol; 1,4-cyclohexanedimethanol; 4,4 '- (propane-2,2-diyl) dicyclohexanol [4,4' - (propane-2,2-diyl) dicyclohexanol]; 2,2 '- (2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diyl) bis (2-methylpropan- Octahydro-exo-4,7-methano-1H-indene [octahydro-exo (2-methyl) -4,7-methano-1H-indene], and the like, and 1,4-cyclohexanedimethanol can be preferably used. When 1,4-cyclohexane dimethanol is used, the rate of the esterification reaction and the polycondensation reaction is increased, and the molecular weight of the finally produced copolymerized polycarbonate resin can be improved.

The aliphatic diol having the cyclic structure, the aliphatic diol having the chain structure, the aliphatic carbonate compound and the aromatic ester compound may further comprise a base catalyst or a metal catalyst.

Examples of the base catalyst include, but are not limited to, sodium hydride (NaH), sodium hydroxide (NaOH), sodium methoxide (NaOMe), sodium ethoxide NaOEt), potassium carbonate _{(potassium carbonate, K 2 CO 3} ), potassium hydride (potassium hydride, KH), ammonium hydroxide _{(ammonium hydroxide, NH 4 OH)} , lithium hydroxide (lithium hydroxide, LiOH), methoxide lithium (lithium methoxide , LiOMe), lithium ethoxide (LiOEt), or a mixture of two or more thereof.

The metal catalyst may be a titanium compound, a germanium compound, an antimony compound, or a mixture of two or more thereof. Examples of the germanium compound include germanium oxide (GeO ₂ ), germanium methoxide (Ge (OMe) ₂ ) and germanium ethoxide (Ge (OEt) ₂ ). Examples of the antimony compound include antimony oxide (Sb ₂ O ₃ ), and antimony acetate (Sb (OAc) ₃ ).

The amount of the catalyst to be added is not particularly limited. For example, in the case of the base catalyst, the amount of the catalyst may be 0.05 mol to 0.1 mol.

According to the present invention, there can be provided a copolymerized polycarbonate resin having an appropriate level of biodegradation rate, high molecular weight and excellent processability, improved heat resistance, and a copolymerized polycarbonate resin exhibiting a high yield with a simple and quick reaction under mild conditions A method can be provided.

Fig. 1 shows a ¹ H-NMR spectrum of the copolymerized polycarbonate resin prepared in Example 1. Fig.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

< Example  1 to 17: Preparation of Copolymerized Polycarbonate Resin>

Example  One

50 g (0.555 mol) of 1,4-butanediol, 60 g (0.666 mol) of dimethyl carbonate and 0.606 mol of dimethyl terephthalate (DME) were charged in a 500 ml three- , 19.3 g (0.111 mol) of dimethyl adipate (Sigma-Aldrich) and 36 mg (0.072 mol) of sodium methoxide (NaOMe; Sigma-Aldrich) And stirred in a slurry state. Then, nitrogen gas was introduced into the reactor and the distillation apparatus was connected. Then, the reactor was placed in a thermostatic chamber and esterified at a temperature of 130 ° C. under atmospheric pressure to remove methanol and unreacted dimethyl carbonate. The time point at which the generation of methanol was terminated was defined as the end of the esterification reaction.

After the completion of the esterification reaction, the reactor temperature was raised to 210 ° C and the pressure of the reactor was reduced to 0.5 mmHg to perform a polycondensation reaction to remove volatiles. When the polycondensation reaction is terminated at the end of the polycondensation reaction in the state where the temperature inside the reactor is lowered and no further change is maintained and the speed of the stirrer installed in the reactor is lowered, And then terephthaloyl chloride (0.5 equivalents of sodium methoxide) was dissolved in tetrahydrofuran, and the mixture was stirred in a reactor to obtain a copolymerized polycarbonate resin containing repeating units represented by the following chemical formulas (51), (52) .

