WO2015108254A1 - Copolymère d'acide polylactique-polyalkylène glycol ayant une vitesse de cristallisation rapide, et composition le contenant - Google Patents

Copolymère d'acide polylactique-polyalkylène glycol ayant une vitesse de cristallisation rapide, et composition le contenant Download PDF

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WO2015108254A1
WO2015108254A1 PCT/KR2014/005295 KR2014005295W WO2015108254A1 WO 2015108254 A1 WO2015108254 A1 WO 2015108254A1 KR 2014005295 W KR2014005295 W KR 2014005295W WO 2015108254 A1 WO2015108254 A1 WO 2015108254A1
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polylactic acid
polyalkylene glycol
glycol copolymer
group
integer
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PCT/KR2014/005295
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English (en)
Korean (ko)
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김완근
이도훈
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한화토탈 주식회사
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Priority to JP2016541537A priority Critical patent/JP6334712B2/ja
Priority to CN201480070469.0A priority patent/CN105934461B/zh
Publication of WO2015108254A1 publication Critical patent/WO2015108254A1/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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the present invention relates to a polylactic acid-polyalkylene glycol copolymer and a composition comprising the same, and more particularly, to a polylactic acid-polyalkylene glycol copolymer and a composition comprising the same, having a high crystallization rate and excellent processability and heat resistance. It is about.
  • plastics derived from petroleum have a wide range of applications, from necessities to aerospace materials, with easy control of mechanical properties and thermal stability. However, when these plastics are disposed of in the environment, they do not decompose and accumulate. Incineration of plastic waste also releases harmful by-products and large amounts of carbon dioxide, accelerating environmental pollution and global warming.
  • Polylactic acid is a relatively hard polymer, and its flexural modulus is similar to that of general-purpose plastics, but it lacks heat resistance and is not easily molded. Because of these disadvantages there is a limit that can not be applied to the field requiring high heat resistance. As a result, research has been conducted to compensate for the poor properties of polylactic acid by mixing polylactic acid with petroleum-based plastics such as polypropylene or polycarbonate, but in most cases, the content of polylactic acid does not exceed 50% by weight. It is difficult to call this.
  • crystallinity of the polymer In order to secure high heat resistance and moldability of polylactic acid, there is a method of improving the crystallinity of the polymer.
  • a nucleating agent to promote the crystallization rate of the polylactic acid hereinafter also referred to as crystallization degree. Crystal nucleating agents serve as primary crystal nuclei of crystalline polymers to promote crystal growth, to refine the crystal size, and to increase the crystallization rate.
  • Non-Patent Documents 1 and 2 suggest a method of adding a nucleating agent and a plasticizer as another method for increasing the degree of crystallization and the rate of crystallization of polylactic acid. Unlike the method of adding an excessive amount of plasticizer to give flexibility to the polymer, the method adds a certain amount of plasticizer to improve the mobility of the polymer chain to increase the crystallization rate (anti-plasticization).
  • plasticizer to improve the mobility of the polymer chain to increase the crystallization rate (anti-plasticization).
  • polylactic acid, talc and polyethylene glycol were mixed to lower the crystallization rate of polylactic acid, but the crystallization rate was not fast enough.
  • even when using less than 5% by weight of polyethylene glycol has a disadvantage that the surface spillage phenomenon is not easy injection molding.
  • a polylactic acid-polyethylene glycol copolymer is prepared by adding polyethylene glycol during the polymerization of polylactic acid.
  • the reaction takes a long time, a large amount of organic solvents harmful to the human body must be used, and the reaction conditions must be finely controlled.
  • crystallinity and crystallization rate the object of the present invention is to give flexibility in the production of polylactic acid film, there is a problem that the crystallinity is lowered by using a high content of polyethylene glycol.
  • Non Patent Literature 1 Polymer, 48, 6855 (2007)
  • Non-Patent Document 2 Society of Plastics Engineers, DOI: 10.1002 / spepro.002983
  • the present invention is to solve the problems of the prior art as described above, an object of the present invention is to use poly-lactic acid and polyethylene glycol modified at the end of the epoxy group in a short time through the extrusion reactor, the use of an organic solvent harmful to the human body It is to provide a polylactic acid-polyethylene glycol copolymer obtained without.
  • It is also an object of the present invention to provide a composition comprising a polylactic acid-polyethylene glycol copolymer having a high crystallinity and fast crystallization rate and excellent injection molding by adding a crystallization nucleating agent to the polylactic acid-polyethylene glycol copolymer.
