WO2016186470A1

WO2016186470A1 - Polylactic acid copolymer having significantly improved elasticity, and preparation method therefor

Info

Publication number: WO2016186470A1
Application number: PCT/KR2016/005349
Authority: WO
Inventors: 진선철; 권영도; 신경무
Original assignee: 주식회사 삼양사
Priority date: 2015-05-21
Filing date: 2016-05-20
Publication date: 2016-11-24
Also published as: KR101606480B1

Abstract

The present invention relates to a polylactic acid copolymer having significantly improved elasticity, and a preparation method therefor. More specifically, the present invention relates to a polylactic acid copolymer having significantly improved elasticity compared to a polylactic acid homopolymer, and a preparation method therefor, the polylactic acid copolymer comprising: a monocyclic compound having, as a repeating unit, (A) a lactic acid and (B) two or more hydroxy-terminated poly (aliphatic ether) chains; a polycyclic compound; or a fused cyclic compound.

Description

Polylactic acid copolymer with remarkably improved elasticity and preparation method thereof

The present invention relates to a polylactic acid copolymer with remarkably improved elasticity and a method for preparing the same, and more particularly, having two or more (A) lactic acid and (B) hydroxy-terminated poly (aliphatic ether) chains as repeating units. By including a monocyclic, polycyclic or fused cyclic compound, the present invention relates to a polylactic acid copolymer having a significantly improved elasticity as compared to a polylactic acid homopolymer and a method for producing the same.

Research on environmentally friendly biomass to reduce carbon dioxide emission, which is a major cause of global warming, and to replace limited resources and expensive petroleum raw materials is being actively conducted. For example, polylactic acid (PLA) resins obtained by fermenting corn starch are attracting attention as main raw materials of eco-friendly materials for the replacement of general purpose resins due to their low price and ease of supply. It is also widely used as a surgical suture or a sustained release polymer of a drug.

The PLA polymerization method is a method of obtaining PLA through condensation polymerization directly from lactic acid, a method of obtaining high molecular weight PLA through solid phase polymerization from low molecular weight PLA, and PLA through azeotropic condensation using a low boiling solvent. The method of obtaining is known, and recently, there is a high interest in PLA synthesis through ring opening polymerization, which has an advantage of controlling optical purity and obtaining PLA of high molecular weight (for example, Korean Patent Laid-Open Publication No. 10-A). 2011-0064122).

However, polylactic acid homopolymers have limitations in the field of practical applicability because they do not have sufficient mechanical properties such as heat resistance and impact resistance. In particular, it is not satisfactory in the elasticity required for use in general textile products or film products.

Therefore, there is a need for the development of a new PLA copolymer having improved elasticity compared to the polylactic acid homopolymer.

The present invention is to solve the problems of the prior art as described above, it is a technical problem to provide a novel polylactic acid copolymer and a method for producing the same significantly improved compared to the polylactic acid homopolymer.

To solve the above technical problem, the present invention provides a monocyclic, polycyclic or fused cyclic compound having two or more (A) lactic acid and (B) hydroxy-terminated poly (aliphatic ether) chain as a repeating unit. It provides a polylactic acid copolymer comprising.

According to another aspect of the invention, (1) prepolymerizing lactic acid, lactic acid oligomer or lactide; And (2) copolymerizing the lactic acid prepolymer obtained in step (1) with a monocyclic, polycyclic or fused cyclic compound having two or more hydroxy-terminated poly (aliphatic ether) chains. To provide a method for producing a polylactic acid copolymer is provided.

According to another aspect of the present invention, a processed resin article prepared using the polylactic acid copolymer is provided.

Since the novel polylactic acid copolymers according to the present invention are biodegradable and exhibit significantly improved elasticity (i.e., significantly lower glass transition temperature and modulus than Homo-PLA) compared to polylactic acid homopolymers (Homo-PLA), In particular, the present invention can be suitably used for resin processed products such as textile products or film materials (especially surgical sutures, medical films, etc.) that require elasticity.

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

The present invention provides a polylactic acid copolymer comprising a monocyclic, polycyclic or fused cyclic compound having two or more (A) lactic acid and (B) hydroxy-terminated poly (aliphatic ether) chain as repeating units. to provide.

As used herein, the term "aliphatic ether" refers to a group having an ether bond (-O-) at one end of a linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon, for example-(saturated or It may have a structure of unsaturated alkyl) -O-, but is not limited thereto.

