WO2020197147A1 - Procédé de préparation d'un copolymère séquencé - Google Patents

Procédé de préparation d'un copolymère séquencé Download PDF

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Publication number
WO2020197147A1
WO2020197147A1 PCT/KR2020/003638 KR2020003638W WO2020197147A1 WO 2020197147 A1 WO2020197147 A1 WO 2020197147A1 KR 2020003638 W KR2020003638 W KR 2020003638W WO 2020197147 A1 WO2020197147 A1 WO 2020197147A1
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Prior art keywords
block copolymer
hydroxypropionate
poly
polylactide
ring
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PCT/KR2020/003638
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English (en)
Korean (ko)
Inventor
최정윤
허성운
김철웅
Original Assignee
주식회사 엘지화학
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.)
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Publication date
Priority claimed from KR1020200031968A external-priority patent/KR102539511B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US17/269,963 priority Critical patent/US11840604B2/en
Priority to CN202080003703.3A priority patent/CN112689653B/zh
Priority to EP20779074.2A priority patent/EP3795606B1/fr
Priority to JP2020571536A priority patent/JP7171120B2/ja
Publication of WO2020197147A1 publication Critical patent/WO2020197147A1/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
    • 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
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

Definitions

  • the present invention relates to a method of preparing a polylactide-poly(3-hydroxypropionate) block copolymer.
  • Polylactide (or polylactic acid) resin is a plant-derived resin obtained from plants such as corn, and is attracting attention as an eco-friendly material having biodegradable properties and excellent tensile strength and elastic modulus.
  • petroleum resins such as polystyrene resin, polyvinyl chloride (PVC) resin, and polyethylene, which are used in the past, it has effects such as preventing depletion of petroleum resources and suppressing carbon dioxide gas emissions. It can reduce environmental pollution, a disadvantage of petroleum plastic products.
  • the polylactide resin has a low impact resistance and heat resistance compared to the conventional petroleum resin and has a limited application range.
  • materials such as PBS (poly(butylene succinate)) and PBAT (poly(butylene adipate-co-terephthalate)), which are biodegradable and have relatively excellent elongation properties, are compounded with polylactide or form block copolymers.
  • PBS poly(butylene succinate)
  • PBAT poly(butylene adipate-co-terephthalate)
  • the present invention is to provide a polylactide-poly(3-hydroxypropionate) block copolymer having excellent mechanical properties such as tensile modulus, tensile strength, elongation and impact strength while maintaining environment-friendly and biodegradability. .
  • a poly (3-hydroxypropionate) initiator comprising the step of ring-opening polymerization of a lactide monomer to prepare a polylactide-poly (3-hydroxypropionate) block copolymer
  • a method for preparing a block copolymer may be provided.
  • lactide monomer may be defined as follows.
  • lactide may be classified into L-lactide consisting of L-lactic acid, D-lactide consisting of D-lactic acid, and meso-lactide consisting of one L-form and one D-form respectively.
  • a mixture of L-lactide and D-lactide in a 50:50 weight ratio is called D,L-lactide or rac-lactide.
  • L- or D-polylactide (PLLA or PDLA) with very high stereoregularity is known to be obtained when polymerization is performed using only L-lactide or D-lactide with high optical purity.
  • lactide monomer is defined as including all types of lactide regardless of the difference in properties of lactide according to each type and the difference in properties of the polylactide formed therefrom.
  • polylactide-poly(3-hydroxypropionate) block copolymer refers to polylactide including polylactide repeating units and poly(3-hydroxypropionate) repeating units. -Refers to a poly(3-hydroxypropionate) block copolymer, and such "polylactide-poly(3-hydroxypropionate) block copolymer” refers to the aforementioned poly(3-hydroxypropionate) )
