KR102589197B1 - Biodegradable polyester copolymer comprising anhydrosugar alcohol based polycarbonate diol and preparation method thereof, and molded article comprising the same - Google Patents

Abstract

The present invention relates to a biodegradable copolymer polyester resin containing anhydrosugar alcohol-based polycarbonate diol, a method for producing the same, and a molded article containing the same, and more specifically, to a dicarboxylic component containing adipic acid or an ester thereof. Compared to a conventional biodegradable polyester resin (e.g., PBAT resin) by including a repeating unit derived from a diol component containing a specific content of anhydrosugar alcohol-based polycarbonate diol and a repeating unit derived from a diol component in a specific content ratio. Therefore, the present invention relates to a method for producing a polyester resin that maintains excellent biodegradability and has significantly improved heat resistance and mechanical properties (e.g., elongation), and a molded article containing the same.

Description

Biodegradable copolymer polyester resin containing anhydrosugar alcohol-based polycarbonate diol and method for producing the same, and molded article containing the same

The present invention relates to a biodegradable copolymer polyester resin containing anhydrosugar alcohol-based polycarbonate diol, a method for producing the same, and a molded article containing the same, and more specifically, to a dicarboxylic component containing adipic acid or an ester thereof. Compared to a conventional biodegradable polyester resin (e.g., PBAT resin) by including a repeating unit derived from a diol component containing a specific content of anhydrosugar alcohol-based polycarbonate diol and a repeating unit derived from a diol component in a specific content ratio. Therefore, the present invention relates to a method for producing a polyester resin that maintains excellent biodegradability and has significantly improved heat resistance and mechanical properties (e.g., elongation), and a molded article containing the same.

Hydrogenated sugar (also called “sugar alcohol”) refers to a compound obtained by adding hydrogen to the reducing terminal group of a saccharide, and is generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer from 2 to 5) ) and is classified into tetritol, pentitol, hexitol, and heptitol (carbon numbers 4, 5, 6, and 7, respectively) depending on the carbon number. Among them, hexitol with 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

Anhydrous sugar alcohol has a diol form with two hydroxy groups in the molecule, and can be manufactured using hexitol derived from starch (e.g., Korean Patent No. 10-1079518, Korean Patent Publication No. 10). -2012-0066904). Since anhydrous sugar alcohol is an eco-friendly material derived from renewable natural resources, there has been a lot of interest and research on its production method for a long time. Among these anhydrous sugar alcohols, isosorbide prepared from sorbitol currently has the widest range of industrial applications.

The uses of anhydrous sugar alcohol are very diverse, including treatment of heart and vascular diseases, adhesive for patches, pharmaceuticals such as mouthwash, solvent for compositions in the cosmetics industry, and emulsifier in the food industry. In addition, it can raise the glass transition temperature of polymer materials such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, and has the effect of improving the strength of these materials. Since it is an eco-friendly material derived from natural products, it is very useful in the plastic industry such as bioplastics. useful. It is also known to be used as an eco-friendly solvent for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

As such, non-sugar alcohol is receiving a lot of attention due to its diverse potential for use, and its use in actual industry is gradually increasing.

Meanwhile, efforts are being made to reduce the use of fossil resources in order to respond to the depletion of fossil resources, the increase in carbon dioxide in the atmosphere due to mass consumption of petroleum resources, and the resulting global warming problem. In this regard, interest in environmentally cyclical polymers is high, and research on polyester resins using biomass raw materials such as anhydrous sugar alcohol is actively underway. Aliphatic polyester resin using biomass raw materials is widely used in fields such as packaging materials, molded products, and films, and is one of the eco-friendly plastics that do not contain environmental hormones. In addition, because it is biodegradable, it is attracting attention as an eco-friendly material that can solve the problem of environmental pollution caused by waste plastic, which has recently become an issue.

Recently, as the harmfulness of bisphenol A has been revealed in polycarbonate, which is mainly used in heat-resistant food containers, the need for polyester resins that are environmentally friendly, transparent, and heat-resistant is increasing.

In the case of conventional homopolyester composed of terephthalic acid and ethylene glycol, mechanical properties and heat resistance can be improved to some extent through stretching crystallization and heat setting, but there are limitations in application and heat resistance improvement. Therefore, a method of improving the heat resistance of polyester resin has recently been developed by using isosorbide, a biomass-derived compound derived from starch, as a comonomer of polyester resin. However, since isosorbide is a secondary alcohol, it has low reactivity and is known to be difficult to form a high-viscosity polyester resin used in the manufacture of sheets and bottles.

In addition, PBAT (polybutylene adipate-co-terephthalate) resin, a representative biodegradable aliphatic polyester resin, is a copolymer resin containing aliphatics and aromatics and has various processability. However, the unit price is high, causing a significant increase in the unit cost of products such as packaging films manufactured using it as a raw material, and it has the disadvantage of poor heat resistance and mechanical properties.

Therefore, there is a need for the development of a biodegradable polyester resin that improves the problems of poor mechanical properties and heat resistance of conventional biodegradable polyester resins (for example, PBAT resin) while maintaining excellent biodegradability.

The present invention is intended to solve the problems of the prior art described above. Compared to conventional biodegradable polyester resins (e.g., PBAT resins), the present invention maintains excellent biodegradability and improves heat resistance and mechanical properties (e.g., elongation). ) The technical task is to provide a polyester resin with significantly improved properties, a method for manufacturing the same, and a molded article containing the same.

In order to achieve the above-described technical problem, the present invention includes a repeating unit derived from a dicarboxylic component; and a repeating unit derived from a diol component, wherein the dicarboxylic component is more than 20 mol% and less than 80 mol% of an aliphatic dicarboxylic compound and 20 mol% based on 100 mol% of the total dicarboxyl component. Contains more than 80 mol% of an aromatic dicarboxylic compound, the aliphatic dicarboxylic compound includes adipic acid or an ester thereof, and the diol component contains 0.5 mol% based on 100 mol% of the total diol component. A biodegradable polyester resin is provided, comprising greater than 35 mole percent of anhydrosugar alcohol-based polycarbonate diol.

According to another aspect of the present invention, (1) subjecting a dicarboxyl component and a diol component to an esterification reaction or transesterification reaction; and (2) subjecting the reaction product obtained in step (1) to a polycondensation reaction, wherein the dicarboxylic component is greater than 20 mol% to 80 mol% based on 100 mol% of the total dicarboxylic component. less than an aliphatic dicarboxylic compound and less than 20 mol% to less than 80 mol% of an aromatic dicarboxylic compound, wherein the aliphatic dicarboxylic compound comprises adipic acid or an ester thereof, and the diol component comprises a diol A method for producing a biodegradable polyester resin is provided, which includes more than 0.5 mol% to less than 35 mol% of anhydrosugar alcohol-based polycarbonate diol based on 100 mol% of the total components.

According to another aspect of the present invention, a molded article comprising the biodegradable polyester resin according to the present invention is provided.

