KR20150001527A - Biodegradable polyester resin and article including the same - Google Patents

Abstract

Disclosed are a biodegradable polyester resin and an article including the same. The disclosed biodegradable polyester resin comprises an aliphatic diol residue including an ethylene glycol residue or a butanediol residue, and an aliphatic dicarboxylic acid residue including a succinic acid residue, thereby having improved elasticity and biodegradability.

Description

[0001] The present invention relates to a biodegradable polyester resin and an article containing the biodegradable polyester resin,

Disclosed are biodegradable polyester resins and articles comprising the same. More particularly, the present invention relates to a biodegradable polyester resin having excellent elasticity and an article comprising the same, which is produced by an esterification reaction of an aliphatic dicarboxylic acid and an aliphatic diol and a subsequent condensation polymerization reaction.

Due to its high functionality and durability, plastics are useful in real life. However, conventional plastics have a problem in that degradation rate by microorganisms at the time of embedding is low, and noxious gas is released at the time of incineration to cause environmental pollution, and development of biodegradable plastics has progressed.

Of these biodegradable plastics, polyester resins having biodegradability are attracting attention. Biodegradable polyester resins are polymers that can be decomposed into water, carbon dioxide, or water and methane gas by microorganisms that exist in nature, such as bacteria, algae and fungi. Such a biodegradable polyester resin is proposed as a powerful solution for preventing environmental pollution caused by landfill or incineration.

Furthermore, studies for replacing conventional non-degradable elastic resins such as styrene butadiene rubber, nitrile rubber, butadiene rubber, ethylene propylene rubber, urethane rubber, acrylic rubber and the like have been progressing by improving such biodegradable polyester resins.

One embodiment of the present invention provides a biodegradable polyester resin having excellent elasticity while maintaining biodegradability by including an aliphatic dicarboxylic acid residue and an aliphatic diol residue.

Another embodiment of the present invention provides an article comprising the biodegradable polyester resin.

According to an aspect of the present invention,

An aliphatic diol residue comprising an ethylene glycol residue or a butanediol residue; And

There is provided a biodegradable polyester resin comprising an aliphatic dicarboxylic acid residue including a succinic acid residue.

The content of the aliphatic diol residue may be 1 to 2 moles per 1 mole of the aliphatic dicarboxylic acid residue.

Wherein the biodegradable polyester resin comprises the ethylene glycol residue as the aliphatic diol residue and further comprises an adipic acid residue as the aliphatic dicarboxylic acid residue, wherein the amount of the aliphatic dicarboxylic acid residue 0.3 to 0.8 mole part of the succinic acid residue and 0.2 to 0.7 mole part of the adipic acid residue.

Wherein the biodegradable polyester resin comprises the ethylene glycol residue as the aliphatic diol residue and further comprises the adipic acid residue as the aliphatic dicarboxylic acid residue and further comprises a terephthalic acid residue, 0.2 to 0.7 mole part of the succinic acid residue and 0.3 to 0.8 mole part of the sum of the adipic acid residue and the terephthalic acid residue relative to 1 mole part of the sum of the carboxylic acid residue and the terephthalic acid residue.

The biodegradable polyester resin may contain 0.1 to 0.79 mole part of the adipic acid residue and 0.01 to 0.7 mole part of the terephthalic acid residue relative to 1 mole part of the sum of the aliphatic dicarboxylic acid residue and the terephthalic acid residue.

Wherein the biodegradable polyester resin comprises the butanediol moiety as the aliphatic diol moiety and further comprises at least one of a diethylene glycol moiety and a triethylene glycol moiety as the aliphatic diol moiety, Of the butanediol residue and 0.3 to 0.7 mole portion of the sum of the diethylene glycol residue and the triethylene glycol residue.

The aliphatic diol moiety may comprise from 0.1 to 0.6 mole part of the diethylene glycol moiety and from 0.1 to 0.6 mole moiety of the triethylene glycol moiety relative to a total mole thereof.

The biodegradable polyester resin may have a weight average molecular weight of 150,000 to 500,000.

According to another aspect of the present invention,

And an article comprising the biodegradable polyester resin.

According to one embodiment of the present invention, a biodegradable polyester resin excellent in both elasticity and biodegradability can be provided by including an aliphatic dicarboxylic acid residue and an aliphatic diol residue.

Hereinafter, the biodegradable polyester resin according to one embodiment of the present invention will be described in detail.

