KR101200824B1 - Hydrolysis resistant and biodegradable aliphatic/aromatic copolyester resin composition - Google Patents

Abstract

PURPOSE: An aliphatic/aromatic copolyester resin is provided to manufacture a molded product through extrusion and injection molding while solving properties, processability, reaction rate, etc. CONSTITUTION: An aliphatic/aromatic copolyester resin is manufactured through: a step of mixing 30-70 mol% of aliphatic dicarboxylic acid or anhydride thereof, 30-70 mol% of aromatic dicarboxylic acid or anhydride thereof, aliphatic glycol, and an oxazoline compound represented by chemical formula 1 or anhydride thereof, carbodiimide represented by chemical formula 2 or a mixture thereof; and a step of esterification or transesterification by adding a catalyst and stabilizer; and a step of polycondensation by adding a polycondensation catalyst and stabilizer.

Description

Hydrolyzable and biodegradable aliphatic / aromatic copolyester resin composition {HYDROLYSIS RESISTANT AND BIODEGRADABLE ALIPHATIC / AROMATIC COPOLYESTER RESIN COMPOSITION}

The present invention provides an oxazoline compound and a carbodiimide compound in an aliphatic / aromatic copolyester molecular structure in order to improve long reaction time, weak mechanical properties and weak hydrolysis resistance which are problems in the production of conventional biodegradable resins. The present invention relates to an aliphatic / aromatic copolyester resin composition having excellent hydrolysis resistance by introducing the above problem. The aliphatic / aromatic copolyester resin obtained at this time is characterized by a number average molecular weight of 25,000 to 80,000, a weight average molecular weight of 40,000 to 300,000 and a melting point of 80 to 150 ° C.

Aliphatic / aromatic copolyester resins have been known for several decades and their compositions and manufacturing methods, and are still being studied for use expansion, processability, and mechanical properties.

For example, according to US Patent Nos. 4094721 (June 13. 1978) and 4966959 (Oct. 30. 1996), the aromatic acid component is at least 40 mol% or more in the copolyester molecular structure, and the remaining acid component is composed of aliphatic acid component. The total acid component is 100 mol%, and an aliphatic / aromatic copolyester resin composition prepared by using a mixed component of 1,4-butanediol and other diols as a glycol component is reacted with each melting point. And properties are described.

In the above-mentioned conventional technology, the aliphatic / aromatic copolyester prepared in the aliphatic / aromatic copolyester resin composition, in particular, provides a detailed range of the composition of components such as aliphatic acid components and aromatic acid components, which may exhibit biodegradability. The various characteristics such as melting point, intrinsic viscosity, etc. according to the composition of the components at this time are described in detail.

All plastics can be used as adhesives for their purpose by using the property of melting after cooling by heat, and the aliphatic / aromatic copolyester can also be used as a hot melt adhesive. (US Patent No. 4,401,805) , Aug. 30. 1983, and 4,328,059, May 4. 1982).

Aliphatic / aromatic copolyesters exhibit tackiness depending on the type and number of components thereof, and US Pat. No. 4,966,959 (1990, Cox. A. Heyer. MF) has tackiness in preparing aliphatic / aromatic copolyesters. The glycol component used for this purpose states that it must contain two dialcohol components.

In Korean Patent Application No. 10-1993-0701622, the adhesiveness of the aliphatic / aromatic copolyester in the conventional technology is used to prepare aliphatic / aromatic copolyester to solve this problem because of problems in molding plastic products. It was suggested that the glycol component was overcome by using a single component rather than a mixed component. However, this is a well known fact that the adhesive can be removed by controlling the number and type of aliphatic / aromatic copolyester components in the art, and US Pat. No. 4,328,059 also uses aliphatic aliphatic alcohols. Processes for the production of aromatic copolyesters are known.

In addition to the patent, the Journal of Macromolecule, SCI-Chem A-23 (3), 1986, P393-409, describes the presence of biodegradability when aliphatic acid components are present in more than a certain component in aliphatic / aromatic copolyester compositions. .

However, the aliphatic / aromatic copolyester prepared by the above method is still poor in processability and mechanical properties compared to general-purpose resins such as polyethylene, polypropylene, polystyrene, etc. Research for resolution is actively in progress.

For example, in the case of Korean Patent Application No. 10-1999-7002353, in the preparation of aliphatic / aromatic copolyester, diisocyanate, a chain extender, is prepared by oligomerizing hexamethylene diisonate to control NCO content, which is a chain extension functional group. To disclose a method for producing the same. It uses polyfunctional and isocyanate in order to secure high processability and mechanical properties by high molecular weight of copolyester to be manufactured.In this case, it is safe to natural environment and human body during worker's safety and biodegradation of copolyester during isocyanate. Hazards may occur and are economically vulnerable due to increased work processes.

Korean Patent Application No. 10-1997-2703252 discloses a method of using a sulfonate compound or a compound having three or more ester-forming functional groups to prepare an aliphatic / aromatic copolyester resin. However, this method can shorten the reaction time and increase the average molecular weight, but the molecular weight distribution of the resulting aliphatic / aromatic copolyester composition is widened, resulting in a large amount of low molecular weight copolyester. This causes easy pyrolysis in the processing process and weakens the durability of the manufactured product which is vulnerable to moisture in the atmosphere.

In the case of the Republic of Korea Patent Application No. 10-1997-0703253, a dihydroxy compound containing an ether functional group was used to prepare an aliphatic / aromatic copolyester resin. In the examples shown, polyols represented by polyethylene glycol were used. It was. In this case, due to the long chain of the polyol, the esterification reaction and the polycondensation reaction are not performed smoothly, so that it is difficult to obtain a high molecular weight aliphatic / aromatic copolyester, and the reaction time is long, which is disadvantageous in terms of production cost.

