WO2011060650A1 - Copolyester aromatique-aliphatique biodégradable et son procédé de préparation - Google Patents

Copolyester aromatique-aliphatique biodégradable et son procédé de préparation Download PDF

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Publication number
WO2011060650A1
WO2011060650A1 PCT/CN2010/075536 CN2010075536W WO2011060650A1 WO 2011060650 A1 WO2011060650 A1 WO 2011060650A1 CN 2010075536 W CN2010075536 W CN 2010075536W WO 2011060650 A1 WO2011060650 A1 WO 2011060650A1
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Prior art keywords
acid
copolyester
preparation
biodegradable
molecular weight
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PCT/CN2010/075536
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English (en)
Chinese (zh)
Inventor
顾群
黎俊
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中国科学院宁波材料技术与工程研究所
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Publication of WO2011060650A1 publication Critical patent/WO2011060650A1/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
    • 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
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • 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
    • C08G63/80—Solid-state polycondensation

Definitions

  • the present invention relates to a copolyester of biodegradable polylactic acid or polyglycolic acid, polyglycol and aromatic polyester, and to a process for preparing the copolyester. Background technique
  • Aromatic polyesters such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate ( ⁇ ), due to its excellent mechanical properties, It is widely used in heat resistance and chemical resistance, and is currently used mainly in the fields of fibers, packaging and coatings. However, aromatic polyesters have a long degradation cycle, and their extensive use has caused great environmental pollution, making an unfriendly environment unfriendly material.
  • PET polyethylene terephthalate
  • PTT polytrimethylene terephthalate
  • ⁇ polybutylene terephthalate
  • PET is mainly blended with natural polymers or synthetic polymer materials such as starch, PLA, PEG and PCL.
  • natural polymers or synthetic polymer materials such as starch, PLA, PEG and PCL.
  • the results of blending show that the degradation of easily degradable components can induce partial biodegradation of non-degradable materials.
  • Bastoli has mentioned in Chinese patent application CN148961 that blending an aromatic-aliphatic polyester, an aliphatic polyester and a polylactic acid polymer can obtain a blend material having good biodegradability.
  • the degradation properties of the aromatic polyester are improved mainly by introducing structural units or segments of the aliphatic polyester onto the main chain of the aromatic polyester.
  • Significant results have been achieved in this area, such as the PBAT copolyesters produced by BASF and Dupont under the trade names Ecoflex and Biomax, which are made from butanediol, adipic acid and terephthalic acid.
  • Ecoflex and Biomax which are made from butanediol, adipic acid and terephthalic acid.
  • the polycondensation reaction is synthesized and is a typical fully biodegradable aromatic-aliphatic copolyester material.
  • PET-PBS Polym. Degrad. Stabi l.
  • PET -PHB Imu et al., Japanese Patent, 08 217 865 A2
  • PET-PCL Tokiwa et al. Polymer degradation stability (Polym. Degrad. Stabi l.), 1994; 45: 205)
  • PET-PEA He idary Environmental Polymer Degradation (J. Environ. Polym. Degrad.), 1994; 2: 19)
  • PET-PGA Nekraszewicz and other Polish patents Pol i sh patent, 171 062 Bl; Polymer Preparation (Polym. Prepr.) , 1989; 30: 197).
  • polyalcoholic acid (PLA), polyglycolic acid (PGA) and other hydroxyalkyd polymers are a very promising biodegradable material. They not only have good biodegradability, but also have biomass properties.
  • Environmentally friendly materials The main chain of these substances consists of ester bonds, which are easily degraded into oligomers or monomers by a large number of microorganisms or enzymes in animals and plants in nature, and then converted into carbon dioxide and water by microorganisms. It is a completely natural circulation type.
  • Biodegradable materials therefore, copolymerization of such polymers with aromatic polyesters can develop a biodegradable copolyester material.