As used herein, the term " polyester " refers to an esterification reaction of one or more difunctional or higher polyfunctional carboxylic acids with one or more bifunctional or higher polyfunctional hydroxyl compounds and subsequent condensation polymerization ≪ / RTI > The bifunctional carboxylic acid may be a dicarboxylic acid, and the bifunctional hydroxyl compound may be a dihydric alcohol, for example, glycol or diol.

As used herein, the term " butanediol " means a compound in which two hydrogens of butane are substituted with hydroxy groups, and specifically includes 1,4-butanediol, 1,3-butanediol and / do.

The biodegradable polyester resin according to one embodiment of the present invention is an aliphatic diol residue containing an ethylene glycol residue or a butanediol residue; And an aliphatic dicarboxylic acid residue comprising a succinic acid residue.

As used herein, the term " residue " refers to a certain moiety or unit derived from a particular compound when it participates in a chemical reaction and is included in the result of the chemical reaction. For example, the terms "aliphatic dicarboxylic acid residue", "aliphatic diol residue" and "terephthalic acid residue" refer to an aliphatic dicarboxylic acid or a derivative thereof in a polyester formed by an esterification reaction and a subsequent condensation polymerization reaction , A part derived from an aliphatic diol or a derivative component thereof, and a part derived from a terephthalic acid or a derivative component thereof.

For example, a succinic acid residue is _{(- (O =) CC 2} H 4 -C (= O) -) can be expressed as, adipic acid residue is _{(- (O =) CC 4} H 8 -C (= O) -), the ethylene glycol residue may be represented by (-O-C ₂ H ₄ -O-), and the butanediol residue may be represented by (-O-C ₄ H ₈ -O-) And the terephthalic acid residue may be represented by (- (O═) CC ₆ H ₄ -C (═O) -), and the diethylene glycol residue may be represented by (-OC ₂ H ₄ -OC ₂ H ₄ -O-) And the triethylene glycol residue may be represented by (-OC ₂ H ₄ -O- C ₂ H ₄ -O-C ₂ H ₄ -O-).

In the present specification, the term "aliphatic dicarboxylic acid derivative" means a compound including an ester derivative, an acyl halide derivative, an anhydride derivative, and the like of an aliphatic dicarboxylic acid compound.

As used herein, the term "aliphatic diol derivative" refers to a compound comprising dimethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, diethylene glycol, triethylene glycol, and the like.

As used herein, the term "terephthalic acid derivative" means a compound including an ester derivative, an acyl halide derivative, an anhydride derivative, etc. of a terephthalic acid compound.

The biodegradable polyester resin may be represented by the following formula (1).

[Chemical Formula 1]

Wherein a, b and c are each an integer of 0 to 2,500, a + b + c? 2, and m is an integer of 1 to 1,500. In the formulas, -OR ¹ -O-, -OR ³ -O-, and -OR ⁵ -O- are each an ethylene glycol residue, - (O═) CR ² -C (═O) ) CR ⁴ -C (= O) -, and - (O =) CR ⁶ -C (= O) - may each independently be a succinic acid residue, an adipic acid residue or a terephthalic acid residue.

The biodegradable polyester resin may be represented by the following formula (2).

(2)

Wherein a, b and c are each an integer of 0 to 2,500, a + b + c? 2, and m is an integer of 1 to 1,500. In the formula, -OR ¹ -O-, -OR ³ -O-, and -OR ⁵ -O- are each independently a butanediol residue, a diethylene glycol residue, or a triethylene glycol residue, - (O = ^{2 -C (= O) -,} - (O =) CR 4 -C (= O) -, and ^{- (O =) CR 6 -C} (= O) - can be an acid, each cup.

The aliphatic dicarboxylic acid and the aliphatic diol may react at a molar ratio of 1: 1 when they are reacted at the stoichiometric ratio during the polymerization for the production of the biodegradable polyester resin. The amount of the aliphatic dicarboxylic acid to be used may be 1: 1, but the amount of the aliphatic diol to be used may be excessive relative to the amount of the aliphatic dicarboxylic acid used to promote the reaction and increase the yield . For example, the aliphatic diol may be used in an amount of 1 to 2 moles per mole of the aliphatic dicarboxylic acid. Accordingly, the content of the aliphatic diol residue in the biodegradable polyester resin may be 1 to 2 moles per 1 mole of the aliphatic dicarboxylic acid residue.

Wherein the biodegradable polyester resin comprises the ethylene glycol residue as the aliphatic diol residue and further comprises an adipic acid residue as the aliphatic dicarboxylic acid residue, wherein the amount of the aliphatic dicarboxylic acid residue 0.3 to 0.8 mole part of the succinic acid residue and 0.2 to 0.7 mole part of the adipic acid residue.