Therefore, the inventors of the present invention is characterized by introducing a double bond into the molecular structure of the aliphatic / aromatic copolyester composition to solve the above problems, and also the optimum composition ratio of the raw material composition suitable for the production of sugar composition and its reaction conditions The study of optimization has led to the completion of the present invention.

The aliphatic / aromatic copolyester resin composition of the present invention is composed of aromatic dicarboxylic acid, aliphatic dicarboxylic acid (including cyclic aliphatic), aliphatic (including cyclic aliphatic) glycol, oxazoline compound, and carbodiimide compound. It is prepared by using.

According to the present invention, by providing an excellent aliphatic / aromatic copolyester resin composition in which an oxazoline group and a carbodiimide group are introduced into a molecular structure, problems of physical properties, processability, reaction rate, and moisture fragility of conventional biodegradable resins are solved. It is possible to manufacture all molded products such as extrusion and injection.

The present invention provides an aliphatic / aromatic copolyester resin composition comprising as essential elements a compound represented by the following general formula (1) and general formula (2) among all components:

Wherein D is a linear and branched alkylene group having 1 to 6 carbon atoms, and n is 0 to 10.

The aliphatic / aromatic copolyester resin composition of the present invention is an oxazoline compound represented by 0.001 to 10 parts by weight of formula (1) and 0.001 to 10 parts by weight of the formula (1) based on 100 parts by weight of the total acid component mixture and aliphatic glycol. The carbodiimide compound represented by 2) is composed of the following components together with 0.001 to 10 parts by weight:

Iii) 30 mole% to 70 mole% aliphatic dicarboxylic acid monocomponent (or mixture thereof) and 30 mole% to 70 mole% aromatic dicarboxylic acid monocomponent (or mixture thereof) as the acid component described below as A component. And acid component mixtures of carboxylic acids (or mixtures thereof) having three or more functional groups of 0 mol% to 2 mol%.

Ii) Glycol (or mixtures thereof) having from 98 mol% to 100 mol% of alkanediol or cyclodiol, or mixtures thereof and 0 mol% to 2 mol% of three or more functional groups as glycol components described below as component B Aliphatic glycol mixtures,

Iii) an unsaturated carboxylic acid (or anhydride thereof) sole component (or a mixture thereof) described below as component C, which is used at 0 to 10 parts by weight based on 100 parts by weight of the total weight of component A and component B, and

Iii) unsaturated glycol sole component (or mixture thereof) described as 0 to 10 parts by weight of the following D component based on 100 parts by weight of total weight of A and B.

Among the above components, C component and D component can also be used together in the preparation of the resin composition of the present invention.

Durable aliphatic / aromatic copolyester resin composition prepared in the present invention is the A, B, C, D component or A, B, C component or A, B, D component or A, B component 0.001 to 10 parts by weight of the selected composition consisting of the components or the oxazoline compounds represented by the formulas (1) and (2) and the cardodiimide compounds, respectively, alone or mixed It is prepared just before the esterification reaction, transesterification reaction or polycondensation reaction. The obtained aliphatic / aromatic copolyester resin has a number average molecular weight of 25,000 to 80,000, a weight average molecular weight of 40,000 to 300,000, and a melting point of 80 to 150 ° C.

The aliphatic dicarboxylic acid used among the acid components represented by A is as follows:

Where

n is an integer of 2-10 or less, and R is hydrogen or a methyl group.

Examples of the aliphatic dicarboxylic acid used among the acid components represented by A are succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid. . The above components are used alone or in combination.

The aromatic dicarboxylic acid used among the acid components represented by component A is terephthalic acid, isophthalic acid, 2,6-naphthoic acid and ester forming derivatives thereof. Terephthalic acid (or its ester forming derivatives) is particularly useful, and the components can be used alone or in combination.

The ratio of aliphatic dicarboxylic acid and aromatic dicarboxylic acid in the dicarboxylic acid component used as the above-mentioned A component is 70 mol%: 30 mol%-30 mol%: 70 mol%, More preferably, 60 Mol%: 40 mol%-40 mol%: 60 mol%.

When the aliphatic dicarboxylic acid is less than 30 mol% and the aromatic dicarboxylic acid exceeds 70 mol% with respect to the total dicarboxylic acid composition, the obtained resin composition does not show biodegradability and thus loses the meaning of the present invention. If the acid is more than 70 mol%, aromatic dicarboxylic acid is less than 30 mol%, the resulting composition has a low melting point, resulting in a low moldability.

The glycol component represented by component B is a linear alkanediol having 2 to 12 carbon atoms or a cycloalkanediol having 5 to 10 carbon atoms.

Alkanediols used are ethylene glycol, 1,2-propanediol, 1.2-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol and the like, in particular 1,4-butanediol alone Good ingredients but more than two diols can be mixed. It is preferable that the input amount is excessively charged in the range of 1.1 to 1.5 moles relative to 1 mole of the dicarboxylic acid component represented by the injected A component. If the molar ratio of the added diol is less than 1.1 mole transesterification or esterification is not smooth and may affect the color of the resulting resin. When the molar ratio of the added diol exceeds 1.5 moles, the economic efficiency is reduced by reducing the vacuum degree and increasing the production cost in terms of cost in the reaction process.

As the compound having three or more functional groups among the acid components represented by component A, malic acid, citric acid, trimesic acid and tartaric acid may be used alone or in combination, and the dosage is 0 to 2 mol% based on 100 mol% of A component. to be.

As a compound having three or more functional groups that can be mixed with glycol represented by the B component, glycerol and pentaerythritol are used alone or in combination. The use amount is 0-2 mol% based on 100 mol% of B components. When the amount of each exceeds 2 mol%, crosslinking is formed in the resin molecular structure obtained during the reaction, making it difficult to process and discharge the resin, and a lot of low molecular weight resin is present, thereby deteriorating the mechanical properties.

