WO2023165120A1 - Copolymère acide lactique/acide pentanoïque, procédé de préparation et stéréocomplexe de ce dernier - Google Patents

Copolymère acide lactique/acide pentanoïque, procédé de préparation et stéréocomplexe de ce dernier Download PDF

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Publication number
WO2023165120A1
WO2023165120A1 PCT/CN2022/121605 CN2022121605W WO2023165120A1 WO 2023165120 A1 WO2023165120 A1 WO 2023165120A1 CN 2022121605 W CN2022121605 W CN 2022121605W WO 2023165120 A1 WO2023165120 A1 WO 2023165120A1
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Prior art keywords
lactide
lactic acid
acid
preparation
acid copolymer
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PCT/CN2022/121605
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English (en)
Chinese (zh)
Inventor
康小玲
唐曦
郑伯川
梁勇军
李明全
刘晓花
邹志刚
唐圆桦
汪彦生
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上海东庚化工技术有限公司
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Publication of WO2023165120A1 publication Critical patent/WO2023165120A1/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a lactic acid/valeric acid copolymer, a preparation method and a stereocomplex thereof.
  • Polylactic acid also known as polylactide, is a polymer material obtained by polymerizing lactic acid as the main raw material. It can be used in injection molding, spinning, blown film, stretched film, 3D printing and other fields. The price of polylactic acid is relatively low, and it is currently recognized as one of the most cost-effective biodegradable polymer materials.
  • lactic acid is 2-hydroxypropionic acid or ⁇ -hydroxypropionic acid, which is the simplest ⁇ -hydroxycarboxylic acid.
  • Lactic acid molecule contains chiral carbon atoms, so it has two optical isomers.
  • the cyclic dimer-lactide obtained by dehydration polycondensation of lactic acid also has chirality.
  • the two chiral carbon atoms in the lactide molecule are both L-type or D-type, and the obtained lactide is L-lactide or D-lactide, and the obtained polylactic acid also has different optical activity. .
  • polylactic acids with the same chemical structure but different optical activity such as poly-L-lactic acid and poly-D-lactic acid
  • crystallization forms stereocomplex crystals.
  • polylactic acid stereocomplex crystal has a very high spherulite growth rate and a very short induction period, and the melting point of the formed copolymer is lower than that of homogeneous crystal.
  • the material is 50°C higher.
  • the patent document whose publication number is CN106366594A discloses a preparation method of a high-toughness polylactic acid blend containing a polylactic acid stereocomplex, which uses high optical purity D-polylactic acid at room temperature as The nucleating agent reacts with L-polylactic acid in a solvent for a period of time, which improves the toughness of the prepared polylactic acid blend.
  • the toughness of the blends prepared by this method needs to be further improved.
  • the object of the present invention is to provide a lactic acid/valeric acid copolymer, a preparation method and a stereocomplex thereof, so as to further improve the toughness of the polylactic acid stereoblend.
  • the present invention provides a kind of preparation method of lactic acid/valeric acid copolymer, comprising:
  • L-lactide also known as L-lactide
  • L-lactide also known as L-3,6-dipropyl-1,4-dioxane-2,5-dione, L-valerolide
  • the lactic acid/valeric acid copolymer is obtained by performing a polymerization reaction with dextrolactide (also known as D-lactide) and dextrolactide (also known as D-valerolide) as monomers.
  • dextrolactide also known as D-lactide
  • dextrolactide also known as D-valerolide
  • the polymerization reaction temperature is 120-150°C, preferably 125-150°C; the polymerization reaction time is 4-15h, preferably 5-15h.
  • the mass percentage of said L-lactide and L-valerolide is 50wt%-90wt%: 50wt%-10wt%, preferably 50wt%-80wt%: 50wt%-20wt%, the total amount of the two is 100% meter.
  • the mass percentage of D-lactide and D-valerolide is 50wt%-90wt%: 50wt%-10wt%, preferably 50wt%-80wt%: 50wt%-20wt%. Quantities are based on 100%.
