WO2018105823A1 - Copolymère de poly(acide lactique) et procédé pour sa préparation - Google Patents

Copolymère de poly(acide lactique) et procédé pour sa préparation Download PDF

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WO2018105823A1
WO2018105823A1 PCT/KR2017/004488 KR2017004488W WO2018105823A1 WO 2018105823 A1 WO2018105823 A1 WO 2018105823A1 KR 2017004488 W KR2017004488 W KR 2017004488W WO 2018105823 A1 WO2018105823 A1 WO 2018105823A1
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groups
substituted
group
polylactic acid
acid copolymer
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PCT/KR2017/004488
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English (en)
Korean (ko)
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김능현
권영도
노형진
허성현
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주식회사 삼양사
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Publication of WO2018105823A1 publication Critical patent/WO2018105823A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • the present invention relates to a polylactic acid copolymer and a method for producing the same, and more particularly, to (A) lactic acid as a repeating unit; And (B) a monocyclic, polycyclic, or fused cyclic compound having a hydroxy-tetramethylene-oxy-hydrocarbon group at its terminal; thereby, a polylactic acid copolymer having improved elasticity and thermal stability compared to a polylactic acid homopolymer. And to a method for producing the same.
  • biodegradable polylactic acid (PLA) resin obtained through fermentation of corn starch which is easily obtained in nature, is attracting attention as a substitute material for general purpose resins because of low price and ease of supply.
  • Application has been attempted in various ranges, such as for general molded products, for textile, medical, packaging.
  • the PLA polymerization method is a method of synthesizing by direct condensation polymerization from lactic acid, a method of synthesizing high molecular weight PLA through solid phase polymerization from low molecular weight PLA, and azeotropic condensation using a low boiling solvent.
  • a method of synthesizing PLA is known, and recently, there is high interest in PLA synthesis through ring opening polymerization having an advantage of easily synthesizing various high molecular weight PLA.
  • polylactic acid homopolymer has a limitation in that mechanical properties such as heat resistance and impact resistance are not sufficient, and satisfies elasticity, which is a major industrial requirement such as general textile products and packaging products. Since the situation is difficult to make, the application range is not expanded.
  • the present invention is to solve the problems of the prior art as described above, and to improve the low elasticity inherent to polylactic acid (PLA) and at the same time improve the thermal stability that is a problem during processing and polylactic acid copolymer to increase the production efficiency and It is a technical subject to provide the manufacturing method.
  • PLA polylactic acid
  • the present invention to solve the above technical problem, (A) lactic acid as a repeating unit; And (B) a monocyclic, polycyclic or fused cyclic compound having a hydroxy-tetramethylene-oxy-hydrocarbon group at the end thereof.
  • a method for producing a polylactic acid copolymer is provided.
  • a processed resin article prepared using the polylactic acid copolymer is provided.
  • the present invention it is possible to provide a novel biodegradable polylactic acid copolymer which significantly improves the low elasticity and thermal stability of a conventional polylactic acid homopolymer, thereby securing a processing range of the same flexibility as conventional general-purpose resins.
  • Increasing processing efficiency it is possible to overcome the difficulties of secondary processing due to low elasticity and thermal stability, thereby extending the scope of conventional applications of textile products, film products, packaging products and medical supplies.
  • the present invention provides a random or block repeating unit comprising lactic acid; And a monocyclic, polycyclic or fused cyclic compound having a hydroxy-tetramethylene-oxy-hydrocarbon group at the end thereof.
  • 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% by weight based on 100% by weight of the copolymer, preferably 85 to 98% by weight, more preferably 90 It may be ⁇ 97% by weight, but is not limited thereto. If the lactic acid content in the polylactic acid copolymer is less than 70% by weight, the degree of polymerization of the polylactic acid copolymer may be low and the biodegradable effect may be insignificant, and if it exceeds 99% by weight, the improvement in elasticity and thermal stability of the polylactic acid copolymer may be achieved. The effect may be low.