When the content of the succinic acid residue and the content of the adipic acid residue are within the above ranges, the biodegradable polyester resin may have good processability and elasticity.

Wherein the biodegradable polyester resin contains the ethylene glycol residue as the aliphatic diol residue and further includes an adipic acid residue as the aliphatic dicarboxylic acid residue and further includes a terephthalic acid residue, 0.2 to 0.7 molar parts of the succinic acid residue and 0.3 to 0.8 molar parts of the sum of the adipic acid residue and the terephthalic acid residue relative to 1 molar part of the sum of the acid residue and the terephthalic acid residue.

The terephthalic acid moiety may be derived from terephthalic acid or dimethyl terephthalate which is not included in the aliphatic dicarboxylic acid moiety but is capable of reacting with the diol to cause an esterification reaction.

When the content of the succinic acid residue and the total content of the adipic acid residue and the terephthalic acid residue are within the above ranges, the biodegradable polyester resin may have excellent processability and elasticity.

The biodegradable polyester resin may contain 0.1 to 0.79 mole part of the adipic acid residue and 0.01 to 0.7 mole part of the terephthalic acid residue relative to 1 mole part of the sum of the aliphatic dicarboxylic acid residue and the terephthalic acid residue.

When the content of the adipic acid residue and the content of the terephthalic acid residue are within the above ranges, the biodegradable polyester resin may have excellent biodegradability and processability.

Wherein the biodegradable polyester resin comprises as the aliphatic diol residue, the butanediol residue and additionally at least one of diethylene glycol and triethylene glycol, wherein the aliphatic diol residue is present in an amount ranging from 0.3 to 0.7 Mol, and 0.3 to 0.7 mol parts of the sum of the diethylene glycol moiety and the triethylene glycol moiety.

When the content of the butanediol residue and the total content of the diethylene glycol residue and the triethylene glycol residue are within the above ranges, the biodegradable polyester resin may have good processability and elasticity.

The aliphatic diol residue in the biodegradable polyester resin may include 0.1 to 0.6 molar parts of the diethylene glycol residue and 0.1 to 0.6 molar equivalents of the triethylene glycol residue per 1 molar amount of the aliphatic diol residue.

When the content of the diethylene glycol residue and the content of the triethylene glycol residue are within the above ranges, the biodegradable polyester resin may have excellent processability and elasticity.

The biodegradable polyester resin may have a weight average molecular weight of 150,000 to 500,000. For example, the biodegradable polyester resin may have a weight average molecular weight of 200,000 to 400,000.

Another embodiment of the present invention provides an article comprising the biodegradable polyester resin.

The articles may include, for example, wire covers, automotive tires, conveyor belts, packing materials and the like. The biodegradable polyester resin may be a non-degradable elastic resin such as styrene butadiene rubber, nitrile rubber, butadiene rubber, ethylene propylene rubber, urethane rubber, or acrylic rubber.

Hereinafter, the method for producing the biodegradable polyester resin will be described in detail.

The biodegradable polyester resin as described above can be produced by the following method. That is, the biodegradable polyester resin may be an aliphatic diol or a derivative thereof; Aliphatic dicarboxylic acids or derivatives thereof; And optionally terephthalic acid or a derivative thereof, by esterification reaction and polycondensation reaction.

In the esterification reaction, the aliphatic diol or its derivative may be used in an amount of 1.0 to 2.0 mols based on 1 mol of the aliphatic dicarboxylic acid or its derivative. When the terephthalic acid or a derivative thereof is further used, the amount of the aliphatic diol or its derivative used in the esterification reaction is preferably in the range of 1 mole part to the total amount of the aliphatic dicarboxylic acid or a derivative thereof and the terephthalic acid or a derivative thereof May be 1.0 to 2.0 mols.

When the amount of the aliphatic diol or its derivative is within the above range, not only the aliphatic dicarboxylic acid or the derivative thereof is completely reacted, but also the ester bond is destroyed by the acidolysis reaction due to the residual dicarboxylic acid There is no possibility of depolymerization occurring due to excessive use of the aliphatic diol, and there is no problem of increase in cost due to excessive use of the aliphatic diol.

When succinic acid or a derivative thereof and adipic acid or a derivative thereof are used as an aliphatic dicarboxylic acid, which is an aliphatic diol, which is a reaction substance of the esterification reaction, and ethylene glycol or a derivative thereof is used as another reactant, The amount of the succinic acid or its derivative to be used may be 0.3 to 0.8 molar parts and the amount of the adipic acid or its derivative may be 0.2 to 0.7 molar parts relative to 1 molar amount of the total amount of the aliphatic dicarboxylic acid or its derivative.