  • the polylactic acid-polyalkylene glycol copolymer according to the present invention is prepared by the reaction of polylactic acid and polyalkylene glycol modified at the end of the epoxy group, characterized in that the polyalkylene glycol is contained 0.05 to 25% by weight do.
  • the polylactic acid may be L-polylactic acid or D-polylactic acid.
  • the weight average molecular weight of the polylactic acid is 10,000 g / mol or more, but less than 10,000 g / mol is not preferable because of poor workability and poor physical properties of the injected product.
  • the polyalkylene glycol is a polyalkylene glycol whose terminal is modified with epoxy, and may be selected from the group represented by the following Chemical Formulas 1, 2 and 3. .
  • R 1 is epoxy
  • R 2 is hydrogen, C 1 -C 8 alkyl group, alkenyl group, or aryl group
  • R 3 is C 1 -C 8 alkyl group, alkene group, alkenyl group, or aryl group
  • l is an integer from 0 to 200
  • m is an integer from 0 to 200. Also, the positions of l and m can be interchanged.
  • R 4 and R 8 are epoxy, R 5 to R 7 are hydrogen or a C 1 to C 8 alkyl group, alkenyl group, or aryl group, x is an integer from 0 to 100, y is 1 to 200 Is an integer of 0, and z is an integer of 0 to 100.
  • R 9 , R 14 and R 17 are epoxy, R 10 to R 13, R 15 and R 16 are hydrogen or a C 1 to C 8 alkyl group, alkenyl group, or aryl group, o is 1 to 200 Is an integer of 1, p is an integer of 1 to 200, q is an integer of 1 to 200.
  • the content of the polyalkylene glycol is 0.05 to 25% by weight, preferably 1 to 20% by weight based on the total weight of the copolymer. Preferably it is 2 to 10% by weight, but less than 0.05% by weight is undesirable because the copolymerization crystallization rate is lowered, when it exceeds 25% by weight, the stiffness of the polylactic acid is lowered than the faster the crystallization rate, unreacted polyalkyl The outflow of ethylene glycol is observed and is undesirable.
  • the polylactic acid-polyalkylene glycol copolymer according to the present invention may be obtained by melt extrusion reaction of the polylactic acid and polyalkylene glycol, and the carboxyl group or the hydroxyl group of the polylactic acid may be used during the melt reaction of the polylactic acid and the polyalkylene glycol. Copolymers may be prepared through chemical bonding of epoxy groups of polyalkylene glycols.
  • the temperature of the melting reaction is 160 ⁇ 250 °C, preferably 170 ⁇ 220 °C, more preferably 180 ⁇ 200 °C, if the melt reaction temperature is less than 160 °C polylactic acid resin does not melt and flowability is poor
  • the amide bond reaction is slowed down, which is undesirable. If the temperature exceeds 250 ° C., decomposition of the polylactic acid is accelerated, resulting in a low crystallization rate of the resin and a yellowing of the resin.
  • the polylactic acid-polyalkylene glycol copolymer according to the present invention does not use an organic solvent harmful to the human body, and since 90 wt% or more of the copolymer is made of biodegradable material, it has high environmentally friendly characteristics.
  • the polylactic acid-polyalkylene glycol copolymer according to the present invention is easy to injection molding, and the injected product is characterized by having excellent heat resistance. More specifically, the cycle time during injection molding is 10 times faster than general polylactic acid at 110 ° C, and the heat deformation temperature of the injection molded product is 70 ° C or higher, preferably 100 ° C or higher, and more preferably 115 ° C or higher. .
  • the polylactic acid-polyalkylene glycol copolymer may be used in molded products in the field where heat resistance is important, for example, automobile parts, battery electronic parts, machine parts, office equipment such as computers, and the like.
  • the polylactic acid-polyalkylene glycol copolymer composition according to the present invention is characterized by containing 0.01 to 5 parts by weight of a crystallization nucleating agent with respect to 100 parts by weight of the polylactic acid-polyalkylene glycol copolymer of the present invention.
  • crystallization nucleating agent polyglycolide, benzohydrazide derivative, talc, sodium stearate, calcium lactate, ethylene bis (12-hydroxystearylamide), terephthalimide derivative (terephthalimide) derivative: NU-100), 1,4-cyclohexanedicarboxylic dianilide, and zinc phenyl phosphate.
  • the amount of the crystallization nucleating agent is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the polylactic acid-polyalkylene glycol copolymer, but less than 0.01 parts by weight is not preferable because the crystallization rate is not fast. As I become saturated, the rate of crystallization no longer increases, which is economically undesirable.
  • the polylactic acid-polyalkylene glycol copolymer composition according to the present invention can be prepared by blending a crystallization nucleating agent together when melting the polylactic acid and polyalkylene glycol.
  • a crystallization nucleating agent in addition to the crystallization nucleating agent, conventional additives such as general lubricants, inorganic particles, heat stabilizers, antioxidants, and the like may be further blended.