  • Acar et al. (Polym-Plast Tech Eng 2006; 45: 351-59) reported the use of polylactic acid and recycled PET polyester as raw materials, dibutyltin oxide as catalyst in o-nitrophenol solution. The copolymerization was carried out to obtain a multi-block copolyester of polyethylene terephthalate-poly-L-lactic acid, but they were not reported on material-related properties and structures.
  • Olewnik et al. reported a multi-block copolyester of polyethylene terephthalate-poly L-lactic acid.
  • the transesterification catalyst used in the system stannous chloride and p-toluenesulfonic acid, easily catalyze the formation of by-product lactide at the higher temperature by the lactic acid multimer, and consume a large amount of polylactic acid;
  • the alcohol ester multimer has a high melting point (210 ⁇ 225 °C), high transesterification temperature, and polylactic acid is easily degraded at a high transesterification temperature, so that the polycondensation reaction of the system cannot be completely carried out, so the obtained product
  • the molecular weight is only a few thousand and cannot be used as a material.
  • the first technical problem to be solved by the present invention is to provide an aromatic-aliphatic copolyester having a high molecular weight, easy synthesis, and biodegradability in view of the above state of the art.
  • a second technical problem solved by the present invention is to provide a process for preparing an aromatic-aliphatic copolyester which is simple and inexpensive.
  • a biodegradable copolyester consisting of one or more aromatic polyester structural units, a polyglycol structural unit and polylactic acid, It is composed of one or more structural units in a polyhydroxy acid polyester such as polyglycolic acid.
  • the technical solution adopted by the present invention to solve the above second technical problem is: first melt polycondensation, followed by solid phase polycondensation. details as follows:
  • the transesterification product of the aromatic polyester and the polyglycol and the hydroxy acid polyester prepolymer are subjected to melt polycondensation under the action of a catalyst under the action of a catalyst of 160 to 300 Torr under reduced pressure, and the reaction is carried out. 5-8h to obtain a certain molecular weight of the copolymer; then add a certain amount of catalyst, melt and mix evenly and then extrude granulation to obtain the initial section; finally sliced in 140 ⁇ 17 (TC, high vacuum conditions (0. 03KPa) Solid phase polycondensation is carried out, and a high molecular weight copolyester is obtained after 6 to 32 hours of reaction.
  • the invention has the advantages that: the copolyester of the invention is easy to synthesize, has high molecular weight, can be a biodegradable material, and combines the heat resistance of the aromatic polyester with the aliphatic polyester.
  • the biodegradability, the copolymer can be widely applied to fiber materials and plastic products, and the preparation method is simple in process and low in cost.
  • the mixture of the mixture is added in a one-liter reaction vessel at 230 ⁇ 250 ° C, 0. 3 ⁇ 0.
  • the prepolymer of the intrinsic viscosity is 0.32.
  • the polycondensation reaction is carried out at a temperature of 270 to 280 ° C, 0. 07 KPa, and a prepolymer having an intrinsic viscosity of 0.32 is finally obtained.
  • the lyophilized solution of the aqueous solution of L-lactic acid (88%) (200%) and the mixture of 3 g of butane diol was subjected to atmospheric distillation in a liter polymerization vessel. After dehydration was more than 90%, 0.02 g of stannous octoate catalyst was added, and the mixture was stirred and heated to 180 ° C. The pressure was gradually reduced to 70 Pa, and preliminary polycondensation was carried out for 2 hours to obtain a white powdery terminal hydroxylactic acid prepolymer.
  • the prepolymer had a weight average molecular weight of 5 kg/mol as determined by gel permeation chromatography (GPC), and a melting point of 126 ° C as measured by differential scanning calorimetry (DSC). 4) Preparation of polyethylene terephthalate-polyethylene glycol-polylactic acid
  • the mixture of the mixture is added in a one-liter reaction vessel at 230 ⁇ 250 ° C, 0. 3 ⁇ 0.
  • the prepolymer of the intrinsic viscosity is 0.32.