The lactic acid repeating unit included in the polylactic acid copolymer of the present invention has the following structure in the copolymer.

The lactic acid repeating unit may be introduced into the copolymer by lactic acid, lactic acid oligomers or lactide (cyclic dimers of lactic acid).

The content of lactic acid included as a repeating unit in the polylactic acid copolymer of the present invention may be 70 to 99.9% by weight, based on 100% by weight of the copolymer, preferably 85 to 99.9% by weight, more preferably 90 It may be ~ 99.5% by weight, but is not limited thereto. If the lactic acid content in the copolymer is too small, there may be a problem that the degree of polymerization or biodegradation of the PLA copolymer is worse, on the contrary, if the amount of lactic acid in the copolymer is too large, there may be a problem that the elasticity of the PLA copolymer does not reach the desired level.

Monocyclic, polycyclic or fused cyclic compounds having two or more hydroxy-terminated poly (aliphatic ether) chains, which are included as repeating units in the polylactic acid copolymer of the present invention (hereinafter referred to as “hydroxy-polyether Cyclic compounds ”are compounds having a structure in which two or more (eg 2 to 4) hydroxy-terminated poly (aliphatic ether) chains are linked to a monocyclic, polycyclic or fused cyclic central site As such, at least two hydroxyl groups are present at both ends.

The content of the hydroxy-polyether cyclic compound included as a repeating unit in the polylactic acid copolymer of the present invention may be 0.1 to 30% by weight based on 100% by weight of the copolymer, preferably 0.2 to 15% by weight. %, More preferably 0.5 to 10% by weight, but is not limited thereto. When the amount of hydroxy-polyether cyclic compound in the copolymer is too small, there may be a problem that the elasticity of the PLA copolymer does not reach the desired level. On the contrary, when the amount of hydroxy-polyether cyclic compound is too low, the degree of polymerization or biodegradability of the PLA copolymer may be deteriorated. Can be.

According to an embodiment of the present invention, the monocyclic, polycyclic or fused cyclic compound having two or more hydroxy-terminated poly (aliphatic ether) chains may have a structure represented by the following Chemical Formula 1:

[Formula 1]

HO- (RO) _n -A- (O-R ') _m -OH

In Chemical Formula 1,

R and R 'each independently represent a substituted or unsubstituted divalent linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group;

n and m are each independently an integer from 2 to 100;

A is a substituted or unsubstituted divalent aliphatic or aromatic monocyclic, polycyclic or fused cyclic group, or a substituted or unsubstituted divalent monohetero containing at least one atom selected from N, O and S. Cyclic, polyheterocyclic or fused heterocyclic groups, which may comprise two or more (eg, 2-4) bonds selected from the group consisting of ether bonds, thioether bonds, ester bonds, ketone bonds and urethane bonds Can be.

As used herein, the term "substituted" or "substituted" means that a hydrogen atom has a halogen atom (eg, Cl or Br), a hydroxy group, an alkyl group having 1 to 13 carbon atoms (eg, methyl, ethyl or propyl, etc.), having 1 to 13 carbon atoms. It means what is substituted by substituents, such as an alkoxy group (for example, methoxy, ethoxy, or propoxy), or an aryl group (for example, phenyl, chlorophenyl, tolyl, etc.) of 6 to 10 carbon atoms, a combination thereof.

More specifically, in Chemical Formula 1,

R and R 'each independently represent a substituted or unsubstituted divalent, linear, branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms (more specifically, 2 to 6);

n and m are each independently integers of 10 to 80 (more specifically, 20 to 80);

A is a substituted or unsubstituted divalent, aliphatic having 5 to 30 carbon atoms or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 30 carbon atoms, or an atom selected from N, O and S Substituted or unsubstituted, divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic group having 5 to 30 ring atoms, and includes an ether bond, a thioether bond, an ester bond, a ketone bond, and the like. It may include two or more bonds selected from the group consisting of urethane bonds.

More specifically, in Chemical Formula 1,

R and R 'each independently represent a substituted or unsubstituted divalent alkyl group having 2 to 10 carbon atoms (more specifically, 2 to 6),

A is a substituted or unsubstituted divalent, unsubstituted, aromatic monocyclic, polycyclic, or fused cyclic group having 6 to 20 carbon atoms in total, or includes one or more atoms selected from N, O and S A divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic group having 5 to 20 total ring atoms and a bond selected from the group consisting of ether bonds, thioether bonds, ester bonds, ketone bonds and urethane bonds It may include two or more.

