WO2009082924A1 - Procédé de préparation d'acide l-polylactique de poids moléculaire élevé - Google Patents

Procédé de préparation d'acide l-polylactique de poids moléculaire élevé Download PDF

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Publication number
WO2009082924A1
WO2009082924A1 PCT/CN2008/073518 CN2008073518W WO2009082924A1 WO 2009082924 A1 WO2009082924 A1 WO 2009082924A1 CN 2008073518 W CN2008073518 W CN 2008073518W WO 2009082924 A1 WO2009082924 A1 WO 2009082924A1
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WIPO (PCT)
Prior art keywords
lactic acid
molecular weight
acid
solid phase
phase polymerization
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Application number
PCT/CN2008/073518
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English (en)
Chinese (zh)
Inventor
Jianhua Ma
Shigen Bao
Yujun Zhu
Shiliang Wang
Xiaowu Xie
Jing Wu
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Anhui Zhongren Science & Technology Co., Ltd.
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Application filed by Anhui Zhongren Science & Technology Co., Ltd. filed Critical Anhui Zhongren Science & Technology Co., Ltd.
Publication of WO2009082924A1 publication Critical patent/WO2009082924A1/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
    • 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 process for preparing a biodegradable high molecular weight poly(L-lactic acid) by melt polycondensation-solid phase polymerization using tartaric acid as a central molecule.
  • the first step is to reduce the discharge of waste plastics and replace the existing petroleum products with new types of materials with natural degradation ability, so as to save valuable non-renewable resources and reduce environmental pollution.
  • Polylactic acid or lactic acid copolymer prepared from lactic acid comes from renewable plant resources, which not only can alleviate the supply shortage of non-renewable resources such as oil and coal, but also eliminates environmental pollution caused by its degradability. Become the most promising material for the 21st century. Although the large-molecular-weight polylactic acid prepared by the conventional two-step open-loop polymerization process can have good processing properties instead of plastic, the current production cost is relatively high and cannot be widely used.
  • the polylactic acid is prepared by direct melt polycondensation.
  • the molecular weight of polylactic acid is difficult to exceed 100,000.
  • the molecular weight can be further increased by solid phase polymerization after melt polycondensation, the molecular weight of polylactic acid can only reach about 200,000 from the current published data.
  • S.I. Moon et al. have done a lot of work in this area (Polymer, 2001, volume 42, Issuell, 5059-5062).
  • ZL 200410041426.8, ZL 200410052604.7 which have greatly improved the molecular weight of polylactic acid, but the molecular weight it can achieve cannot meet the requirements of using polylactic acid as a general plastic application.
  • the present invention is a process for melt polycondensation-solid phase polymerization using L-lactic acid and tartaric acid as a raw material to prepare a biodegradable high molecular weight branched poly(L-lactic acid).
  • a biodegradable high molecular weight branched poly(L-lactic acid) For the polymer obtained by the polymerization of L-lactic acid and tartaric acid, in which tartaric acid acts as a central molecule of the reaction, like a crosslinking agent, the resulting polymer is also referred to in the art as poly(L-lactic acid).
  • Tartaric acid has two carboxyl groups and two hydroxyl groups, and it is easy to form a four-arm branched poly(L-lactic acid) by polycondensation with L-lactic acid. Since the number of hydroxyl groups and carboxyl groups in the four terminal groups of the branched poly(L-lactic acid) is equal, the molecular weight can be further increased by solid phase polymerization, and branched poly(L-lactic acid) having a molecular weight of more than one million can be synthesized. The increase in molecular weight increases the mechanical strength of the product; the branched molecular structure reduces the melt viscosity of the product, facilitates melt processing, and also improves the brittleness of the product.
  • tartaric acid is a tetrafunctional molecule, a crosslinking reaction occurs when the amount is too large to form a thermosetting poly(L-lactic acid); when the amount of tartaric acid is appropriate, a high molecular weight branched poly(L-lactic acid) can be produced by polycondensation-solid phase polymerization.
  • tartaric acid is a food additive, the resulting poly(L-lactic acid) has good safety and biodegradability.
  • the invention has the following steps:
  • the advantage of the present invention is that it does not require special reaction equipment, and uses inexpensive L-lactic acid and tartaric acid as raw materials, and the amount of catalyst is small, and it is not necessary to use an organic solvent to refine the product, so the production cost is low.
  • the obtained poly(L-lactic acid) has a molecular weight of 30 to 1.5 million, and has high mechanical strength and good processing performance.
  • the implementation method is as follows:
  • the negative pressure removes free water and a small amount of reaction water.
  • the reaction temperature is raised while the degree of vacuum is increased.
  • the temperature rises to 150 ⁇ 200 °C keep the pressure at 100 ⁇ 2,500Pa, and react for 8 ⁇ 20 hours.
  • the material is discharged and cooled to obtain a crude poly(L-lactic acid) prepolymer having a colorless transparent resin and a molecular weight of 10,000 to 50,000.