The anhydrosugar alcohol-based polycarbonate diol in the biodegradable polyester resin of the present invention can improve heat resistance by increasing the glass transition temperature (T _g ), and at the same time disturbs the structural regularity of the molecular chain in the biodegradable polyester resin. Biodegradability can be further improved. Therefore, according to the present invention, compared to conventional biodegradable polyester resins such as PBAT resin, not only can the heat resistance and mechanical properties (e.g., elongation) of the biodegradable polyester resin be significantly improved, but also the biodegradability is further improved. You can do it.

Hereinafter, the present invention will be described in more detail.

The biodegradable polyester resin of the present invention includes a repeating unit derived from a dicarboxylic component; and repeating units derived from diol components.

Dicarboxylic component

The dicarboxylic component included as a repeating unit in the biodegradable polyester resin of the present invention includes aliphatic dicarboxylic compounds and aromatic dicarboxylic compounds.

The aliphatic dicarboxylic compound includes adipic acid or its ester.

In one embodiment, the aliphatic dicarboxylic compound may include adipic acid or its ester in an amount of 50 to 100 mol%, more specifically, based on 100 mol% of the total aliphatic dicarboxylic compound. It may be included in an amount of from 100 mol% or 80 to 100 mol%, but is not limited thereto.

In one embodiment, the aliphatic dicarboxylic compound may further include an aliphatic dicarboxylic compound other than adipic acid or an ester thereof, and more specifically, an aliphatic dicarboxylic acid having 4 to 14 carbon atoms or an ester thereof. It may further include. Aliphatic dicarboxylic compounds other than adipic acid or its esters may be included in an amount of, for example, 0 to 50 mol%, more specifically, 0 to 40 mol%, based on 100 mol% of the total aliphatic dicarboxylic compound. % or 0 to 20 mol%, but is not limited thereto.

Additionally, in one embodiment, the aromatic dicarboxylic compound may include an aromatic dicarboxylic acid or an ester thereof having 8 to 16 carbon atoms.

More specifically, the aliphatic dicarboxylic compounds other than adipic acid or its esters include cyclohexanedicarboxylic acid or its esters, sebacic acid or its esters, isodecylsuccinic acid or its esters, maleic acid or its esters, and fumaric acid. or its ester, succinic acid or its ester, glutaric acid or its ester, azelaic acid or its ester, itaconic acid or its ester, glutamic acid or its ester, 2,5-furandicarboxylic acid or its ester, tetrahydrofuran- 2,5-dicarboxylic acid or its ester, tetrahydrofuran-3,5-dicarboxylic acid or its ester, undecanedioic acid or its ester, dodecanedioic acid or its ester, tridecanedioic acid or its ester, tetra It may be selected from the group consisting of decanedioic acid, esters thereof, and combinations thereof.

In addition, more specifically, the aromatic dicarboxylic compound is phthalic acid or its ester, terephthalic acid or its ester, isophthalic acid or its ester, 1,5-naphthalenedicarboxylic acid or its ester, 2,6-naphthalenedicarboxylic acid or its ester, 2,6-naphthalenedicarboxylic acid or its ester, It may be selected from the group consisting of boxylic acid or its ester, diphenic acid or its ester, p-phenylene diacetic acid or its ester, o-phenylene diacetic acid or its ester, and combinations thereof.

In one embodiment, the ester compound of the aliphatic dicarboxylic acid may be a monoester compound, a diester compound, or a mixture thereof, and preferably a diester compound. For example, the ester compound of the aliphatic dicarboxylic acid may be a di(C1-C6)alkyl ester of an aliphatic dicarboxylic acid, such as dimethyl adipate, diethyl adipate, dimethyl succinate, or diethyl succinate. there is.

Additionally, in one embodiment, the ester compound of the aromatic dicarboxylic acid may be a monoester compound, a diester compound, or a mixture thereof, and preferably a diester compound. For example, the ester compound of the aromatic dicarboxylic acid may be a di(C1-C6)alkyl ester of an aromatic dicarboxylic acid, such as dimethyl terephthalate, diethyl terephthalate, dimethyl isophthalate, or diethyl isophthalate. You can.

The dicarboxylic component included as a repeating unit in the biodegradable polyester resin of the present invention is an aliphatic dicarboxylic compound in an amount of more than 20 mol% to less than 80 mol% based on 100 mol% of the total dicarboxylic component. Included. If the aliphatic dicarboxylic compound content in the total 100 mol% of dicarboxylic components is 20 mol% or less, the biodegradability of the produced biodegradable polyester resin rapidly decreases, and the mechanical properties (elongation) become very poor. On the other hand, if the content of aliphatic dicarboxylic compounds within 100 mol% of the total dicarboxylic component is more than 80 mol%, the glass transition temperature of the produced biodegradable polyester resin decreases, heat resistance becomes very poor, and mechanical properties are also poor. It becomes.

The dicarboxylic component included as a repeating unit in the biodegradable polyester resin of the present invention is an aromatic dicarboxylic compound in an amount of more than 20 mol% to less than 80 mol% based on 100 mol% of the total dicarboxylic component. Included. If the aromatic dicarboxylic compound content in the total 100 mol% of dicarboxylic components is 20 mol% or less, the glass transition temperature of the produced biodegradable polyester resin decreases, heat resistance becomes very poor, and mechanical properties also become poor. On the contrary, if the aromatic dicarboxylic compound content in the total 100 mol% of dicarboxylic components is more than 80 mol%, the biodegradability of the produced biodegradable polyester resin rapidly decreases, and the mechanical properties (elongation) become very poor.

In a specific example, the content of the aliphatic dicarboxylic compound in the dicarboxylic component is greater than 20 mol%, greater than 21 mol%, greater than 23 mol%, greater than 25 mol%, based on 100 mol% of the total dicarboxylic component. It may be 27 mol% or more, 29 mol% or more, or 30 mol% or more, and may also be less than 80 mol%, 79 mol% or less, 77 mol% or less, 75 mol% or less, 73 mol% or less, 71 mol% or less, or 70 mol% or less. It may be less than mole%, but is not limited thereto.

In one embodiment, the content of the aromatic dicarboxylic compound in the dicarboxylic component is greater than 20 mol%, greater than 21 mol%, greater than 23 mol%, greater than 25 mol%, based on 100 mol% of the total dicarboxylic component. , may be 27 mol% or more, 29 mol% or more, or 30 mol% or more, and may also be less than 80 mol%, 79 mol% or less, 77 mol% or less, 75 mol% or less, 73 mol% or less, 71 mol% or less. It may be 70 mol% or less, but is not limited thereto.

Dior ingredient

The diol component included as a repeating unit in the biodegradable polyester resin of the present invention includes more than 0.5 mol% to less than 35 mol% of anhydrosugar alcohol-based polycarbonate diol, based on 100 mol% of the total diol component.