  • the polycondensation reaction is carried out at a temperature of 270 to 280 ° C, 0. 07 KPa, and a prepolymer having an intrinsic viscosity of 0.32 is finally obtained.
  • the lyophilized solution of the aqueous solution of L-lactic acid (88%) (200%) and the mixture of 3 g of butane diol was subjected to atmospheric distillation in a liter polymerization vessel. After dehydration was more than 90%, 0.02 g of stannous octoate catalyst was added, and the mixture was stirred and heated to 180 ° C. The pressure was gradually reduced to 70 Pa, and the initial polycondensation was carried out for 2 hours to obtain a white powdery terminal hydroxylactic acid prepolymer.
  • the prepolymer had a weight average molecular weight of 5 kg/mol as determined by gel permeation chromatography (GPC) and a melting point of 126 ° C by differential scanning calorimetry (DSC).
  • the mixture of the mixture is added in a one-liter reaction vessel at 230 ⁇ 250 ° C, 0. 3 ⁇ 0.
  • the prepolymer of the intrinsic viscosity is 0.32.
  • the polycondensation reaction is carried out at a temperature of 270 to 280 ° C, 0. 07 KPa, and a prepolymer having an intrinsic viscosity of 0.32 is finally obtained.
  • the lyophilized solution of the aqueous solution of L-lactic acid (88%) (200%) and the mixture of 3 g of butane diol was subjected to atmospheric distillation in a liter polymerization vessel. After dehydration was more than 90%, 0.02 g of stannous octoate catalyst was added, and the mixture was stirred and heated to 180 ° C. The pressure was gradually reduced to 70 Pa, and preliminary polycondensation was carried out for 2 hours to obtain a white powdery terminal hydroxylactic acid prepolymer.
  • the prepolymer had a weight average molecular weight of 5 kg/mol as determined by gel permeation chromatography (GPC) and a melting point of 126 ° C by differential scanning calorimetry (DSC).
  • the mixture of the mixture is added in a one-liter reaction vessel at 230 ⁇ 250 ° C, 0. 3 ⁇ 0.
  • the prepolymer BHET having an intrinsic viscosity of 0.32 is obtained.
  • the polycondensation reaction is carried out at a temperature of 270 to 280 ° C.
  • the lyophilized solution of the aqueous solution of L-lactic acid (88%) (200%) and the mixture of 3 g of butane diol was subjected to atmospheric distillation in a liter polymerization vessel. After dehydration was more than 90%, 0.02 g of stannous octoate catalyst was added, and the mixture was stirred and heated to 180 ° C. The pressure was gradually reduced to 70 Pa, and preliminary polycondensation was carried out for 2 hours to obtain a white powdery terminal hydroxylactic acid prepolymer.
  • the prepolymer had a weight average molecular weight of 5 kg/mol as determined by gel permeation chromatography (GPC) and a melting point of 126 ° C by differential scanning calorimetry (DSC).
  • the prepolymer BHTT having an intrinsic viscosity of 0.45 is obtained by the polycondensation reaction at a temperature of 250 to 260 ° C, 0. 07 KPa. .
  • the poly(trimethylene terephthalate-polyethylene glycol) having an intrinsic viscosity of 0.53 was obtained after blending for 30 minutes under vacuum ( ⁇ 0.07 KPa), and then rapidly heating to about 255 for transesterification and polycondensation. Block copolymer.
  • the lyophilized solution of the aqueous solution of L-lactic acid (88%) (200%) and the mixture of 3 g of butane diol was subjected to atmospheric distillation in a liter polymerization vessel. After dehydration was more than 90%, 0.02 g of stannous octoate catalyst was added, and the mixture was stirred and heated to 180 ° C. The pressure was gradually reduced to 70 Pa, and preliminary polycondensation was carried out for 2 hours to obtain a white powdery terminal hydroxylactic acid prepolymer.
  • the prepolymer had a weight average molecular weight of 5 kg/mol as determined by gel permeation chromatography (GPC) and a melting point of 126 ° C by differential scanning calorimetry (DSC).
  • Solid phase polycondensation 50g of the above slice was subjected to solid phase polycondensation at 150 ° C under high vacuum ( ⁇ 0. 03 KPa), and polycondensation was carried out for 33 h to obtain a high molecular weight polytrimethylene terephthalate-polyethylene glycol-polylactic acid copolymer, as determined by GPC.
  • the weight average molecular weight was 92 kg/mol.