  • By ring-opening polymerization of “lactide monomer” in the presence of an initiator to form the polylactide repeating unit and the poly(3-hydroxypropionate) repeating unit, and such ring-opening polymerization and The polymer after the process of forming the repeating unit is completed may be referred to as the “polylactide-poly(3-hydroxypropionate) block copolymer”. In this case, it is as described above that all types of lactide are included in the category of “lactide monomer” in the presence
  • polymers in all states after the ring-opening polymerization and forming the repeating unit are completed, eg
  • a polymer in an unrefined or purified state after the ring-opening polymerization is completed a polymer included in a liquid or solid resin composition before product molding, or a polymer included in a plastic or fabric after product molding has been completed may be included.
  • the physical properties (weight average molecular weight, etc.) of the “polylactide-poly(3-hydroxypropionate) block copolymer” are in any state after the ring-opening polymerization and the forming process of the repeating unit are completed. It can be defined as the physical properties of the polymer exhibiting.
  • the present inventors in the case of preparing a block copolymer through ring-opening polymerization of a lactide monomer in the presence of a poly(3-hydroxypropionate) initiator, polylactide repeating unit and poly(3-hydroxyl) Propionate) block copolymers containing repeating units can be prepared, and these block copolymers have excellent mechanical properties such as tensile modulus, tensile strength, elongation and impact strength while maintaining eco-friendliness and biodegradability. To find out, the present invention was completed.
  • a poly (3-hydroxypropionate) initiator by ring-opening polymerization of a lactide monomer to prepare a polylactide-poly (3-hydroxypropionate) block copolymer It is possible to provide a block copolymer comprising the step.
  • the polymerization reaction of a polylactide resin by ring-opening polymerization of a lactide monomer is initiated by a compound having a terminal hydroxy group, and the lactide monomer is continuously flowering and added to the compound having a terminal hydroxy group. Proceeds.
  • the poly(3-hydroxypropionate) initiator includes a hydroxy group and/or an alkoxy group at the end, and the hydroxy group and/or alkoxy group at the end of the poly(3-hydroxypropionate) initiator
  • a group is added to the ring-opening polymerization reaction of the lactide monomer, the lactide monomer starts to be added from the end, resulting in the production of a polylactide-poly(3-hydroxypropionate) block copolymer. do.
  • the poly(3-hydroxypropionate) acts as a polymerization initiator and blocks copolymerization. It is included as a repeating unit in the coalescence, and mechanical properties such as flexibility and impact strength of the final block copolymer can be improved. Specifically, since the poly(3-hydroxypropionate) is included in the block copolymer to be finally prepared, flexibility may be increased by lowering the glass transition temperature (Tg) of the block copolymer.
  • Tg glass transition temperature
  • the dosage amount of the poly(3-hydroxypropionate) initiator is the content of the repeating unit of the poly(3-hydroxypropionate) contained in the block copolymer and the minimum required for starting polymerization. It may be selected from an appropriate range in consideration of the molar ratio of the hydroxy group and/or the alkoxy group of the initiator.
  • the poly(3-hydroxypro) based on 100 parts by weight of the lactide monomer Cypionate) Initiator may be added in an amount of 0.01 parts by weight or more, 0.1 parts by weight to 100 parts by weight, 0.5 to 90 parts by weight, 0.7 to 80 parts by weight, or 0.9 to 70 parts by weight.
  • the poly(3-hydroxypropionate) initiator may have a weight average molecular weight of 1,500 to 50,000, 2,000 to 40,000, or 2,200 to 30,000 in order to exhibit excellent physical properties of the block copolymer without deteriorating polymerization activity. . If the weight average molecular weight of the poly(3-hydroxypropionate) initiator is less than 1,500, the content of poly(3-hydroxypropionate) may decrease, and if it exceeds 50,000, the polymerization activity may decrease.
  • the poly(3-hydroxypropionate) initiator may be prepared by condensation polymerization of 3-hydroxypropionate.
