[go: up one dir, main page]

WO2016186470A1 - Copolymère d'acide polylactique possédant une élasticité nettement améliorée, et son procédé de préparation - Google Patents

Copolymère d'acide polylactique possédant une élasticité nettement améliorée, et son procédé de préparation Download PDF

Info

Publication number
WO2016186470A1
WO2016186470A1 PCT/KR2016/005349 KR2016005349W WO2016186470A1 WO 2016186470 A1 WO2016186470 A1 WO 2016186470A1 KR 2016005349 W KR2016005349 W KR 2016005349W WO 2016186470 A1 WO2016186470 A1 WO 2016186470A1
Authority
WO
WIPO (PCT)
Prior art keywords
bonds
polylactic acid
group
substituted
polycyclic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2016/005349
Other languages
English (en)
Korean (ko)
Inventor
진선철
권영도
신경무
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Samyang Corp
Original Assignee
Samyang Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Samyang Corp filed Critical Samyang Corp
Publication of WO2016186470A1 publication Critical patent/WO2016186470A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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

Definitions

  • 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.
  • 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.
  • PHA polylactic acid
  • 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).
  • 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.
  • 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.
  • 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.
  • a method for producing a polylactic acid copolymer is provided.
  • a processed resin article prepared using the polylactic acid copolymer is provided.
  • 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),
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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:
  • 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.
  • 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.
  • 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.
  • 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.
  • n and m are each independently integers of 10 to 80 (more specifically, 20 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
  • 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) :
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • additional copolymerizing units there is no particular limitation on the type of copolymerization unit of.
  • a method for producing a polylactic acid copolymer is provided.
  • the method or condition for prepolymerizing lactic acid, lactic acid oligomer for example, number average molecular weight (Mn) 100 to 5,000
  • lactide in step (1)
  • 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.
  • step (2) the lactic acid prepolymer obtained in step (1) and the hydroxy-polyether cyclic compound are copolymerized.
  • 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.
  • 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.
  • 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.
  • 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.
  • a comonomer for polylactic acid copolymer was prepared according to the following reaction.
  • a polylactic acid homopolymer (Homo-PLA) product (NatureWorks, 6201D), which is currently commercialized and used, was used as a comparative example.
  • Mn number average molecular weight
  • 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 °C.
  • 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 °C, 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un copolymère d'acide polylactique possédant une élasticité nettement améliorée, et son procédé de préparation. Plus spécifiquement, la présente invention concerne un copolymère d'acide polylactique possédant une élasticité nettement améliorée par rapport à un homopolymère d'acide polylactique, et son procédé de préparation, le copolymère d'acide polylactique comportant: un composé monocyclique comprenant, en tant qu'unité de répétition, (A) un acide lactique et (B) au moins deux chaînes poly (éther aliphatique) à terminaison hydroxyle; un composé polycyclique; ou un composé cyclique fusionné.
PCT/KR2016/005349 2015-05-21 2016-05-20 Copolymère d'acide polylactique possédant une élasticité nettement améliorée, et son procédé de préparation Ceased WO2016186470A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2015-0070741 2015-05-21
KR1020150070741A KR101606480B1 (ko) 2015-05-21 2015-05-21 신축성이 현저히 개선된 폴리락트산 공중합체 및 그 제조방법

Publications (1)

Publication Number Publication Date
WO2016186470A1 true WO2016186470A1 (fr) 2016-11-24

Family

ID=55799355

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2016/005349 Ceased WO2016186470A1 (fr) 2015-05-21 2016-05-20 Copolymère d'acide polylactique possédant une élasticité nettement améliorée, et son procédé de préparation

Country Status (2)

Country Link
KR (1) KR101606480B1 (fr)
WO (1) WO2016186470A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101792037B1 (ko) * 2016-05-16 2017-11-01 주식회사 휴비스 신축성이 우수한 폴리락트산 섬유 및 그의 제조방법
WO2018105823A1 (fr) * 2016-12-06 2018-06-14 주식회사 삼양사 Copolymère de poly(acide lactique) et procédé pour sa préparation
CN114276511B (zh) * 2022-01-10 2023-08-18 浙江海正生物材料股份有限公司 一种支化嵌段共聚物及其制备方法
KR20250053697A (ko) 2023-10-13 2025-04-22 주식회사 파인트코리아 마이크로니들용 생체흡수성 조성물의 제조방법, 및 이를 사용하여 제조된 마이크로니들

