KR102069509B1 - Biodegradable poly(butylene tetramethyleneglutarate-co-butylene terephthalate) aliphatic and aromatic polyester resin and the manufacturing method thereof - Google Patents

Abstract

The present invention relates to a biodegradable poly (butylene tetramethylene glutarate-co-butylene terephthalate) aliphatic/aromatic polyester resin, and a method for producing the same and, more specifically, to a poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic/aromatic polyester resin which is obtained by simultaneously introducing an aliphatic ring and an aromatic ring to a main chain by esterifying and polymerizing 3,3-tetramethyleneglutaric acid as an aliphatic acid component and aliphatic diol 1,4-butanediol and dimethyl terephthalate as an aromatic acid component; and a method for producing the same. A biodegradable film produced from the poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic/aromatic polyester resin: has excellent mechanical strength superior to a film produced from conventional biodegradable polyester resin by simultaneously having an aliphatic ring structure and an aromatic ring structure in a main chain and increasing the rigidity and tear strength of the produced film; improves workability and productivity by having a high solidification rate of resin; and greatly contributes to environmental improvement by being fully biodegraded under natural environment in a case of landfill.

Description

Biodegradable poly (butylene tetramethyleneglutarate-co-butylene terephthalate) aliphatic and aromatic polyester resin and the manufacturing method about}

The present invention relates to a biodegradable poly (butylenetetramethyleneglutarate-co-butyleneterephthalate) aliphatic / aromatic polyester resin and a method for preparing the same, and more particularly, to 3,3-tetra as an aliphatic acid component. Poly (butylenetetramethylenegluta) obtained by simultaneously introducing an aliphatic ring and an aromatic ring into the main chain by esterification and condensation polymerization of dimethyl terephthalate and aliphatic diol with 1,4-butanediol as methylene glutaric acid and an aromatic acid component Latex-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin and a method for producing the same.

The biodegradable film prepared from the poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin has an aliphatic ring structure and an aromatic ring structure in the main chain, so The stiffness and tear strength are increased and the solidification rate of the resin during the work is improved, which shows the effect that the workability is improved over the film made from the existing biodegradable polyester resin.

Plastic is not only able to be mass-produced in various ways, but also has been used as a very important material in modern life because of its light weight, durability, chemical resistance and mechanical properties.

However, the environmental pollution situation has reached a level of considerable concern around the world, and recently, as plastic wastes, especially disposable wastes, have emerged as the main culprit of such environmental pollution, the application and development of biodegradable resins for disposable products has been actively performed. .

The biodegradable resins developed so far are polycaprolactone and diol-diet chemically synthesized starting from polylactic acid (PLA), epsilon caprolactone monomer, which are synthesized by ring-opening reaction of lactic acid or lactide in the presence of a chemical catalyst or enzyme. Seed-based aliphatic polyesters, polyhydroxybutylate (PHB) produced by in vivo synthesis of other microorganisms, and the like.

However, despite these efforts, the price of biodegradable resins is still higher than that of existing non-degradable plastics, and there are many restrictions on use due to weak processability and mechanical properties compared to general-purpose resins.

Polylactic acid is relatively inexpensive compared to other biodegradable resins, and its consumption is increasing, but heat resistance is low, it is weak to impact, and polycaprolactone has a disadvantage of poor workability due to its low melting point. When it is applied to, the storage stability, heat sealability, weak mechanical properties and disadvantages of high price and practical use is delayed.

In order to solve this problem, thermoplastic biodegradable aliphatic polyester resins having a number average molecular weight of 25,000 to 45,000 are prepared by appropriately adjusting the condensation polymerization temperature, vacuum degree, and catalyst conditions of aliphatic dicarboxylic acids and aliphatic diols. Although the method of synthesizing is known from Korea Patent Application No. 0120326 (August 16, 1997), however, the aliphatic polyester resin produced by this method has a low weight average molecular weight and is extremely sensitive to heat, thereby degrading moldability. .