The unsaturated carboxylic acid or anhydride thereof represented by the above C component is fumaric acid, maleic acid, 1-hexene-1,6-dicarboxylic acid, 2,5-dimethyl-3-hexene-1,6-dicarboxylic acid Acid, 3-heptene-1,7-dicarboxylic acid, allylmalonic acid, itaconic acid and anhydride derivatives thereof, or a mixture of two or more selected from the group consisting of maleic anhydride, succinic anhydride and itaconic anhydride. Any one or two or more selected may be used and should be used in an amount of 10 parts by weight or less based on 100 parts by weight of the total weight of the acid mixture and aliphatic glycol. For example, exceeding 10 parts by weight causes gelation of the resin.

Examples of the unsaturated glycol compound represented by D component include 2-butene-1,4-diol, 2-pentene-1,5-diol, 3-hexene-1,6-diol, 2-hexene-1, Preference is given to using any one or a mixture of two or more selected from the group consisting of 6-diol, 2-butene-1,4-dimethyl-1,4-diol, the amount of which is the total weight of the acid component mixture and the aliphatic glycol 100 10 parts by weight or less based on parts by weight.

The oxazoline compound (formula (1)) used in the present invention is 2,2-bis- (2-oxazoline), N, N'-hexamethylene-bis- (2-carbamoyl-2-oxazoline) , 2,2'-methylene-bis- (2-oxazoline), 2,2'-ethylene-bis- (2-oxazoline), 2,2'-propylene-bis- (2-oxazoline), 1 , 3-phenylene-bis- (2-oxazoline), 2,2-P-phenylene-bis- (2-oxazoline), the dosage of which is 100% by weight of the total weight of the acid component mixture and aliphatic glycol added It is 0.001-10 weight part based on parts. If the dosage exceeds 10 parts by weight gelation may occur.

The carbodiimide compound (formula (2)) used in the present invention is 1,3-dicyclohexylcarbodiimide, HMV-8CA, HMV-10B, bis- (2,6-di) sold by Nisshinbo, Japan Isopropyl-phenyline-2,4-carbodiimide), poly- (1,3,5-triisopropyl-phenylri-2,4-carbodiimide), and the like, and the dosage is based on the acid mixture and It is 0.001-10 weight part based on 100 weight part of total weight of aliphatic glycol. If the dosage exceeds 10 parts by weight gelation may occur.

In the present invention, isocyanate may be used as a chain extender by adding 0 to 5 parts by weight based on 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol. Examples include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, and the like, and particularly 1,6-hexamethylene diisocyanate. Isocyanate shows the best effect, and it is preferable to add 0.01-5 weight part based on 100 weight part of total weight of an acid component mixture and aliphatic glycol.

The aliphatic / aromatic copolyester resin composition of the present invention will be described in more detail by dividing it into six types.

(1) The aliphatic / aromatic copolyester resin composition is composed mainly of aliphatic (including cyclic aliphatic) dicarboxylic acid and aromatic dicarboxylic acid or anhydrides thereof and aliphatic (including cyclic aliphatic) glycol, and aliphatic (cyclic) The case where an unsaturated compound or its anhydride is added is considered.

Examples of the aliphatic dicarboxylic acid used among the acid components represented by the A component are succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid. to be. The above components are used alone or in combination.

The aromatic dicarboxylic acid used among the acid components represented by component A is terephthalic acid, isophthalic acid, 2,6-naphthoic acid and ester forming derivatives thereof. Terephthalic acid (or its ester forming derivatives) is particularly useful and the components can be used alone or in combination.

The ratio of aliphatic dicarboxylic acid and aromatic dicarboxylic acid in the dicarboxylic acid component used as the above-mentioned A component is 70 mol%: 30 mol%-30 mol%: 70 mol%, More preferably, 60 Mol%: 40 mol%-40 mol%: 60 mol%.

When the aliphatic dicarboxylic acid is less than 30 mol% and the aromatic dicarboxylic acid exceeds 70 mol% with respect to the total dicarboxylic acid composition, the obtained resin composition does not show biodegradability and thus loses the meaning of the present invention. If the acid is more than 70 mol%, aromatic dicarboxylic acid is less than 30 mol%, the resulting composition has a low melting point, resulting in a low moldability.

The aliphatic glycol component represented by component B in the above is a linear alkanediol having 2 to 12 carbon atoms or a cycloalkanediol having 5 to 10 carbon atoms.

Alkanediols used are ethylene glycol, 1,2-propanediol, 1.2-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol and the like, in particular 1,4-butanediol alone The components are good but two or more diols can be mixed. It is preferable that the amount is excessively added in the range of 1.1 to 1.5 moles relative to 1 mole of the dicarboxylic acid component represented by the A component to be added. If the molar ratio of the added diol is less than 1.1 mole transesterification or esterification is not smooth and may affect the color of the resulting resin. When the molar ratio of the added diol exceeds 1.5 moles, the economic efficiency is reduced by reducing the vacuum degree and increasing the production cost in terms of cost in the reaction process.

0.001 to 10 parts by weight of the oxazoline compound and carbodiimide compound represented by Chemical Formulas 1 and 2 are added to the total weight parts of the A and B components based on 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol, respectively. It is preferable that the effect is less than 0.001 parts by weight can not be expected, if it exceeds 10 parts by weight may be gelation. The oxazoline compounds used at this time are 2,2-bis- (2-oxazoline), N, N'-hexamethylene-bis- (2-carbamoyl-2-oxazoline), 2,2'-methylene- Bis- (2-oxazoline), 2,2'-ethylene-bis- (2-oxazoline), 2,2'-propylene-bis- (2-oxazoline), 1,3-phenylene-bis- (2-oxazoline), 2,2-P-phenylene-bis- (2-oxazoline), and the carbodiimide compound used at this time is 1,3-dicyclohexylcarbodiimide, Nisshinbo Corporation of Japan HMV-8CA, HMV-10B, bis- (2,6-diisopropyl-phenyline-2,4-carbodiimide), poly- (1,3,5-triisopropyl-phenyl)- 2,4-carbodiimide).