  • Monocyclic, polycyclic or fused cyclic compounds having hydroxy-tetramethylene-oxy-hydrocarbon groups at the ends, which are included as copolymerized repeating units together with lactic acid repeating units in the polylactic acid copolymers of the present invention are hydroxy-tetramethylene-oxy groups (i.e., HO- (CH 2 ) at the ends via a hydrocarbon group around a monocyclic, polycyclic or fused cyclic moiety)
  • a hydroxy-tetramethylene-oxy group is preferably present at both ends.
  • the content of the tetramethylene glycol ether-terminal cyclic compound included in the polylactic acid copolymer of the present invention as a repeating unit together with the lactic acid repeating unit may be 1 to 30% by weight based on 100% by weight of the copolymer. May be 2 to 15% by weight, more preferably 3 to 10% by weight, but is not limited thereto. If the content of the tetramethylene glycol ether-terminal cyclic compound as a comonomer in the polylactic acid copolymer is less than 1% by weight, the improvement effect on the elasticity and thermal stability of the polylactic acid copolymer may be insignificant, and if it is more than 30% by weight.
  • the degree of polymerization of the polylactic acid copolymer and the biodegradability of the polylactic acid copolymer may be low.
  • the tetramethylene glycol ether-terminated cyclic compound may have a structural formula represented by the following Chemical Formula 1-1.
  • R 1 and R 2 each independently represent a substituted or unsubstituted divalent hydrocarbon group, wherein R 1 and R 2 each independently comprise one or more bonds selected from ether bonds, ester bonds, ketone bonds and urethane bonds Can do it,
  • the anhydrosugar alcohol may be in the form of substituted or unsubstituted alkylene glycol at one or both ends thereof, the alkylene glycol is not particularly limited , Preferably ethylene glycol, propylene glycol or combinations thereof;
  • A is a substituted or unsubstituted divalent aliphatic or aromatic monocyclic, polycyclic or fused cyclic group; Or a substituted or unsubstituted divalent monoheterocyclic, polyheterocyclic or fused heterocyclic group comprising at least one hetero atom selected from N, O and S, wherein A is an ester group, ether It may comprise one or more functional groups selected from the group consisting of groups, thioether groups, ketone groups and urethane groups.
  • hydrocarbon group refers to a linear, branched or cyclic saturated or unsaturated hydrocarbon group, which may include, but is not limited to, saturated or unsaturated alkyl, alkoxy, aryl and combinations thereof.
  • substituted or “substituted” means that a hydrogen atom is a halogen atom (eg, Cl or Br, etc.), a hydroxyl group, an alkyl group having 1 to 13 carbon atoms (eg, methyl, ethyl or propyl). Etc.), an alkoxy group having 1 to 13 carbon atoms (e.g., methoxy, ethoxy or propoxy), an aryl group having 6 to 10 carbon atoms (e.g., phenyl, chlorophenyl or tolyl, etc.), or these It means what was substituted by substituents, such as a combination.
  • anhydrous alcohol is obtained by removing one or more water molecules from a compound obtained by adding hydrogen to a reducing terminal group of a saccharide, called hydrogenated sugar or sugar alcohol. It means any substance.
  • anhydrosugar alcohol substituted with alkylene glycol refers to the terminal (eg, both ends) hydroxyl group of the anhydrosugar alcohol.
  • an alkylene oxide eg, C 1 -C 4 alkylene oxide, more specifically ethylene oxide, propylene oxide or mixtures thereof
  • the terminal (eg, amount of anhydrosugar alcohol) Terminal) means a compound of the form in which hydrogen of the hydroxyl group is substituted with hydroxyalkylene oxide of alkylene oxide.
  • the result of adding ethylene oxide to both terminal hydroxyl groups of isosorbide is as follows.