If the anhydrosugar alcohol-based polycarbonate diol content in the total 100 mol% of the diol component is 0.5 mol% or less, the glass transition temperature of the produced biodegradable polyester resin decreases and the heat resistance becomes poor. On the other hand, if the anhydrous sugar alcohol-based polycarbonate diol content in the total 100 mol% of the diol component is more than 35 mol%, a low molecular weight biodegradable polyester resin is produced due to a decrease in reactivity, and the intrinsic viscosity of the produced biodegradable polyester resin decreases. And the glass transition temperature decreases, heat resistance becomes very poor, and mechanical properties (elongation) also become poor.

In one embodiment, the anhydrosugar alcohol-based polycarbonate diol content in the diol component is greater than 0.5 mol%, 0.6 mol% or more, 1 mol% or more, 1.5 mol% or more, 2, based on 100 mol% of the total diol component. It may be more than 35 mol%, more than 2.5 mol%, or more than 3 mol%, and also less than 35 mol%, less than 34 mol%, less than 32 mol%, less than 30 mol%, less than 28 mol%, less than 26 mol%, or less than 25 mol%. It may be less than %, but is not limited to this.

In the present invention, “anhydrous sugar alcohol” refers to a compound obtained by adding hydrogen to a reducing terminal group of a saccharide, commonly called hydrogenated sugar or sugar alcohol, by removing one or more water molecules. It refers to any material obtained.

The anhydrosugar alcohol may be monosugar alcohol, dianhydrosugar alcohol, or a combination thereof.

The monohydrosugar alcohol is anhydrosugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetraol form with four hydroxy groups in the molecule. In the present invention, the type of monosugar alcohol is not particularly limited, but is preferably monosususu hexitol, and more specifically, 1,4-anhydrohexitol, 3,6-anhydrohexitol. , 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more of these.

The dianhydrosugar alcohol is an anhydrosugar alcohol formed by removing two water molecules from the inside of a hydrogenated sugar. It has a diol form with two hydroxy groups in the molecule, and can be produced using hexitol derived from starch. . Since dianhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, there has been a lot of interest for a long time and research on its production method has been conducted. Among these dianhydrosugar alcohols, isosorbide prepared from sorbitol currently has the widest range of industrial applications. In the present invention, the type of dianhydrosugar alcohol is not particularly limited, but is preferably dianhydrosugar hexitol, and more specifically, 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

In a preferred embodiment of the present invention, the anhydrosugar alcohol is dianhydrosugar hexitol, more preferably isosorbide (1,4:3,6-dianhydrosorbitol), isomannide (1,4: One selected from the group consisting of 3,6-dianhydromonitol), isoidide (1,4:3,6-dianhydroyditol), or a mixture thereof, most preferably isosorbide, can be used.

In one embodiment, the anhydrosugar alcohol-based polycarbonate diol includes (1) a repeating unit derived from the ether diol of anhydrosugar alcohol; and (2) a repeating unit derived from carbonic acid diester.

The ether diol of anhydrous sugar alcohol is a diol compound derived from anhydrous sugar alcohol having an ether bond in the molecule, and is manufactured by addition reaction of anhydrous sugar alcohol and alkylene oxide, or anhydrous sugar alcohol and alkylene carbonate (especially ethylene carbonate). It may be obtained by reacting, and is preferably prepared by addition reaction of anhydrous sugar alcohol and alkylene oxide.

Specifically, the alkylene oxide may be a linear alkylene oxide having 2 to 20 carbon atoms or a branched alkylene oxide having 3 to 20 carbon atoms, and more specifically, a linear alkylene oxide having 2 to 10 carbon atoms or a branched alkylene oxide having 3 to 10 carbon atoms. branched alkylene oxides, more specifically linear alkylene oxides having 2 to 8 carbon atoms or branched alkylene oxides having 3 to 8 carbon atoms, even more specifically linear alkylene oxides having 2 to 4 carbon atoms or 3 carbon atoms to 4 branched alkylene oxides.

In one embodiment, the alkylene oxide may be ethylene oxide, propylene oxide, or a combination thereof.

In one embodiment, the ether diol of anhydrous sugar alcohol obtained by reacting the anhydrous sugar alcohol with alkylene oxide or alkylene carbonate (particularly ethylene carbonate) may be a compound represented by the following formula (A):

[Formula A]

In Formula A,

R ₁ and R ₂ are each independently a linear alkylene group having 2 to 20 carbon atoms or a branched alkylene group having 3 to 20 carbon atoms, more specifically a linear alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms , more specifically, a linear alkylene group with 2 to 8 carbon atoms or a branched alkylene group with 3 to 8 carbon atoms, even more specifically a linear alkylene group with 2 to 4 carbon atoms or a branched alkylene group with 3 to 4 carbon atoms. ,

m and n each independently represent an integer from 0 to 15, provided that m+n represents an integer from 1 to 30.

More preferably, in formula A,

R ₁ and R ₂ each independently represent an ethylene group, a propylene group, or an isopropylene group, and R ₁ and R ₂ may be the same or different from each other, but preferably R ₁ and R ₂ are the same as each other,

m and n each independently represent an integer of 1 to 14, provided that m+n represents an integer of 2 to 15, preferably an integer of 3 to 15.

In one embodiment, the following isosorbide-propylene glycol, isosorbide-ethylene glycol, or a mixture thereof may be used as the ether diol of the anhydrosugar alcohol.

[Isosorbide-propylene glycol]

In the above formula,

a and b are each independently an integer from 0 to 15, provided that a+b is an integer from 1 to 30, and preferably a and b are each independently an integer from 1 to 14, provided that a+b is an integer from 2 to 14. It may be an integer of 15 (preferably 3 to 15).

[Isosorbide-ethylene glycol]

In the above formula,

c and d are each independently an integer from 0 to 15, provided that c+d is an integer from 1 to 30, and preferably c and d are each independently an integer from 1 to 14, provided that c+d is an integer from 2 to 14. It may be an integer of 15 (preferably 3 to 15).

The reaction of anhydrosugar alcohol with alkylene oxide is, for example, in the presence of an acid or alkali catalyst, at 100°C to 150°C for 3 to 8 hours, more specifically at 100°C to 140°C for 5 to 6 hours. It may be performed, but is not particularly limited thereto.

The reaction of anhydrous sugar alcohols with alkylene carbonates (especially ethylene carbonate) is, for example, carried out in the presence of an acid or alkali catalyst at 150°C to 200°C for 6 to 12 hours, more specifically at 150°C to 180°C for 8 hours. It may be performed for 1 to 10 hours, but is not particularly limited thereto.

In one embodiment, the content of the anhydrosugar alcohol ether diol-derived repeating units in the anhydrosugar alcohol-based polycarbonate diol is 15 to 80% by weight, based on a total of 100% by weight of the repeating units in the anhydrosugar alcohol-based polycarbonate diol. %, more specifically 20 to 70 wt%, more specifically 30 to 60 wt%, and even more specifically 40 to 55 wt%, but is not limited thereto. .

The type of carbonic acid diester is not particularly limited, but for example, dialkyl carbonate, diaryl carbonate, alkylene carbonate, or a combination thereof can be used.