(51)

(52)

(53)

Example  2

The reaction was carried out in the same manner as in Example 1 except that 54 mg (0.099 mol) of sodium methoxide was used to obtain a copolymerized polycarbonate resin (a) containing the repeating units represented by the above formulas (51), (52) .

Example 3

The reaction was carried out in the same manner as in Example 1 except that sodium hydroxide (NaOH; Sigma-Aldrich) was used in place of the sodium methoxide, thereby obtaining a solution containing the repeating units represented by the above Formulas 51, 52 and 53 To prepare a copolymerized polycarbonate resin.

Example 4

The reaction was carried out in the same manner as in Example 2 except that sodium hydroxide (NaOH; Sigma-Aldrich) was used in place of the sodium methoxide, thereby obtaining a solution containing the repeating units represented by the above Formulas 51, 52 and 53 To prepare a copolymerized polycarbonate resin.

Example 5

The reaction was carried out in the same manner as in Example 1 except that sodium hydride (NaH; Sigma-Aldrich) was used in place of the sodium methoxide, thereby obtaining a solution containing the repeating units represented by the above Formulas 51, 52 and 53 To prepare a copolymerized polycarbonate resin.

Example 6

The reaction was carried out in the same manner as in Example 2 except that sodium hydride (NaH; Sigma-Aldrich) was used in place of the sodium methoxide, to obtain a solution containing the repeating units represented by the above Formulas 51, 52 and 53 To prepare a copolymerized polycarbonate resin.

Example 7

The reaction was carried out in the same manner as in Example 1 except that sodium carbonate (Na ₂ CO ₃ ; Sigma-Aldrich) was used in place of the sodium methoxide to obtain the repeating units represented by the above Formulas 51, 52 and 53 To prepare a copolymerized polycarbonate resin.

Example 8

The reaction was carried out in the same manner as in Example 2, except that sodium carbonate (Na ₂ CO ₃ ; Sigma-Aldrich) was used in place of sodium methoxide, thereby obtaining the repeating units represented by the above Formulas 51, 52 and 53 To prepare a copolymerized polycarbonate resin.

Example 9

The reaction was carried out in the same manner as in Example 1 except that lithium methoxide (LiOMe) (Sigma-Aldrich) was used in place of the sodium methoxide, to thereby obtain a solution containing the repeating units represented by the above Formulas 51, 52 and 53 Based on the total amount of the copolymerized polycarbonate resin.

Example 10

The reaction was carried out in the same manner as in Example 2 except that lithium methoxide (LiOMe) (Sigma-Aldrich) was used in place of the sodium methoxide, to thereby obtain a solution containing the repeating units represented by the above Formulas 51, 52 and 53 Based on the total amount of the copolymerized polycarbonate resin.

Example 11

Polymerization was carried out in the same manner as in Example 1 except that 24 g (0.166 mol) of 1,4-cyclohexanedimethanol (Sigma-Aldrich) was further used, A copolymerized polycarbonate resin further comprising the repeating units represented by the following chemical formulas (54), (55) and (56) together with the chemical formulas (52) and (53) was prepared.

(54)

(55)

(56)

Example 12

The reaction was carried out in the same manner as in Example 1 except that 11 g (0.055 mol) of dimethyl terephthalate was used, thereby obtaining a copolymerized polycarbonate resin containing the repeating units represented by the above formulas (51), (52) and .

Example 13

The reaction was carried out in the same manner as in Example 1 except that 22 g (0.11 mol) of dimethyl terephthalate was used, thereby obtaining a copolymerized polycarbonate resin containing the repeating units represented by Chemical Formulas 51, 52 and 53 .

Example 14

The reaction was carried out in the same manner as in Example 1 except that 44 g (0.22 mol) of dimethyl terephthalate was used, thereby obtaining a copolymerized polycarbonate resin containing the repeating units represented by the above Formulas 51, 52 and 53 .

Example 15

The reaction was carried out in the same manner as in Example 1, except that 9.7 g (0.055 mol) of the dimethyl adipate was used to obtain a copolymerized polycarbonate resin having the repeating units represented by the above formulas (51), (52) and .

