KR20000059815A - Method for the preparation of the aliphatic polyester - Google Patents

Abstract

PURPOSE: A method for preparing aliphatic polyester is provided, which has high melt viscosity, is degraded to harmless substances rapidly, is cheap, and is applied to blown-film molding, foaming molding and vacuum molding. CONSTITUTION: The method comprises the steps of injecting an aliphatic diol selected from ethylene glycol, 1,4-butanediol and 1,6-hexanediol, an acid selected from succinic acid, adipic acid and adipic anhydride, and a monomer selected from maleic acid and maleic anhydride for improve the high melt viscosity, into a reactor provided with a stirrer and a condenser and carrying out the esterification of the mixture at the temperature below 220°C; and injecting a catalyst into the reactor and carrying out the deglycolization and addition reaction at 190-250°C and at the pressure of 0.005-1 mmHg to obtain aliphatic polyester.

Description

Method for producing aliphatic polyester {METHOD FOR THE PREPARATION OF THE ALIPHATIC POLYESTER}

The present invention relates to a process for producing aliphatic polyester, and in particular, it can be used for blown film molding, foam molding, vacuum molding, etc., in which high melt viscosity is required, and also quickly decomposed into harmless materials in municipal waste composting facilities. It also relates to a method for producing aliphatic polyester which is cheaper than conventional biodegradable resins.

Conventional general-purpose plastics are widely used in daily life because of their excellent mechanical properties, chemical resistance and durability. Disposal after use has the disadvantage that it does not decompose causing serious environmental pollution. In particular, in the case of disposable packaging containers, despite the recent rapid increase in demand, disposable packaging containers discarded after use are not collected for recycling, so countries have been banning the use of disposable packaging containers. In addition, even in the case of agricultural film is difficult to recover completely, it is embedded in the soil polluting the soil while causing a lot of problems in crop growth. As environmental pollution caused by such plastic wastes has emerged as a social problem, development of degradable resins that automatically decompose within a certain time when used and disposed of is being actively conducted in order to protect environment.

Degradable resins are classified into biodegradable resins, which are completely decomposed naturally by moisture and microorganisms, and biodegradable resins which are decomposed by self-decomposing or promoting decomposition by starch or metal compounds added to the matrix. In addition, the polymer backbone is cleaved by ultraviolet rays in the 290-320 nm wavelength band of sunlight, and the molecular weight is lowered.

Among these, photodegradable resins are decomposed only when received in sunlight, so they are buried in soil and are not decomposed in an environment blocked from light. In addition, biodegradable resins only degrade the biodegradable raw materials such as starch, and the remaining non-degradable resins do not decompose and remain in the soil in small pieces, thus causing secondary pollution of the soil.

Among these, photodegradable resins are decomposed only when received in sunlight, so they are buried in soil and are not decomposed in an environment blocked from light. In addition, biodegradable resins only degrade the biodegradable raw materials such as starch, and the remaining non-degradable resins do not decompose and remain in the soil in small pieces, thus causing secondary pollution of the soil. In addition, biodegradable resins have the advantage that they do not cause environmental pollution by being fully decomposed, while having a disadvantage of high manufacturing cost.

Biodegradable resins can be further classified into microbial production type that produces microorganisms, natural product utilization types that use natural polymers present in nature, and synthetic polymer types that are easily decomposed by microorganisms. Only aliphatic polyesters are known to be 100% fully degradable.

Aliphatic polyesters can be prepared through condensation polymerization based on glycol and divalent carboxylic acid, ring-opening polymerization of cyclic monomers, transesterification reaction between polyesters, etc. Active research is being conducted, and in the 1960s, American Cyanamide Inc. developed absorbent surgical sutures made of polyglycolide under the trade name DEXON. Recently, polylactide-based polymer materials have been developed and will be commercialized. Union Carbide has commercialized biodegradable resins under the trade name TONE.

The ring-opening polymerization of the cyclic ester monomer is mainly a 4, 5, 6, 7-membered ring lactone is used, it is generally known that the high molecular weight of the moldable. However, polyglycolide or polylactide, which has been used for medical purposes until now, is not suitable as a general-purpose polymer material due to its poor physical properties and economic feasibility, and polycaprolactone has a low melting point and has problems with thermal stability and dimensional stability. It is becoming.