As another existing example, Korean Patent No. 10-0129794 (November 13, 1997) shows a number average molecular weight of about 15,000-20,000 in the presence of a monomer of a trivalent or higher polyhydric alcohol or a trivalent or higher polyhydric carboxylic acid as an auxiliary component of the reaction. A method of obtaining an aliphatic polyester resin having a number average molecular weight of about 20,000-70,000 obtained by reacting a polyisocyanate as a coupling agent after obtaining an aliphatic polyester of is known. However, this method requires a long reaction time. As a result, productivity is low and polyisocyanate, a coupling agent used to increase molecular weight, is extremely harmful to the human body.

In order to solve the problem of the aliphatic polyester, an aliphatic / aromatic copolyester prepared by adding an aromatic monomer has been developed, and as a manufacturable method therefor, US Patent US4328059, US4094721, Korean Patent Nos. 10-1255826, 10-1068030 It is presented in the back.

However, to this day, aliphatic / aromatic copolyester has a slow cooling rate, which makes it difficult to process, and has strong stickiness between films during film production, which is highly likely to cause defects such as wrinkles during winding, and it is not easy to unwrap the wound film. However, the plastic bag manufactured therefrom does not have an opening property and thus is not valuable as a commodity.

In order to solve the above problems, aliphatic or aliphatic / aromatic copolyester is mainly used in the composition of the resin composition mixed with polylactic acid (PLA), starch, talc, calcium carbonate and the like. For example, a method of preparing starch by compounding with biodegradable resin after preparing thermoplastic starch by a separate device and process (Korea Patent No. 10-0339789), a chain extender of biodegradable aliphatic polyester resin and polylactic acid in a twin screw extruder And a polybutylene succinate (including polybutylene succinate-co-butylene adipate) based aliphatic polyester polylactic acid (or Attempts have been made to blend 7 to 60 parts by weight of the copolymer (JP-A-1997-111107), but the product molded using the resin thus obtained has a disadvantage in that the physical properties of the product are significantly reduced over time. Indicates.

As a conventional technique for improving the disadvantages of such biodegradable resins, Korean Patent Laid-Open Publication No. 10-2001-0032052 (April 16, 2001) discloses polylactic acid (or a copolymer thereof), adipic acid and dicarboxylic acid. 30 to 70% of the trade name Bionolle 3001 of Nippon Showa Polymer, a polybutylene succinate copolymer obtained by condensation polymerization of 1,4-butanediol as succinic acid and aliphatic diol, was added to 100 parts by weight of polylactic acid, Compounding both components was attempted to improve the physical properties.

In addition, Korean Patent Registration No. 10-428687 (April 12, 2004) to prepare a composition of 3 to 65 parts by weight of polylactic acid based on 100 parts by weight of aliphatic polyester and aliphatic / aromatic copolyester through compounding using a twin screw extruder The preparation method of the biodegradable resin composition is shown. In this case, due to the high melting point of polylactic acid in the compounding process of polylactic acid (or its copolymers) and polybutylene succinate (or its copolymers), the thermal stability of the resin produced during extrusion at high temperatures is significantly reduced. There was also a problem that the mechanical properties of the prepared resin is also reduced.

[Patent Document 001] Korean Patent Registration No. 0120326 (August 16, 1997) [Patent Document 002] Korea Patent Registration 10-0129794 (November 13, 1997) [Patent Document 003] Korea Patent Publication 10-2001-0032052 (April 16, 2001) [Patent Document 004] Korea Patent Registration 10-428687 (April 12, 2004)

In order to solve the above problems, the main chain is obtained by esterification and condensation polymerization of 1,4-butanediol with dimethyl terephthalate and aliphatic diol with 3,3-tetramethyleneglutaric acid as an aliphatic acid component and an aromatic acid component. Poly (butylenetetramethyleneglutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester with superior processability, productivity and mechanical properties compared to existing biodegradable polyester resins by introducing aliphatic ring and aromatic ring at the same time It is a problem to be solved to provide resin and its manufacturing method.

In order to solve the above problems, the main chain is obtained by esterification and condensation polymerization of 1,4-butanediol with dimethyl terephthalate and aliphatic diol with 3,3-tetramethyleneglutaric acid as an aliphatic acid component and aromatic acid component. A poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin obtained by introducing an aliphatic ring and an aromatic ring at the same time as do.