According to a more preferred embodiment of the present invention, the monocyclic, polycyclic or fused cyclic compound having two or more hydroxy-terminated poly (aliphatic ether) chain may have a structure represented by the following formula (2) :

[Formula 2]

HO- (RO) _n -L-Cy-L '-(O-R') _m -OH

In Chemical Formula 2,

R, R ', n and m are as defined in Formula 1 above;

L and L 'are each independently selected from the group consisting of ether bonds, thioether bonds, ester bonds, ketone bonds and urethane bonds;

Cy is a substituted or unsubstituted divalent aliphatic or aromatic monocyclic, polycyclic or fused cyclic group, or a substituted or unsubstituted divalent monohetero containing one or more atoms selected from N, O and S. Cyclic, polyheterocyclic or fused heterocyclic groups.

More specifically, in Formula 2,

L and L 'are each independently selected from the group consisting of ester bonds, ketone bonds and urethane bonds;

Cy is a substituted or unsubstituted divalent, aliphatic having 5 to 30 carbon atoms or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 30 carbon atoms, or an atom selected from N, O and S Substituted or substituted, unsubstituted divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic groups having 5 to 30 ring atoms in total.

More specifically, in Chemical Formula 2,

L and L 'are each independently selected from the group consisting of ester bonds and ketone bonds;

Cy is substituted or unsubstituted, divalent, unsubstituted, aromatic monocyclic, polycyclic, or fused cyclic group having 6 to 20 carbon atoms in total, or includes one or more atoms selected from N, O and S Divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic groups having from 5 to 20 ring atoms in total.

There is no particular limitation on the method for preparing a monocyclic, polycyclic or fused cyclic compound having two or more of the above hydroxy-terminated poly (aliphatic ether) chains, which are included as repeating units in the polylactic acid copolymer of the present invention. . According to one embodiment of the present invention, the hydroxy-terminated poly (aliphatic ether) compound may be prepared by reacting a monocyclic, polycyclic or fused cyclic diacyl halide, but is not limited thereto.

In addition to the lactic acid and hydroxy-polyether cyclic compound repeating units described above, the copolymer of the present invention may further include one or more additional copolymerizing units within the scope of achieving the object of the present invention. There is no particular limitation on the type of copolymerization unit of.

There is no particular limitation on the method or condition for prepolymerizing lactic acid, lactic acid oligomer (for example, number average molecular weight (Mn) 100 to 5,000) or lactide in step (1), and generally known methods or conditions may be used. According to one embodiment of the present invention, the present invention is not limited thereto, but in the presence of a catalyst, lactic acid, lactic acid oligomer or lactide is heated at elevated temperature (eg, 100 to 210 ° C, more specifically 110 to 150 ° C) and reduced pressure conditions. The prepolymer can be formed by reacting for an appropriate time (for example, 0.1 to 2 hours, more specifically, 0.2 to 1 hour). The number average molecular weight (Mn) of the obtained lactic acid prepolymer may be, for example, 2,000 to 10,000, but is not limited thereto.

Catalysts that can be used for the prepolymerization are, for example, zinc oxide, antimony oxide, antimony chloride, lead oxide, calcium oxide, aluminum oxide, iron oxide, calcium chloride, zinc acetate, paratoluene sulfonic acid, tin tin chloride, a sulfate agent Tin tin, first tin oxide, second tin oxide, first tin octanoate, tetraphenyl tin, tin powder, titanium tetrachloride or mixtures thereof. The catalyst may be used in an amount of 0.0005 to 5 parts by weight, preferably 0.003 to 1 part by weight based on 100 parts by weight of lactic acid, lactic acid oligomer or lactide. If the amount of the catalyst is used too little, the reaction rate is slow. On the contrary, if the amount is used too much, the residual catalyst may discolor the product or degrade the physical properties.

In step (2), the lactic acid prepolymer obtained in step (1) and the hydroxy-polyether cyclic compound are copolymerized. Examples of the hydroxy-polyether cyclic compound usable in step (2) include those described above. The copolymerization method and conditions in step (2) are also not particularly limited, and conventionally known lactic acid copolymer production methods and conditions may be used. Although not limited thereto, according to one embodiment of the present invention, an initiator and a hydroxy-polyether cyclic compound are added to the resultant mixture (including the catalyst) of step (1), and heated in a nitrogen atmosphere (eg, A copolymer can be formed by making it react by 100-210 degreeC, more specifically 110-150 degreeC, and pressure-reduced conditions (for example, 0.5 to 4 hours, More specifically, 1 to 3 hours). The number average molecular weight (Mn) of the obtained polylactic acid copolymer may be, for example, 50,000 to 300,000, but is not limited thereto.