  • the catalyst used in the polycondensation reaction is an inorganic acid such as sulfuric acid or phosphoric acid; an inorganic tin such as stannous oxide, stannous chloride or tin tetrachloride; or an organic tin such as stannous octoate or monobutyl sesquioxide.
  • the amount of the catalyst is 0.03 - 0.5 % of L-lactic acid.
  • Solid phase polymerization The prepolymer is pulverized into 20 to 200 mesh fine particles, and placed in a vacuum reactor such as a vacuum oven, a vacuum dryer or a vacuum kneader for solid phase polymerization.
  • the temperature is controlled at 120 ⁇ 170 ° C, the pressure is 100 ⁇ 3,000 Pa, and the reaction is 24 ⁇ 120 hours, and a high molecular weight branched poly(L-lactic acid) having a molecular weight of 3 to 1.5 million can be obtained.
  • the catalyst used in the invention has a small amount of catalyst, high catalytic activity and high speed, greatly shortens the production cycle, is advantageous for improving industrial production efficiency, and reduces cost, and at the same time, the molecular weight of the obtained poly(L-lactic acid) is large.
  • the residual catalyst in the product can be extracted and separated by water or dilute acid. After the wastewater is neutralized, it can be used as non-living water without polluting the environment. detailed description
  • Example 3 The experimental apparatus and operation were the same as in Example 1, 500 g of L-lactic acid (concentration: 90.0%, optical purity: 97.6%), 3.77 g of tartaric acid, 0.24 ml of sulfuric acid (98%), and the reaction time after the temperature was raised to 190 Q C was 12 hours.
  • the molecular weight of the obtained poly(L-lactic acid) prepolymer was 22,400.
  • the pressure in the vacuum oven was 1,500 Pa
  • the temperature was 160 ° C
  • the polymerization time was 72 hours
  • the crosslinked poly(L-lactic acid) was obtained, and the gel fraction was 52%.
  • Example 4 The experimental apparatus and operation were the same as in Example 1, 500 g of L-lactic acid (concentration: 90.0%, optical purity: 97.6%), 3.77 g of tartaric acid, 0.12 ml of sulfuric acid (98%), and the reaction time after the temperature was raised to 180 Q C was 16 hours.
  • the molecular weight of the obtained poly(L-lactic acid) prepolymer was 20,300.
  • the pressure in the vacuum oven was 1,500 Pa
  • the temperature was 150 ° C
  • the polymerization time was 48 hours
  • the branched poly(L-lactic acid) was obtained, and the molecular weight was 348,000.
  • Example 4 Example 4:
  • Example 5 The experimental apparatus and operation were the same as in Example 1, 500 g of L-lactic acid (concentration: 90.0%, optical purity: 97.6%), 2.52 g of tartaric acid, 0.92 g of stannous chloride (98%), and the reaction time after the temperature was raised to 180 Q C.
  • the resulting poly(L-lactic acid) prepolymer had a molecular weight of 38,200 for 18 hours.
  • the pressure in the vacuum oven was 1,200 Pa
  • the temperature was 155 ° C
  • the polymerization time was 72 hours
  • the branched poly(L-lactic acid) was obtained, and the molecular weight was 735,000.
  • Example 5 Example 5:
  • Example 2 The experimental apparatus and operation were the same as in Example 1, 500 g of L-lactic acid (concentration: 90.0%, optical purity: 97.6%),
  • Example 7 The experimental apparatus and operation were the same as in Example 1, 500 g of L-lactic acid (concentration: 90.0%, optical purity: 97.6%), 0.96 g of tartaric acid, 1.38 g of stannous chloride (98%), and the reaction time after the temperature was raised to 190 Q C.
  • the molecular weight of the obtained poly(L-lactic acid) prepolymer was 47,300 for 20 hours.
  • the pressure in the vacuum oven was 1,500 Pa
  • the temperature was 150 ° C
  • the polymerization time was 120 hours
  • the branched poly(L-lactic acid) was obtained, and the molecular weight was 863,000.
  • Example 8 The experimental apparatus and operation were the same as in Example 1, 500 g of L-lactic acid (concentration: 90.0%, optical purity: 97.6%), 0.85 g of tartaric acid, and 1.82 g of stannous octoate. The reaction time after the temperature was raised to 180 Q C was 18 hours.
  • the poly(L-lactic acid) prepolymer has a molecular weight of 42,400. In the solid phase polymerization, the pressure in the vacuum oven was 1,500 Pa, the temperature was 155 ° C, the polymerization time was 72 hours, and the branched poly(L-lactic acid) was obtained, and the molecular weight was 378,000.
  • Example 8 Example 8
  • Example 2 The experimental apparatus and operation were the same as in Example 1, 500 g of L-lactic acid (concentration: 90.0%, optical purity: 97.6%),
  • Example 10 The experimental apparatus and operation were the same as in Example 1, 500 g of L-lactic acid (concentration 90.0%, optical purity 97.6%), 2.53 g of tartaric acid, 1.38 g of stannous chloride (98%), and the reaction time after the temperature was raised to 180 Q C. For 20 hours, the resulting poly(L-lactic acid) prepolymer had a molecular weight of 43,800.
  • the solid phase polymerization reactor is a rotary evaporator with a rotation speed of 10 rpm, an oil bath temperature of 160 ° C, a pressure of 1,800 Pa, a polymerization time of 120 hours, a branched poly(L-lactic acid), and a molecular weight of 1,408,000. .
  • Example 10 Example 10:
  • the experimental apparatus and operation were the same as in Example 1, 500 g of L-lactic acid (concentration: 90.0%, optical purity: 97.6%), 1.52 g of tartaric acid, and 0.24 ml of sulfuric acid (98%).
  • the reaction time after the temperature was raised to 175 Q C was 18 hours, and the obtained poly(L-lactic acid) prepolymer had a molecular weight of 35,200.
  • the solid phase polymerization reactor is a rotary evaporator with a rotation speed of 15 rpm, an oil bath temperature of 160 ° C, a pressure of 1,600 Pa, a polymerization time of 108 hours, a branched poly(L-lactic acid), and a molecular weight of 1,267,000. .