Example 16

The reaction was carried out in the same manner as in Example 1 except that 24 g (0.138 mol) of the dimethyl adipate was used to obtain a copolymerized polycarbonate resin (a) containing the repeating units represented by the above formulas (51), (52) .

Example 17

The reaction was carried out in the same manner as in Example 1 except that 29 g (0.166 mol) of dimethyl adipate was used to obtain a copolymerized polycarbonate resin containing the repeating units represented by the above Formulas 51, 52 and 53 .

< Comparative Example  1 to 3: Preparation of Copolymerized Polycarbonate Resin>

Comparative Example  One

The reaction was carried out in the same manner as in Example 1 except that dimethyl terephthalate and dimethyl adipate were not used.

Comparative Example  2

The reaction was carried out in the same manner as in Example 1 except that the dimethyl terephthalate was not used.

Comparative Example  3

The reaction was carried out in the same manner as in Example 1 except that the dimethyl adipate was not used.

< Experimental Example  : Example  And In the comparative example  Measurement of Physical Properties of the Copolymerized Polycarbonate Resin Obtained>

The properties of the copolymerized polycarbonate resin obtained in the above Examples and Comparative Examples were measured by the following methods.

One. ^One H- NMR

(1) The copolymerized polycarbonate resin obtained in Example 1 was measured by 500 MHz NMR using a chloroform (CDCl ₃ ) solvent, and the results are shown in FIG.

(2) From the NMR spectrum analysis of the copolymer polycarbonate resin of Example 1 described in the following 1, 47 mol% of the repeating unit represented by the formula (51), 27 mol% of the repeating unit represented by the formula (52) Can be confirmed to be a copolymerized polycarbonate resin.

2. Heat resistance

The copolymerized polycarbonate resin obtained in Examples and Comparative Examples was annealed at 300 ° C for 5 minutes by differential scanning calorimetry (DSC), cooled to room temperature, and then resampled at a heating rate of 10 ° C / min to obtain a glass transition temperature Tg) and melting point (Tm) were measured. The results are shown in Table 1 below.

3. Crystallinity

A specimen having a thickness of 4 mm was prepared using the copolymer polycarbonate resin obtained in Examples and Comparative Examples. The transparency of the specimen was measured according to ASTM D1003-00 standard using a UV apparatus, Are shown in Table 1.

4. Reactivity

4-1. Reaction time (min)

The esterification reaction time and the polycondensation reaction time were measured in Examples and Comparative Examples, and the results are shown in Table 2 below.

4-2. Yield (%)

The copolycarbonate resins obtained in Examples and Comparative Examples were dried in a vacuum oven at 70 캜 for 2 hours, and their yields were measured. The results are shown in Table 2 below.

4-3. Weight average molecular weight (g / mol)

The weight average molecular weights of the copolymerized polycarbonate resins obtained in Examples and Comparative Examples were measured by gel permeation chromatography (GPC), and the results are shown in Table 2 below.

Heat resistance and crystallinity of Examples and Comparative Examples division Heat resistance Crystallinity Glass transition temperature (캜) Melting point (℃) Example 1 -17 117 decision Example 2 -17 116 decision Example 3 -15 119 decision Example 4 -16 120 decision Example 5 -16 114 decision Example 6 -16 114 decision Example 7 -15 118 decision Example 8 -15 116 decision Example 9 -18 117 decision Example 10 -17 117 decision Example 11 -15 - Indeterminate Example 12 -31 - Indeterminate Example 13 -24 - Indeterminate Example 14 -8 125 decision Example 15 -13 110 decision Example 16 -19 119 decision Example 17 -23 125 decision Comparative Example 1 -33 60 decision Comparative Example 2 -40 - Indeterminate Comparative Example 3 -10 105 decision

As shown in Table 1, the glass transition temperature of the copolymerized polycarbonate resin obtained in the above Example was measured at -31 캜 to -8 캜, and the glass transition of Comparative Example 1 in which dimethyl terephthalate and dimethyl adipate were not used The temperature was -33 캜, and the glass transition temperature of Comparative Example 2 in which dimethyl terephthalate was not used was higher than -40 캜. Thus, it can be confirmed that the heat resistance of the copolymerized polycarbonate resin obtained in the above example is improved as compared with the comparative example.