In one embodiment, examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl n-butyl carbonate, and ethyl isobutyl carbonate, and the dia Examples of the alkylene carbonate include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and dim-cresyl carbonate, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1,4 -Pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate and neopentylene carbonate.

In one embodiment, the carbonic acid diester may be selected from dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, or a combination thereof, and more preferably, diphenyl carbonate.

In one embodiment, the content of the carbonic acid diester-derived repeating unit in the anhydrosugar alcohol-based polycarbonate diol is 10 to 50% by weight, based on a total of 100% by weight of the repeating units in the anhydrosugar alcohol-based polycarbonate diol. It may be, more specifically, 10 to 40% by weight, and more specifically 15 to 36% by weight, but is not limited thereto.

In one embodiment, the anhydrosugar alcohol-based polycarbonate diol may further include a repeating unit derived from an aliphatic diol.

The aliphatic diol may be a linear aliphatic diol having 2 to 10 carbon atoms or a branched aliphatic diol having 3 to 10 carbon atoms, and more specifically, a linear aliphatic diol having 2 to 8 carbon atoms or a branched aliphatic diol having 3 to 8 carbon atoms, More specifically, it may be a linear aliphatic diol having 2 to 6 carbon atoms or a branched aliphatic diol having 3 to 6 carbon atoms.

In one embodiment, the aliphatic diol is ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 , 8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, 2-methyl-1,3-propanediol, 2-ethyl -1,3-propanediol, 2-butyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,2 -diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, 2,2,4,4-tetramethyl-1,5- Pentanediol, 2-ethyl-1,6-hexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, It may be norbornane-2,3-dimethanol or a combination thereof.

In one embodiment, when the aliphatic diol-derived repeating unit is present in the anhydrosugar alcohol-based polycarbonate diol, its content ranges from 0.1 to 0.1% based on a total of 100% by weight of the repeating units in the anhydrosugar alcohol-based polycarbonate diol. It may be 35% by weight, more specifically 5 to 30% by weight, and even more specifically 15 to 25% by weight, but is not limited thereto.

In one embodiment, the anhydrosugar alcohol-based polycarbonate diol may include a repeating unit having the structure of Formula 1 below:

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently a linear alkylene group having 2 to 20 carbon atoms (more specifically, 2 to 10 carbon atoms, even more specifically 2 to 8 carbon atoms, even more specifically 2 to 4 carbon atoms) or 3 carbon atoms It is a branched alkylene group having to 20 carbon atoms (more specifically, 3 to 10 carbon atoms, more specifically 3 to 8 carbon atoms, and even more specifically 3 to 4 carbon atoms), and R ₁ and R ₂ may be the same or different from each other. there is.

In one embodiment, the repeating unit having the structure of Formula 1 may be derived from the reaction of an ether diol of anhydrosugar alcohol and a carbonic acid diester.

Additionally, in one embodiment, the anhydrosugar alcohol-based polycarbonate diol may further include a repeating unit having the structure of Formula 2 below:

[Formula 2]

In Formula 2,

R ₃ is a linear alkylene group having 2 to 10 carbon atoms (more specifically, 2 to 8 carbon atoms, and even more specifically 2 to 6 carbon atoms) or a linear alkylene group having 3 to 10 carbon atoms (more specifically, 3 to 8 carbon atoms, even more specifically is a branched alkylene group having 3 to 6 carbon atoms.

In one embodiment, the repeating unit having the structure of Formula 2 may be derived from the reaction of an aliphatic diol and a carbonic acid diester.

The number average molecular weight (Mn) of the anhydrosugar alcohol-based polycarbonate diol can be adjusted depending on the intended use, for example, the lower limit may be 250 or more, 500 or more, 600 or more, 700 or more, or 1,000 or more. , the upper limit may be 6,000 or less, 5,500 or less, 5,000 or less, 4,000 or less, or 3,000 or less, preferably 600 to 5,500, but is not limited thereto.

The polydispersity index (PDI) of the anhydrosugar alcohol-based polycarbonate diol is not particularly limited, but its lower limit is 1.0 or more, 1.1 or more, or 1.2 or more, and its upper limit may be 3.0 or less, 2.5 or less, or 2.0 or less. However, it is not limited to this. The polydispersity index is calculated as weight average molecular weight (Mw)/number average molecular weight (Mn), and can usually be determined by measurement using gel permeation chromatography (GPC).

In one embodiment, the Gardner color number of the anhydrosugar alcohol-based polycarbonate diol may be 1 or less. The Gardner color number can be measured using a spectrophotometer capable of measuring Gardner color number (for example, Konica Minolta's CM-5) according to ASTM D 1544, and the lower the Gardner color number, the closer it is to colorlessness. do.

In the production of the anhydrous sugar alcohol-based polycarbonate diol, an ether diol of anhydrous sugar alcohol and optionally an aliphatic diol are used as diol components, thereby essentially using anhydrous sugar alcohol to produce a solid anhydrous sugar alcohol-based polycarbonate diol. Compared to the process, the reaction temperature can be lowered, it is manufactured in a liquid form, and the reaction time can be shortened, preventing discoloration of the final produced anhydrosugar alcohol-based polycarbonate diol, thereby reducing the Gardner color number to 1 or less. It can be maintained.

The content of phenol as a by-product contained in the anhydrosugar alcohol-based polycarbonate diol is not particularly limited, but the smaller the content, the more preferable, and the amount of residual phenol in the anhydrosugar alcohol-based polycarbonate diol may be 50 ppm or less, which is the detection limit.

The anhydrosugar alcohol-based polycarbonate diol can be prepared by reacting a mixture containing the ether diol and carbonic acid diester of the anhydrosugar alcohol described above in the presence of a transesterification catalyst, wherein the mixture optionally further contains an aliphatic diol. It may also be included.

The anhydrous sugar alcohol-based polycarbonate diol used in the present invention is prepared by a method comprising reacting a mixture containing (i) an ether diol of anhydrous sugar alcohol and (ii) a carbonic acid diester in the presence of a transesterification catalyst. It can be prepared by, and in this case, the mixture may optionally further include an aliphatic diol. The ether diol, carbonic acid diester, and aliphatic diol of anhydrosugar alcohol that can be used herein are as described above.

In one embodiment, when producing the anhydrosugar alcohol-based polycarbonate diol, anhydrosugar alcohol itself is not used as a diol component. That is, in one embodiment, the anhydrosugar alcohol-based polycarbonate diol does not include a repeating unit derived from anhydrosugar alcohol itself.

When producing the anhydrosugar alcohol-based polycarbonate diol, the amount of anhydrosugar alcohol ether diol used may be 30 to 95% by weight, more specifically 40 to 90% by weight, based on 100% by weight of the total reaction starting material mixture. It may be, more specifically, 50 to 85% by weight, and even more specifically, 55 to 80% by weight, but is not limited thereto.