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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 copolyester aromatique-aliphatique biodégradable, constitué d'un motif structural de type polyester aromatique, d'un motif structural de type polydiol et d'un motif structural de type polyester de polyhydroxyacide. Ledit copolyester peut être obtenu par polycondensation à l'état fondu-polycondensation en phase solide, d'un polydiol, d'acide polylactique et d'un polyester aromatique à bas point de fusion.
PCT/CN2010/075536 2009-11-23 2010-07-29 Copolyester aromatique-aliphatique biodégradable et son procédé de préparation WO2011060650A1 (fr)

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CN200910153947.5 2009-11-23
CN2009101539475A CN101717494B (zh) 2009-11-23 2009-11-23 一种可生物降解的芳香族-脂肪族共聚酯的制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101717494B (zh) * 2009-11-23 2012-07-18 中国科学院宁波材料技术与工程研究所 一种可生物降解的芳香族-脂肪族共聚酯的制备方法
CN101864062B (zh) * 2010-06-07 2012-05-23 中国科学院宁波材料技术与工程研究所 一种不饱和聚乳酸嵌段共聚物及其制备方法
CN102827362B (zh) * 2011-05-12 2014-04-09 中国科学院宁波材料技术与工程研究所 一种聚乳酸嵌段共聚物
CN103113561B (zh) * 2011-10-12 2014-08-06 苏州莫立克新型材料有限公司 一种可快速降解的聚酯类聚合物及其制备方法和应用
CN105367770B (zh) * 2014-08-29 2018-06-29 中国科学院长春应用化学研究所 一种脂肪族-芳香族-聚乳酸嵌段共聚物
CN109438682B (zh) * 2018-11-16 2022-04-26 中国科学院宁波材料技术与工程研究所 共聚酯及其制备方法、制品
CN109762143A (zh) * 2019-01-29 2019-05-17 中国科学院理化技术研究所 可水解的共聚酯及其制备方法和应用
CN111393620B (zh) * 2020-04-22 2022-07-05 浙江恒逸石化研究院有限公司 一种可降解聚对苯二甲酸丙二醇酯共聚酯的制备方法
CN115124702A (zh) * 2021-03-26 2022-09-30 华润化学材料科技股份有限公司 可降解的芳香族-脂肪族共聚酯材料及其制备方法和应用
CN115124699A (zh) * 2021-03-26 2022-09-30 华润化学材料科技股份有限公司 可降解的芳香族-脂肪族共聚酯材料及其制备方法和应用
CN115651174B (zh) * 2022-11-14 2023-03-10 富海(东营)新材料科技有限公司 有机胍催化合成生物降解pbat-pla共聚酯的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1476459A (zh) * 2000-11-30 2004-02-18 ����贻�ѧ��ҵ��ʽ���� 脂肪族聚酯共聚物及其制造方法、脂肪族聚酯系生物降解性树脂成形物、和含内酯的树脂
CN1675283A (zh) * 2002-07-03 2005-09-28 三菱化学株式会社 脂族聚酯聚醚共聚物、其制备方法及应用该共聚物的脂族聚酯组合物
CN1817939A (zh) * 2006-03-22 2006-08-16 南昌大学 原位酯交换低聚乳酸合成可降解性芳香/脂肪共聚酯的方法
CN101104680A (zh) * 2007-07-30 2008-01-16 南昌大学 三元反应性共混制备可降解共聚酯的方法
CN101492542A (zh) * 2008-01-25 2009-07-29 东丽纤维研究所（中国）有限公司 一种从聚酯预聚物和聚醚预聚物制备嵌段聚酯聚醚共聚物的方法
CN101717494A (zh) * 2009-11-23 2010-06-02 中国科学院宁波材料技术与工程研究所 一种可生物降解的芳香族-脂肪族共聚酯及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3307748B2 (ja) * 1993-03-31 2002-07-24 大日本インキ化学工業株式会社 乳酸系共重合ポリエステルの製造方法
RU2312871C2 (ru) * 2003-08-12 2007-12-20 Мицуи Кемикалз, Инк. Смола на основе сложного полиэфира и формованный продукт из ламината на основе смолы из сложного полиэфира
CN101412804B (zh) * 2008-11-23 2011-01-19 浙江大学宁波理工学院 制备芳香族-脂肪族共聚酯的方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1476459A (zh) * 2000-11-30 2004-02-18 ����贻�ѧ��ҵ��ʽ���� 脂肪族聚酯共聚物及其制造方法、脂肪族聚酯系生物降解性树脂成形物、和含内酯的树脂
CN1675283A (zh) * 2002-07-03 2005-09-28 三菱化学株式会社 脂族聚酯聚醚共聚物、其制备方法及应用该共聚物的脂族聚酯组合物
CN1817939A (zh) * 2006-03-22 2006-08-16 南昌大学 原位酯交换低聚乳酸合成可降解性芳香/脂肪共聚酯的方法
CN101104680A (zh) * 2007-07-30 2008-01-16 南昌大学 三元反应性共混制备可降解共聚酯的方法
CN101492542A (zh) * 2008-01-25 2009-07-29 东丽纤维研究所（中国）有限公司 一种从聚酯预聚物和聚醚预聚物制备嵌段聚酯聚醚共聚物的方法
CN101717494A (zh) * 2009-11-23 2010-06-02 中国科学院宁波材料技术与工程研究所 一种可生物降解的芳香族-脂肪族共聚酯及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHU XIANGJUN: "Syntheses of Aliphatic-aromatic Copolyesters by a Melting Bulk Reactive lending and Its Biodegrability", CHINESE MASTER'S THESES FULL-TEXT DATABASE, ENGINEERING SCIENCE AND TECHNOLOGY, vol. 1, 15 June 2008 (2008-06-15) *

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