Initiators that may be used in the copolymerization may be aliphatic alcohols (eg, linear or branched aliphatic alcohols having 6 to 20 carbon atoms, more specifically 1-dodecanol, 1-octanol, or mixtures thereof, etc.). . The initiator may be used in an amount of 0.0005 to 5 parts by weight, preferably 0.003 to 0.1 parts by weight based on 100 parts by weight of lactic acid, lactic acid oligomer or lactide. If the amount of the initiator is too small, there may be a problem in controlling the molecular weight of the copolymer, on the contrary too much, there may be a problem in the degree of polymerization of the copolymer.

The polylactic acid copolymer of the present invention as described above is biodegradable and exhibits significantly improved elasticity compared to polylactic acid homopolymers, so that resin processed products, in particular textile products or film materials (especially medical materials that require elasticity) As a surgical suture, a medical film, etc.) can be used very well.

Thus, according to another aspect of the present invention, there is provided a resin processed article produced using the polylactic acid copolymer of the present invention.

The method for producing a resin processed product using the polylactic acid copolymer of the present invention is not particularly limited, and the method generally used for processing the copolymer resin can be used as it is or as appropriately modified.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to these.

[[ 실시예Example ]]

실시예Example 1~3: 1 to 3: 폴리락트산Polylactic acid 공중합체의 제조 Preparation of Copolymer

Lactide Prepolymer ( PLA Manufacturing

After 1.5 kg of lactide was added to the 3L reactor, water was removed for at least 12 hours under reduced pressure of less than 1 torr. After the water removal process, a catalyst was added thereto, followed by stirring at 120 ° C. for 2 hours to prepare a lactide prepolymer. Tin octanoate (Sn (Oct) ₂ , Sigma Aldrich) was used as the catalyst.

PTMEG derivative Comonomer Produce

On the other hand, according to the following reaction to prepare a comonomer for polylactic acid copolymer.

Poly (tetrahydrofuran) (100 g, 34.5 mmol) was dissolved by heating to 100 ° C. Terephthaloyl chloride (3.5 g, 17.2 mmol) was added to the dissolved poly (tetrahydrofuran) and triethylamine (2.4 ml, 17.2 mmol) was added to THF (7.2 ml) while stirring. The dissolved solution was dropped for 30 minutes to 1 hour. After completion of the addition, the reaction was performed at room temperature for 1 to 2 hours. The reaction product was extracted with ethyl acetate (EA) and water, and then treated with MgSO ₄ to remove water and blow off the solvent. Thereafter, the resultant was dried under vacuum at 80 ° C. under heating to obtain a PTMEG derivative of the above reaction formula as a comonomer (n = 60).

Polylactic acid Preparation of Copolymer

After the prepared lactide prepolymer (PLA) was stirred for 2 hours in a nitrogen atmosphere, the prepared PTMEG derivative comonomer was added according to the comonomer content shown in Table 1 below, and polymerization was performed at 180 ° C.

NMR spectra were measured using an Avance DRX 300 manufactured by Bruker to confirm the synthesis of the copolymer. From the results of NMR analysis, it was confirmed that the peak attributable to the -OH group at the terminal of the PTMEG derivative comonomer observed at 3.6 to 3.7 ppm was observed at 4.1 to 4.2 ppm in the polylactic acid copolymer. This was shifted because the -OH group terminal of the PTMEG derivative comonomer was changed into an ester group through copolymerization, thereby changing the electronic environment, and it was confirmed that PLA and PTMEG derivative comonomer were copolymerized.

실시예Example 4~6: 4 ~ 6: 폴리락트산Polylactic acid 공중합체의 제조 Preparation of Copolymer

PTMEG derivative Comonomer Produce

A comonomer for polylactic acid copolymer was prepared according to the following reaction.