In addition, when producing the anhydrosugar alcohol-based polycarbonate diol, the amount of carbonic acid diester used may be 5 to 70% by weight, more specifically, 10 to 60% by weight, based on 100% by weight of the total reaction starting material mixture. It may be, more specifically, 15 to 50% by weight, and even more specifically 20 to 45% by weight, but is not limited thereto.

In addition, when aliphatic diol is additionally used as an optional component when producing the anhydrosugar alcohol-based polycarbonate diol, the amount used may be 0.1 to 30% by weight based on the total 100% by weight of the reaction starting material mixture, and may be more. Specifically, it may be 0.5 to 25% by weight, more specifically 1 to 20% by weight, and even more specifically 5 to 18% by weight, but is not limited thereto.

As the transesterification catalyst, metals generally considered to have transesterification ability, or compounds thereof such as hydroxides or salts, can be used without limitation.

Examples of catalyst metals include Group 1 metals such as lithium, sodium, potassium, rubidium, and cesium; Group 2 metals such as magnesium, calcium, strontium, and barium; Group 4 metals such as titanium and zirconium; Group 5 metals such as hafnium; Group 9 metals such as cobalt; Group 12 metals such as zinc; Group 13 metals such as aluminum; Group 14 metals such as germanium, tin, and lead; Group 15 metals such as antimony and bismuth; and lanthanide-based metals such as lanthanum, cerium, europium, and ytterbium. Among these, from the viewpoint of increasing the transesterification reaction rate, Group 1 metals or Group 2 metals are preferable, and Group 2 metals are especially more preferable.

Examples of using the salt compound of the catalyst metal include halide salts such as chloride, bromide, and iodide; Carboxylic acid salts such as acetate, formate, and benzoate; Sulfonic acid salts such as methanesulfonic acid, toluenesulfonic acid, and trifluoromethanesulfonic acid; Phosphorus-containing salts such as phosphate, hydrogen phosphate, and dihydrogen phosphate; and acetylacetonate salt. The catalyst metal may also be used as an alkoxide such as methoxide or ethoxide.

The catalyst metal, catalyst metal hydroxide, and catalyst metal salt compounds may be used individually or in combination of two or more types.

In one embodiment, when a compound containing a Group 1 metal is used as the transesterification catalyst, examples include sodium hydroxide, potassium hydroxide; cesium hydroxide; lithium hydroxide; sodium bicarbonate; sodium carbonate; potassium carbonate; cesium carbonate; lithium carbonate; sodium acetate; potassium acetate; cesium acetate; lithium acetate; sodium stearate; potassium stearate; cesium stearate; lithium stearate; sodium borohydride; Sodium phenyboride; sodium benzoate; potassium benzoate; cesium benzoate; lithium benzoate; disodium hydrogen phosphate; Dipotassium hydrogen phosphate; Lithium hydrogen phosphate; Disodium phenyl phosphate; Disodium, dipotassium, disesium or dilithium salts of bisphenol A; Examples include sodium salt, potassium salt, cesium salt, or lithium salt of phenol.

In one embodiment, when a compound containing a Group 2 metal is used as the transesterification catalyst, examples include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, and barium bicarbonate. , magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, or magnesium phenyl phosphate.

In producing anhydrosugar alcohol-based polycarbonate diol, the amount of transesterification catalyst used is 0.01 to 500 ppm, more specifically 0.1 to 100 ppm, and even more specifically 1 It may be, but is not limited to, ~50 ppm.

In the method for producing the anhydrous sugar alcohol-based polycarbonate diol, when reacting a mixture containing an ether diol of anhydrous sugar alcohol, a carbonic acid diester, and optionally an aliphatic diol, the reaction temperature is not particularly limited, but is usually 70° C. or higher, 100° C. It may be ℃ or higher, or 130℃ or higher, and usually may be 250℃ or lower, 230℃ or lower, 200℃ or lower, 180℃ or lower, 170℃ or lower, or 165℃ or lower. The reaction may be performed under normal or reduced pressure conditions (e.g., 10 kPa or less, 5 kPa or less, or 1 kPa or less), and is usually performed for 1 to 50 hours, 1 to 20 hours, or 1 to 10 hours. It is not limited to this.

In one embodiment, the diol component included as a repeating unit in the biodegradable polyester resin of the present invention may further include an aliphatic diol (“additional aliphatic diol”) other than the anhydrosugar alcohol-based polycarbonate diol described above.

In one embodiment, the additional aliphatic diol may be an aliphatic diol having 2 to 15 carbon atoms, more specifically, an aliphatic diol having 2 to 10 carbon atoms.

In one embodiment, the additional aliphatic diol content in the diol component may be greater than 65 mol% and less than 99.5 mol%, based on 100 mol% of the total diol component. If the content of the additional aliphatic diol in the diol component is less than the above level, a low molecular weight biodegradable polyester resin is produced due to a decrease in reactivity, and the intrinsic viscosity and glass transition temperature of the produced biodegradable polyester resin are lowered, and the heat resistance is reduced. This becomes very poor, and the mechanical properties (elongation) may also become poor. Conversely, if it exceeds the above level, the glass transition temperature of the produced biodegradable polyester resin may decrease and heat resistance may become poor.

In one embodiment, the additional aliphatic diol content in the diol component is greater than 65 mol%, greater than 66 mol%, greater than 68 mol%, greater than 70 mol%, greater than 72 mol%, based on 100 mol% of the total diol component. It may be 74 mol% or more or 75 mol% or more, and may also be less than 99.5 mol%, 99.4 mol% or less, 99 mol% or less, 98.5 mol% or less, 98 mol% or less, 97.5 mol% or less, or 97 mol% or less. It is not limited to this.

In one embodiment, the additional aliphatic diol is, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propane diol, 1,3-propane diol, 1,2-butane diol, 1,3 -Butane diol, 1,4-butane diol, 1,2-pentane diol, 1,3-pentane diol, 1,4-pentane diol, 1,5-pentane diol, 1,2-hexane diol, 1,3- Hexane diol, 1,4-hexane diol, 1,5-hexane diol, 1,6-hexane diol, neopentyl glycol, 1,2-cyclohexane diol, 1,3-cyclohexane diol, 1,4-cyclohexane Diol, 1,2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, tetramethylcyclobutane diol, tricyclodecane dimethanol, adamantanediol, 2,2- selected from the group consisting of dimethyl-1,3-propane diol, 2-ethyl-2-t-butyl-1,3-propane diol, 2,2,4-trimethyl-1,6-hexane diol, or combinations thereof. It may be, preferably butane diol, but is not limited thereto.

The intrinsic viscosity (IV) of the biodegradable polyester resin of the present invention is obtained by dissolving the biodegradable polyester resin in a mixture of phenol and tetrachloroethane (weight ratio = 50:50) to prepare a 0.5% by weight solution, and then using Ubbe Rod. It can be measured at 35°C using a viscometer, and the intrinsic viscosity value may be greater than 0.8, greater than 0.85 or greater than 0.9, less than 1.3, less than 1.25 or less than 1.2, for example greater than 0.8 to less than 1.3, 0.85 to 1.25. Or it may be 0.9 to 1.2. If the intrinsic viscosity value is 0.8 or less, heat resistance and mechanical properties may be poor, and if the intrinsic viscosity value is 1.3 or more, the color may be poor.