[Formula 1]

(Wherein n and m are 52:48 as molar ratios and x is 35,000 to 70,000 as a number average molecular weight range.)

The poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin has a number average molecular weight of 35,000 to 70,000, a molecular weight distribution of 2.2 to 2.9, a melt flow index of 190 ° C, 2,160 The solution means of 1g / 10min-8g / 10min under g conditions.

In addition, the present invention, (i) esterification reaction of dimethyl 5-hydroxyisophthalate and ethylene glycol in a molar ratio of 1: 1 in the presence of a germanium oxide catalyst at 190 ° C. for two hours, the following [Formula 2] Preparing a multifunctional compound;

[Formula 2]

(Where n is an integer representing the degree of polymerization and is 4 to 15.)

(ii) in the presence of the multifunctional compound prepared in step (i), 3,3-tetramethyleneglutaric acid and 1,4-butanediol were introduced into the reactor at a molar ratio of 1: 1.2 to 1: 1.5 to 190 ° C. Esterifying at 210 [deg.] C. to obtain an oligomer that is a first reaction product;

(iii) In the presence of the oligomer which is the primary reaction product obtained in step (ii), dimethyl terephthalate and 1,4-butanediol were introduced into the reactor at a molar ratio of 1: 1.2 to 1: 1.5, at 190 ° C to 210 ° C. Reacting to obtain an oligomer that is a secondary reaction product;

(iv) condensation polymerization of the oligomer, the secondary reaction product obtained in step (ii), for 200 minutes to 240 minutes under a vacuum degree of less than 3 torr in the temperature range of 235 ° C. to 250 ° C. Rentetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin composition comprising the steps of obtaining a poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable An aliphatic / aromatic polyester resin production method is a solution to the problem.

[Formula 1]

(Wherein n and m are 52:48 as molar ratios and x is 35,000 to 70,000 as a number average molecular weight range.)

The esterification reaction of step (ii) and (iii) and the condensation polymerization reaction of step (iv) include one or two or more selected from tetrabutyl titanate, natriacetate, antimony trioxide, dibutyl tin oxide and zinc acetate. Adding a catalyst is a solution to the problem.

In the esterification reaction of step (ii) and (iii) and the polycondensation reaction of step (iv), one or more stabilizers selected from trimethyl phosphate, phosphoric acid and triphenyl phosphate are added as a solution to the problem. .

Biodegradable films made from poly (butylenetetramethyleneglutarate-co-butyleneterephthalate) biodegradable aliphatic / aromatic polyester resins according to the invention are produced by having an aliphatic ring structure and an aromatic ring structure in the main chain at the same time The mechanical strength is higher than that made from existing biodegradable polyester resins, such as increased stiffness and tear strength of the resulting film, and the solidification speed of the resin is faster, improving workability and productivity, and fully biodegrading under natural environment at the time of landfill. By doing so, there is an excellent effect that can greatly contribute to environmental improvement.

The present invention provides an aliphatic ring and an aromatic ring in the main chain by esterification and condensation polymerization of 3,3-tetramethyleneglutaric acid with an aliphatic acid component and 1,4-butanediol with aliphatic diol with an aromatic acid component. The poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin obtained by simultaneously introducing the above is represented by the technical structure.

[Formula 1]

(Wherein n and m are 52:48 as molar ratios and x is 35,000 to 70,000 as a number average molecular weight range.)

The poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin has a number average molecular weight of 35,000 to 70,000, a molecular weight distribution of 2.2 to 2.9, a melt flow index of 190 ° C, 2,160 Characterized in the technical configuration is that from 1g / 10min to 8g / 10min under g conditions.

In addition, the present invention, (i) esterification reaction of dimethyl 5-hydroxyisophthalate and ethylene glycol in a molar ratio of 1: 1 in the presence of a germanium oxide catalyst at 190 ° C. for two hours, the following [Formula 2] Preparing a multifunctional compound;

[Formula 2]

(Where n is an integer representing the degree of polymerization and is 4 to 15.)