Crystalline polymer synthesized by using a glycolide obtained by ring-opening polymerization of polyglycolide in the presence of a catalyst as a monomer has high molecular weight and glass transition temperature but has a hard and low solubility. Lactone-based polymer is flexible and has excellent molecular weight and solubility. But the glass transition temperature is low. In view of this, efforts have been made to copolymerize glycolide and various lactones in the presence of a catalyst or to synthesize block copolymers of? -Caprolactone and other lactones to compensate for the shortcomings of each single polymer.

On the other hand, composite materials using natural materials such as starch and cellulose are also being actively studied. The production of composites filled with cellulose in polyhydroxybutyrate, a microorganism-producing polymer, or physically applying starch to general-purpose polymers such as polyolefins Attempts have been made to make them biodegradable. The method of filling starch into general purpose polymer is one of the most useful methods because it is easy to manufacture and can use the existing molding plant as it is, but since the hydrophilic starch is not compatible with hydrophobic general purpose polymer, it contains a large amount of starch. In this case, a lot of researches have been made to solve this problem, which is accompanied by a decrease in mechanical properties due to aggregation. However, the introduction of natural materials has a lot of problems in commercialization because it is difficult to obtain quality uniformity of the produced product.

On the other hand, inadequate disposal of municipal waste in landfills and increased plastics and non-degradable impurities in municipal waste not only increases landfill costs but also drastically reduces usable landfills. Recyclable plastic is the most desirable method of recycling, but it is very difficult to recycle plastic products that are difficult to collect, such as diapers, sanitary towels, and garbage bags. Recently, there has been a move to reduce the volume of solid waste to be reclaimed by composting non-recyclable solid waste or to convert waste into fertilizer to commercialize it, but to sell compost produced by composting of municipal waste. Because of the constraints in place, this too is not progressing well. In other words, during composting of municipal waste, plastic products do not decompose and remain in the form of small pieces.

The present invention has been made in view of the above-mentioned conventional problems, and can be used for applications such as blown film forming, foam molding, vacuum forming, etc., which require a high melt viscosity, and can be quickly used as a harmless material in urban waste composting facilities. It is an object of the present invention to provide aliphatic polyester which is not only decomposed but also inexpensive as compared with conventional biodegradable resins.

In order to achieve the above object, the aliphatic polyester produced by the manufacturing method according to the present invention is composed of aliphatic dihydric alcohol and aliphatic dicarboxylic acid as a main component, it is possible to compost while having biodegradability and high melting point It is suitable for the field of processing requiring the degree of characteristics. That is, the aliphatic polyester produced by the manufacturing method according to the present invention is suitable for use as a coating material, an adhesive, etc., unlike an aromatic polyester having a high melting point such as polyethylene terephthalate, and greatly improves the melt viscosity through the improvement of the molecular weight. It is excellent in film formability. In addition, by improving the melt viscosity, it is possible to use in blown film molding, foam molding, vacuum molding, etc. by reducing the melt viscosity variation between polymer chips at the beginning and end of discharging during aliphatic polyester production.

In general, in the case of forming a chip shape suitable for molding by production discharge of aliphatic polyester, the discharge time is short from 20 minutes to as much as 1 hour. At this time, the difference in physical properties, especially melt viscosity, between chips obtained at the beginning of discharge and at the end of discharge is remarkable, resulting in deterioration of the physical properties of the product after molding, but according to the present invention, aliphatic polys are stable for a long time by solving this problem. Ester can be prepared.

Other features and advantages of the present invention will become more apparent from the following detailed description.

The aliphatic polyester production method according to the present invention is largely divided into an esterification step and a condensation polymerization step.

The monomer component used for the esterification reaction is (1) an aliphatic diol, which has one component selected from ethylene glycol, 1,4-butanediol, and 1,6-hexanediol as a main component, and (2) succinic acid as an acid component. And one component selected from adipic acid or anhydride thereof, and (3) maleic acid or anhydride thereof as a component for promoting high melt viscosity.

The monomer component configured as described above was introduced into a reactor equipped with a stirrer and a condenser, and the esterification reaction was carried out at a temperature of 220 ° C. or lower, and a catalyst was added to deglycol at a temperature of 190 ° C. to 250 ° C. and a high vacuum of 0.005 to 1 mmHg. By carrying out the reaction and the addition reaction, an aliphatic polyester having a high melt viscosity can be obtained.