  • the reaction product including the prepared poly(3-hydroxypropionate) initiator and lactide monomer was dried, and then the dried poly(3-hydroxypropionate) initiator and lactide monomer were ring-opened and polymerized to form the above-described block. Copolymers can be prepared.
  • the catalyst used in the ring-opening polymerization all catalysts generally used in the production of a polylactide resin by ring-opening polymerization of a lactide monomer may be used.
  • the ring-opening polymerization may be performed under one or more catalysts selected from the group consisting of an organometallic complex catalyst and an organic catalyst.
  • the organometallic composite catalyst may be used without limitation in its configuration, as long as it is generally used for the production of a polylactide resin by ring-opening polymerization of a lactide monomer.
  • the organometallic composite catalyst is represented by the following formula It may be a catalyst represented by 1.
  • M is Al, Mg, Zn, Ca, Sn, Fe, Y, Sm, Lu, Ti or Zr, p is an integer of 0 to 2, A 1 and A 2 are each independently alkoxy or It is a carboxyl group.
  • the MA 1 p A 2 2-p may be tin (II) 2-ethylhexanoate (Sn(Oct) 2 ).
  • the organic catalyst may be used without limitation of its configuration, as long as it is generally used for preparing a polylactide resin by ring-opening polymerization of a lactide monomer.
  • the organic catalyst is the following 1,5,7-triazobicyclo-[4,4,0]de-5-cene (TBD), the following 1,8-diazabicyclo[5.4.0]unde- 7-sen (DBU), the following 7-methyl-1,5,7-triazabicyclo[4.4.0]de-5-cene (MTBD), the following 4-dimethylaminopyridine (DMAP), the following 4-(1) -Pyrrolidinyl) pyridine (PPY), imidazole, triazolium, thiourea, tertiary amine, and may be one or more selected from the group consisting of creatinine.
  • the imidazole may be one or more selected from the group consisting of the following compounds.
  • the trizolium may be the following compound.
  • the thiourea may be one or more selected from the group consisting of the following compounds.
  • the tertiary amine may be one or more selected from the group consisting of the following compounds.
  • the content of the catalyst is 0.01 to 10 mol%, 0.05 to 8 mol%, 0.07 to 5 mol%, or 0.09 to 3 mol% based on 100 mol% of the lactide monomer. It can be %.
  • the content of the catalyst relative to 100 mol% of the lactide monomer is less than 0.01 mol%, the polymerization activity may not be sufficient, and when it exceeds 10 mol%, the prepared polylactide-poly(3-hydroxypropionate)
  • the residual catalyst amount of the block copolymer is large, and decomposition of the copolymer due to depolymerization such as a transesterification reaction or a decrease in molecular weight may be caused.
  • the ring-opening polymerization may be performed at 150 to 200°C for 5 minutes to 10 hours.
  • the ring-opening polymerization reaction can be carried out in bulk polymerization that does not use a solvent.
  • the fact that the solvent is not substantially used may include a case of using a small amount of solvent for dissolving the catalyst, for example, a maximum of less than 1 ml of solvent per 1 kg of lactide monomer used.
  • the ring-opening polymerization proceeds to bulk polymerization, it becomes possible to omit a process for removing the solvent after polymerization, and decomposition or loss of the resin in the solvent removal process can be suppressed.
  • the bulk polymerization the polylactide-poly(3-hydroxypropionate) block copolymer can be obtained with high conversion and yield.
  • the polylactide-poly(3-hydroxypropionate) block copolymer prepared by the method according to the embodiment has a weight average molecular weight of 10,000 to 400,000, 15,000 to 350,000, 20,000 to 300,000, or 25,000 to 250,000.
  • a weight average molecular weight 10,000 to 400,000, 15,000 to 350,000, 20,000 to 300,000, or 25,000 to 250,000.
  • the conventional polylactide resin As described above, in the case of the conventional polylactide resin, it has been in the spotlight for its mechanical properties that are relatively excellent as a biodegradable resin, but it is limited to be applied to various products due to a high tensile modulus value, i.e. there was.
  • the polylactide-poly(3-hydroxypropionate) block copolymer according to the above embodiment has excellent flexibility and excellent mechanical properties such as tensile strength and elongation, so that the conventional polylactide By solving the problem of brittleness of resin, its application field can be expanded.