  • R 1 and R 2 each independently represent a substituted or unsubstituted divalent hydrocarbon group having 12 to 328 carbon atoms, wherein R 1 and R 2 are each independently from an ether bond, an ester bond, a ketone bond and a urethane bond May comprise one or more bonds selected;
  • 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 a substituted or unsubstituted divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic group having 5 to 30 ring atoms, including one or more hetero atoms selected from N, O and S. And A may also include one or more functional groups selected from the group consisting of ester groups, ether groups, thioether groups, ketone groups and urethane groups.
  • R 1 and R 2 each independently represent a substituted or unsubstituted divalent hydrocarbon group having 12 to 248 carbon atoms, wherein R 1 and R 2 are each independently from an ether bond, an ester bond, a ketone bond and a urethane bond May comprise one or more bonds selected;
  • A is a substituted or unsubstituted divalent, aromatic monocyclic, polycyclic or fused cyclic group having 6 to 20 carbon atoms in total; Or a substituted or unsubstituted divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic group having from 5 to 20 ring atoms, including one or more hetero atoms selected from N, O and S. And A may also include one or more functional groups selected from the group consisting of ester groups, ether groups, thioether groups, ketone groups and urethane groups.
  • the tetramethylene glycol ether-terminated cyclic compound may have a structural formula represented by Formula 1-2.
  • R 3 and R 4 each independently represent a substituted or unsubstituted divalent hydrocarbon group
  • the anhydrosugar alcohol may be in the form of substituted or unsubstituted alkylene glycol at one or both ends thereof, the alkylene glycol is not particularly limited , Preferably ethylene glycol, propylene glycol or combinations thereof;
  • A is a substituted or unsubstituted divalent aliphatic or aromatic monocyclic, polycyclic or fused cyclic group; Or a substituted or unsubstituted divalent monoheterocyclic, polyheterocyclic or fused heterocyclic group comprising at least one hetero atom selected from N, O and S, wherein A is an ester group, ether May comprise one or more functional groups selected from the group consisting of groups, thioether groups, ketone groups and urethane groups;
  • n and m each independently represent the integer of 1-80.
  • R 3 and R 4 each independently represent a substituted or unsubstituted alkylene group
  • 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 a substituted or unsubstituted divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic group having 5 to 30 ring atoms, including one or more hetero atoms selected from N, O and S. And A may also include one or more functional groups selected from the group consisting of ester groups, ether groups, thioether groups, ketone groups and urethane groups;
  • n and m each independently represent the integer of 1-70.
  • R 3 and R 4 are each independently a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms, preferably a substituted or unsubstituted alkylene group having 3 to 5 carbon atoms, more preferably a substituted or unsubstituted group Represented tetramethylene group;
  • A is a substituted or unsubstituted divalent, aromatic monocyclic, polycyclic or fused cyclic group having 6 to 20 carbon atoms in total; Or a substituted or unsubstituted divalent, monoheterocyclic, polyheterocyclic or fused heterocyclic group having from 5 to 20 ring atoms, including one or more hetero atoms selected from N, O and S. And A may also include one or more functional groups selected from the group consisting of ester groups, ether groups, thioether groups, ketone groups and urethane groups;
  • n and m each independently represent the integer of 1-60.
  • the tetramethylene glycol ether-terminated cyclic compound may have a structural formula represented by Chemical Formula 1-3.
  • n represents the integer of 1-80, Preferably it is 1-70, More preferably, it is 1-60.
  • the tetramethylene glycol ether-terminated cyclic compound may have a structural formula represented by the following Chemical Formula 2-1.
  • R 1 , R 2 and A are as defined in Formula 1-1.
  • the tetramethylene glycol ether-terminal cyclic compound may have a structural formula represented by the following formula (2-2).
  • R 3 , R 4 , C, C ', A, n and m are as defined in Formula 1-2 above.
  • the tetramethylene glycol ether-terminal cyclic compound may have a structural formula represented by the following formula 2-3, 2-4 or 2-5.