It is preferable to use ethylene glycol or a derivative thereof as an aliphatic diol as a reaction material of the esterification reaction and to use succinic acid or a derivative thereof and adipic acid or a derivative thereof as an aliphatic dicarboxylic acid as another reactant, When the reaction material terephthalic acid or a derivative thereof is additionally used, the amount of the succinic acid or its derivative is preferably 0.2 to 0.7 moles per mole of the total amount of the aliphatic dicarboxylic acid or its derivative and the terephthalic acid or its derivative, , And the sum of the amount of the adipic acid or its derivative and the amount of the terephthalic acid or its derivative may be 0.3 to 0.8 mole part.

The amount of the adipic acid or a derivative thereof and the amount of the terephthalic acid or a derivative thereof are 0.1 to 0.79 parts by mole and 0.01 to 1 part by mole based on the amount of the aliphatic dicarboxylic acid or its derivative used and the amount of the terephthalic acid or its derivative used, To 0.7 mole fraction.

Also, at least one of the butanediol or a derivative thereof and a diethylene glycol or a derivative thereof and triethylene glycol or a derivative thereof may be used as an aliphatic diol as a reactant in the esterification reaction, and the aliphatic dicarboxylic acid When succinic acid or a derivative thereof is used as the acid, the butanediol or the derivative thereof is used in an amount of 0.3 to 0.7 molar parts based on 1 mol of the total amount of the aliphatic diol or the derivative thereof, and the amount of the diethylene glycol or its derivative, The sum of the amounts of the glycols or derivatives thereof used may be 0.3 to 0.7 mols.

The amount of the diethylene glycol or its derivative and the amount of the triethylene glycol or its derivative may be 0.1 to 0.6 mol and 0.1 to 0.6 mol, respectively, based on 1 mol of the total amount of the aliphatic diol or its derivative.

Such an esterification reaction can be carried out at 140 to 200 ° C for 80 to 450 minutes. For example, when ethylene glycol is used as the aliphatic diol, the esterification reaction may be conducted at 140 to 190 ° C for 80 to 240 minutes. When butanediol is used as the aliphatic diol, the esterification reaction may be performed at 140 to 200 Lt; 0 > C for 150 to 450 minutes.

The end point of the esterification reaction can be determined by measuring the amount of alcohol or water as a by-product in the reaction. For example, when 0.6 mol and 0.4 mol of succinic acid and adipic acid are used as the aliphatic dicarboxylic acid, respectively, and 1.3 mol of ethylene glycol is used as the aliphatic diol, the total amount of succinic acid and adipic acid Is reacted with ethylene glycol, the esterification reaction may be terminated when at least 90%, that is, 1.8 mol or more of 2 moles of maximum possible by-product, is produced. As another example, when 0.5 mol, 0.4 mol, and 0.1 mol of succinic acid, adipic acid, and dimethyl terephthalate are used as the above dicarboxylic acid, respectively, and 1.3 mol of ethylene glycol is used as the aliphatic diol, Assuming that all amounts of diphenylmethane, dibasic acid, and dimethyl terephthalate are reacted with ethylene glycol, at least 90% of the maximum possible by-product of water and 0.2 mol of maximally naturally occurring methanol, ie, 1.62 mol of water and 0.18 mol of methanol, The esterification reaction can be terminated.

In order to increase the reaction rate by moving the chemical equilibrium in the esterification reaction, the by-produced alcohol, water and / or unreacted diol compound may be discharged out of the reaction system by evaporation or distillation.

In order to facilitate the esterification reaction, the esterification reaction may be carried out in the presence of a catalyst, a branching agent, a heat stabilizer and / or a color tone ablation agent.

The catalyst may be selected from the group consisting of magnesium acetate, stannous acetate, tetra-n-butyl titanate, acetic acid, sodium acetate, potassium acetate, antimony trioxide, N, N-dimethylaminopyridine, N-methylimidazole, can do. The catalyst is usually added at the same time as the monomer when the monomer is added. The amount of the catalyst to be used may be, for example, 0.00001 to 0.2 mole per 1 mole of the aliphatic dicarboxylic acid. When the content of the catalyst is within the above range, the reaction time can be shortened, a desired degree of polymerization can be obtained, and an elastically biodegradable polyester resin having good chromaticity can be obtained.