In the present invention, the main component of the aliphatic diol component means a component occupying 70 mol% or more of the total diol components, and ethylene glycol, 1,3-propanediol, 1,4- as an auxiliary component of the aliphatic diol component. Butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexadiol, 1,8-octanediol, 1,10-decanediol, 2,2-dimethyl-1,3-propanediol , 1,6-cyclohexanedimethanol and the like can be mixed and used. The molar ratio of the esterification reaction between the aliphatic diol and the aliphatic dicarboxylic acid component is preferably in the range of 1: 1 to 1: 2, and more preferably, the reaction is carried out at a ratio in the range of 1: 1.1 to 1: 1.7. And it is advantageous in terms of physical properties and color tone of the obtained polymer.

On the other hand, in the present invention, the meaning of the main component of the acid component means that composed of more than 70 mol% of the total acid component used, adipic acid, subberic acid, azelaic acid, sebacic acid, dodecanoic acid as auxiliary components Or the like can be used in combination.

Further, in the present invention, maleic acid or anhydride thereof is used as a method for improving the processing characteristics and mechanical properties of the polymer through solid solution melting viscosity. In this invention, maleic acid or its anhydride is added in 0.01-1 mol% with respect to all acid components. When maleic acid or its anhydride is not added and reacted, the melt viscosity variation of the polymer obtained at the beginning and the end of the discharge at the time of discharging the synthesized polycondensation polyester is very large, resulting in poor moldability and the like. Therefore, in the present invention, by adding and reacting maleic acid or its anhydride in the range of 0.01 to 1 mol%, it is possible to reduce the melting point variation of the polymer obtained at the beginning and the end of the discharge at the time of discharging the synthesized polycondensation polyester, thereby obtaining excellent moldability. Can be.

In addition, since maleic acid or its anhydride has an unsaturated double bond in addition to having a carboxylic acid or its anhydride-type reactor capable of esterification, some residual double bonds remain in the polymer formed after the esterification and condensation polymerization. As a result, even after exposure to heat for a long time in a process such as during discharging after condensation polymerization or molding, the remaining double bonds are broken and a reaction occurs, so that the melt viscosity decreases very slowly, thereby maintaining a solid melting state. On the other hand, when the amount of maleic acid or its anhydride exceeds 1% by weight, the crosslinking reaction occurs severely, resulting in very poor molding process characteristics of the produced polyester and significantly degrading degradability.

The aliphatic copolyester in the present invention exhibits a property that the solid solution melt viscosity is continuously maintained even when exposed to heat, wherein the melt viscosity is evaluated as the melt index. The melt index is expressed as the amount of polymer discharged over a 10 minute period through a 1 cm diameter die at a pressure of 2.16 kgf / cm 2 at a temperature of 190 ° C., the smaller the value, the higher the melt viscosity. By controlling the preheating time of the polymer measured during the melt index measurement, it is possible to analyze the change of the melt index according to the time the polymer is exposed to heat. The smaller the deviation of the melt index according to the preheating time, the better the heat resistance of the polymer.

In the present invention, the heat resistance of the polymer was evaluated by setting the preheating time to 5 minutes and 20 minutes, respectively, in the evaluation of the melt index, and the relative value was measured by measuring the value of the deviation.

On the other hand, the polycondensation catalyst used in the present invention is preferably a tin compound system or a titanium compound system. Examples of the tin compound include tin oxides such as tin oxide and tin oxide, halogen tins such as tin chloride, tin chloride, and tin sulfide, monobutyl tin oxide, dibutyl tin oxide, and oxidation. Organotin compounds such as monobutylhydroxytin, dibutyltin dichloride, tetraphenyltin, tetrabutyltin and the like. In addition, tetrabutyl titanate, tetramethyl titanate, tetraisopropyl titanate, tetra (2-ethylhexyl) titanate, or the like may be used as the titanium compound.

As for the addition amount of the polymerization catalyst used by this invention, the range of 0.01-0.1 mol% with respect to an acid component is preferable. If the amount of the catalyst is used too much, the discoloration of the polymer may occur severely, and if the amount of the catalyst is used too little, the reaction rate may be slowed.

In addition, a phosphorus compound may be used as the heat stabilizer used in the present invention. Phosphorous compounds include, for example, phosphoric acid, monomethylphosphoric acid, triphenylphosphoric acid, trimethylphosphoric acid and derivatives thereof, divalentox1010, divalentox1222, divalent 168, phenylphosphonic acid, and in particular phosphoric acid and trimethyl. The effect of phosphoric acid and triphenylphosphoric acid is excellent. The amount of phosphorus compound used as a heat stabilizer is 1.0 × 10 ^-7 to 1.0 × 10 ^-6 mol / g oligomer with respect to the oligomer obtained by esterification or transesterification reaction, more preferably 0.5 × 10 ^-7 to 1.5 × 10 ^-6 mol / g oligomer.