(ii) in the presence of the multifunctional compound prepared in step (i), 3,3-tetramethyleneglutaric acid and 1,4-butanediol were introduced into the reactor at a molar ratio of 1: 1.2 to 1: 1.5 to 190 ° C. Esterifying at 210 [deg.] C. to obtain an oligomer that is a first reaction product;

(iii) In the presence of the oligomer which is the primary reaction product obtained in step (ii), dimethyl terephthalate and 1,4-butanediol were introduced into the reactor at a molar ratio of 1: 1.2 to 1: 1.5, at 190 ° C to 210 ° C. Reacting to obtain an oligomer that is a secondary reaction product;

(iv) condensation polymerization of the oligomer, which is a secondary reaction product obtained in step (iii), at a temperature range of 235 ° C. to 250 ° C. under a vacuum degree of less than 3 torr for 200 minutes to 240 minutes, to give a poly (butyl Rentetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin composition comprising the steps of obtaining a poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable The process for producing aliphatic / aromatic polyester resins is characterized by a technical configuration.

[Formula 1]

(Wherein n and m are 52:48 as molar ratios and x is 35,000 to 70,000 as a number average molecular weight range.)

The esterification reaction of step (ii) and (iii) and the condensation polymerization reaction of step (iv) include one or two or more selected from tetrabutyl titanate, natriacetate, antimony trioxide, dibutyl tin oxide and zinc acetate. Adding a catalyst is a feature of the technical construction.

The esterification reaction of step (ii) and (iii) and the polycondensation reaction of step (iv) are characterized by adding one or more stabilizers selected from trimethyl phosphate, phosphoric acid and triphenyl phosphate. .

Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

The poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin of the present invention is a dimethyl terephthalate as an aliphatic acid component and 3,3-tetramethyleneglutaric acid and an aromatic acid component. And aliphatic diols are obtained by introducing an aliphatic ring and an aromatic ring into the main chain at the same time by esterification and condensation polymerization of 1,4-butanediol. The reaction formula is as follows.

 The poly (obtained by introducing an aliphatic ring and an aromatic ring into the main chain simultaneously by esterification and condensation polymerization of dimethyl terephthalate and 1,4-butanediol with aliphatic diol as the 3,3-tetramethylene glutaric acid and an aromatic acid component) Butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin has a number average molecular weight of 35,000 to 70,000, a molecular weight distribution of 2.2 to 2.9, a melt flow index of 190 ° C and 2,160g. 1g / 10min to 8g / 10min, the molecular structure of this resin is shown in the following [Formula 1].

[Formula 1]

(Wherein n and m are 52:48 as molar ratios and x is 35,000 to 70,000 as a number average molecular weight range.)

In the present invention, in order to prepare the above-mentioned resin, in order to improve the reaction speed and processability of the produced resin, the reaction is performed by adding a polyfunctional compound obtained by esterification of dimethyl-5-hydroxyisophthalate and ethylene glycol under a nitrogen atmosphere. Use as a supplement. [Formula 2] shows the chemical structure of the polyfunctional compound obtained from the reaction.

[Formula 2]

(Where n is an integer representing the degree of polymerization and is 4 to 15.)

The polyfunctional compound is added to the esterification step in the synthesis of poly (butylene tetramethylene glutarate-co-butylene terephthalate) which is a reactant of the present invention to facilitate the connection between the polymer chains to increase the molecular weight of the reactants. In addition, it plays a role of enhancing the processability of the poly (butylene tetramethylene glutarate-co-butylene terephthalate) resin obtained by widening the molecular weight distribution due to random linkage. In addition, since the reactivity is good because it contains an aromatic component having a resonance structure, since the activity of each reaction site is different, the gelation problem of the resin due to the use of a multifunctional group is generally easy to control and suppress.