The heat stabilizer may be an organic or inorganic compound. The organic or inorganic phosphorus compound may be, for example, phosphoric acid and organic esters thereof, phosphorous acid and organic esters thereof. For example, the heat stabilizer may be a commercially available material, such as phosphoric acid, alkyl or aryl phosphate. For example, the heat stabilizer may be triphenyl phosphate. The amount of the heat stabilizer to be used in the case of using the catalyst and the heat stabilizer may be 0.00001 to 0.2 mol per 1 molar amount of the aliphatic dicarboxylic acid. When the amount of the heat stabilizer used is within the above range, deterioration and discoloration of the biodegradable polyester resin can be prevented.

The branching agent is used for the purpose of controlling the biodegradability and physical properties of the polyester resin. As such a branching agent, a compound having at least three ester or amide-forming group selected from a carboxyl group, a hydroxyl group and an amine group may be used. Specifically, as the branching agent, trimellitic acid, citric acid, maleic acid, glycerol, monosaccharide, disaccharide, dextrin or reduced sugar may be used.

The amount of the branching agent used may be 0.00001 to 0.2 moles per mole of the aliphatic dicarboxylic acid. When the amount of the branching agent used is within the above range, a high molecular weight biodegradable polyester resin having excellent elasticity can be obtained.

The esterification reaction can proceed under atmospheric pressure. As used herein, " atmospheric pressure " means a pressure in the range of 760 10 torr.

The hue ablation is an additive used for adjusting the chromaticity of the biodegradable polyester resin. Cobalt acetate or the like may be used as the color modifier. Such a hue abstraction may be used in the esterification reaction step together with an aliphatic diol and an aliphatic dicarboxylic acid, or may be used in the condensation polymerization step described later. The amount of the hue ablation may be 0.00001 to 0.2 moles per mole of the aliphatic dicarboxylic acid.

An oligomer having an ester bond is produced by the esterification reaction as described above.

The product (oligomer) of the esterification reaction as described above can be further subjected to condensation polymerization for high molecular weight. The condensation polymerization may be carried out at 220 to 290 ° C for 120 to 360 minutes. For example, when ethylene glycol is used as the aliphatic diol, the condensation polymerization may proceed at 240 to 290 ° C for 240 to 360 minutes. When butanediol is used as the aliphatic diol, Lt; 0 > C for 120-280 minutes.

The polycondensation reaction can proceed at a pressure of less than 1 torr. By proceeding the condensation polymerization under vacuum in this manner, a biodegradable polyester resin having a high molecular weight can be obtained while removing unreacted raw materials (unreacted monomers), low molecular oligomers and by-produced water and / or methanol.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example

< Example  1 to 3: Synthesis of biodegradable polyester resin>

(Esterification reaction)

(EG), dimethyl terephthalate (DMT), tetra-n-butyl titanate (TBT) and malonic acid (TBT) in the amounts indicated in the following Table 1 were placed in a 500 ml 3-neck round bottom flask equipped with a stirrer, MA) to prepare a mixture. The mixture was heated to the temperature shown in Table 2 below and reacted under stirring in a nitrogen atmosphere until methanol of 90% or more of the theoretical value (see Table 2 below) was released. The generated methanol was completely discharged out of the system through a condenser. Subsequently, succinic acid (SA) and adipic acid (AA) shown in the following Table 1 were added to the three-necked round bottom flask, and the temperature was raised to the temperature shown in Table 2, ) Was reacted under agitation until it was released, and the water produced was discharged to the outside of the system with a condenser. Then, threylphenylphosphate (TPP), cobalt acetate (CA) and antimony trioxide (AT) in the amounts shown in the following Table 1 were added to the three-neck round bottom flask, followed by stirring for 5 minutes.

The amounts of monomers and additives used in the above Examples are shown in Table 1 below.

(Condensation polymerization)

Then, the three-necked round bottom flask was heated to a temperature shown in Table 2 under a vacuum of 1 torr or less, and the reaction was allowed to proceed for a period of time shown in Table 2, followed by discharging the contents of the flask.

< Example  4 to 6: Synthesis of biodegradable polyester resin>

(Esterification reaction)

(EG), succinic acid (SA), adipic acid (AA), tetra-n-butyl titanate (manufactured by Wako Pure Chemical Industries, Ltd.) in the amounts shown in the following Table 1 were placed in a 500 ml 3-neck round bottom flask equipped with a stirrer, TBT) and malic acid (MA) were added to prepare a mixture. Thereafter, the mixture was heated to the temperature indicated in Table 2 below and reacted under stirring in a nitrogen atmosphere until 90% or more of the theoretical value (see Table 2 below) was released. The resulting water was completely drained out of the system through a condenser. Then, triphenylphosphate (TPP), cobalt acetate (CA) (5 wt% in ethylene glycol) in the three- ) And antimony trioxide (AT) were added thereto, followed by stirring for 5 minutes.