According to the present invention, in order to obtain an aliphatic copolyester having a high melt viscosity, it is important to carry out the polycondensation reaction under high vacuum conditions, and the reaction temperature is preferably 230 to 260 ° C. If the reaction temperature is less than 230 ℃, the polycondensation reaction rate is very slow, it is difficult to obtain a polymer of the desired high melting point viscosity, and if it exceeds 260 ℃ the thermal decomposition is rather severe, the resulting physical properties and color tone is poor.

According to the present invention, the melt viscosity of the copolyester is measured by the amount of polymer discharged upon application of 2.16 kgf / cm 2 pressure at 190 ° C. by KS M3070. In this case, the smaller the value, the higher the melt viscosity.

After the polyester film was manufactured using Rheocord 90 blown film processing equipment of Haake, biodegradability evaluation was carried out according to ASTM G21-70 and degradability acceleration evaluation method.

The measurement procedure of ASTM G21-70 is as follows.

Place the sample film on agar, solid media, and place on it with aspergillus niger, penicillium-funiculosum, trichoderma SP and pullularia pullulans After 2 ~ 4 weeks of spraying the mixed spore solution, the degree of mold growth was confirmed. If it is less than 10% of the specimen area, it is 1, 10 ~ 30% is 2, 30 ~ 60% is 3, and more than 60% is 4 It was.

On the other hand, the measurement process of the degradation acceleration evaluation method is as follows.

The medium was prepared as shown in Table 1 below to meet the composition ratio of waste generated in Korea, and the internal environment was adjusted as shown in Table 2 and maintained for 10 weeks after inserting the sample film to measure the weight loss of the sample film. The decomposition degree was evaluated by doing this.

Composition ratio of garbage for compost ingredient content(%) Food (white rice cake, Chinese cabbage, pork, fish cake) 39.8 Paper (computer paper, newspaper) 20.7 sawdust 5.3 Superfluous 7.3 plastic 7.7 Rubber 4.5 leaf 14.7 sum 100

Internal environment setting condition of Compost method Item Condition pH 7.0 Water content of medium (%) 60.0 Initial value of the carbon / nitrogen component of the medium 23.0 Air supply amount (ml / min) 100 Internal holding temperature (℃) 55

Hereinafter, examples and comparative examples for making an aliphatic copolyester by the production method according to the present invention will be described in detail.

Abbreviations used in the Examples and Comparative Examples are defined as follows.

SA: succinic acid

AA: adipic acid

DEG: diethylene glycol

TEG: triethylene glycol

BD: 1,4-butanediol

HD: 1,6-hexanediol

MA: maleic acid

MAN: maleic anhydrige

TBT: Titanium tetrabutoxide

<Example 1>

1,372 g (11.615 mole), BD 1,070 g (11.618 mole), HD 343 g (2.902 mole), MAN 0.6 g (0.0058 mole) were added to the reactor equipped with the stirrer and condenser. It heated up to 120 degreeC over, and it heated up to 210 degreeC over 120 minutes, stirring. Water produced at this time was discharged out of the system through a condenser, and the reaction was stopped when the final effluent reached 95% of the theoretical effluent. The temperature in the tube was 210 ° C. This resulted in 2,480 g of esterification reactant. Then, 1.70 g of TBT as a catalyst and 0.2 g of phosphoric acid as a heat stabilizer were added, and the pressure in the tube was gradually reduced to 0.5 mmHg over 45 minutes, and the reaction was performed by stirring for 180 minutes while raising the temperature of the tube to 240 ° C., followed by stirring. The desired aliphatic copolyester was obtained by stopping the mixture and injecting nitrogen into the tube to pressurize and discharge the polymer.

Then, the aliphatic copolyester prepared as described above was made into a blown film through hot air drying. Blown film processing conditions include blow up ratio 4 and take-up using a Rheocord 90 blown film processing facility from Haake, whose tubular die is 25 mm in diameter. speed) 10 m / min, screw speed 9 rpm, barrel temperature conditions were set to 140 ℃, 150 ℃, 150 ℃, 150 ℃ blown film processing was performed. And the physical property about the film thus obtained was measured and the result of the following Table 3 was obtained.