  • the raw materials used also include an initiator and a catalyst.
  • the initiator uses alcohol, such as monohydric alcohols, polyhydric alcohols, etc., monohydric alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, benzyl alcohol, phenylethyl alcohol, benzene Propanol, phenylbutanol, phenylpentyl alcohol, phenylhexanol, and the like, and examples of the polyhydric alcohol include ethylene glycol, glycerin, pentaerythritol, and the like.
  • monohydric alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, benzyl alcohol, phenylethyl alcohol, benzene Propanol, phenylbutanol, phenylpentyl alcohol, phenylhexanol, and the like
  • the mass ratio of the initiator to L-lactide or D-lactide is 0.01-0.5:50-90, preferably 0.05-0.5:50-90.
  • the catalyst is an organotin catalyst.
  • the organotin catalyst includes one or more of stannous octoate, stannous chloride and butyltin.
  • examples of the butyltin include butylstannoic acid, tetrabutyltin, dibutyltin dilaurate and the like.
  • the mass ratio of the catalyst to L-lactide or D-lactide is 0.01-0.5:50-90, preferably 0.1-0.5:50-90.
  • a purification step is also included.
  • the purification includes: dissolving the reaction product with a solvent, then removing unreacted monomers with a precipitant, and then drying.
  • the solvent is halogenated alkanes, such as monochloromethane, dichloromethane, difluoromethane, monoiodopropane, and the like.
  • the mass ratio of the solvent to the reaction product is 5-15:1, preferably 10-15:1.
  • alcohol is used as the precipitating agent, such as ethanol, methanol, propanol, butanol, pentanol and the like.
  • the present invention provides the lactic acid/valeric acid copolymer prepared according to the above-mentioned preparation method.
  • the present invention also provides a method for preparing a polylactic acid stereocomplex, comprising the following steps:
  • D-lactide and D-valerolide as monomers to carry out polymerization reaction to obtain lactic acid/valeric acid copolymer, and then mix lactic acid/valeric acid copolymer with L-polylactic acid to obtain Crystalline and heterostereocrystalline polylactic acid stereocomplexes.
  • the mixing may adopt solution mixing or melt mixing.
  • the mass ratio of the lactic acid/valeric acid copolymer to D-polylactic acid or L-polylactic acid is 1-9:9-1, preferably 2-8:8-2.
  • the present invention also provides the polylactic acid stereocomplex prepared according to the above-mentioned preparation method.
  • lactic acid/valeric acid copolymer, preparation method and polylactic acid stereocomplex thereof of the present invention have the following beneficial effects:
  • the present invention improves the toughness of the obtained lactic acid/valeric acid copolymer by introducing the left-handed (or right-handed) valeride containing flexible segments into the left-handed (or right-handed) lactide through polymerization reaction, And then improve the toughness of the stereocomplex formed with D-(or L-) polylactic acid.
  • the raw material D-polylactic acid or L-polylactic acid used in the present invention has good biodegradability, and the prepared polylactic acid stereocomplex has good biocompatibility.