  • n represents an integer of 2 to 80, preferably 2 to 70, more preferably 2 to 60.
  • n represents the integer of 1-80, Preferably it is 1-70, More preferably, it is 1-60.
  • n represents the integer of 1-80, Preferably it is 1-70, More preferably, it is 1-60.
  • a monocyclic, polycyclic or fused solution of anhydrous sugar alcohol eg, isosorbide, isomannide, isoidide, etc.
  • anhydrous sugar alcohol eg, isosorbide, isomannide, isoidide, etc.
  • an ethylene acetate solvent or a methylene chloride solvent e.g., ethylene acetate solvent or a methylene chloride solvent
  • cyclic dicarboxylic acid or its diester for example, dimethyl terephthalate, etc.
  • PTMEG polytetramethylene ether glycol
  • aromatic monocyclic, polycyclic or fused cyclic compounds having a total of 6 to 30 carbon atoms dissolved in ethylene acetate solvent or methylene chloride solvent (e.g., naphthalenedicarboxylic acid, naphthalenedicar
  • ethylene acetate solvent or methylene chloride solvent e.g., naphthalenedicarboxylic acid, naphthalenedicar
  • the secondary reactant is removed by several washings with an alkaline solution and several washings with distilled water, and the solvent is removed by vacuum depressurization, thereby removing Methylene glycol ether-terminated cyclic compounds can be prepared.
  • aromatic monocyclic, polycyclic or fused cyclic compounds having 6 to 30 carbon atoms dissolved in ethylene acetate solvent or methylene chloride solvent (e.g., diphenol, naphthalenediol and the like) )
  • ethylene acetate solvent or methylene chloride solvent e.g., diphenol, naphthalenediol and the like
  • the solution and the monocyclic, polycyclic or fused cyclic dicarboxylic acid or diester thereof e.g., dimethyl terephthalate, etc.
  • PTMEG polytetramethylene ether glycol
  • the reaction was carried out by adding a secondary reaction, and then the secondary reactant was removed through several washings with an alkaline solution and several washings with distilled water, and the solvent was removed by vacuum decompression, thereby the chemical formula 2-4 or 2-5 Tetramethylene glycol ether-terminated cyclic compounds can be prepared.
  • the copolymer of the present invention may further include one or more additional copolymerization repeating units within the scope of achieving the object of the present invention.
  • additional copolymerized repeating units there is no particular limitation on the kind of such additional copolymerized repeating units.
  • the copolymer repeating unit that may be further included in the copolymer of the present invention may include polyether, diol, and the like.
  • tetramethylene glycol ether- A method for producing a polylactic acid copolymer is provided.
  • the method or condition for prepolymerizing the lactic acid the lactic acid oligomer (eg, number average molecular weight (Mn) 100 to 5,000) or lactide in step (1), and generally known methods or conditions may be used.
  • lactic acid, lactic acid oligomer or lactide in the presence of a catalyst, lactic acid, lactic acid oligomer or lactide is raised at elevated temperature (eg, 100 to 210 ° C, more specifically 110 to 150 ° C) and reduced pressure conditions.
  • a prepolymer can be manufactured by making reaction for a suitable time (for example, 0.1 to 2 hours, more specifically 0.2 to 1.5 hours).
  • 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 preliminary polymerization of lactic acid 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, First tin sulfate, 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.
  • amount of the catalyst used is less than 0.0005 parts by weight, the reaction rate is slowed.
  • amount of the catalyst used is more than 5 parts by weight, the residual catalyst may discolor the product or degrade the physical properties.
  • step (2) the lactic acid prepolymer obtained in step (1) is copolymerized with the tetramethylene glycol ether-terminated cyclic compound.
  • Tetramethylene glycol ether-terminated cyclic compounds 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.