In one embodiment, the poly (butylenetetramethyleneglutarate-co-butyleneterephthalate) biodegradable resin of the present invention comprises: (i) esterifying a dimethyl 5-hydroxyisophthalate and ethylene glycol; (ii) reacting 3,3-tetramethyleneglutaric acid with 1,4-butanediol in the presence of the multifunctional compound of step (i) to obtain a primary esterification product (oligomer); (iii) reacting dimethylterephthalate with 1,4-butanediol in the presence of the reaction product of step (ii) to obtain a secondary esterification reaction product (oligomer); (iv) polycondensation of the reaction product of step (iii).

Preferably, the poly (butylenetetramethyleneglutarate-co-butyleneterephthalate) biodegradable resin of the present invention comprises (i) 1: 1 molar ratio of dimethyl 5-hydroxyiso in the presence of germanium oxide catalyst. Preparing a multifunctional compound of the following [Formula 2] by proceeding an esterification reaction between phthalate and ethylene glycol at 190 ° C. for two hours;

[Formula 2]

(Where n is an integer representing the degree of polymerization and is 4 to 15.)

(ii) in the presence of the multifunctional compound obtained in step (i), 3,3-tetramethyleneglutaric acid and 1,4-butanediol were introduced into the reactor at a molar ratio of 1: 1.2 to 1: 1.5, ranging from 190 ° C to Reacting at 210 ° C. to obtain an oligomer that is a primary reaction product;

(iii) in the presence of the reaction product obtained in step (ii), dimethyl terephthalate and 1,4-butanediol were introduced into the reactor in a molar ratio of 1: 1.2 to 1: 1.5 and reacted at 190 ° C to 210 ° C for a secondary reaction. Obtaining an oligomer that is a product;

(iv) condensation polymerization of the oligomer, which is a secondary reaction product obtained in step (iii), at a temperature range of 235 ° C. to 250 ° C. under a vacuum degree of less than 3 torr for 200 minutes to 240 minutes, to give a poly (butyl Rentetramethylene glutarate-co-butylene terephthalate) to obtain a biodegradable aliphatic / aromatic polyester resin.

[Formula 1]

(Wherein n and m are 52:48 as molar ratios and x is 35,000 to 70,000 as a number average molecular weight range.)

In a preferred embodiment, the multifunctional compound synthesized in the above-mentioned step (iii) of the present invention is charged with dimethyl 5-hydroxyisophthalate and ethylene glycol in a molar ratio of 1: 1 in a reactor, germanium oxide as a catalyst and dimethyl 5 -0.05 g per mole of hydroxyisophthalate is added and then the theoretical amount of methanol is completely discharged while maintaining the temperature of the reactor at 190 ° C. The polyfunctional compound thus prepared is used in the range of 0.01 to 0.05 g per mole of 3,3-tetramethyleneglutaric acid component introduced into the reactor when synthesizing the biodegradable resin composition.

In step (ii), the 3,3-tetramethyleneglutaric acid and 1,4-butanediol used are used in a molar ratio of 1: 1.2 to 1: 1.5 and more preferably in a molar ratio range of 1.30 to 1.35.

In another preferred embodiment, the temperature range in which the esterification of step (ii) is carried out is preferably maintained at 190 ° C to 210 ° C.

In step (iii), the dimethyl terephthalate and 1,4-butanediol used are used in a molar ratio of 1: 1.2 to 1: 1.5 and more preferably in a molar ratio range of 1.30 to 1.35.

In another preferred embodiment, the temperature range in which the esterification of step (iii) is carried out is preferably maintained at 190 ° C to 210 ° C.

In another preferred embodiment, the polycondensation reaction of step (iv) is preferably carried out for 200 minutes to 240 minutes under a vacuum degree of less than 3 torr in the temperature range of 230 ℃ to 250 ℃.

In another preferred embodiment, further catalysts may be added at the beginning or end of the esterification and polycondensation reactions. Such catalysts may be used in the range of 0.05 to 0.1 parts by weight based on the total reactant weight. Specific examples of such catalysts are selected from tetrabutyl titanate, sodium acetate, antimony trioxide, dibutyl tin oxide, zinc acetate or mixtures of two or more thereof.