(2) In the aliphatic / aromatic copolyester resin composition of the above (1), as a compound having three or more functional groups among the acid components represented by component A, malic acid, citric acid, trimesic acid, tartaric acid may be used alone or in combination. The dosage is 0 to 2 mol% based on 100mol% of A component.

As a compound having three or more functional groups that can be mixed with glycol represented by the B component, glycerol and pentaerythritol are used alone or in combination. The use amount is 0-2 mol% based on 100 mol% of B components. When the amount of each exceeds 2 mol%, crosslinking is formed in the resin molecular structure obtained during the reaction, making it difficult to process and discharge the resin, and a lot of low molecular weight resin is present, thereby deteriorating the mechanical properties.

(3) When unsaturated carboxylic acid (or anhydride thereof) is added to the aliphatic / aromatic copolyester resin composition of (1) above, the unsaturated carboxylic acid (or anhydride thereof) compound to be used at this time is fumaric acid, Maleic acid, 1-hexene-1,6-dicarboxylic acid, 2,5-dimethyl-3-hexene-1,6-dicarboxylic acid, 3-heptene-1,7-dicarboxylic acid, allylmalonic acid , An itaconic acid and an anhydride derivative thereof, or a mixture of one or two or more thereof, and as the unsaturated anhydride, any one or two or more selected from the group consisting of maleic anhydride, succinic anhydride, and itaconic anhydride are used. It should be used less than 10 parts by weight based on 100 parts by weight. For example, exceeding 10 parts by weight causes gelation of the resin.

(4) When an unsaturated glycol compound is added to the aliphatic / aromatic copolyester resin composition of (1) above and used, for example, 2-butene-1,4-diol, 2-pentene-1,5-diol, Using any one or a mixture of two or more selected from the group consisting of 3-hexene-1,6-diol, 2-hexene-1,6-diol, 2-butene-1,4-dimethyl-1,4-diol Preferably, the amount thereof is 10 parts by weight or less based on 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol.

(5) Types of polyfunctional compounds used in the case where a compound having a polyfunctional group, an unsaturated carboxylic acid (or its anhydride) compound, or an unsaturated glycol compound is added to and used in the aliphatic / aromatic copolyester resin composition of (1). And the amount thereof is as described above in the resin composition of (2), the type of unsaturated carboxylic acid (or anhydride thereof) used and the amount thereof are as described above in the resin composition of (3), and the unsaturated The kind and amount of the glycol compound are the same as described above in (4).

(6) In the case where an isocyanate compound is added as a chain extender to each of the resin compositions described in (1) to (5) above, the dosage is 0 based on 100 parts by weight of the total weight of the acid component mixture and the aliphatic glycol. ? 5 parts by weight can be used, and compounds such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate can be used. In particular, 1,6-hexamethylene diisocyanate shows the best effect, and it is preferable to add 0.01 to 5 parts by weight based on 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol.

The biodegradable aliphatic copolyester resin preparation method according to the present invention will be described in detail as follows. Method for producing a resin composition according to the present invention,

Aliphatic (including cyclic aliphatic) dicarboxylic acids or their anhydrides and acidic mixtures of aromatic dicarboxylic acids or their anhydrides, aliphatic (including cyclic aliphatic) glycols, and aliphatic (including cyclic aliphatic) unsaturated carbohydrates Acids or anhydrides thereof or aliphatic (including cyclic aliphatic) unsaturated glycols and mixtures thereof are mixed, and catalysts and stabilizers are added at 0.0001 to 1 parts by weight based on 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol, respectively. Esterification or transesterification, 0.3 to 1.5 parts by weight of the polycondensation reaction catalyst is added to the reaction product based on 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol, and a stabilizer is added to the acid component mixture and the aliphatic glycol. Consisting of polycondensation reaction by adding 0.0001 ~ 0.5 parts by weight based on 100 parts by weight of total weight And a gong.

Aliphatic (cyclic aliphatic) with respect to the total moles of the aliphatic (including cyclic aliphatic) dicarboxylic acid or its anhydride and aromatic dicarboxylic acid (or its anhydride) in the esterification or transesterification reaction It is preferable that the reaction molar ratio of glycol is 1: 1.1 to 1: 1.5, wherein if the molar ratio of glycol added per mole of the dicarboxylic acid is less than 1.1, the color becomes poor and the degree of polymerization is lowered. When the molar ratio of glycol exceeds 1.5, there is a problem in that only the manufacturing cost is increased without effect in terms of reactivity.

As for esterification reaction or transesterification temperature in this invention, about 170-230 degreeC is suitable.

As the compound having three or more functional groups among the acid components represented by component A, malic acid, citric acid, trimesic acid and tartaric acid may be used alone or in combination, and the dosage is 0 to 2 mol% based on 100 mol% of A component. to be.

As a compound having three or more functional groups that can be mixed with glycol represented by the B component, glycerol and pentaerythritol are used alone or in combination. The use amount is 0-2 mol% based on 100 mol% of B components. When the amount of each exceeds 2 mol%, crosslinking is formed in the resin molecular structure obtained during the reaction, making it difficult to process and discharge the resin, and a lot of low molecular weight resin is present, thereby deteriorating the mechanical properties.