Poly (tetrahydrofuran) (100 g, 34.5 mmol) was dissolved by heating to 100 ° C. Phthaloyl chloride (3.5 g, 17.2 mmol) is added to the dissolved poly (tetrahydrofuran) and triethylamine (2.4 ml, 17.2 mmol) is added to THF (7.2 ml) while stirring. The dissolved solution was dropped for 30 minutes to 1 hour. After completion of the addition, the reaction was performed at room temperature for 1 to 2 hours. The reaction product was extracted with ethyl acetate (EA) and water, and then treated with MgSO ₄ to remove water and blow off the solvent. Thereafter, the resultant was dried under vacuum at 80 ° C. under heating to obtain a PTMEG derivative of the above reaction formula as a comonomer (n = 60).

Polylactic acid Preparation of Copolymer

After the lactide prepolymer (PLA) prepared in Examples 1 to 3 was stirred for 2 hours in a nitrogen atmosphere, the prepared PTMEG derivative comonomer was added according to the comonomer content shown in Table 1 below, followed by polymerization at 180 ° C. Proceeded.

NMR analysis of the prepared copolymer was performed in the same manner as in Examples 1 to 3, and the peak attributable to the -OH group at the terminal of the PTMEG derivative comonomer observed at 3.6 to 3.7 ppm was 4.1 to 4.2 ppm in the polylactic acid copolymer. Observation was possible. This was shifted because the -OH group terminal of the PTMEG derivative comonomer was changed into an ester group through copolymerization, thereby changing the electronic environment, and it was confirmed that PLA and PTMEG derivative comonomer were copolymerized.

비교예Comparative example : : 폴리락트산Polylactic acid 단독중합체( Homopolymer ( NatureWorks사NatureWorks , 6201D), 6201D)

A polylactic acid homopolymer (Homo-PLA) product (NatureWorks, 6201D), which is currently commercialized and used, was used as a comparative example.

The properties of the following items were measured for the copolymers and the comparative examples prepared in Examples 1 to 6, and the results are shown in Table 1 together with the PTMEG derivative comonomer content in the copolymer.

One) Number average molecular weight (Mn)

The number average molecular weight (Mn) was measured using gel permeation chromatography (Gel Permeation Chromatography, Waters 2690, PL) at a temperature of 40 ° C. and a flow rate of 1 ml / min. (Standard: polystyrene)

2) Glass transition temperature Tg )

Perkin Elmer's Diamond DSC (Differential Scanning Calorimetry) was used to measure the glass transition temperature of the copolymer.

3) initial Modulus (G ')

Initial modulus (storage modulus) of the copolymer was measured using a Pysis diamond DMA (Dynamic Mechanical Analyzer) manufactured by PerkinElmer. Dynamic analysis was performed at a frequency of 1Hz in the temperature range of 30 ~ 150 ℃.

TABLE 1

As shown in Table 1, the polylactic acid copolymers of the example in which the hydroxy-polyether cyclic compound was introduced as a comonomer according to the present invention were all glass transition temperatures compared to commercially available polylactic acid homopolymers (NatureWorks, 6201D). It is lower than about 10 ℃, the initial modulus is reduced to about 10 ~ 41% level, the elasticity is significantly improved. Therefore, when the fiber is produced from the polylactic acid copolymer according to the present invention, a marked improvement in the elasticity of the fiber product is expected.

Claims

A polylactic acid copolymer comprising a monocyclic, polycyclic or fused cyclic compound having at least two (A) lactic acid and (B) hydroxy-terminated poly (aliphatic ether) chains as repeat units.
The polylactic acid copolymer according to claim 1, wherein the lactic acid repeating unit is introduced into the copolymer by lactic acid, lactic acid oligomer or lactide.
The polylactic acid aerial according to claim 1, wherein the monocyclic, polycyclic or fused cyclic compound having two or more hydroxy-terminated poly (aliphatic ether) chains has a structure represented by the following Chemical Formula 1. coalescence:

[Formula 1]

HO- (RO) n -A- (O-R ') m -OH

In Chemical Formula 1,

R and R 'each independently represent a substituted or unsubstituted divalent linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group;

n and m are each independently an integer from 2 to 100;

A is a substituted or unsubstituted divalent aliphatic or aromatic monocyclic, polycyclic or fused cyclic group, or a substituted or unsubstituted divalent monohetero containing at least one atom selected from N, O and S. It is a cyclic, polyheterocyclic or fused heterocyclic group, and may include two or more bonds selected from the group consisting of ether bonds, thioether bonds, ester bonds, ketone bonds and urethane bonds.
The method of claim 3, wherein in Formula 1,