In addition, the biodegradable polyester resin of the present invention has a low rate of change in intrinsic viscosity and has excellent heat resistance. The rate of change in intrinsic viscosity can be calculated by, for example, manufacturing biodegradable polyester resin in the form of pellets, placing 1 g of biodegradable polyester pellets on an aluminum plate, leaving it in an oven at 65°C for 72 hours, then taking it out again and measuring the heat history at room temperature. After removal, the intrinsic viscosity can be measured to calculate the rate of change compared to the initial intrinsic viscosity. The rate of change in intrinsic viscosity of the biodegradable polyester resin of the present invention may be less than 30%, and preferably less than 20%. A lower rate of change in intrinsic viscosity of the biodegradable polyester resin means less denaturation by heat, that is, excellent heat resistance.

In addition, the biodegradable polyester resin of the present invention has high elongation and excellent mechanical properties. The elongation of the biodegradable polyester resin can be measured according to ASTM D638. The elongation of the biodegradable polyester resin of the present invention may be, for example, 500% or more, and more preferably 600% or more or 700% or more.

According to another aspect of the present invention, (1) subjecting a dicarboxyl component and a diol component to an esterification reaction or transesterification reaction; and (2) subjecting the reaction product obtained in step (1) to a polycondensation reaction, wherein the dicarboxylic component is greater than 20 mol% to 80 mol% based on 100 mol% of the total dicarboxylic component. less than an aliphatic dicarboxylic compound and less than 20 mol% to less than 80 mol% of an aromatic dicarboxylic compound, wherein the aliphatic dicarboxylic compound comprises adipic acid or an ester thereof, and the diol component comprises a diol A method for producing a biodegradable polyester resin is provided, which includes more than 0.5 mol% to less than 35 mol% of anhydrosugar alcohol-based polycarbonate diol based on 100 mol% of the total components.

The dicarboxyl component and the diol component including anhydrosugar alcohol-based polycarbonate diol used in the biodegradable polyester resin production method of the present invention are as described above.

In addition, the diol component may further include an aliphatic diol (“additional aliphatic diol”) other than anhydrosugar alcohol-based polycarbonate diol, and such additional aliphatic diol is as described above.

According to one specific example, in step (1), the reaction molar ratio of the diol component to the dicarboxyl component (total number of moles of diol component/total number of moles of dicarboxylic component) is added to 1.0 to 1.5, and then 150 Esterification reaction at a temperature of 250°C to 250°C, preferably 200 to 250°C, more preferably 200 to 240°C, and pressure conditions (reduced pressure conditions) of 0.1 to 3.0 kgf/cm2, preferably 0.2 to 2.0 kgf/cm2 Alternatively, a transesterification reaction may be performed.

Here, if the reaction molar ratio of the diol component to the dicarboxyl component (total number of moles of diol component/total number of moles of dicarboxylic component) is less than 1, unreacted dicarboxylic component remains during the polymerization reaction and causes the polyester resin to There is a risk that mechanical properties and color may deteriorate, and if it exceeds 1.5, the polymerization reaction rate may be too slow and the productivity of the polyester resin may decrease.

The esterification reaction time or transesterification reaction time is usually about 1 to 5 hours, preferably about 3 to 4 hours, and may vary depending on the reaction temperature and pressure, and the reaction molar ratio of the diol component to the dicarboxyl component.

A catalyst is not required in step (1), but in one embodiment, a catalyst may be used to shorten the reaction time. The esterification reaction or transesterification reaction in step (1) may be performed in a batch or continuous manner, and each reaction raw material may be added separately.

According to one embodiment, in step (2), a polycondensation catalyst and a stabilizer may be added to the reaction product of the esterification reaction or transesterification reaction before the start of the polycondensation reaction. As the polycondensation catalyst, polycondensation catalysts commonly used in this field can be used without limitation, for example, selected from titanium-based compounds, germanium-based compounds, antimony-based compounds, aluminum-based compounds, and tin-based compounds. One type or a mixture of two or more types can be used. As the stabilizer added to the polycondensation reaction, phosphorus-based compounds can generally be used, for example, phosphoric acid, trimethyl phosphate, triethyl phosphate, or mixtures thereof.

The polycondensation reaction is carried out at a temperature of 200 to 280°C, preferably 210 to 260°C, more preferably 220 to 240°C, and reduced pressure of 500 to 0.1 mmHg. The reduced pressure conditions are for removing by-products of the polycondensation reaction.

In one embodiment, (a) (i) a dicarboxylic component comprising adipic acid and dimethyl terephthalate and an aliphatic dicarboxylic compound other than adipic acid; and (ii) a polymerization reaction product containing anhydrosugar alcohol-based polycarbonate diol and, if necessary, a diol component containing other aliphatic diols, at a pressure of 0.1 to 3.0 kgf/cm2 and a temperature of 150 to 250°C. Esterification or transesterification reaction is carried out for an average residence time of 5 hours. (b) Next, the esterification or transesterification reaction product is subjected to a polycondensation reaction under reduced pressure conditions of 500 to 0.1 mmHg and a temperature of 200 to 280°C for an average residence time of 1 to 10 hours to produce the poly according to the present invention. Ester resin can be manufactured. Preferably, the final vacuum degree of the polycondensation reaction is 1.0 mmHg or less, and the esterification or transesterification reaction may be performed under an inert gas atmosphere.

Compared to conventional biodegradable polyester resins such as PBAT resin, the biodegradable polyester resin according to the present invention not only has significantly improved heat resistance and mechanical properties (e.g., elongation), but also further improves biodegradability, so it can be molded. Therefore, it can be usefully used in various products.

Therefore, according to another aspect of the present invention, a molded article comprising the biodegradable polyester resin according to the present invention is provided. In the present invention, 'molded product' refers to a molded product obtained by extrusion, injection, or other known processing.

Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, the scope of the present invention is not limited by these examples.

[Example]

<Manufacture of anhydrosugar alcohol-alkylene glycol>

Preparation Example A1: Preparation of isosorbide-ethylene glycol (5 mole adduct of isosorbide to ethylene oxide)

1,460 g of isosorbide and 3.0 g of potassium hydroxide were placed in a reactor capable of pressurization and heating, the inside of the reactor was replaced with nitrogen, heated to 100°C, and moisture in the reactor was removed through vacuum decompression. Afterwards, 2,200 g of ethylene oxide was slowly added and the reaction was carried out at 100°C to 140°C for 5 to 6 hours. At this time, the reaction temperature was adjusted not to exceed 140°C. When the reaction was completed, the reaction product was cooled to 50°C, 40 g of metal adsorbent (AMBOSOL MP20) was added, heated again, and stirred at 100°C to 120°C for 1 to 5 hours to remove residual metal ions (at this time, nitrogen was added or vacuum decompression was performed). After confirming that no metal ions are detected, the temperature is cooled to 60°C to 90°C and the remaining by-products are removed through filtration to produce a transparent liquid in which the hydrogens of the hydroxy groups at both ends of isosorbide are replaced with hydroxyethyl groups. 3,500 g of isosorbide-ethylene glycol (5 mole adduct of isosorbide to ethylene oxide) was obtained.