Unsaturated carboxylic acid or its anhydride and unsaturated glycol may be used for the stability of the reaction in the reaction process, examples of the unsaturated carboxylic acid or its anhydride are fumaric acid, maleic acid, 1-hexene-1,6-dicar One or two selected from acids, 2,5-dimethyl-3-hexene-1,6-dicarboxylic acid, 3-heptene-1,7-dicarboxylic acid, allylmalonic acid, itaconic acid and its anhydride derivatives As the above mixture and unsaturated anhydride, any one or two or more selected from the group consisting of maleic anhydride, succinic anhydride and itaconic anhydride are used. Examples of the unsaturated glycol include 2-butene-1,4-diol and 2-pentene-1. Any one or more selected from the group consisting of, 5-diol, 3-hexene-1,6-diol, 2-hexene-1,6-diol, 2-butene-1,4-dimethyl-1,4-diol As a mixture, in the range of 0 to 10 parts by weight based on 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol. Is used.

In addition, the isocyanate may be used by adding 0 to 5 parts by weight based on 100 parts by weight of the total weight of the acid component mixture and the aliphatic glycol as a chain extender. Examples include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, and the like, and particularly 1,6-hexamethylene diisocyanate. Isocyanate shows the best effect, and it is preferable to add 0.01-5 weight part based on 100 weight part of total weight of an acid component mixture and aliphatic glycol.

In the initial stage of the esterification reaction or transesterification and stabilizers can be added. As the catalyst, dibutyl tin oxide and tetrabutyl titanate are used alone or as mixed catalysts, and as the stabilizer, triphenyl phosphate and trimethyl phosphate are used alone or as mixed stabilizers.

The addition amount of the catalyst and the stabilizer is appropriate from 0.0001 to 1 parts by weight based on 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol, when the addition amount of the catalyst is less than 0.0001 parts by weight, the rate of transesterification is slow, while 1 part by weight If exceeded, the reaction rate is high but the color is deteriorated.

In addition, when the amount of the stabilizer is less than 0.0001 parts by weight, the reaction product during the transesterification reaction does not prevent the factor that can be gas-decomposed, while if it exceeds 0.5 parts by weight, the reaction rate is lowered.

In the initial stage of the polycondensation of the present invention, a catalyst for promoting the polycondensation reaction may be added. As the catalyst, any one or two or more mixed catalysts selected from magnesium acetate, tetrapropyl titanate, zinc acetate, tetrabutyl titanate, dibutyl tin oxide, tetrapropyl titanate, calcium acetate and tetraisopropyl titanate can be used. The addition amount is suitably 0.3 to 1.5 parts by weight based on 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol based on 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol. If the added amount is less than 0.3 parts by weight, there is a limit to increase the molecular weight by losing activity as a catalyst at any given time, and if the amount exceeds 1.5 parts by weight, the reaction rate increases but there is a concern that the color is lowered.

In addition, a stabilizer may be added in the polycondensation step, and as the stabilizer, any one or two or more mixed stabilizers selected from trimethyl phosphate, trimethyl phosphine, triphenyl phosphate, and phosphate may be used. About 0.0001-0.5 weight part is preferable based on 100 weight part of total weight of an aliphatic glycol. At this time, if the amount of the stabilizer added is less than 0.0001 parts by weight, it does not play a role as a stabilizer, whereas if it exceeds 0.5 parts by weight, the reaction is delayed to increase the reaction time.

In the present invention, the polycondensation reaction temperature is preferably 230 to 260 ° C. When the polycondensation reaction temperature is less than 230 ° C, the polycondensation reaction time is long, while the polycondensation reaction temperature is higher than 260 ° C. Moreover, although polycondensation reaction time changes with quantity of a catalyst and a stabilizer, about 50 minutes-about 250 minutes are preferable.

The aliphatic / aromatic copolyester resins prepared by this method not only have biodegradation properties but are similar to or better than those of general-purpose general purpose polyethylene resins.

Preferably, the present invention is a hydrolyzable and biodegradable aliphatic / aromatic copolyester resin composition, comprising 30 mol% to 70 mol% of aliphatic dicarboxylic acid or anhydride thereof and 30 mol% to 70 mol% of aromatic dica Acid component mixtures of leric acid or anhydrides thereof; Aliphatic glycol in a ratio of 1.1 to 1.5 moles per 1 mole of the acid component mixture; And 0.001 to 10 parts by weight of an oxazoline compound of formula (1) or an anhydride thereof, a carbodiimide of formula (2), or a mixture thereof, based on 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol On the basis of 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol, 0.0001 to 1 part by weight of a catalyst and a stabilizer are added to esterify or transesterify, and to the reaction product, the acid component mixture and aliphatic Hydrolyzable and biodegradable aliphatic / aromatic copolyester resin composition prepared by polycondensation reaction with 0.3 to 1.5 parts by weight of polycondensation reaction catalyst and 0.0001 to 0.5 parts by weight of stabilizer based on 100 parts by weight of total glycol Provides:

Wherein D is a linear or branched alkylene group having 1 to 6 carbon atoms, and n is 0 to 10.

R ₁ and R ₂ are the same as or different from each other and are a C 4-20 alkyl group or a C 4-20 cycloalkyl group.

The present invention also provides a product injection or extrusion molded from the hydrolyzable and biodegradable aliphatic / aromatic copolyester resin composition.

In addition, the present invention provides a compound or a product molded therefrom by adding an inorganic substance of starch, calcium carbonate, or talc to the hydrolyzable and biodegradable aliphatic / aromatic copolyester resin composition.

Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1

Substitute 500 ml of round bottom flask with nitrogen, add 93.2 g of dimethyl terephthalate, 121.6 g of 1,4-butanediol, add 0.1 g of tetramethyl titanate, and proceed with the esterification reaction at 200 ° C. for 2 hours. After distilling off methanol, 76 g of adipic acid was added thereto, and then the reaction temperature was fixed at 200 deg. At this time, 0.1 g of antimony acetate, 0.1 g of thibutyltin oxide, 0.1 g of tetrabutyl titanate, and 0.2 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was increased and the polycondensation reaction was carried out for 150 minutes at 250 ° C. under a reduced pressure of 2.0 Torr or less, and then 2,2-bis- (2-oxazoline) 10 minutes before product discharge. 0.2 g, 0.1 g of HMV-8CA (Nisshinbo Co., Ltd., Japan) was added as a carbodiimide compound and then discharged after 10 minutes of reaction. The resin obtained at this time had a number average molecular weight of 34,400, a weight average molecular weight of 75,120, and a melting point measured by the DSC method of 123.8 ° C.