R and R 'each independently represent a substituted or unsubstituted divalent, linear, branched, or cyclic, saturated or unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms;

n and m are each independently an integer from 10 to 80;

A is a substituted or unsubstituted divalent, aliphatic having 5 to 30 carbon atoms or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 30 carbon atoms, or an atom selected from N, O and S Substituted or unsubstituted, divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic group having 5 to 30 ring atoms, and includes an ether bond, a thioether bond, an ester bond, a ketone bond, and the like. May contain two or more bonds selected from the group consisting of urethane bonds,

Polylactic acid copolymer.
The method of claim 4, wherein in Formula 1,

R and R 'each independently represent a substituted or unsubstituted divalent alkyl group having 2 to 10 carbon atoms;

n and m are each independently an integer from 10 to 80;

A is a substituted or unsubstituted divalent, unsubstituted, aromatic monocyclic, polycyclic, or fused cyclic group having 6 to 20 carbon atoms in total, or includes one or more atoms selected from N, O and S A divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic group having 5 to 20 total ring atoms and a bond selected from the group consisting of ether bonds, thioether bonds, ester bonds, ketone bonds and urethane bonds Can contain more than one

Polylactic acid copolymer.
The polylactic acid aerial according to claim 1, wherein the monocyclic, polycyclic or fused cyclic compound having two or more hydroxy-terminated poly (aliphatic ether) chains has a structure represented by the following formula (2). coalescence:

[Formula 2]

HO- (RO) n -L-Cy-L '-(O-R') m -OH

In Chemical Formula 2,

R, R ', n and m are as defined in formula 1 of claim 3;

L and L 'are each independently selected from the group consisting of ether bonds, thioether bonds, ester bonds, ketone bonds and urethane bonds;

Cy is a substituted or unsubstituted divalent aliphatic or aromatic monocyclic, polycyclic or fused cyclic group, or a substituted or unsubstituted divalent monohetero containing one or more atoms selected from N, O and S. Cyclic, polyheterocyclic or fused heterocyclic groups.
The method of claim 6, wherein in Formula 2,

L and L 'are each independently selected from the group consisting of ester bonds, ketone bonds and urethane bonds;

Cy is a substituted or unsubstituted divalent, aliphatic having 5 to 30 carbon atoms or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 30 carbon atoms, or an atom selected from N, O and S Substituted or unsubstituted divalent, containing 5 to 30 monocyclic, polyheterocyclic or fused heterocyclic group,

Polylactic acid copolymer.
The method of claim 6, wherein in Formula 2,

L and L 'are each independently selected from the group consisting of ester bonds and ketone bonds;

Cy is substituted or unsubstituted, divalent, unsubstituted, aromatic monocyclic, polycyclic, or fused cyclic group having 6 to 20 carbon atoms in total, or includes one or more atoms selected from N, O and S Divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic group having 5 to 20 total ring atoms,

Polylactic acid copolymer.
The content of a monocyclic, polycyclic or fused cyclic compound having at least two hydroxy-terminated poly (aliphatic ether) chains included as repeating units is based on 100% by weight of the copolymer. Polylactic acid copolymer, characterized in that 0.1 to 30% by weight.
The polylactic acid copolymer according to claim 1, wherein the number average molecular weight (Mn) is 50,000 to 300,000.
(1) prepolymerizing lactic acid, lactic acid oligomers or lactide; And

(2) copolymerizing the lactic acid prepolymer obtained in step (1) with a monocyclic, polycyclic or fused cyclic compound having two or more hydroxy-terminated poly (aliphatic ether) chains; ,

Method for producing a polylactic acid copolymer.
The method for producing a polylactic acid copolymer according to claim 11, wherein the prepolymerization of step (1) is performed in the presence of a catalyst.
13. The catalyst of claim 12 wherein the catalyst is zinc oxide, antimony oxide, antimony chloride, lead oxide, calcium oxide, aluminum oxide, iron oxide, calcium chloride, zinc acetate, paratoluene sulfonic acid, first tin chloride, first tin sulfate, oxidizing agent 1 tin, a second tin oxide, a first tin octanoate, tetraphenyl tin, tin powder, titanium tetrachloride or a mixture thereof.
The resin processed product manufactured using the polylactic acid copolymer of any one of Claims 1-10.
The resin processed product according to claim 14, which is a fiber or a film.