  • an initiator and a tetramethylene glycol ether-terminated cyclic compound as described above are added to the resultant mixture (including the catalyst) of step (1), and a nitrogen atmosphere
  • the copolymer may be formed by reacting at an elevated temperature (eg, 100 to 210 ° C, more specifically, 110 to 150 ° C) and a decompression condition under an appropriate time (for example, 0.5 to 4 hours, more specifically 1 to 3 hours). have.
  • 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.
  • the initiator that may be used in the copolymerization step may be an aliphatic alcohol (eg, linear or branched aliphatic alcohol having 6 to 20 carbon atoms, more specifically 1-dodecanol, 1-octanol, or a mixture thereof). have.
  • 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.
  • the amount of the initiator is less than 0.0005 parts by weight, there may be a problem in controlling the molecular weight of the copolymer, and if it is more than 5 parts by weight, there may be a problem in the degree of polymerization of the copolymer.
  • the polylactic acid copolymer of the present invention is biodegradable and eco-friendly, and at the same time exhibits improved elasticity and thermal stability compared to polylactic acid homopolymers, and thus can be applied to various applications, and particularly high elasticity and thermal stability. It can be used suitably for resin processed products, such as textile products, medical products (such as surgical sutures or medical films) and film materials, and can increase the efficiency of production processing.
  • 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.
  • n 1
  • the initiator 0.1 g of 1-dodecanol (Sigma Aldrich) was used, and 6 g of tin (II) octanoate (Sn (Oct) 2 , Sigma Aldrich) purified on toluene anhydride was used as a catalyst.
  • the number average molecular weight (Mn) of the prepared lactic acid prepolymer was 2,000 to 10,000.
  • the tetramethylene glycol ether-terminated cyclic compound of Chemical Formula 1-3 36 g was added at a temperature of 180 ° C., followed by copolymerization at a temperature of 200 ° C.
  • the number average molecular weight (Mn) of the polylactic acid copolymer prepared was 50,000 to 300,000.
  • Tetramethylene glycol ether-terminated cyclic compound of Formula 1-3 The content of the repeating unit was 3% by weight based on the total weight of the polylactic acid copolymer prepared.
  • the NMR spectrum of the polylactic acid copolymer prepared above was measured using a Bruker Avance DRX 300. NMR spectral analysis showed that the position shifted due to the hydroxyl group at the end of the tetramethylene glycol ether-terminal cyclic compound was shifted due to electronic environmental change as the ester group was changed through polylactic acid copolymerization. It can be confirmed that the copolymerization result.
  • Tetramethylene glycol ether-terminated cyclic compound of Formula 1-3 A polylactic acid copolymer was prepared in the same manner as in Example 1, except that the content of the repeating unit was changed to 10% by weight (based on the total weight of the copolymer).
  • a naphthalenedicarboxylate solution and a PTMEG solution dissolved in an ethylene acetate solvent were added to a two neck flask provided with a Deanstock trap, and the reaction was performed by heating and stirring to the reflux temperature of the ethylene acetate solvent. Subsequently, the secondary reactants were removed by washing with an alkaline solution and washing with distilled water, and a tetramethylene glycol ether-terminated cyclic compound of the following Chemical Formula 2-3 was prepared through a solvent removal process under vacuum and reduced pressure.
  • n 2
  • Lactic acid prepolymer was prepared in the same manner as in Example 1.
  • step (1) After the lactic acid prepolymer prepared in step (1) was stirred for 2 hours in a nitrogen atmosphere, 36 g of the tetramethylene glycol ether-terminated cyclic compound of Chemical Formula 2-3 was added at 180 ° C., followed by 200 ° C. Copolymerization was carried out at temperature.
  • the number average molecular weight (Mn) of the polylactic acid copolymer prepared was 50,000 to 300,000.
  • the content of the tetramethylene glycol ether-terminated cyclic compound repeating unit of Formula 2-3 was 3 wt% based on the total weight of the polylactic acid copolymer prepared.