Example 2

Substitute 500 ml of round bottom flask with nitrogen, add 93.2 g of dimethyl terephthalate, 121.6 g of 1,4-butanediol, add 0.1 g of tetramethyl titanate, and proceed with the esterification reaction at 200 ° C. for 2 hours. After distilling off methanol, 0.12 g of fumaric acid and 76 g of adipic acid were added thereto, and the reaction temperature was fixed at 200 ° C., and water was distilled out. At this time, 0.1 g of antimony acetate, 0.1 g of thibutyltin oxide, 0.1 g of tetrabutyl titanate, and 0.2 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was increased and the polycondensation reaction was carried out for 150 minutes at 250 ° C. under a reduced pressure of 2.0 Torr or less, and then 2,2-bis- (2-oxazoline) 10 minutes before product discharge. 0.4g was added and then reacted for 10 minutes and then discharged. The resin obtained at this time had a number average molecular weight of 37,260, a weight average molecular weight of 82,830, and a melting point measured by the DSC method of 124.2 ° C.

Example 3

A 500 ml liter round bottom flask was replaced with nitrogen, 93.2 g of dimethyl terephthalate, 121.6 g of 1,4-butanediol, 0.15 g of malic acid, 5 g of 2,2-bis- (20 oxazoline), and tetramethyl titanate 0.1 g was added and the esterification reaction was performed at 200 ° C. for 2 hours, and the theoretical amount of methanol was distilled out. Then, 6 g of HMV-8CA (Nisshinbo Co., Ltd.) and 76 g of adipic acid were added as a carbodiimide compound. Fix at 200 ° C. and drain the water. At this time, 0.1 g of antimony acetate, 0.1 g of tetrabutyl titanate, and 0.2 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was continuously increased, and the polycondensation reaction was carried out for 100 minutes under a reduced pressure of 2.0 Torr or less at 250 ° C., followed by HMV-8CA (Nisshinbo Co., Ltd., Japan). ) 0.3g was added and then reacted for 10 minutes and then discharged. The resin obtained at this time had a number average molecular weight of 33,400, a weight average molecular weight of 96,750, and a melting point measured by the DSC method of 125.4 ° C.

Example 4

A 500 ml liter round bottom flask was replaced with nitrogen, 93.2 g of dimethyl terephthalate, 121.6 g of 1,4-butanediol, and 7 g of 2-butene-1,4-diol were added thereto, and 0.1 g of tetramethyl titanate was added thereto at 200 ° C. After the esterification reaction proceeded for two hours, the theoretical amount of methanol was distilled out, and then 76 g of adipic acid was added thereto, and the reaction temperature was fixed at 200 ° C., and water was distilled out. At this time, 0.1 g of antimony acetate, 0.1 g of thibutyltin oxide, 0.1 g of tetrabutyl titanate, and 0.2 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was increased and the polycondensation reaction was carried out for 220 minutes at 250 ° C. under a reduced pressure of 2.0 Torr or less, and then 2,2-bis- (2-oxazoline) 10 minutes before product discharge. 0.17g, 0.15g of HMV-8CA (Nisshinbo Co., Ltd., Japan) was added as a carbodiimide compound, followed by reaction for 10 minutes and then discharged. The resin obtained at this time had a number average molecular weight of 34,100, a weight average molecular weight of 72,310, and a melting point measured by the DSC method of 123.3 ° C.

Example 5

Substitute 500 ml of round bottom flask with nitrogen, add 93.2 g of dimethyl terephthalate, 121.6 g of 1,4-butanediol, and 0.1 g of tetramethyl titanate. After distilling out, 5.3 g of malic acid and 76 g of adipic acid were added thereto, and the reaction temperature was fixed at 200 ° C., and water was distilled out. At this time, 0.1 g of antimony acetate, 0.1 g of thibutyltin oxide, 0.1 g of tetrabutyl titanate, and 0.2 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was increased and the polycondensation reaction was carried out for 130 minutes under reduced pressure at 250 ° C. or lower than 2.0 Torr. 2,2-bis- (2-oxazoline) 10 minutes before product discharge. 0.2g, 0.1g of 1,6-hexamethylene diisocyanate was added thereto, followed by reaction for 10 minutes and then discharged. The resin obtained at this time had a number average molecular weight of 51,560, a weight average molecular weight of 120,530, and a melting point measured by the DSC method of 126.7 ° C.

Example 6

A 500 ml liter round bottom flask was replaced with nitrogen, 93.2 g of dimethyl terephthalate, 121.6 g of 1,4-butanediol, and 10 g of 2-butene-1,4-diol were added thereto, and 0.1 g of tetramethyl titanate was added thereto at 200 ° C. After esterification was carried out for two hours, the theoretical amount of methanol was distilled off, and 0.2 g of fumaric acid and 76 g of adipic acid were added thereto, and the reaction temperature was fixed at 200 ° C. and water was distilled off. At this time, 0.1 g of antimony acetate, 0.1 g of thibutyltin oxide, 0.1 g of tetrabutyl titanate, and 0.2 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water flowed out, the temperature was increased and the polycondensation reaction was carried out for 120 minutes under a reduced pressure of 2.0 Torr or less at 255 ° C., 2,2-bis- (2-oxazoline) 10 minutes before product discharge. The reaction was completed after 10 minutes after adding 0.14 g of HMV-8CA (Nisshinbo Co., Ltd. Japan) and 0.1 g of 1,6-hexamethylene diisocyanate as 0.3 g and a carbodiimide compound. The resin obtained at this time had a number average molecular weight of 41,320, a weight average molecular weight of 100,060, and a melting point measured by the DSC method of 125.7 ° C.