(Condensation polymerization)

Then, the three-necked round bottom flask was heated to a temperature shown in Table 2 under a vacuum of 1 torr or less, and the reaction was performed for the time indicated in Table 2 below, and the content of the flask was discharged.

The amounts of the monomers and additives used in the above Examples are shown in Table 1 below and the conditions of the esterification reaction and condensation polymerization reaction are shown in Table 2 below.

Diol Diacid MA
(g (mmol))
TPP
(g (mmol))
TBT
(g (mmol))
CA
(g (mmol))
AT
(g (mmol))
EG
(g (mol)) SA
(g (mol)) AA
(g (mol)) DMT
(g (mol)) Example 1
124.14
(2.0) 23.62
(0.2) 102.30
(0.7) 19.42
(0.1) 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) 0.05
(0.172) Example 2
148.97
(2.4) 99.2
(0.84) 17.54
(0.12) 46.60
(0.24) 0.48
(3.580) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) 0.05
(0.172) Example 3
124.14
(2.0) 59.05
(0.5) 43.84
(0.3) 38.84
(0.2) 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) 0.05
(0.172) Example 4
124.14
(2.0) 59.05
(0.5) 73.07
(0.5) - 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) 0.05
(0.172) Example 5
124.14
(2.0) 35.43
(0.3) 102.30
(0.7) - 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) 0.05
(0.172) Example 6
148.97
(2.4) 113.37
(0.96) 35.07
(0.24) - 0.48
(3.580) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) 0.05
(0.172)

Esterification reaction temperature
(° C) 90% of the theoretical value
Methanol
(ml) Theoretical
More than 90% water
(ml) Condensation polymerization
Temperature
(° C) Condensation polymerization
time
(minute) Example 1 182 7 30 275 172 Example 2 180 17.5 31 275 177 Example 3 180 14.5 26 275 173 Example 4 180 - 32 280 155 Example 5 180 - 32 280 159 Example 6 180 - 39 280 158

< Example  7 to 9: Synthesis of biodegradable polyester resin>

(Esterification reaction)

1,4-butanediol (BDO), diethylene glycol (DEG), triethylene glycol (TEG), succinic acid (SA) in the amounts shown in the following Table 3 were added to a 500 ml 3-neck round bottom flask equipped with a stirrer, a condenser, Tetra-n-butyl titanate (TBT) and malic acid (MA) were charged to prepare a mixture. Then, the mixture was heated to the temperature shown in Table 4 and heated to 90% or more of the theoretical value (specifically, 32 ml ) Was reacted with stirring until the water was released, and the resulting water was completely discharged out of the system through the condenser. Then, threylphenylphosphate (TPP) and cobalt acetate (CA) shown in Table 3 were added to the three-necked round bottom flask, followed by stirring for 5 minutes.

 (Condensation polymerization)

Then, the three-necked round bottom flask was heated to a temperature shown in Table 4 under a vacuum of 1 torr or less, and the reaction was allowed to proceed for the time indicated in Table 4, followed by discharging the content of the flask.

The amounts of the monomers and additives used in the above Examples are shown in Table 3 below, and the conditions of the esterification reaction and the condensation polymerization reaction are shown in Table 4, respectively.

< Example  10: Synthesis of biodegradable polyester resin &gt;

The same procedure as in Examples 7 to 9 was used except that triethylene glycol (TEG) was not used. The amounts of monomers and additives used in the above examples are shown in Table 3 below.

< Example  11: Synthesis of biodegradable polyester resin &gt;

The same procedure as in Examples 7 to 9 was used except that diethylene glycol (DEG) was not used. The amounts of monomers and additives used in the above examples are shown in Table 3 below.

Diacid Diol MA
(g (mmol)) TPP
(g (mmol)) TBT
(g (mmol)) CA
(g (mmol)) SA
(g (mol)) BDO
(g (mol)) DEG
(g (mol)) TEG
(g (mol)) Example 7
118.09
(1.0) 32.44
(0.36) 63.67
(0.6) 36.04
(0.24) 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) Example 8
118.09
(1.0) 75.70
(0.84) 12.73
(0.12) 36.04
(0.24) 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) Example 9
118.09
(1.0) 54.07
(0.6) 45.05
(0.3) 31.535
(0.3) 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) Example 10
118.09
(1.0) 54.07
(0.6) 90.10
(0.6) -
0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) Example 11
118.09
(1.0) 54.07
(0.6) - 63.67
(0.6) 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201)

Esterification reaction
Temperature (℃) Condensation polymerization
Temperature (℃) Condensation polymerization
Time (minutes) Example 7 200 240 253 Example 8 200 240 182 Example 9 200 240 134 Example 10 200 240 213 Example 11 200 240 277

Comparative Example  1-3

A biodegradable polyester resin was produced in the same manner as in Examples 1 to 3 except that monomers and additives of the kind and content shown in Table 5 were used and the conditions were shown in Table 7 below Respectively.