  • the invention provides a kind of preparation method of lactic acid/valeric acid copolymer, comprises the following steps:
  • L-lactide and L-valerolide as monomers, under the action of an alcohol initiator and an organic tin catalyst, carry out a polymerization reaction at 120-150°C for 4-15 hours, wherein, L-lactide and L-valerolide
  • the mass percentage of lactide is 50wt%-90wt%: 50wt%-10wt%, preferably 50wt%-80wt%: 50wt%-20wt%, the total amount of monomers is calculated as 100%;
  • the mass ratio of the ester is 0.01-0.5: 50-90, preferably 0.05-0.5: 50-90;
  • the organotin catalyst comprises one or more of stannous octoate, stannous chloride and butyltin, and the organotin catalyst and
  • the mass ratio of L-lactide is 0.01-0.5:50-90, preferably 0.1-0.5:50-90;
  • the mass ratio of halogenated alkanes to reaction products is 5-15:1, preferably 10-15:1; then use excess alcohol to remove unreacted monomers, and then dry to obtain lactic acid/valeric acid copolymer ;
  • D-lactide and D-valerolide as monomers to carry out polymerization reaction, under the action of alcohol initiator and organic tin catalyst, carry out polymerization reaction at 120-150°C for 4-15h, wherein, The mass percentage of D-lactide and D-valerolide is 50wt%-90wt%: 50wt%-10wt%, preferably 50wt%-80wt%: 50wt%-20wt%, and the total amount of monomers is calculated as 100%;
  • the mass ratio of the alcohol initiator to D-lactide is 0.01-0.5: 50-90, preferably 0.05-0.5: 50-90;
  • the organotin catalyst includes a combination of stannous octoate, stannous chloride and butyltin One or more, the mass ratio of organotin catalyst to D-lactide is 0.01-0.5:50-90, preferably 0.1-0.5:50-90;
  • the mass ratio of halogenated alkanes to reaction products is 5-15:1, preferably 10-15:1; then use excess alcohol to remove unreacted monomers, and then dry to obtain lactic acid/valeric acid copolymer .
  • the present invention also provides a preparation method of polylactic acid stereocomplex, comprising the following steps:
  • L-lactide and L-valerolide as monomers, under the action of alcohol initiator and organic tin catalyst, carry out polymerization reaction at 120-150°C for 4-15h, L-lactide and L-valerolide
  • the mass percentage is 50wt%-90wt%: 50wt%-10wt%, preferably 50wt%-80wt%: 50wt%-20wt%, the total amount of monomers is based on 100%;
  • the alcohol initiator and L-lactide The mass ratio is 0.01-0.5:50-90, preferably 0.05-0.5:50-90;
  • the organotin catalyst includes one or more of stannous octoate, stannous chloride and butyltin, and the organotin catalyst and L-propyl
  • the mass ratio of lactide is 0.01-0.5:50-90, preferably 0.1-0.5:50-90;
  • the mass ratio of halogenated alkanes to reaction products is 5-15:1, preferably 10-15:1; then use excess alcohol to remove unreacted monomers, and then dry to obtain lactic acid/valeric acid copolymerization thing;
  • the mass percent of L-lactide and L-lactide is 50wt%-90wt%: 50wt%-10wt%, preferably 50wt%-80wt%: 50wt%-20wt%, the total amount of monomers is 100%;
  • the mass ratio of alcohol initiator to D-lactide is 0.01-0.5:50-90, preferably 0.05-0.5:50-90;
  • organic tin catalysts include stannous octoate and stannous chloride and one or more of butyltin, the mass ratio of organotin catalyst to D-lactide is 0.01-0.5:50-90, preferably 0.1-0.5:50-90;
  • the mass ratio of halogenated alkanes to reaction products is 5-15:1, preferably 10-15:1; then use excess alcohol to remove unreacted monomers, and then dry to obtain lactic acid/valeric acid copolymerization thing;
  • the lactic acid/valeric acid copolymer and the L-polylactic acid are mixed according to the mass ratio of 1-9:9-1 to obtain a polylactic acid stereocomplex containing homogeneous stereo crystals and heterogeneous stereo crystals.
  • Synthesis of lactic acid/valeric acid copolymer heat 30 parts of D-3,6-dipropyl-1,4-dioxane-2,5-dione (D-valeride) to melt state, add 0.01 part of ethylene glycol and 0.01 part of stannous chloride to the molten D-valerolactide in turn, and react at 150°C for 40 minutes. At this time, the reaction system is in the form of viscous liquid; add 70 parts of D-lactide preheated to a molten state, stirred to make the mixture uniform, and continued to react at 150°C for 4 hours to obtain the reaction product;
  • D-valeride D-3,6-dipropyl-1,4-dioxane-2,5-dione
  • step S2 the D-polylactic acid obtained in step S1 and the L-polylactic acid are blended with 15 times the mass of methylene chloride respectively to obtain a D-polylactic acid solution and a L-polylactic acid solution, and the D-polylactic acid solution and the L-polylactic acid solution are mixed
  • the L-polylactic acid solution was mixed under electromagnetic stirring for 3 hours according to the mass ratio of 1:9, poured into a smooth petri dish, volatilized at room temperature to form a film, and vacuum-dried to constant weight at -0.095Pa, 55°C to obtain a polylactic acid stereocomplex things.