In another preferred embodiment, further stabilizers may be added at the beginning or end of the esterification and condensation polymerization. Such stabilizers are suitably used in the range of 0.05 to 0.1 parts by weight based on the total reactant weight. Such stabilizers include, but are not limited to, trimethylphosphate, phosphoric acid, triphenylphosphate or mixtures of two or more thereof.

The poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin of the present invention is prepared by the above method and has an aliphatic ring and an aromatic ring in the molecular backbone at the same time, the number average The molecular weight is 35,000 to 70,000, the molecular weight distribution is 2.2 to 2.9, and the melt flow index is 1 g / 10 min to 8 g / 10 min under conditions of 190 ° C and 2160 g.

<Production of Polyfunctional Compound>

1L round bottom flask was replaced with nitrogen, 210.19 g of dimethyl 5-hydroxyisophthalate, 62.07 g of ethylene glycol and 0.05 g of germanium oxide were added to the catalyst, followed by esterification at 190 ° C. for 2 hours. When 2 moles of the theoretical amount of methanol, a byproduct of the reaction, flowed out with respect to 1 mole of 5-hydroxyisophthalate, it was confirmed that the reaction was completed and the reaction was terminated to prepare a multifunctional compound of the following [Formula 2].

[Formula 2]

(Where n is an integer representing the degree of polymerization and is 4 to 15.)

<Production of Biodegradable Resin>

The 100L reactor was replaced with nitrogen, 37.24kg of 3,3-tetramethyleneglutaric acid, 24.33kg of 1,4-butanediol, and 2g of the polyfunctional compound prepared above were added thereto, and then the reaction temperature was fixed at 200 ° C. and water was discharged. Thereafter, 18.64 kg of dimethyl terephthalate and 11.68 kg of 1,4-butanediol were added thereto, and methanol of the theoretical amount was distilled off to obtain an oligomer. At this time, 20 g of dibutyl tin oxide, 10 g of tetrabutyl titanate, and 30 g of trimethyl phosphate were added as a stabilizer. Thereafter, the temperature was continuously raised, and 10 g of antimony trioxide was added as a catalyst, followed by a polycondensation reaction under a reduced pressure of 2.5 torr for 200 minutes at a temperature of 240 ° C. to give poly (butylene tetramethylene glutarate-co-butylene terephthalate ) Biodegradable aliphatic / aromatic polyester resins were obtained. The number average molecular weight of the resin obtained at this time was 39,218, the molecular weight distribution was 2.33, and the melt flow index was 7.8 g / 10 min (190 ° C, 2,160 g).

<Production of Biodegradable Resin>

Replace the 100L reactor with nitrogen, add 19.36kg of 3,3-tetramethyleneglutaric acid, 12.65kg of 1,4-butanediol and 5g of the polyfunctional compound, fix the reaction temperature at 200 ° C, and drain the water of theoretical effluent. After letting go. 18.64 kg of dimethyl terephthalate and 11.68 kg of 1,4-butanediol were added thereto to distill the theoretical amount of methanol to obtain an oligomer. At this time, 10 g of dibutyl tin oxide, 10 g of tetrabutyl titanate, and 15 g of trimethyl phosphate were added as stabilizers as catalysts. Thereafter, the temperature was continuously increased, and 10 g of antimony trioxide was added as a catalyst, followed by a polycondensation reaction under a reduced pressure of 1.5 torr for 188 minutes at a temperature of 240 ° C. to give poly (butylenetetramethylglenlutarate-co-butylene terephthalate ) To obtain a resin. The number average molecular weight of the obtained resin was 44.686, the molecular weight distribution was 2.58, and the melt flow index was 5.1 g / 10 min (190 ° C, 2,160 g).