  • a polylactide-poly(3-hydroxypropionate) block copolymer having excellent mechanical properties such as tensile modulus, tensile strength, elongation and impact strength while maintaining eco-friendliness and biodegradability is provided. I can.
  • poly(3-hydroxypropionate) was subjected to condensation polymerization at a temperature of 130° C. for 24 hours in the presence of a p-Toluene Sulfonic Acid (p-TSA) catalyst. Nate) oligomers were prepared.
  • p-TSA p-Toluene Sulfonic Acid
  • the weight average molecular weight of the prepared poly(3-hydroxypropionate) oligomer was 2,430.
  • the flask was placed in a 130° C. pre-heated oil bath, and the temperature was raised to 180° C., followed by ring-opening polymerization for 2-30 minutes. After the reaction was completed, the reaction product was dissolved in chloroform and extracted with methanol to recover the block copolymer.
  • Example 1 16.00 0.02 0.16
  • Example 2 16.00 0.02 0.80
  • Example 3 16.00 0.02 1.60
  • Example 4 16.00 0.02 0.32
  • the flask was placed in a 130° C. pre-heated oil bath, and the temperature was raised to 180° C., followed by ring-opening polymerization for 20 minutes. After the reaction was completed, the reaction product was dissolved in chloroform and extracted with methanol to recover the polymer.
  • NMR analysis was performed at room temperature using an NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer having a triple resonance 5 mm probe.
  • the block copolymers and polymers prepared in Examples 1 to 4 and Comparative Example 1, respectively, were diluted to a concentration of about 10 mg/ml and used as an analysis target material in a solvent for NMR measurement (CDCl 3 ), and the chemical shift was ppm Expressed.
  • FIG. 1 is a graph showing the NMR analysis results of the block copolymer prepared in Example 3
  • FIG. 2 is a graph showing the NMR analysis results of the polymer prepared in Comparative Example 1.
  • the NMR analysis graph of the block copolymer of Example 3 shows that, unlike the NMR analysis graph of the polymer of Comparative Example 1, a poly(3-hydroxypropionate) peak appears. Confirmed.
  • the integral ratio of the poly(3-hydroxypropionate) peak was calculated from the NMR analysis result graphs of Examples 1 to 4, and this was poly(3-hydroxypropionate analyzed by NMR in Table 3 below. ) Content'.
  • Example 1 Example 2
  • Example 3 Example 4 Actual content of poly(3-hydroxypropionate) used 0.160 g 0.800 g 1.600 g 0.320 g Content of poly(3-hydroxypropionate) analyzed by NMR 0.384 g 0.800 g 1.600 g 0.640 g
  • Example 3 the poly(3-hydroxypropionate) peak appears in NMR analysis in Examples 1, 2 and 4, and in particular, the method for preparing the block copolymer of Examples 1 to 4 It can be predicted that the poly(3-hydroxypropionate) oligomer used in was mostly used as a reactant.
  • the block copolymers of Examples 1 to 4 and the polymers of Comparative Examples 1 and 2 were subjected to gel permeation chromatography (GPC) (Waters: Waters707) to determine weight average molecular weight (Mw) and number average molecular weight (Mn).
  • GPC gel permeation chromatography
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • the block copolymer/polymer to be measured was dissolved in chloroform to a concentration of 4000 ppm, and 100 ⁇ l was injected into GPC. Chloroform was used as the mobile phase of GPC, flow rate was 1.0 mL/min, and analysis was performed at 35°C.
  • the column was connected to 4 Waters HR-05,1,2,4E in series. As a detector, it was measured at 35°C using RI and PAD Detecter.
  • Mn theoric Number average molecular weight
  • Mw Weight average molecular weight
  • PDI Polyvariance Index
  • -Mn theorical Theoretical number average molecular weight calculated using the molar ratio of the initiator- Polydispersity Index (PDI): Calculated by dividing the measured weight average molecular weight by the number average molecular weight.
  • PDI initiator- Polydispersity Index
  • the tensile elongation of the film was measured according to the measurement method of IPC-TM-650 using a tensile strength meter (manufacturer: Instron, model name: 3345 UTM) for the prepared specimen.
  • Example 1 Example 4 Comparative Example 1 Tensile elongation (%) 225 130 2.5