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013155223A (ja) * 2012-01-27 2013-08-15 Toray Ind Inc ポリ乳酸系フィルム
KR20140007859A (ko) * 2011-02-24 2014-01-20 도레이 카부시키가이샤 폴리락트산계 필름
KR20140051913A (ko) * 2011-06-27 2014-05-02 사빅 이노베이티브 플라스틱스 아이피 비.브이. 폴리(아릴렌 에테르)-폴리(히드록시 에테르) 블록 공중합체 및 제조방법
KR20140071747A (ko) * 2012-12-04 2014-06-12 주식회사 엘지화학 생분해성 수지 조성물

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140007859A (ko) * 2011-02-24 2014-01-20 도레이 카부시키가이샤 폴리락트산계 필름
KR20140051913A (ko) * 2011-06-27 2014-05-02 사빅 이노베이티브 플라스틱스 아이피 비.브이. 폴리(아릴렌 에테르)-폴리(히드록시 에테르) 블록 공중합체 및 제조방법
JP2013155223A (ja) * 2012-01-27 2013-08-15 Toray Ind Inc ポリ乳酸系フィルム
KR20140071747A (ko) * 2012-12-04 2014-06-12 주식회사 엘지화학 생분해성 수지 조성물

Also Published As

Publication number Publication date
KR101606480B1 (ko) 2016-04-01

Similar Documents

Publication Publication Date Title
CN105218813B (zh) 二酸酐与聚酰亚胺
WO2016186470A1 (fr) Copolymère d'acide polylactique possédant une élasticité nettement améliorée, et son procédé de préparation
WO2015023027A1 (fr) Macro-polyol composé de polycarbonate aliphatique et copolymère de polyester aromatique associé
US5686559A (en) Poly(imide-amic ester), process for preparing the same, and processes for preparing polyimide film and polyimide fiber from the same
WO2015065050A1 (fr) Polycarbonate aliphatique ayant une longue chaîne ramifiée et copolymère de polyester aromatique de celui-ci
TWI763922B (zh) 聚苯并咪唑、其前驅物聚醯胺及該等之製造方法
CN102947360B (zh) 来自基于双失水己糖醇的非对称性单体的新聚酯
KR20200115166A (ko) 트리블록 공중합체 및 이의 제조 방법
JP2850432B2 (ja) 共重合体及びその製造方法
JPS6218568B2 (fr)
KR102873099B1 (ko) 분지형 폴리(락트산-3-하이드록시프로피온산) 공중합체 및 이의 제조 방법
Chen et al. Synthesis and characterizations of novel phosphorous–nitrogen containing poly (ether sulfone) s
KR20150124257A (ko) 신축성이 우수한 폴리락트산 공중합체 및 그 제조방법
WO2020197148A1 (fr) Copolymère tribloc et son procédé de préparation
WO2016093395A1 (fr) Résine polyester biodégradable et mousse obtenue à partir de celle-ci
TW202219112A (zh) 含磷之（2,6-二甲基苯醚）寡聚物及其製備方法與固化物
US3074915A (en) Diels-alder polymers
US4142037A (en) Readily curable fluorocarbon ether bibenzoxazole polymers
CN114222778A (zh) 树脂原料用组合物
WO2023182687A1 (fr) Composition de résine de polylactide ayant un excellent demi-temps de cristallisation, et son procédé de préparation
Hui Zhao et al. Synthesis and characterization of poly (l‐lactic acid)‐b‐poly (ethylene terephthalate‐co‐sebacate)‐b‐poly (l‐lactic acid) copolyesters
US3793296A (en) Heterocyclized polymer
WO2023182686A1 (fr) Composition de résine de polylactide ayant une excellente cristallinité, et son procédé de préparation
WO2023182688A1 (fr) Composition de résine de polylactide ayant une excellente cristallinité, et un procédé pour le préparer
JP3867749B2 (ja) 重合体およびその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16796797

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16796797

Country of ref document: EP

Kind code of ref document: A1