  • the polylactic acid-polyalkylene glycol copolymer composition according to the present invention may have a higher degree of crystallinity and faster crystallization rate than general polylactic acid. More specifically, it is preferable that the crystallinity is 40% or more, and the crystallization rate (t 1/2 ) is 15 to 30 seconds when inducing crystal formation at 110 ° C.
  • the degree of crystallinity is measured by using a differential scanning calorimeter (DSC) to heat up to 200 ° C. at 10 ° C./min, comparing ⁇ H m , the amount of heat found at 150 to 180 ° C., with ⁇ H 0 m , the calculated melting point of polylactic acid. It is the obtained value.
  • DSC differential scanning calorimeter
  • the crystallization rate is the time that crystallization is completed on the basis of the time when the crystallization is started by increasing the temperature to 30 °C / min up to 200 °C using a polarizing microscope to maintain the temperature 200 °C to 100 °C / min for 3 minutes Is the measured value.
  • the polylactic acid-polyalkylene glycol copolymer prepared according to the present invention and a composition comprising the same have a high crystallization rate, high crystallinity, and high heat resistance, and thus may be usefully used in various applications.
  • L-polylactic acid resin 4032D, 3001D, and 3251D manufactured by NatureWorks LLC were used.
  • Polyalkylene glycol was used to modify the end of the epoxy prepared from Hajin Chemtech, Nagase Chemtech, Aldrich and the like.
  • Polylactic acid, polyalkylene glycol, and optionally crystallization nucleating agent were melt kneaded using a twin-screw extruder.
  • the polyalkylene glycol was injected into an extruder having an extrusion temperature of 180 to 200 ° C. using a liquid feeder, and after melt kneading, the polyalkylene glycol was obtained as a pellet using a pelletizer.
  • Heat deflection temperature was measured according to ASTM D648.
  • the relative crystallinity ⁇ c over time was calculated by Equation 1 below and the value was plotted on the graph as the time (seconds) compared to ⁇ c .
  • ⁇ c is 0.5
  • the corresponding time is defined as t 1/2 . It was.
  • I (t) is the light intensity at time t
  • I (0) is the light intensity before the crystallization of the resin starts
  • I ⁇ is the light intensity when the crystallization is completed.
  • ⁇ H m is the experimental value of the calorific value at the time of melting of the resin
  • ⁇ H 0 m is the calculated value of the calorific value at the melting of the polylactic acid resin, 93.1 J / g, this value is reported in Non-Patent Document 3 Was based on that.
  • Non-Patent Document 3 Kolloid Z. Z. Polym. 251, 980 (1973)
  • the pellet sample was completely dissolved in THF (tetrahydrofuran) at a concentration of 2 mg / ml, the sample was injected into Malvern's Viscotek OmniSEC GPC, and then the concentration of the polymer eluted by the RI detector was measured. The molecular weight according to) was measured.
  • Flexural strength test specimens were stored in a constant temperature and humidity chamber at a temperature of 60 ° C and a relative humidity of 90%, and then the change in flexural strength was measured at regular intervals.
  • compositions and physical properties of the compositions of Examples 1 to 2 and Comparative Examples 1 to 3 are shown in Table 1 below.
  • Example 1 to 2 and Comparative Examples 1 to 3 of Table 1 after mixing with the components and contents according to the composition of Table 1, and melt-kneaded in a twin screw extruder 190 °C extruded. After the pellet sample is dried at 80 ° C. for at least 4 hours, the temperature of the injection mold is maintained at 110 ° C., and after injection molding and left at room temperature for 24 hours, the physical properties of the specimens are measured in the same manner as described above. It is shown in Table 1 below.
  • B-1 Polyalkylene glycol having a weight average molecular weight of 1000 g / mol in which one end is modified with epoxy, trade name: EX-171, manufactured by Nagase ChemteX Corporation
  • B-2 Polyalkylene glycol having a weight average molecular weight of 600 g / mol whose both ends are modified with epoxy, trade name: HJ EPIOL-DE208, manufactured by Hajin Chemtech
  • B-3 Polyalkylene glycol having a weight average molecular weight of 2000 g / mol at one end of which is modified with an amine, product name: Jeffamine ® M-2070, manufactured by Huntsman Corporation
  • B-4 Polyalkylene glycol having an unmodified weight average molecular weight of 1000 g / mol, manufactured by YAKURI PURE CHEMICALS
  • Examples 1 and 2 are polylactic acid-polyalkylene glycol air prepared by using polyalkylene glycol modified at one end with epoxy and polyalkylene glycol modified at both ends with epoxy.
  • the composition and physical properties of the coalescing composition As shown in Table 1, the compositions of Examples 1 and 2 have high crystallinity, fast crystallization rate (t 1/2 ), and are easy to be injected because there is no surface leakage phenomenon of unreacted polyalkylene glycol.
  • the heat deflection temperatures of the compositions of Examples 1 and 2 were measured at 138 ° C. and 121 ° C., respectively, which were significantly higher than 56 ° C., the heat deflection temperature of general polylactic acid.
  • the weight average molecular weight of the copolymer of Example 1 and 2 with the comparative example 3 it can confirm that the molecular weight of the comparative example 3 is remarkably high as shown in Table 1.