<Example 2>

SA 1,372g (11.618mol), BD 1,338g (14.525mol) and MAN 0.8g (0.0076mol) were added to the reactor equipped with the stirrer and condenser, and the temperature in the reactor was raised from room temperature to 120 ° C over 20 minutes and stirred. It heated up to 210 degreeC over 120 minutes. Water produced at this time was discharged out of the system through a condenser, and the reaction was stopped when the final effluent reached 95% of the theoretical effluent. The temperature in the tube was 210 ° C. This resulted in 2425 g of esterification reactant. Subsequently, condensation polymerization was carried out in the same manner as in Example 1, the stirring was stopped, nitrogen was introduced into the tube, and the polymer was pressurized and discharged to obtain the desired aliphatic copolyester.

Then, the aliphatic copolyester prepared as described above was made into a blown film through hot air drying. Blown film processing conditions include blow up ratio 4 and take-up using a Rheocord 90 blown film processing facility from Haake, whose tubular die is 25 mm in diameter. speed) 10 m / min, screw speed 9 rpm, barrel temperature conditions were set to 140 ℃, 150 ℃, 150 ℃, 150 ℃ blown film processing was performed. And the physical property about the film thus obtained was measured and the result of the following Table 3 was obtained.

<Example 3>

1,372 g (11.615 mole), BD 1,338 g (14.525 mole), DEG 515 g (4.36 mole) and MAN 0.6 g (0.0076 mole) were added to the reactor equipped with a stirrer and a condenser. It heated up to 120 degreeC over, and it heated up to 210 degreeC over 120 minutes, stirring. Water produced at this time was discharged out of the system through a condenser, and the reaction was stopped when the final effluent reached 95% of the theoretical effluent. The temperature in the tube was 210 ° C. Then, 1.70 g of TBT as a catalyst and 0.2 g of phosphoric acid as a heat stabilizer were added, and the pressure in the tube was gradually reduced to 0.5 mmHg over 45 minutes, and the reaction was performed by stirring for 180 minutes while raising the temperature of the tube to 240 ° C., followed by stirring. The desired aliphatic copolyester was obtained by stopping the mixture and injecting nitrogen into the tube to pressurize and discharge the polymer.

Then, the aliphatic copolyester prepared as described above was made into a blown film through hot air drying. Blown film processing conditions include blow up ratio 4 and take-up using a Rheocord 90 blown film processing facility from Haake, whose tubular die is 25 mm in diameter. speed) 10 m / min, screw speed 9 rpm, barrel temperature conditions were set to 140 ℃, 150 ℃, 150 ℃, 150 ℃ blown film processing was performed. And the physical property about the film thus obtained was measured and the result of the following Table 3 was obtained.

<Example 4>

In a reactor equipped with a stirrer and a condenser, SA 1,240g (10.500mol), BD 1,120g (12.158mol), TEG 480g (3.427mol) and MAN 0.8g (0.0076mol) were added and the temperature in the reactor was reduced from room temperature to 20 minutes. It heated up to 120 degreeC over, and it heated up to 210 degreeC over 120 minutes, stirring. Water produced at this time was discharged out of the system through a condenser, and the reaction was stopped when the final effluent reached 95% of the theoretical effluent. The temperature in the tube was 210 ° C. Then, 1.70 g of TBT as a catalyst and 0.2 g of phosphoric acid as a heat stabilizer were added, and the pressure in the tube was gradually reduced to 0.5 mmHg over 45 minutes, and the reaction was performed by stirring for 180 minutes while raising the temperature of the tube to 240 ° C., followed by stirring. The desired aliphatic copolyester was obtained by stopping the mixture and injecting nitrogen into the tube to pressurize and discharge the polymer.

Then, the aliphatic copolyester prepared as described above was made into a blown film through hot air drying. Blown film processing conditions include blow up ratio 4 and take-up using a Rheocord 90 blown film processing facility from Haake, whose tubular die is 25 mm in diameter. speed) 10 m / min, screw speed 9 rpm, barrel temperature conditions were set to 140 ℃, 150 ℃, 150 ℃, 150 ℃ blown film processing was performed. And the physical property about the film thus obtained was measured and the result of the following Table 3 was obtained.