  • the NMR spectrum of the polylactic acid copolymer prepared above was measured using a Bruker Avance DRX 300. NMR spectral analysis showed that the position shifted due to the hydroxyl group at the end of the tetramethylene glycol ether-terminal cyclic compound was shifted due to electronic environmental change as the ester group was changed through polylactic acid copolymerization. It can be confirmed that the copolymerization result.
  • a biphenol solution and a dimethyl terephthalate solution dissolved in an ethylene acetate solvent were added to a two neck flask equipped with a Dean Stark trap, and heated and stirred at the reflux temperature of the ethylene acetate solvent to proceed with the first reaction, followed by addition of PTMEG.
  • the secondary reaction was advanced. Subsequently, the secondary reactants were removed by washing with an alkaline solution and washing with distilled water, and a tetramethylene glycol ether-terminated cyclic compound of the following Chemical Formula 2-4 was prepared through a solvent removal process under vacuum and reduced pressure.
  • n 1
  • Lactic acid prepolymer was prepared in the same manner as in Example 1.
  • step (1) After the lactic acid prepolymer prepared in step (1) was stirred for 2 hours in a nitrogen atmosphere, 36 g of the tetramethylene glycol ether-terminated cyclic compound of Formula 2-4 was added at 180 ° C., followed by 200 ° C. Copolymerization was carried out at temperature.
  • the number average molecular weight (Mn) of the polylactic acid copolymer prepared was 50,000 to 300,000.
  • the content of the tetramethylene glycol ether-terminated cyclic compound repeat unit of Formula 2-4 was 3 wt% based on the total weight of the polylactic acid copolymer prepared.
  • the NMR spectrum of the polylactic acid copolymer prepared above was measured using a Bruker Avance DRX 300. NMR spectral analysis showed that the position shifted due to the hydroxyl group at the end of the tetramethylene glycol ether-terminal cyclic compound was shifted due to electronic environmental change as the ester group was changed through polylactic acid copolymerization. It can be confirmed that the copolymerization result.
  • n 1
  • Lactic acid prepolymer was prepared in the same manner as in Example 1.
  • step (1) After stirring the lactic acid prepolymer prepared in step (1) in a nitrogen atmosphere for 2 hours, 36 g of the tetramethylene glycol ether-terminated cyclic compound of Chemical Formula 2-5 was added at 180 ° C., and then 200 ° C. Copolymerization was carried out at temperature.
  • the number average molecular weight (Mn) of the polylactic acid copolymer prepared was 50,000 to 300,000.
  • the content of the tetramethylene glycol ether-terminated cyclic compound repeat unit of Formula 2-5 was 3% by weight based on the total weight of the polylactic acid copolymer prepared.
  • the NMR spectrum of the polylactic acid copolymer prepared above was measured using a Bruker Avance DRX 300. NMR spectral analysis showed that the position shifted due to the hydroxyl group at the end of the tetramethylene glycol ether-terminal cyclic compound was shifted due to electronic environmental change as the ester group was changed through polylactic acid copolymerization. It can be confirmed that the copolymerization result.
  • a polylactic acid homopolymer was prepared in the same manner as in Example 1, except that the tetramethylene glycol ether-terminated cyclic compound of Chemical Formula 1-3 was not used as the copolymer repeating unit.
  • Example 2 The same method as in Example 1, except that isosorbide (content of 3% by weight based on the total weight of the copolymer) was used instead of the tetramethylene glycol ether-terminated cyclic compound of Chemical Formula 1-3 as a copolymer repeating unit. Polylactic acid copolymer was prepared.
  • Example 2 The same method as Example 1, except that isosorbide (content of 10% by weight based on the total weight of the copolymer) was used instead of the tetramethylene glycol ether-terminated cyclic compound of Chemical Formula 1-3 as a copolymer repeating unit. Polylactic acid copolymer was prepared.