More specifically, in Examples 12 to 14 of Table 1, it was confirmed that as the amount of dimethyl terephthalate monomer was increased, the glass transition temperature was increased. In Examples 15 to 17, the amount of dimethyl adipate monomer It can be confirmed that the glass transition temperature decreases.

In the case of the copolycarbonate resins of Examples 1 to 10 and 14 to 17, it was confirmed that the melting point was measured to be a crystalline resin, and in the case of the copolycarbonate resins of Examples 11 to 13, the melting point was not measured It can be confirmed that it is an amorphous resin.

Reactivity of Examples and Comparative Examples division Reaction time Yield (%) Weight average molecular weight (g / mol) ester
Reaction time (min) Polycondensation
Reaction time (min) Total (minutes) Example 1 92 408 500 88 112,000 Example 2 82 430 512 90 124,000 Example 3 98 395 493 84 109,000 Example 4 85 350 435 87 116,000 Example 5 88 381 469 81 112,500 Example 6 79 354 433 86 109,000 Example 7 95 397 492 83 118,000 Example 8 89 385 474 90 109,000 Example 9 96 405 501 87 120,000 Example 10 87 392 479 91 130,300 Example 11 90 401 491 91 138,200 Example 12 95 381 476 - 61,500 Example 13 99 402 501 - 95,000 Example 14 106 420 526 - 139,000 Example 15 97 381 478 - 81,500 Example 16 100 391 491 - 110,000 Example 17 107 425 532 - 132,000 Comparative Example 1 95 375 470 84 45,000 Comparative Example 2 90 360 450 - 42,600 Comparative Example 3 95 369 464 - 55,000

As shown in Table 2, the weight average molecular weight of the copolymerized polycarbonate resin obtained in the above Example was measured to be 61,500 g / mol to 139,000 g / mol, which was 45,000 g / mol in Comparative Example 1, 42,600 g / mol and 55,000 g / mol in Comparative Example 3, respectively. As described above, by the production of the copolymerized polycarbonate resin having a high molecular weight, the molding processability of the copolymerized polycarbonate resin can be improved.

More specifically, in Examples 12 to 14 in Table 2, it was confirmed that the weight average molecular weight was increased with an increase in the amount of dimethyl terephthalate monomer. In Examples 15 to 17, the amount of dimethyl adipate monomer And the weight average molecular weight increases as the amount of the monomer increases.

Claims (16)

An aliphatic polycarbonate repeating unit having a chain structure;
Aromatic polyester repeating units; And
An aliphatic polyester repeating unit having a chain structure;
Wherein the aliphatic polycarbonate repeating unit of the chain structure comprises a repeating unit represented by the following formula (1)
Wherein the aromatic polyester repeating unit comprises a repeating unit represented by the following formula (2)
Wherein the aliphatic polyester repeating unit of the chain structure comprises a repeating unit represented by the following formula (3)
The molar ratio of the aromatic polyester repeating unit and the aliphatic polyester repeating unit of the chain structure is 1: 1 to 5: 1,
Wherein the copolymerized polycarbonate resin has a weight average molecular weight of 60,000 g / mol to 150,000 g / mol,
A copolymerized polycarbonate resin having a glass transition temperature of -50 占 폚 to 0 占 폚;
[Chemical Formula 1]

In the formula (1), R ₁ is a linear or branched alkylene of 3 to 30 carbon atoms; Or straight or branched chain C3-C30 heteroalkylene;
(2)