Comparative Example  4 to 6

A biodegradable polyester resin was prepared in the same manner as in Examples 4 to 6 except that the monomers and additives of the kind and content shown in Table 5 were used and the conditions were as shown in Table 7 below . The amounts of the monomers and additives used in each example are shown in Table 5 below.

Comparative Example  7 to 8

A biodegradable polyester resin was prepared in the same manner as in Examples 7 to 9 except that monomers and additives of the type and content shown in Table 6 were used and the conditions were shown in Table 7 below Respectively.

Diol Diacid MA
(g (mmol)) TPP
(g (mmol)) TBT
(g (mmol)) CA
(g (mmol)) AT
(g (mmol)) EG
(g (mol)) SA
(g (mol)) AA
(g (mol)) DMT
(g (mol)) Comparative Example 1
124.14
(2.0) 11.81
(0.1) 73.07
(0.5) 77.68
(0.4) 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) 0.05
(0.172) Comparative Example 2
124.14
(2.0) 94.47
(0.8) 7.31
(0.05) 29.13
(0.15) 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) 0.05
(0.172) Comparative Example 3
148.97
(2.4) - 87.68
(0.6) 116.51
(0.6) 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) 0.05
(0.172) Comparative Example 4
124.14
(2.0) 23.62
(0.2) 116.91
(0.8) - 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) 0.05
(0.172) Comparative Example 5
124.14
(2.0) 112.19
(0.95) 7.31
(0.05) - 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) 0.05
(0.172) Comparative Example 6
186.21
(3.0) 159.42
(1.35) 21.92
(0.15) - 0.6
(4.475) 1.5
(4.598) 0.3
(0.881) 1.0
(0.201) 0.05
(0.172)

Diacid Diol MA
(g (mmol)) TPP
(g (mmol)) TBT
(g (mmol)) CA
(g (mmol)) SA
(g (mol)) BDO
(g (mol)) DEG
(g (mol)) TEG
(g (mol)) Comparative Example 7 118.09
(1.0) 21.63
(0.24) 89.14
(0.84) 18.02
(0.12) 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201) Comparative Example 8 118.09
(1.0) 86.52
(0.96) 6.37
(0.06) 27.03
(0.18) 0.4
(2.983) 1.0
(3.065) 0.2
(0.587) 1.0
(0.201)

Esterification reaction temperature
(° C) More than 90% of the theoretical value of methanol
(ml) Theoretical
More than 90% water
(ml) Condensation polymerization
Temperature
(° C) Condensation polymerization
time
(minute) Comparative Example 1 180 29 19.5 280 153 Comparative Example 2 180 11 27.5 275 180 Comparative Example 3 190 44 20 275 160 Comparative Example 4 190 - 32 280 163 Comparative Example 5 180 - 32 280 158 Comparative Example 6 180 - 48 280 158 Comparative Example 7 200 - 32 240 266 Comparative Example 8 200 - 32 240 166

Evaluation example

The weight average molecular weight (Mw), elasticity and biodegradability of the biodegradable polyester resin synthesized in Examples 1 to 11 and Comparative Examples 1 to 8 were measured by the following methods, and the results are shown in Table 8 Respectively.

&Lt; Measurement of weight average molecular weight (Mw)

A solution in which the polyester resin of each of the above Examples and Comparative Examples was diluted with chloroform in a concentration of 1 wt% was analyzed by gel permeation chromatography (GPC) to determine the weight average molecular weight. At this time, the measurement temperature was 35 ° C and the flow rate was 1 ml / min.

<Elasticity Measurement>

The elasticity of the polyester resin synthesized in each of the Examples and Comparative Examples was measured using a universal test measuring instrument (Instron 5569) at 25 ° C after preparing a specimen of 5 mm × 100 mm × 1 mm in width, , The stretched length of the specimen was 200 mm, and the specimen was allowed to stand for 10 minutes. Then, when the force was removed, the ratio of the recovered length of the specimen was calculated by the following equation (1). The higher the elasticity, the better the elasticity.