Comparative Example 1

Substitute 500 ml of round bottom flask with nitrogen, add 93.2 g of dimethyl terephthalate, 121.6 g of 1,4-butanediol, add 0.1 g of tetramethyl titanate, and proceed with the esterification reaction at 200 ° C. for 2 hours. After distilling off methanol, 76 g of adipic acid was added thereto, and the reaction temperature was fixed at 200 ° C., and water was distilled out. At this time, 0.1 g of antimony acetate, 0.1 g of thibutyltin oxide, 0.1 g of tetrabutyl titanate, and 0.2 g of trimethyl phosphate were added as a stabilizer. After the theoretical amount of water had flowed out, the temperature was continuously raised and the polycondensation reaction was carried out for 320 minutes under a reduced pressure of 2.0 Torr or less at 255 ° C. The resin thus obtained had a number average molecular weight of 23,000, a weight average molecular weight of 51,000, and a melting point measured by the DSC method of 125 ° C.

Comparative Example 2

After replacing the 500 ml Erlenmeyer flask with nitrogen, 23.6 g of succinic acid, 27 g of 1,4-butanediol, and 0.1 g of tetrabutyl titanate as a catalyst were added thereto, followed by esterification while raising the temperature in a stream of nitrogen to allow water to flow out. At this time, the temperature is fixed at 205 ° C.

After completely flowing out the theoretical amount of water to produce 34.4 g of an "aliphatic low molecular weight polymer" having a molecular weight of about 600, 77.5 g of dimethyl terephthalate, 135.2 g of 1,4-butanediol and tetrabutyl tita as a catalyst were added to the Erlenmeyer flask. 0.2g of nate is added to raise the temperature slowly, and methanol is discharged through a transesterification reaction. At this time, the methanol was completely discharged while maintaining the temperature at 205 ° C, and then 35.4 g of succinic acid and 43.8 g of adipic acid were added to the Erlenmeyer flask to carry out an esterification reaction. At this time, after fixing the temperature at 180 ° C. and completely distilling water, 0.1 g of antimony trioxide, 0.3 g of dibutyl tin oxide, 0.07 g of tetrabutyl titanate, and 0.1 g of trimethylphosphate were added as a stabilizer. Then, the temperature was raised and the polycondensation reaction was carried out for 180 minutes at 245 ° C. under a reduced pressure of 0.3 Torr. The number average molecular weight was 48,000, the weight average molecular weight was 310,000, and the melting point measured by the DSC method was 80 ° C.

Comparative Example 3

The 500 ml Erlenmeyer flask was replaced with nitrogen, and then 116.8 g of 1,4-butanediol, 35 g of adipic acid and 0.25 g of tindioctate were added and reacted at a temperature ranging from 230 to 240 ° C. to completely remove the theoretical water flow rate. did. After taking 82.6 g of the obtained polymer, 65.5 g of dimethyl terephthalate and 85 g of 1,4-butanediol were added, and then methanol was generated while heating to 180 ° C. while gradually stirring. In this process, 0.235 g of tetrabutyl ortho titanate, 0.0825 g of pyromellitic dianhydride, and 0.095 g of 50% aqueous phosphite solution were added, and the polycondensation reaction was carried out at a temperature of 230 to 240 ° C. and a high vacuum of less than 1 torr for about 120 minutes. After cooling, the melt was cooled to 200 ° C., 1.45 g of hexamethylene diisocyanate was added over 15 minutes, and then the mixture was stirred.

The melting point of the resin obtained at this time was 108.3 ° C., the number average molecular weight was 17,589 and the weight average molecular weight was 113,550.

Table 1 shows the properties of the resins obtained from the examples and the comparative examples.

The number average molecular weight and the weight average molecular weight were measured by gel chromatography method using polystyrene as a base material, and melting point was measured by DSC method and biodegradation evaluation was recovered after 3 months after landfilling by 30cm depth from soil surface index and measured by weight loss method. It was.

The hydrolysis resistance was very good when the obtained resin was left at 25 ° C. and 50% humidity for 3 months after producing a 30 탆 film using a hot press, and when the tensile strength was 90% or more compared to the initial measurement value, 80 It is excellent when more than 90% and less than 90%, usually 70% or more and less than 80%, and less than 70%.

Claims (16)

As a hydrolyzable and biodegradable aliphatic / aromatic copolyester resin composition,
Acid component mixtures of 30 mol% to 70 mol% of aliphatic dicarboxylic acid or anhydride thereof and 30 mol% to 70 mol% of aromatic dicarboxylic acid or anhydride thereof; Aliphatic glycol in a ratio of 1.1 to 1.5 moles per 1 mole of the acid component mixture; And 0.001 to 10 parts by weight of an oxazoline compound of formula (1) or an anhydride thereof, a carbodiimide of formula (2), or a mixture thereof, based on 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol and,
On the basis of 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol, 0.0001 to 1 parts by weight of a catalyst and a stabilizer are added to esterify or transesterify,
Hydrolysis resistance prepared by polycondensation reaction by adding 0.3-1.5 parts by weight of polycondensation reaction catalyst and 0.0001-0.5 parts by weight of stabilizer to the reaction product based on 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol. And biodegradable aliphatic / aromatic copolyester resin compositions:

Wherein D is a linear or branched alkylene group of 1 to 6 carbon atoms, n is 0 to 10,
R ₁ and R ₂ are the same as or different from each other and are a C 4-20 alkyl group or a C 4-20 cycloalkyl group.
The compound of claim 1, wherein the oxazoline compound of formula (1) is 2,2-bis- (2-oxazoline), N, N'-hexamethylene-bis- (2-carbamoyl-2-oxazoline), 2,2'-methylene-bis- (2-oxazoline), 2,2'-ethylene-bis- (2-oxazoline), 2,2'-propylene-bis- (2-oxazoline), 1, Hydrolyzable, characterized in that it is selected from the group consisting of 3-phenylene-bis- (2-oxazoline), and 2,2-P-phenylene-bis- (2-oxazoline) and mixtures of two or more thereof. And biodegradable aliphatic / aromatic copolyester resin compositions. The carbodiimide compound of formula (2) according to claim 1, wherein the carbodiimide compound of formula (2) is 1,3-dicyclohexylcarbodiimide, HMV-8CA, HMV-10B, bis- (2,6-diisopropyl-phenyline-2 Hydrolysis resistance, characterized in that it is selected from the group consisting of, 4-carbodiimide), poly- (1,3,5-triisopropyl-phenylri-2,4-carbodiimide) and mixtures of two or more thereof. And biodegradable aliphatic / aromatic copolyester resin compositions. The group of claim 1 wherein the aliphatic dicarboxylic acid consists of succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid and mixtures of two or more thereof. Hydrolyzable and biodegradable aliphatic / aromatic copolyester resin composition, characterized in that it is selected from. The hydrolyzable and biodegradable aliphatic / according to claim 1, characterized in that the aromatic dicarboxylic acid is selected from the group consisting of terephthalic acid, isophthalic acid, 2.6-naphthoic acid and ester forming derivatives thereof, and mixtures of two or more thereof. Aromatic copolyester resin composition. The process of claim 1 wherein the aliphatic glycol is ethylene glycol, 1,2-propanediol, 1.2-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol and mixtures of two or more thereof Hydrolyzable and biodegradable aliphatic polyester resin composition, characterized in that it is selected from the group consisting of. The method of claim 1, wherein in the esterification or transesterification reaction, based on 100 mol% of the acid component in which a polyfunctional compound selected from the group consisting of malic acid, citric acid, trimesic acid, tartaric acid alone or a mixture of two or more is used. Hydrolysable and biodegradable aliphatic / aromatic copolyester resin composition, further comprising an amount of up to 2% by weight. The polyfunctional compound according to claim 1, wherein the polyfunctional compound selected from the group consisting of glycerol and pentaerythritol alone or in a mixture at the time of esterification or transesterification is in an amount of 2 mol% or less based on 100 mol% of a glycol component. Hydrolysable and biodegradable aliphatic / aromatic copolyester resin composition, further comprising. The method of claim 1, wherein in the esterification or transesterification reaction, fumaric acid, maleic acid, 1-hexene-1,6-dicarboxylic acid, 2,5-dimethyl-3-hexene-1,6-dicar Acid component mixtures include unsaturated carboxylic acids or anhydrides thereof selected from the group consisting of acids, 3-hepten-1,7-dicarboxylic acids, allylmalonic acid, itaconic acid and its anhydride derivatives, and mixtures of two or more thereof. It is further included in an amount of 10 parts by weight or less based on 100 parts by weight of the total weight of the aliphatic glycol, preferably, the anhydride is selected from the group consisting of maleic anhydride, succinic anhydride, itaconic anhydride and mixtures of two or more thereof Hydrolyzable and biodegradable aliphatic / aromatic copolyester resin composition, characterized in that. The 2-butene-1,4-diol, 2-pentene-1,5-diol, 3-hexene-1,6-diol, 2-hexene- according to claim 1, in the esterification reaction or transesterification reaction. Unsaturated glycols selected from the group consisting of 1,6-diol, 2-butene-1,4-dimethyl-1,4-diol and mixtures of two or more thereof, based on 100 parts by weight of the total weight of the acid component mixture and aliphatic glycol Hydrolysable and biodegradable aliphatic / aromatic copolyester resin composition, further comprising an amount of 10 parts by weight or less. The method according to claim 10, wherein in the esterification reaction or transesterification reaction, fumaric acid, maleic acid, 1-hexene-1,6-dicarboxylic acid, 2,5-dimethyl-3-hexene-1,6-dicar Acid component mixtures include unsaturated carboxylic acids or anhydrides thereof selected from the group consisting of acids, 3-hepten-1,7-dicarboxylic acids, allylmalonic acid, itaconic acid and its anhydride derivatives, and mixtures of two or more thereof. Hydrolysable and biodegradable aliphatic / aromatic copolyester resin composition, characterized in that it is further included in an amount of 10 parts by weight or less based on 100 parts by weight of the total weight of aliphatic glycol. The 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane according to any one of claims 1 to 10 as a chain extender at the time of esterification reaction or transesterification reaction. The isocyanate compound selected from the group consisting of diisocyanate, 2,2'-diphenylmethane diisocyanate and mixtures of two or more thereof may be contained in an amount of 5 parts by weight or less based on 100 parts by weight of the total weight of the acid component mixture and the aliphatic glycol. A hydrolyzable and biodegradable aliphatic / aromatic copolyester resin composition, which is further used. The hydrolyzable and biodegradable aliphatic / aromatic according to any one of claims 1 to 10, characterized in that the number average molecular weight is 25,000 to 80,000, the weight average molecular weight is 40,000 to 300,000 and the melting point is 80 to 150 ° C. Copolyester resin composition. The hydrolyzable and biodegradable aliphatic / aromatic copolyester resin composition according to claim 11, wherein the anhydride derivative is selected from the group consisting of maleic anhydride, succinic anhydride, itaconic anhydride and mixtures of two or more thereof. An article injection or extrusion molded from the hydrolyzable and biodegradable aliphatic / aromatic copolyester resin composition according to claim 1. A compound or a product molded from the hydrolyzable and biodegradable aliphatic / aromatic copolyester resin composition of claim 1 by adding an inorganic substance of starch, calcium carbonate, or talc.