Preparation Example A2: Preparation of isosorbide-propylene glycol (5 mole propylene oxide adduct of isosorbide)

Except that 2,900 g of propylene oxide was used instead of ethylene oxide, the same method as Preparation Example A1 was performed to produce transparent liquid isosorbide-propylene in which the hydrogens of the hydroxy groups at both ends of isosorbide were replaced with hydroxypropyl groups. 4,200 g of glycol (5 molar propylene oxide adduct of isosorbide) was obtained.

<Manufacture of anhydrosugar alcohol-based polycarbonate diol>

Preparation Example B1: Preparation of anhydrosugar alcohol-based polycarbonate diol using isosorbide-ethylene glycol

500 g of isosorbide-ethylene glycol and 117.5 g of diphenyl carbonate obtained in Preparation Example A1 were added to a five-necked flask connected to a nitrogen gas pipe and a vacuum pump for pressure reduction equipped with a trap for removing by-products and containing a stirrer, thermometer, and heater. , heated to 100°C under a nitrogen atmosphere, and when melting of the reaction raw materials was confirmed, 5.0 mg of magnesium acetate tetrahydrate was added and stirring was started. The nitrogen atmosphere was maintained until the reaction temperature reached 120°C, and then the reaction system was maintained as a closed system and heated to 155°C (at this time, if the nitrogen atmosphere is continuously maintained, the ratio changes due to sublimation of the reaction raw materials and the desired molecular weight is reached. Be careful because it will not be possible to reach). When the set temperature is reached, the reaction proceeds while maintaining the temperature for 1 hour, and after confirming that the by-product phenol is refluxed through the reactor wall, the pressure is reduced to 100 Torr to 120 Torr within 30 minutes using a vacuum pump, and the produced phenol The reaction proceeded for about 1 to 2 hours while removing. When the amount of phenol generated reached 70-80% of the theoretical amount, the pressure was reduced to 5 Torr to 10 Torr, and the reaction was further continued for 1 to 2 hours. After about 95% of the phenol was removed, nitrogen was bubbled into the reaction product for 1 to 2 hours while maintaining reduced pressure to completely remove the remaining remaining phenol. Through this, about 498 g of anhydrosugar alcohol-based polycarbonate diol was obtained.

The obtained anhydrosugar alcohol-based polycarbonate diol was a transparent liquid with a Gardner color number of 1 or less and a hydroxyl value of 185.9. The number average molecular weight calculated from the hydroxyl value was 603.5, the measured PDI was 1.64, and the residual phenol amount was measured below the detection limit of 50 ppm.

Preparation Example B2: Preparation of anhydrosugar alcohol-based polycarbonate diol using isosorbide-propylene glycol

Except that 500 g of isosorbide-propylene glycol obtained in Preparation Example A2 was used instead of the isosorbide-ethylene glycol obtained in Preparation Example A1, and the content of diphenyl carbonate was changed from 117.5 g to 70 g. The same method as Preparation Example B1 was performed to obtain about 423 g of anhydrosugar alcohol-based polycarbonate diol.

The obtained polycarbonate diol was a transparent liquid with a Gardner color number of 1 or less and a hydroxyl value of 180.6. The number average molecular weight converted from the hydroxyl value was 621.1, the measured PDI was 1.66, and the residual phenol amount was measured below the detection limit of 50 ppm.

<Manufacture of biodegradable polyester resin>

Examples 1 to 9 and Comparative Examples 1 to 7

Into a 15 L melt condensation reactor, reactants with the composition shown in Table 1 below were added, 550 ppm of titanium-based catalyst based on the acid component (dimethyl terephthalate, DMT) was added, and esterification was carried out while raising the temperature to 210°C. The reaction proceeded, and the alcohol produced as a by-product was removed. When more than 80% of the theoretical amount of alcohol leaked out of the system, 750 ppm of titanium-based catalyst and antioxidant based on the acid component (DMT) were added, the temperature was raised to 245°C, and the pressure of the reaction system was increased to 1 mmHg. By gradually reducing the pressure, the biodegradable polyester resins of Examples 1 to 9 and Comparative Examples 1 to 7 were prepared.

<Physical property evaluation>

The physical properties of the biodegradable polyester resins of Examples 1 to 9 and Comparative Examples 1 to 7 were measured by the following method, and the results are shown in Table 1 below.

(1) Intrinsic viscosity (IV): Dissolve biodegradable polyester resin in a mixture of phenol and tetrachloroethane (weight ratio = 50:50) to prepare a 0.5% by weight solution, and then measure the intrinsic viscosity at 35°C using an Ubberod viscometer. Viscosity was measured.

(2) Melting point: Using a differential scanning calorimeter (DSC), the temperature was raised at a temperature increase rate of 10°C/min, then cooled to remove heat history, and then the temperature was raised again to measure the melting point.

(3) Glass transition temperature: Measure the glass transition temperature (Tg) when the biodegradable polyester resin is heated at a temperature increase rate of 10℃/min, cooled to room temperature, and then scanned again at a temperature increase rate of 10℃/min. did.

(4) Intrinsic viscosity change rate (heat resistance evaluation item): After producing biodegradable polyester resin in the form of pellets, place 1 g of biodegradable polyester pellets on an aluminum plate, leave in an oven at 65°C for 72 hours, take out again, and cool at room temperature. After removing the heat history, the intrinsic viscosity was measured and the rate of change compared to the initial intrinsic viscosity was calculated.

(5) Elongation: Elongation was measured according to ASTM D638.

(6) Biodegradability: After freezing and pulverizing the biodegradable polyester resin chips, the frozen and pulverized resin chips were placed in compost maintained at a temperature of 30 to 40°C and 55 to 60% humidity to measure biodegradation under compost conditions. The biodegradability was measured at regular time intervals (after 1 month, 2 months, and 3 months) after landfill. The standard soil and landfill conditions used at this time followed ASTM D 5338-92.

<Ingredients Description>

- ISB-EO carbonate diol: anhydrosugar alcohol-based polycarbonate diol obtained in Preparation Example B1

- ISB-PO carbonate diol: anhydrosugar alcohol-based polycarbonate diol obtained in Preparation Example B2

- DMT: dimethyl terephthalate

As shown in Table 1, in Examples 1 to 9 according to the present invention, by including anhydrosugar alcohol-based polycarbonate diol in a specific content range, the glass transition temperature of the resin is high and heat resistance (change in intrinsic viscosity) is excellent. The mechanical properties (elongation) and biodegradability were also excellently maintained.