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un copolymère séquencé, le procédé comprenant une étape de polymérisation par ouverture de cycle de monomères de lactide en présence d'un initiateur de poly(3-hydroxypropionate) pour préparer un copolymère séquencé de polylactide-poly(3-hydroxypropionate).
PCT/KR2020/003638 2019-03-26 2020-03-17 Procédé de préparation d'un copolymère séquencé WO2020197147A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US17/269,963 US11840604B2 (en) 2019-03-26 2020-03-17 Process for preparation of block copolymer
CN202080003703.3A CN112689653B (zh) 2019-03-26 2020-03-17 嵌段共聚物的制备方法
EP20779074.2A EP3795606B1 (fr) 2019-03-26 2020-03-17 Procédé de préparation d'un copolymère séquencé
JP2020571536A JP7171120B2 (ja) 2019-03-26 2020-03-17 ブロック共重合体の製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20190034613 2019-03-26
KR10-2019-0034613 2019-03-26
KR10-2020-0031968 2020-03-16
KR1020200031968A KR102539511B1 (ko) 2019-03-26 2020-03-16 블록 공중합체 제조 방법

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115803359A (zh) * 2021-02-24 2023-03-14 株式会社Lg化学 具有优异的拉伸强度的聚(乳酸-b-3-羟基丙酸)嵌段共聚物和包含其的制品
EP4163316A4 (fr) * 2021-02-24 2023-09-27 Lg Chem, Ltd. Copolymère séquencé de poly(acide lactique-acide b-3-hydroxypropionique) présentant une excellente résistance à la traction, et produit le comprenant

Citations (1)

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US20110245420A1 (en) * 2008-11-13 2011-10-06 Rasal Rahul M Copolymer including polylactic acid, acrylic acid and polyethylene glycol and processes for making the same

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US20110245420A1 (en) * 2008-11-13 2011-10-06 Rasal Rahul M Copolymer including polylactic acid, acrylic acid and polyethylene glycol and processes for making the same

Non-Patent Citations (5)

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Title
HIKI S; MIYAMOTO M; KIMURA Y: "Synthesis and characterization of hydroxy-terminated [RS]-poly (3-hydroxybutyrate) and its utilization to block copolymerization with L-lactide to obtain a biodegradable thermoplastic elastomer", POLYMER, vol. 41, 2000, pages 7369 - 7379, XP004200600, DOI: 10.1016/S0032-3861(00)00086-0 *
JEONG WOOK LEE; HYUN UK KIM; SOL CHOI; JONGHO YI; SANG YUP LEE: "Microbial production of building block chemicals and polymers", CURRENT OPINION IN BIOTECHNOLOGY, vol. 22, 17 March 2011 (2011-03-17), pages 758 - 767, XP028397462, DOI: 10.1016/j.copbio.2011.02.011 *
JULIEN RAMIER, RENARD ESTELLE, GRANDE DANIEL: "Microwave-Assisted Synthesis and Characterization of Biodegradable Block Copolyesters Based on Poly(3-hydroxyalkanoate)s and Poly(D,L-lactide", JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY, vol. 50, no. 7, 1 April 2012 (2012-04-01), pages 1445 - 1455, XP055743447 *
LAKSHMI TRIPATHI, WU LIN-PING, MENG DECHUAN, CHEN JINCHUN, CHEN GUO-QIANG: "Biosynthesis and Characterization of Diblock Copolymer of P(3-Hydroxypropionate)-block-P(4-hydroxybutyrate) from Recombinant Escherichia coli", BIOMACROMOLECULES, vol. 14, no. 3, 25 January 2013 (2013-01-25), pages 862 - 870, XP055743450 *
See also references of EP3795606A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115803359A (zh) * 2021-02-24 2023-03-14 株式会社Lg化学 具有优异的拉伸强度的聚(乳酸-b-3-羟基丙酸)嵌段共聚物和包含其的制品
EP4163316A4 (fr) * 2021-02-24 2023-09-27 Lg Chem, Ltd. Copolymère séquencé de poly(acide lactique-acide b-3-hydroxypropionique) présentant une excellente résistance à la traction, et produit le comprenant

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