  • the melting temperature of the polylactic acid stereocomplex prepared in Examples 1-7 and Comparative Examples 1-2 was detected by Differential Scanning Thermal Discussion (DSC), and the results are 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)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne le domaine technique des matériaux polymères et concerne en particulier un copolymère acide lactique/acide pentanoïque, un procédé de préparation et un stéréocomplexe de ce dernier. Le procédé de préparation du copolymère acide lactique/acide pentanoïque consiste à mettre en œuvre une réaction de polymérisation à l'aide de L-lactide et de L-caprolactide en tant que monomères pour obtenir le copolymère acide lactique/acide pentanoïque, ou à mettre en œuvre une réaction de polymérisation à l'aide de D-lactide et de D-caprolactide en tant que monomères pour obtenir le copolymère acide lactique/acide pentanoïque. Grâce à l'introduction, dans le L- (ou D-) lactide par une réaction de polymérisation, du L- (ou D-) caprolactide contenant un segment mou, il y a amélioration de la ténacité d'un copolymère acide lactique/acide pentanoïque préparé, ce qui améliore la ténacité d'un stéréocomplexe de poly(acide lactique) formé par ce dernier et le poly(acide D- (ou L-) lactique).
PCT/CN2022/121605 2022-03-01 2022-09-27 Copolymère acide lactique/acide pentanoïque, procédé de préparation et stéréocomplexe de ce dernier WO2023165120A1 (fr)

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CN202210199187.7 2022-03-01
CN202210199187.7A CN114479024B (zh) 2022-03-01 2022-03-01 一种乳酸/戊酸共聚物、制备方法及其立构复合物

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Publication number Priority date Publication date Assignee Title
CN114479024B (zh) * 2022-03-01 2023-04-28 上海东庚化工技术有限公司 一种乳酸/戊酸共聚物、制备方法及其立构复合物

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090018646A1 (en) * 2007-07-10 2009-01-15 Zhao Jonathon Z Coating Employing an Anti-Thrombotic Conjugate
US20100166863A1 (en) * 2008-12-31 2010-07-01 Industrial Technology Research Institute Biodegradable copolymer hydrogels
JP2020189905A (ja) * 2019-05-21 2020-11-26 東レ株式会社 ポリエステルコポリマーの製造方法
CN113861640A (zh) * 2021-09-25 2021-12-31 浙江大学衢州研究院 基于立构复合化提高聚乳酸共聚物材料结晶能力的方法
CN114479024A (zh) * 2022-03-01 2022-05-13 上海东庚化工技术有限公司 一种乳酸/戊酸共聚物、制备方法及其立构复合物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090018646A1 (en) * 2007-07-10 2009-01-15 Zhao Jonathon Z Coating Employing an Anti-Thrombotic Conjugate
US20100166863A1 (en) * 2008-12-31 2010-07-01 Industrial Technology Research Institute Biodegradable copolymer hydrogels
JP2020189905A (ja) * 2019-05-21 2020-11-26 東レ株式会社 ポリエステルコポリマーの製造方法
CN113861640A (zh) * 2021-09-25 2021-12-31 浙江大学衢州研究院 基于立构复合化提高聚乳酸共聚物材料结晶能力的方法
CN114479024A (zh) * 2022-03-01 2022-05-13 上海东庚化工技术有限公司 一种乳酸/戊酸共聚物、制备方法及其立构复合物

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