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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'acide L-polylactique de poids moléculaire élevé. Le procédé consiste à préparer un prépolymère en ajoutant, à de l'acide lactique, de l'acide tartarique et un catalyseur pour parvenir à la polycondensation du mélange, à broyer le prépolymère puis à soumettre ce dernier à une polymérisation en phase solide.
PCT/CN2008/073518 2007-12-24 2008-12-16 Procédé de préparation d'acide l-polylactique de poids moléculaire élevé WO2009082924A1 (fr)

Applications Claiming Priority (2)

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CN200710192246.3 2007-12-24
CNA2007101922463A CN101182369A (zh) 2007-12-24 2007-12-24 一种高分子量聚(l-乳酸)的制备方法

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WO2009082924A1 true WO2009082924A1 (fr) 2009-07-09

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Publication number Priority date Publication date Assignee Title
CN101182369A (zh) * 2007-12-24 2008-05-21 安徽中人科技有限责任公司 一种高分子量聚(l-乳酸)的制备方法
CN101921466B (zh) * 2009-06-10 2012-10-24 东丽纤维研究所（中国）有限公司 含有硫酸化合物的聚乳酸组合物及利用硫酸作催化剂制备聚乳酸的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11240941A (ja) * 1998-02-26 1999-09-07 Nishikawa Rubber Co Ltd 加水分解性及び生分解性のポリヒドロキシカルボン酸共重合樹脂の製造方法
CN1594393A (zh) * 2004-07-15 2005-03-16 合肥工业大学 一种熔融缩聚－固相聚合制备高分子量聚l－乳酸的方法
CN1718607A (zh) * 2004-07-07 2006-01-11 同济大学 固相聚合制备高分子量聚乳酸的方法
CN101182369A (zh) * 2007-12-24 2008-05-21 安徽中人科技有限责任公司 一种高分子量聚(l-乳酸)的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11240941A (ja) * 1998-02-26 1999-09-07 Nishikawa Rubber Co Ltd 加水分解性及び生分解性のポリヒドロキシカルボン酸共重合樹脂の製造方法
CN1718607A (zh) * 2004-07-07 2006-01-11 同济大学 固相聚合制备高分子量聚乳酸的方法
CN1594393A (zh) * 2004-07-15 2005-03-16 合肥工业大学 一种熔融缩聚－固相聚合制备高分子量聚l－乳酸的方法
CN101182369A (zh) * 2007-12-24 2008-05-21 安徽中人科技有限责任公司 一种高分子量聚(l-乳酸)的制备方法

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