  • a cyclic compound containing a hydroxy-terminated ester group of Chemical Formula 3 (7 wt% based on the total weight of copolymer) was used as a copolymer repeating unit. Except for producing a polylactic acid copolymer in the same manner as in Example 1.
  • Perkin Elmer's Diamond DSC (Differential Scanning Calorimetry) was used to measure the glass transition temperature of the polylactic acid homopolymer and polylactic acid copolymer, and based on the glass transition temperature of the polylactic acid homopolymer (Comparative Example 1), The rate of glass transition temperature rise was calculated.
  • the initial modulus (storage modulus) of the polylactic acid homopolymer and the polylactic acid copolymer was measured using a Pysis diamond DMA (Dynamic Mechanical Analyzer) manufactured by Perkin Elmer at a frequency of 1 Hz in the temperature range of 30 to 150 ° C.
  • the initial modulus reduction rate of the polylactic acid copolymer was calculated based on the initial modulus of Comparative Example 1).
  • the glass transition temperature rise rate and initial modulus reduction rate of each copolymer were measured as follows.

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Abstract

La présente invention concerne un copolymère de poly(acide lactique) et un procédé pour sa préparation et, plus particulièrement, un copolymère de poly(acide lactique) présentant une élasticité et une stabilité thermique améliorées par rapport à un homopolymère de poly(acide lactique), par inclusion, en tant que motifs récurrents, de (A) acide lactique et de (B) un composé cyclique monocyclique, polycyclique ou condensé présentant un groupe hydroxyl-tétraméthylène-oxy-hydrocarboné au niveau l'extrémité, et un procédé pour sa préparation.
PCT/KR2017/004488 2016-12-06 2017-04-27 Copolymère de poly(acide lactique) et procédé pour sa préparation WO2018105823A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100120957A1 (en) * 2006-01-31 2010-05-13 Cyclics Corporation Processes for making copolymers using macrocyclic oligoesters, and copolymers therefrom
US20100197884A1 (en) * 2007-08-09 2010-08-05 Joseph David Schroeder Method for making copolymers of lactide and a 1:4-3:6 dianhydrohexitol
KR20150124281A (ko) * 2014-04-28 2015-11-05 주식회사 삼양사 신축성이 우수한 폴리락트산 공중합체 및 그 제조방법
KR101606480B1 (ko) * 2015-05-21 2016-04-01 주식회사 삼양사 신축성이 현저히 개선된 폴리락트산 공중합체 및 그 제조방법
KR101650923B1 (ko) * 2010-05-20 2016-08-25 에스케이케미칼주식회사 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드 및 이를 이용한 성형제품

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060141183A1 (en) 2004-12-22 2006-06-29 Williamson David T Polyester clay nanocomposites for barrier applications
JP2008239899A (ja) 2007-03-28 2008-10-09 Techno Polymer Co Ltd 放熱性樹脂組成物及びそれを含む成形品
KR101695926B1 (ko) * 2010-12-02 2017-01-12 에스케이씨 주식회사 폴리에스터 필름 및 이의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100120957A1 (en) * 2006-01-31 2010-05-13 Cyclics Corporation Processes for making copolymers using macrocyclic oligoesters, and copolymers therefrom
US20100197884A1 (en) * 2007-08-09 2010-08-05 Joseph David Schroeder Method for making copolymers of lactide and a 1:4-3:6 dianhydrohexitol
KR101650923B1 (ko) * 2010-05-20 2016-08-25 에스케이케미칼주식회사 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드 및 이를 이용한 성형제품
KR20150124281A (ko) * 2014-04-28 2015-11-05 주식회사 삼양사 신축성이 우수한 폴리락트산 공중합체 및 그 제조방법
KR101606480B1 (ko) * 2015-05-21 2016-04-01 주식회사 삼양사 신축성이 현저히 개선된 폴리락트산 공중합체 및 그 제조방법

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