<Production of Biodegradable Resin Composition>

Substitute 100 L reactor with nitrogen, add 19.36 kg of 3,3-tetramethyleneglutaric acid, 12.65 kg of 1,4-butanediol and 8 g of the multifunctional compound obtained in the one-step reaction, and fix the reaction temperature at 200 ° C. After the outflow of the water. 18.64 kg of dimethyl terephthalate and 11.68 kg of 1,4-butanediol were added thereto to distill the theoretical amount of methanol to obtain an oligomer. At this time, 10 g of dibutyl tin oxide, 10 g of tetrabutyl titanate, and 15 g of trimethyl phosphate were added as stabilizers as catalysts. Thereafter, the temperature was continuously increased, and 10 g of antimony trioxide was added as a catalyst, followed by a polycondensation reaction under a reduced pressure of 1.5 torr for 188 minutes at a temperature of 240 ° C. to give poly (butylenetetramethylglenlutarate-co-butylene terephthalate ) To obtain a resin. The number average molecular weight of the resin obtained at this time was 63,638, the molecular weight distribution was 2.88, and the melt flow index was 1.91 g / 10 min (190 ° C, 2,160 g).

Comparative Example 1

The 100 L reactor was replaced with nitrogen, 23.32 kg of succinic acid, 26 kg of 1,4-butanediol, and 20 g of tetrabutyl titanate were added as a catalyst, and the temperature was raised in a nitrogen stream, and the reaction was carried out at 200 ° C. for 2 hours to allow the theoretical amount of water to flow out. . Then, 20 g of antimony acetate, 20 g of dibutyl tin oxide, 14 g of tetrabutyl titanate, and 40 g of trimethyl phosphate were added as a stabilizer. Then, the temperature was raised and polycondensation reaction was performed for 320 minutes at 245 degreeC under reduced pressure of 0.3 Torr. The resin had a number average molecular weight of 41,023 and a molecular weight distribution of 2.8, a melting point of 115 deg. C and a melt flow index of 11 g / 10 min (190 deg. C, 2,160 g).

Comparative Example 2

After replacing the 100L reactor with nitrogen, adding 19.36kg of 3,3-tetramethyleneglutaric acid and 12.65kg of 1,4-butanediol, the reaction temperature was fixed at 200 ° C., and the theoretical effluent water was distilled off. 18.64 kg of dimethyl terephthalate and 11.68 kg of 1,4-butanediol were added thereto, and the theoretical amount of methanol was distilled off to obtain an oligomer. At this time, 10 g of dibutyl tin oxide, 10 g of tetrabutyl titanate, and 15 g of trimethyl phosphate were added as stabilizers as catalysts. Thereafter, the temperature was continuously raised, and 10 g of antimony trioxide was added as a catalyst, followed by a polycondensation reaction for 188 minutes under a reduced pressure of 1.5 torr at a temperature of 240 ° C. ) To obtain a resin. The number average molecular weight of the resin obtained at this time was 28,324, the molecular weight distribution was 2.11, and the melt flow index was 42 g / 10 min (190 ° C, 2,160 g).

Comparative Example 3

Substitute 100L reactor with nitrogen, add 26.52kg of adipic acid, 2.36kg of succinic acid, 26kg of 1,4-butanediol, add 20g of tetrabutyl titanate as catalyst, raise the temperature in nitrogen stream, and react at 200 ℃ for 2 hours A quantity of water was run out. Then, 20 g of antimony acetate, 20 g of dibutyl tin oxide, 14 g of tetrabutyl titanate, and 40 g of trimethyl phosphate were added as a stabilizer. Then, the temperature was raised and the polycondensation reaction was performed for 260 minutes at 245 degreeC under reduced pressure of 0.3 Torr. The resin had a number average molecular weight of 36,251 and a molecular weight distribution of 2.77, a melting point of 50 占 폚 and a melt flow index of 9.5 g / 10 min (190 占 폚 and 2,160 g).

Experimental Example

<Resin Performance Test>

Examples 1, 2, and 3, and a resin composed similarly to the examples in the conventional manufacturing method as Comparative Examples 1 to 3 using a blown film machine having a screw diameter of 35 mm, a die gap of 2.0 mm, and a die diameter of 80 mm A 30um thick film was produced with an expansion ratio of 2.2 to 1, and tensile strength and tear strength were measured using an Instron Universal Testing Machine, and biodegradation evaluation was recovered 12 months after landfilling at a depth of 30 cm from the soil index. It measured using. Processability was observed visually bubble stability and wrinkles during film production.