In Formula 2, R ₂ is an arylene having 6 to 20 carbon atoms; Or heteroarylene having 6 to 20 carbon atoms,
R ₃ is a linear or branched alkylene of 3 to 30 carbon atoms; Or straight or branched chain C3-C30 heteroalkylene;
(3)

In Formula 3, R ₄ and R ₅ are the same or different from each other and each independently represents a linear or branched alkylene group having 3 to 30 carbon atoms; Or straight or branched chain C3-C30 heteroalkylene.
delete The method according to claim 1,
Wherein the molar ratio of the aromatic polyester repeating unit to the aliphatic polyester repeating unit of the chain structure to the aliphatic polycarbonate repeating unit of the chain structure is from 1: 1 to 1: 5.
delete delete delete delete The method according to claim 1,
Wherein the random copolymer further comprises a repeating unit represented by the following general formula (4), (5) and (6):
[Chemical Formula 4]

In Formula 4, R ₆ is a cycloalkylene having 4 to 30 carbon atoms; Or heterocycloalkylene;
[Chemical Formula 5]

In Formula 5, R ₇ is an arylene having 6 to 20 carbon atoms; Or heteroarylene having 6 to 20 carbon atoms,
R ₈ is cycloalkylene having 4 to 30 carbon atoms; Or heterocycloalkylene;
[Chemical Formula 6]

In Formula 4, R ₉ represents a linear or branched alkylene group having 3 to 30 carbon atoms; Or straight or branched chain C3-C30 heteroalkylene;
R ₁₀ is a cycloalkylene having 4 to 30 carbon atoms; Or heterocycloalkylene.
Chain aliphatic diols containing at least one member selected from the group consisting of 1,4-butanediol, 2,2-dimethylpropane-1,3-diol, and diethylene glycol, aliphatic diols including dialkyl carbonates Esterifying a mixture of a carbonate compound, an aromatic ester compound including a dialkyl phthalate, and a chain-like aliphatic ester compound containing a dialkyl succinate or a dialkyl adipate; And
And subjecting the esterification reaction product to a polycondensation reaction.
10. The method of claim 9,
Wherein the molar ratio of the aromatic ester compound and the aliphatic ester compound having a chain structure is 10: 1 to 1:10.
10. The method of claim 9,
Wherein the molar ratio of the aromatic ester compound to the aliphatic ester compound having a chain structure to the aliphatic carbonate compound is from 10: 1 to 1: 1.
10. The method of claim 9,
Wherein the molar ratio of the aliphatic carbonate compound, the aromatic ester compound and the chain structure aliphatic ester compound to the aliphatic diol having the chain structure is 1: 1 to 1: 5.
10. The method of claim 9,
Wherein the esterification reaction is carried out at a temperature of from 110 DEG C to 150 DEG C and at normal pressure for from 60 minutes to 120 minutes.
10. The method of claim 9,
Wherein the polycondensation reaction is carried out at a temperature of 200 ° C to 250 ° C and a pressure of 0.1 mmHg to 100 mmHg for 200 minutes to 500 minutes.
10. The method of claim 9,
The mixture of the aliphatic diol, the aliphatic carbonate compound, the aromatic ester compound, and the chain-like aliphatic ester compound of the above chain structure,
2,2,4,4-tetramethylcyclobutane-1,3-diol; 1,4-cyclohexanedimethanol; 4,4 '- (propane-2,2-diyl) dicyclohexanol; 2,2 '- (2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diyl) bis (2-methylpropan-1-ol); Octahydro-exo-4,7-methano-1H-indene, wherein the aliphatic diol is at least one selected from the group consisting of an aliphatic diol having a cyclic structure and at least one selected from the group consisting of octahydro-exo-4,7-methano-1H-indene.
10. The method of claim 9,
The mixture of the aliphatic diol, the aliphatic carbonate compound, the aromatic ester compound, and the chain-like aliphatic ester compound of the above chain structure,
A method for producing a copolymerized polycarbonate resin, which further comprises a base catalyst or a metal catalyst.

Images