<Example 5>

AA 1,440g (9.854mol), BD 1,200g (13.026mol), MA 1.5g (0.0123mol) were added to the reactor equipped with a stirrer and a condenser, and the temperature in the reactor was raised from room temperature to 120 ° C over 20 minutes and stirred. It heated up to 210 degreeC over 120 minutes. Water produced at this time was discharged out of the system through a condenser, and the reaction was stopped when the final effluent reached 95% of the theoretical effluent. The temperature in the tube was 210 ° C. Then, 1.70 g of TBT as a catalyst and 0.2 g of phosphoric acid as a heat stabilizer were added, and the pressure in the tube was gradually reduced to 0.5 mmHg over 45 minutes, and the reaction was performed by stirring for 180 minutes while raising the temperature of the tube to 240 ° C., followed by stirring. The desired aliphatic copolyester was obtained by stopping the mixture and injecting nitrogen into the tube to pressurize and discharge the polymer.

Then, the aliphatic copolyester prepared as described above was made into a blown film through hot air drying. Blown film processing conditions include blow up ratio 4 and take-up using a Rheocord 90 blown film processing facility from Haake, whose tubular die is 25 mm in diameter. speed) 10 m / min, screw speed 9 rpm, barrel temperature conditions were 50 ℃, 140 ℃, 140 ℃, 140 ℃ was blown film processing. And the physical property about the film thus obtained was measured and the result of the following Table 3 was obtained.

<Comparative Example 1>

1,372 g (11.615 mole) of SA, 1,070 g (11.618 mole) of BD, and 343 g (2.902 mole) of HD were added to the reactor with the stirrer and condenser, and the temperature in the reactor was raised to 120 ° C. over 20 minutes from room temperature and stirred. It heated up to 210 degreeC over 120 minutes. Water produced at this time was discharged out of the system through a condenser, and the reaction was stopped when the final effluent reached 95% of the theoretical effluent. The temperature in the tube was 210 ° C. This resulted in 2,457 g of esterification reactant. Subsequently, condensation polymerization was carried out in the same manner as in Example 1, the stirring was stopped, nitrogen was introduced into the tube, and the polymer was pressurized and discharged to obtain the desired aliphatic copolyester.

Then, the aliphatic copolyester prepared as described above was made into a blown film through hot air drying. Blown film processing conditions include blow up ratio 4 and take-up using a Rheocord 90 blown film processing facility from Haake, whose tubular die is 25 mm in diameter. speed) 10 m / min, screw speed 9 rpm, barrel temperature conditions were set to 140 ℃, 150 ℃, 150 ℃, 150 ℃ blown film processing was performed. And the physical property about the film thus obtained was measured and the result of the following Table 3 was obtained.

<Comparative Example 2>

SA 1,372g (11.618mol), BD 1,338g (14.525mol) and BD 1.138g (14.525mol) were added to the reactor equipped with the stirrer and condenser, and the temperature in the reactor was raised to 120 ° C. over 20 minutes from room temperature and stirred. It heated up to 210 degreeC over 120 minutes. Water produced at this time was discharged out of the system through a condenser, and the reaction was stopped when the final effluent reached 95% of the theoretical effluent. The temperature in the tube was 210 ° C. This resulted in 2460 g of esterification reactant. Subsequently, condensation polymerization was carried out in the same manner as in Example 1, the stirring was stopped, nitrogen was introduced into the tube, and the polymer was pressurized and discharged to obtain the desired aliphatic copolyester.

Then, the aliphatic copolyester prepared as described above was made into a blown film through hot air drying. Blown film processing conditions include blow up ratio 4 and take-up using a Rheocord 90 blown film processing facility from Haake, whose tubular die is 25 mm in diameter. speed) 10 m / min, screw speed 9 rpm, barrel temperature conditions were set to 140 ℃, 150 ℃, 150 ℃, 150 ℃ blown film processing was performed. And the physical property about the film thus obtained was measured and the result of the following Table 3 was obtained.

<Comparative Example 3>

1,372 g (11.618 mole) of SA, 1,338 g (14.525 mole) of BD, and 14.5 g (0.1394 mole) of MAN were added to the reactor with the stirrer and condenser, and the temperature in the reactor was raised to 120 ° C. over 20 minutes from room temperature and stirred. It heated up to 210 degreeC over 120 minutes. Water produced at this time was discharged out of the system through a condenser, and the reaction was stopped when the final effluent reached 95% of the theoretical effluent. The temperature in the tube was 210 ° C. This resulted in 2425 g of esterification reactant. Subsequently, condensation polymerization was carried out in the same manner as in Example 1, the stirring was stopped, nitrogen was introduced into the tube, and the polymer was pressurized and discharged to obtain the desired aliphatic copolyester.