On the other hand, in the case of a conventional biodegradable polyester resin (PBAT) resin in which anhydrosugar alcohol-based polycarbonate diol is not used (Comparative Example 1), the glass transition temperature is lowered and the intrinsic viscosity change rate is 30% or more to less than 50%. was high, and heat resistance was poor.

In addition, in the case of a biodegradable polyester resin in which anhydrosugar alcohol-based polycarbonate diol was used in excess of the range specified in the present invention (Comparative Examples 2 and 3), a low molecular weight biodegradable polyester resin was obtained due to a decrease in reactivity. , the intrinsic viscosity and glass transition temperature were lowered, the intrinsic viscosity change rate was high from 50% to 100%, so heat resistance was very poor, and the elongation was low at less than 600%, so the mechanical properties were also poor, and the anhydrosugar alcohol-based polycarbonate diol was In the case of biodegradable polyester resin used below the range specified in the present invention (Comparative Examples 4 and 5), the glass transition temperature is lowered and the intrinsic viscosity change rate is high at 30% or more to less than 50%, resulting in poor heat resistance. there was.

In addition, in the case of a biodegradable polyester resin in which the aromatic dicarboxylic compound was used in excess of the range specified in the present invention (Comparative Example 6), biodegradability was drastically reduced, mechanical properties (elongation) were very poor, and aliphatic dicarboxylic compounds were used. In the case of a biodegradable polyester resin in which the reboxyl compound was used in excess of the range specified in the present invention (Comparative Example 7), the glass transition temperature was lowered and the intrinsic viscosity change rate was very high at 50% or more to 100%, resulting in very high heat resistance. It became worse, and the mechanical properties (elongation) also became worse.

Claims (16)

repeating units derived from dicarboxylic moieties; and repeating units derived from diol components,
The dicarboxylic component includes 30 mol% to 70 mol% of an aliphatic dicarboxylic compound and 30 mol% to 70 mol% of an aromatic dicarboxylic compound, based on 100 mol% of the total dicarboxylic component,
The aliphatic dicarboxylic compound is adipic acid or an ester thereof,
The diol component includes 3 mol% to 25 mol% of anhydrosugar alcohol-based polycarbonate diol, based on 100 mol% of the total diol component,
The anhydrosugar alcohol-based polycarbonate diol includes (1) a repeating unit derived from the ether diol of isosorbide; and (2) repeating units derived from carbonic acid diesters,
The ether diol of isosorbide is prepared by addition reaction of isosorbide and alkylene oxide,
Biodegradable polyester resin. The biodegradable polyester resin according to claim 1, wherein the aromatic dicarboxylic compound includes an aromatic dicarboxylic acid having 8 to 16 carbon atoms or an ester thereof. The method of claim 2, wherein the aromatic dicarboxylic compound is phthalic acid or its ester, terephthalic acid or its ester, isophthalic acid or its ester, 1,5-naphthalenedicarboxylic acid or its ester, 2,6-naphthalenedicarboxylic acid. or esters thereof, diphenic acid or esters thereof, p-phenylene diacetic acid or esters thereof, o-phenylene diacetic acid or esters thereof, and combinations thereof. The biodegradable polyester resin according to claim 1, wherein the alkylene oxide is selected from the group consisting of linear alkylene oxides having 2 to 20 carbon atoms or branched alkylene oxides having 3 to 20 carbon atoms. The biodegradable polyester resin according to claim 1, wherein the carbonic acid diester is selected from dialkyl carbonate, diaryl carbonate, alkylene carbonate, or combinations thereof. The biodegradable polyester resin of claim 1, wherein the anhydrosugar alcohol-based polycarbonate diol further comprises a repeating unit derived from an aliphatic diol. The biodegradable polyester resin according to claim 1, wherein the anhydrosugar alcohol-based polycarbonate diol contains a repeating unit having the structure of the following formula (1):
[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently a linear alkylene group having 2 to 20 carbon atoms or a branched alkylene group having 3 to 20 carbon atoms, and R ₁ and R ₂ may be the same or different from each other. The biodegradable polyester resin according to claim 6, wherein the anhydrosugar alcohol-based polycarbonate diol further comprises a repeating unit having the structure of the following formula (2):
[Formula 2]

In Formula 2, R ₃ is a linear alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms. The method of claim 1, wherein the diol component further includes an aliphatic diol other than the anhydrosugar alcohol-based polycarbonate diol, and the content of the aliphatic diol other than the anhydrosugar alcohol-based polycarbonate diol is based on 100 mol% of the total of the diol component. 75 mol% to 97 mol% biodegradable polyester resin. The method of claim 9, wherein the aliphatic diol other than anhydrosugar alcohol-based polycarbonate diol is ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propane diol, 1,3-propane diol, 1,2-butane diol, 1,3-butane diol, 1,4-butane diol, 1,2-pentane diol, 1,3-pentane diol, 1,4-pentane diol, 1,5-pentane diol, 1,2-hexane diol, 1 ,3-hexane diol, 1,4-hexane diol, 1,5-hexane diol, 1,6-hexane diol, neopentyl glycol, 1,2-cyclohexane diol, 1,3-cyclohexane diol, 1,4 -Cyclohexane diol, 1,2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, tetramethylcyclobutane diol, tricyclodecane dimethanol, adamantanediol, 2 ,2-dimethyl-1,3-propane diol, 2-ethyl-2-t-butyl-1,3-propane diol, 2,2,4-trimethyl-1,6-hexane diol, or a group consisting of combinations thereof A biodegradable polyester resin selected from. (1) subjecting the dicarboxyl component and the diol component to an esterification reaction or transesterification reaction; and
(2) subjecting the reaction product obtained in step (1) to a polycondensation reaction,
The dicarboxylic component includes 30 mol% to 70 mol% of an aliphatic dicarboxylic compound and 30 mol% to 70 mol% of an aromatic dicarboxylic compound, based on 100 mol% of the total dicarboxylic component,
The aliphatic dicarboxylic compound is adipic acid or its ester,
The diol component includes 3 mol% to 25 mol% of anhydrosugar alcohol-based polycarbonate diol, based on 100 mol% of the total diol component,
The anhydrosugar alcohol-based polycarbonate diol includes (1) a repeating unit derived from the ether diol of isosorbide; and (2) repeating units derived from carbonic acid diesters,
The ether diol of isosorbide is prepared by addition reaction of isosorbide and alkylene oxide,
Method for producing biodegradable polyester resin. The method of claim 11, wherein the diol component further includes an aliphatic diol other than the anhydrosugar alcohol-based polycarbonate diol, and the content of the aliphatic diol other than the anhydrosugar alcohol-based polycarbonate diol is based on 100 mol% of the total of the diol component. , 75 mol% to 97 mol%, a method for producing a biodegradable polyester resin. The method of claim 11, wherein in step (1), the reaction molar ratio of the diol component to the dicarboxyl component (total number of moles of diol component/total number of moles of dicarboxylic component) is 1.0 to 1.5. method. A molded article comprising the biodegradable polyester resin according to any one of claims 1 to 10. delete delete