Experimental results The film made of the resin obtained in the present invention has good biodegradability and processability, but has an aliphatic ring of molecular backbone and has excellent tensile strength and tear strength due to the fine network of the structure due to the multifunctional group. The results of the experiment are shown in [Table 1].

MD: Longitudinal direction of film

CD: Horizontal direction of film

Machinability: ○ Good, △ Normal, X Bad

In particular, Comparative Example 2 used 3,3-tetramethyleneglutaric acid and dimethyl terephthalate of the present invention, but the condensation polymerization time was 188 minutes. It can be seen that the polycondensation should be carried out for minutes.

As shown in Table 1, the film made of the resin obtained by the present invention has excellent biodegradability and processability, and has excellent tensile strength due to the fine network of the structure due to the polyfunctional group while simultaneously having an aliphatic ring and an aromatic ring of the molecular backbone. It has the characteristics of strength and tear strength.

The above description is merely illustrative of the technical spirit of the present invention, and those skilled in the art to which the present invention pertains may make various modifications and changes without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present invention.

Claims (5)

By esterification and condensation polymerization of 3,3-tetramethyleneglutaric acid as an aliphatic acid component and 1,4-butanediol with aliphatic diol as an aromatic acid component, an aliphatic ring and an aromatic ring are simultaneously introduced into the main chain. As the obtained poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin represented by the following [Formula 1],
[Formula 1]

(Wherein n and m are 52:48 as molar ratios and x is 35,000 to 70,000 as a number average molecular weight range.)
The poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin represented by the above [Formula 1] has a number average molecular weight of 35,000 to 70,000, a molecular weight distribution of 2.2 to 2.9, and melting Poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin, characterized by a flow index of 1 g / 10 min to 8 g / 10 min at 190 ° C. and 2160 g conditions.
delete (i) esterification of dimethyl 5-hydroxyisophthalate and ethylene glycol in a molar ratio of 1: 1 in the presence of a germanium oxide catalyst at 190 ° C. for 2 hours to prepare a multifunctional compound of the following [Formula 2] step;
[Formula 2]

(Wherein n is an integer representing the degree of polymerization and is 4 to 15.)
(ii) in the presence of the multifunctional compound prepared in step (i), 3,3-tetramethyleneglutaric acid and 1,4-butanediol were introduced into the reactor at a molar ratio of 1: 1.2 to 1: 1.5 to 190 ° C. Esterifying at 210 [deg.] C. to obtain an oligomer that is a first reaction product;
(iii) In the presence of the oligomer which is the primary reaction product obtained in step (ii), dimethyl terephthalate and 1,4-butanediol were introduced into the reactor at a molar ratio of 1: 1.2 to 1: 1.5, at 190 ° C to 210 ° C. Reacting to obtain an oligomer that is a secondary reaction product;
(iv) condensation polymerization of the oligomer, which is a secondary reaction product obtained in step (iii), at a temperature range of 235 ° C. to 250 ° C. under a vacuum degree of less than 3 torr for 200 minutes to 240 minutes, to give a poly (butyl Obtaining a tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin; poly (butylene tetramethylene glutarate-co-butylene terephthalate) ) Biodegradable Aliphatic / Aromatic Polyester Resin Manufacturing Method
[Formula 1]

(Wherein n and m are 52:48 as molar ratios and x is 35,000 to 70,000 as a number average molecular weight range.)
The method of claim 3,
The esterification reaction of step (ii) and (iii) and the condensation polymerization reaction of step (iv) include one or two or more selected from tetrabutyl titanate, natriacetate, antimony trioxide, dibutyl tin oxide and zinc acetate. Method for producing poly (butylene tetramethylene glutarate-co-butylene terephthalate) biodegradable aliphatic / aromatic polyester resin characterized by adding a catalyst
The method of claim 3,
In the esterification reaction of step (ii) and (iii) and the polycondensation reaction of step (iv), one or more stabilizers selected from trimethyl phosphate, phosphoric acid and triphenyl phosphate are added. Lentetramethylene glutarate-co-butylene terephthalate) Biodegradable aliphatic / aromatic polyester resin