Then, the aliphatic copolyester prepared as described above was made into a blown film through hot air drying. Blown film processing conditions include blow up ratio 4 and take-up using a Rheocord 90 blown film processing facility from Haake, whose tubular die is 25 mm in diameter. speed) 10 m / min, screw speed 9 rpm, barrel temperature conditions were set to 140 ℃, 150 ℃, 150 ℃, 150 ℃ blown film processing was performed. And the physical property about the film thus obtained was measured and the result of the following Table 3 was obtained.

<Comparative Example 4>

1,372 g (11.615 mol) of SA, 1,338 g (14.525 mol) of BD, and 515 g (4.36 mol) of DEG were added to the reactor with a stirrer and a condenser, and the temperature in the reactor was raised to 120 ° C. over 20 minutes from room temperature and stirred. It heated up to 210 degreeC over 120 minutes. Water produced at this time was discharged out of the system through a condenser, and the reaction was stopped when the final effluent reached 95% of the theoretical effluent. The temperature in the tube was 210 ° C. This resulted in 2460 g of esterification reactant. Subsequently, condensation polymerization was carried out in the same manner as in Example 3, the stirring was stopped, nitrogen was introduced into the tube, and the polymer was pressurized and discharged to obtain the desired aliphatic copolyester.

Then, the aliphatic copolyester prepared as described above was made into a blown film through hot air drying. Blown film processing conditions include blow up ratio 4 and take-up using a Rheocord 90 blown film processing facility from Haake, whose tubular die is 25 mm in diameter. speed) 10 m / min, screw speed 9 rpm, barrel temperature conditions were set to 140 ℃, 150 ℃, 150 ℃, 150 ℃ blown film processing was performed. And the physical property about the film thus obtained was measured and the result of the following Table 3 was obtained.

<Comparative Example 5>

1,240 g (10.500 mole), BD 1,120 g (12.158 mole), TEG 480 g (3.427 mole) was added to the reactor equipped with the stirrer and condenser, and the temperature in the reactor was raised to 120 ° C. over 20 minutes from room temperature and stirred. It heated up to 210 degreeC over 120 minutes. Water produced at this time was discharged out of the system through a condenser, and the reaction was stopped when the final effluent reached 95% of the theoretical effluent. The temperature in the tube was 210 ° C. This resulted in 2460 g of esterification reactant. Subsequently, condensation polymerization was carried out in the same manner as in Example 3, the stirring was stopped, nitrogen was introduced into the tube, and the polymer was pressurized and discharged to obtain the desired aliphatic copolyester.

Then, the aliphatic copolyester prepared as described above was made into a blown film through hot air drying. Blown film processing conditions include blow up ratio 4 and take-up using a Rheocord 90 blown film processing facility from Haake, whose tubular die is 25 mm in diameter. speed) 10 m / min, screw speed 9 rpm, barrel temperature conditions were set to 140 ℃, 150 ℃, 150 ℃, 150 ℃ blown film processing was performed. And the physical property about the film thus obtained was measured and the result of the following Table 3 was obtained.

<Comparative Example 6>

AA 1,440 g (9.854 mole) and BD 1,200 g (13.028 mole) were added to a reactor equipped with a stirrer and a condenser, and the temperature in the reactor was increased from room temperature to 120 ° C. over 20 minutes and stirred to 210 ° C. over 120 minutes. It heated up temperature. Water produced at this time was discharged out of the system through a condenser, and the reaction was stopped when the final effluent reached 95% of the theoretical effluent. The temperature in the tube was 210 ° C. This resulted in 2460 g of esterification reactant. Subsequently, condensation polymerization was carried out in the same manner as in Example 3, the stirring was stopped, nitrogen was introduced into the tube, and the polymer was pressurized and discharged to obtain the desired aliphatic copolyester.

Then, the aliphatic copolyester prepared as described above was made into a blown film through hot air drying. Blown film processing conditions include blow up ratio 4 and take-up using a Rheocord 90 blown film processing facility from Haake, whose tubular die is 25 mm in diameter. speed) 10 m / min, screw speed 9 rpm, barrel temperature conditions were set to 50 ℃, 100 ℃, 100 ℃, 100 ℃ blown film processing. And the physical property about the film thus obtained was measured and the result of the following Table 3 was obtained.