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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)
  • General Chemical & Material Sciences (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

Cette invention concerne un copolymère d'acide polylactique-polyalkylène glycol ayant une excellente vitesse de cristallisation, et une composition le contenant. Le copolymère d'acide polylactique-polyalkylène glycol selon l'invention, préparé par une réaction à l'état fondu d'un acide polylactique avec un polyalkylène glycol dont une terminaison a été modifiée par un groupe époxy, est respectueux de l'environnement, facilite le moulage par injection, présente une excellente résistance thermique, et peut par conséquent être appliqué à divers produits moulés exigeant une résistance thermique tels que des articles jetables, des ustensiles de cuisine, des pièces électriques-électroniques et des pièces pour automobiles.
PCT/KR2014/005295 2014-01-17 2014-06-17 Copolymère d'acide polylactique-polyalkylène glycol ayant une vitesse de cristallisation rapide, et composition le contenant WO2015108254A1 (fr)

Priority Applications (2)

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JP2016541537A JP6334712B2 (ja) 2014-01-17 2014-06-17 速い結晶化速度を有するポリ乳酸−ポリアルキレングリコール共重合体およびこれを含む組成物
CN201480070469.0A CN105934461B (zh) 2014-01-17 2014-06-17 具有快的结晶化速度的聚乳酸-聚亚烷基二醇共聚物及包含其的组合物

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KR10-2014-0006233 2014-01-17
KR1020140006233A KR101555126B1 (ko) 2014-01-17 2014-01-17 빠른 결정화 속도를 갖는 폴리유산-폴리알킬렌글리콜 공중합체 및 이를 포함하는 조성물

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Citations (5)

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Publication number Priority date Publication date Assignee Title
KR20000042641A (ko) * 1998-12-26 2000-07-15 윤덕용 폴리에테르가 그라프트된 생분해성 지방족 폴리에스테르및 그의 제조방법
JP2007002128A (ja) * 2005-06-24 2007-01-11 New Japan Chem Co Ltd ポリ乳酸系樹脂組成物、その成形体及びそれらの製造方法
KR20130110776A (ko) * 2012-03-30 2013-10-10 에스케이씨 주식회사 폴리알킬렌글리콜 폴리락티드 수지
KR20130110777A (ko) * 2012-03-30 2013-10-10 에스케이씨 주식회사 고분자량의 폴리알킬렌글리콜과 락티드의 블록 공중합 폴리락티드
KR20140044077A (ko) * 2012-10-04 2014-04-14 삼성토탈 주식회사 빠른 결정화 속도를 갖는 폴리유산-폴리알킬렌글리콜 공중합체 및 이를 포함하는 조성물

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5593778A (en) * 1993-09-09 1997-01-14 Kanebo, Ltd. Biodegradable copolyester, molded article produced therefrom and process for producing the molded article
JP4063856B2 (ja) * 2004-03-04 2008-03-19 ユニチカ株式会社 生分解性ポリエステル樹脂組成物の製造方法
JP4609091B2 (ja) * 2005-02-01 2011-01-12 東レ株式会社 ポリ乳酸繊維
JP5739738B2 (ja) * 2011-06-13 2015-06-24 大阪瓦斯株式会社 ポリ乳酸樹脂組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000042641A (ko) * 1998-12-26 2000-07-15 윤덕용 폴리에테르가 그라프트된 생분해성 지방족 폴리에스테르및 그의 제조방법
JP2007002128A (ja) * 2005-06-24 2007-01-11 New Japan Chem Co Ltd ポリ乳酸系樹脂組成物、その成形体及びそれらの製造方法
KR20130110776A (ko) * 2012-03-30 2013-10-10 에스케이씨 주식회사 폴리알킬렌글리콜 폴리락티드 수지
KR20130110777A (ko) * 2012-03-30 2013-10-10 에스케이씨 주식회사 고분자량의 폴리알킬렌글리콜과 락티드의 블록 공중합 폴리락티드
KR20140044077A (ko) * 2012-10-04 2014-04-14 삼성토탈 주식회사 빠른 결정화 속도를 갖는 폴리유산-폴리알킬렌글리콜 공중합체 및 이를 포함하는 조성물

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CN105934461B (zh) 2018-06-26
KR101555126B1 (ko) 2015-09-22
JP6334712B2 (ja) 2018-05-30
JP2017500415A (ja) 2017-01-05
CN105934461A (zh) 2016-09-07
KR20150086073A (ko) 2015-07-27

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