[Equation 1]

Elasticity (%) = (200 - L _t ) * 100 / L ₀

L _t = Length (mm) of the specimen when the specimen is stretched 200 mm in the longitudinal direction and left for 10 minutes and then the force is removed.

L ₀ = Length before stretching the specimen. That is,

&Lt; Evaluation of biodegradability &

The evaluation of biodegradability was carried out according to KS M 3100-1, a method of measuring the aerobic biodegradability of plastics under composting conditions. The cumulative biodegradation value for 45 days was calculated by the following equation (2), and the results are shown in Table 8 below.

&Quot; (2) &quot;

(%) = {[CO ₂ ] sf * 100 / [CO ₂ ] st} * 100 / {[CO ₂ ] cf * 100 / [CO ₂ ]

[CO ₂ ] sf: CO ₂ accumulation amount generated by biodegradation of a 45-day sample

[CO ₂ ] Total amount of CO ₂ that can be generated when st: sample is 100% biodegraded

[CO ₂ ] cf: CO ₂ accumulation amount generated by biodegradation of cellulose as a standard sample for 45 days

[CO ₂ ] ct: the total amount of CO ₂ that can be generated when 100% of the cellulose as a standard sample is biodegraded

Molecular weight (Mw) Elasticity (%) Biodegradability (%) Example 1 482,000 82 92 Example 2 379,000 95 86 Example 3 373,000 88 89 Example 4 399,000 100 81 Example 5 388,000 81 81 Example 6 293,000 97 86 Example 7 199,000 82 79 Example 8 379,000 91 86 Example 9 216,000 88 88 Example 10 196,000 93 78 Example 11 22,700 85 90 Comparative Example 1 387,000 Not measurable (gel) 66 Comparative Example 2 210,000 0 (solidification) 62 Comparative Example 3 253,000 Not measurable (gel) 60 Comparative Example 4 421,000 Not measurable (gel) 93 Comparative Example 5 222,000 0 (solidification) 61 Comparative Example 6 284,000 0 (solidification) 64 Comparative Example 7 153,000 Not measurable (gel) 94 Comparative Example 8 188,000 0 (solidification) 61

Referring to Table 8, it can be seen that the biodegradable polyester resins of Examples 1 to 11 maintain excellent biodegradability (78% or more) while having excellent elasticity (81% or more). On the other hand, the resins of Comparative Examples 1 to 8 were found to be in a gel state or solidified, so that elasticity measurement was impossible or elasticity was "0 ".

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

Claims (9)

An aliphatic diol residue comprising an ethylene glycol residue or a butanediol residue; And
A biodegradable polyester resin comprising an aliphatic dicarboxylic acid residue containing a succinic acid residue. The method according to claim 1,
Wherein the content of the aliphatic diol residue is 1 to 2 moles per 1 mole of the aliphatic dicarboxylic acid residue. The method according to claim 1,
Wherein the aliphatic dicarboxylic acid residue further comprises an ethylene glycol residue as the aliphatic dicarboxylic acid residue and the adipic acid residue as the aliphatic dicarboxylic acid residue, And 0.2 to 0.7 part by mol of the adipic acid residue. The method according to claim 1,
Wherein the aliphatic dicarboxylic acid residue and the terephthalic acid residue include the ethylene glycol residue as the aliphatic diol residue and further include an adipic acid residue as the aliphatic dicarboxylic acid residue and further include a terephthalic acid residue, 0.2 to 0.7 mole part of the succinic acid residue and 0.3 to 0.8 mole part of the sum of the adipic acid residue and the terephthalic acid residue relative to one mole part of the sum. 5. The method of claim 4,
0.1 to 0.79 molar parts of the adipic acid residue and 0.01 to 0.7 molar parts of the terephthalic acid residue relative to 1 molar part of the sum of the aliphatic dicarboxylic acid residue and the terephthalic acid residue. The method according to claim 1,
Wherein the aliphatic diol residue comprises the butanediol residue and wherein the aliphatic diol residue further comprises at least one of a diethylene glycol residue and a triethylene glycol residue, 0.7 mol part of the diethylene glycol residue and 0.3-0.7 mol part of the sum of the diethylene glycol residue and the triethylene glycol residue. The method according to claim 6,
Wherein the aliphatic diol residue comprises from 0.1 to 0.6 mole part of the diethylene glycol residue and from 0.1 to 0.6 mole part of the triethylene glycol residue relative to a total of one mole of the aliphatic diol residue. The method according to claim 1,
Wherein the biodegradable polyester resin has a weight average molecular weight of 150,000 to 500,000. An article comprising the biodegradable polyester resin according to any one of claims 1 to 8.