<Comparative Example 7>

AA 1,440g (9.854mol), BD 1,200g (13.026mol), MA 17g (0.1393mol) were charged in a reactor equipped with a stirrer and a condenser, and the temperature in the reactor was raised from room temperature to 120 ° C over 20 minutes while stirring. It heated up to 210 degreeC over 120 minutes. Water produced at this time was discharged out of the system through a condenser, and the reaction was stopped when the final effluent reached 95% of the theoretical effluent. The temperature in the tube was 210 ° C. Then, 1.70 g of TBT as a catalyst and 0.2 g of phosphoric acid as a heat stabilizer were added, and the pressure in the tube was gradually reduced to 0.5 mmHg over 45 minutes, and the reaction was performed by stirring for 180 minutes while raising the temperature of the tube to 240 ° C., followed by stirring. The desired aliphatic copolyester was obtained by stopping the mixture and injecting nitrogen into the tube to pressurize and discharge the polymer.

Then, the aliphatic copolyester prepared as described above was made into a blown film through hot air drying. Blown film processing conditions include blow up ratio 4 and take-up using a Rheocord 90 blown film processing facility from Haake, whose tubular die is 25 mm in diameter. speed) 10 m / min, screw speed 9 rpm, barrel temperature conditions were 50 ℃, 140 ℃, 140 ℃, 140 ℃ was blown film processing. And the physical property about the film thus obtained was measured and the result of the following Table 3 was obtained.

division Melt index Melting Point (℃) Degradable Film processability Mechanical properties Warm up 5 minutes Warm up 20 minutes Mold Compost method (% of weight reduction) MD direction TD direction Tensile Strength (㎏ / ㎠) Elongation (%) Tensile Strength (㎏ / ㎠) Elongation (%) Example 1 4.4 5.9 104.1 4 86.3 ○ 595 515 455 452 Example 2 3.3 4.3 113.7 4 78.2 ○ 564 520 438 405 Example 3 3.4 4.4 100.5 4 82.3 ○ 544 395 457 321 Example 4 1.3 1.7 89.4 4 81.2 ○ 523 464 425 499 Example 5 2.1 3.4 57.3 5 85.6 ○ 142 408 397 384 Comparative Example 1 20.5 49.3 104.7 4 67.1 △ 211 174 188 275 Comparative Example 2 15.6 45.5 114.2 4 72.3 △ 202 160 176 192 Comparative Example 3 Gelation Gelation Gelation One 1.5 × Not measurable - Not measurable - Comparative Example 4 18.7 57.8 101.3 4 81.1 △ 186 173 170 139 Comparative Example 5 16.2 57.1 90.6 4 85.4 △ 187 203 112 245 Comparative Example 6 59.3 123.2 58.5 5 86.1 × Not measurable - Not measurable - Comparative Example 7 Gelation Gelation Gelation One 3.6 × Not available - Not measurable -

In Table 3, ○ indicates that the blown film can be processed by continuous operation for 30 minutes or more, Δ indicates that the blown film can be continuously processed between 1 minute and 30 minutes, and × denotes blown film processability. This is very poor, indicating that you cannot work continuously for more than 1 minute. In addition, MD represents the machine direction and TD represents the transverse direction.

As shown in Table 3, in the case of the film made of the aliphatic polyester of Examples 1 to 5 is excellent in mechanical properties as well as the decomposition performance than the film made of the aliphatic polyester of Comparative Examples 1 to 7 It can be seen.

The aliphatic polyester produced by the manufacturing method according to the present invention configured as described above may be used for applications such as blown film molding, foam molding, vacuum molding, etc., which require high melting point as well as good mechanical properties. In addition, the productivity of the molded article can be increased. It also has excellent degradability, so it can be quickly decomposed into harmless materials to prevent environmental pollution.

Claims (1)

Aliphatic diols based on one component selected from ethylene glycol, 1,4-butanediol and 1,6-hexanediol, and an acid component composed mainly of one component selected from succinic acid, adipic acid or anhydride thereof, and maleic acid or Injecting a monomer component including a component for promoting high melt viscosity consisting of the anhydride into a reactor to which a stirrer and a condenser are attached, and performing an esterification reaction at a temperature of 220 ° C. or less; Preparing an aliphatic polyester having a high melt viscosity by condensation polymerization by introducing a catalyst into the esterification reactor and proceeding a deglycol reaction and an addition reaction at a temperature of 190 ° C to 250 ° C and a high vacuum of 0.005 to 1 mmHg. Aliphatic polyester production method comprising a.