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CN-121975101-A - Polyglycolide-polyether-polycarbonate copolymer and preparation method thereof

CN121975101ACN 121975101 ACN121975101 ACN 121975101ACN-121975101-A

Abstract

The invention discloses a polyglycolide-polyether-polycarbonate copolymer and a preparation method thereof, wherein the number average molecular weight of the polyglycolide-polyether-polycarbonate copolymer is 3-185 kg/mol, the molecular weight distribution is 1.4-6.8, and the content of glycolide chain links in the copolymer is 0.1-90%. The copolymer disclosed by the invention has the characteristics of higher relative molecular mass, higher melting point, adjustable component composition and excellent mechanical property. The preparation method has the advantages of low cost of raw materials, simple operation, mild conditions, no need of complicated post-treatment purification process and more contribution to industrialization.

Inventors

  • ZHANG XINGHONG
  • MA JING
  • ZHANG CHENGJIAN
  • ZHANG XUYANG

Assignees

  • 浙江大学

Dates

Publication Date
20260505
Application Date
20260130

Claims (10)

  1. 1. The polyglycolide-polyether-polycarbonate copolymer is characterized in that the number average molecular weight of the polyglycolide-polyether-polycarbonate copolymer is 3-185 kg/mol, the molecular weight distribution is 1.4-6.8, and the content of glycolide chain links in the copolymer is 0.1-90%.
  2. 2. The polyglycolide-polyether-polycarbonate copolymer of claim 1, wherein the selectivity of polycarbonate in the polyglycolide-polyether-polycarbonate copolymer is greater than 45%.
  3. 3. The polyglycolide-polyether-polycarbonate copolymer according to claim 1, wherein the structural formula of the polyglycolide-polyether-polycarbonate copolymer is represented by the following formulas (I-1) to (I-6): (I-1); (I-2); (I-3); (I-4); (I-5); (I-6); In each formula, x is independently selected from 5 to 1300, y is independently selected from 1 to 700, and z is independently selected from 1 to 130.
  4. 4. A method for preparing the polyglycolide-polyether-polycarbonate copolymer according to any one of claims 1 to 3, comprising: Glycolide, epoxide and carbon dioxide are used as raw materials, and double metal cyanide complex or Lewis acid alkali pair is used as a catalyst to carry out copolymerization reaction.
  5. 5. The method for producing a polyglycolide-polyether-polycarbonate copolymer according to claim 4, wherein: the epoxide is selected from one or more of propylene oxide, butylene oxide, cyclohexene oxide, heptane oxide, octane oxide and 4-vinyl cyclohexene oxide; the feeding mole ratio of glycolide is 1-30% based on the feeding mole number of glycolide and epoxide being 100%; in the reaction system, the pressure of the carbon dioxide is 1-4 MPa.
  6. 6. The method for producing a polyglycolide-polyether-polycarbonate copolymer according to claim 4, wherein: the double metal cyanide complex is selected from Zn-Co (III) DMCC; The mass ratio of the double metal cyanide complex to the epoxide is 1 (400-1000); the Lewis acid-base pair comprises Lewis acid and Lewis base, and the molar ratio of the Lewis acid-base pair to the Lewis base is (2-8): 1; The molar ratio of the Lewis base to the epoxide is 1 (270-300); the lewis acid is selected from trialkylboron; the lewis base is selected from tertiary amines and/or tertiary phosphines.
  7. 7. The method for producing a polyglycolide-polyether-polycarbonate copolymer according to claim 4, wherein: The copolymerization reaction is selected from bulk polymerization or solution polymerization; The temperature of the copolymerization reaction is 40-100 ℃ and the time is 1.5-24 hours.
  8. 8. The method for preparing the polyglycolide-polyether-polycarbonate copolymer according to any one of claims 4 to 7, characterized in that: the epoxide is selected from propylene oxide and/or cyclohexene oxide; the temperature of the copolymerization reaction is 60-80 ℃ and the time is 5-24 hours.
  9. 9. The method for producing a polyglycolide-polyether-polycarbonate copolymer according to claim 8, wherein: The catalyst is selected from double metal cyanide complexes; in the reaction system, the pressure of carbon dioxide was 4 MPa.
  10. 10. The method for producing a polyglycolide-polyether-polycarbonate copolymer according to claim 8, wherein: the catalyst is selected from Lewis acid-base pairs; in the reaction system, the pressure of the carbon dioxide is 1-2 MPa.

Description

Polyglycolide-polyether-polycarbonate copolymer and preparation method thereof Technical Field The invention relates to the technical field of high polymer materials, in particular to a polyglycolide-polyether-polycarbonate copolymer and a preparation method thereof. Background With the development of society and technological progress, green chemistry has become an important and challenging scientific issue. The performance and design of the materials are deeply considered, and the biodegradable plastic is promoted to be the focus of social attention. Glycolide is a dimer of glycolic acid, the glycolic acid can be obtained from petroleum raw materials or some renewable resources, and Polyglycolide (PGA) is biodegradable plastic with great industrial prospect, has higher crystallinity, excellent mechanical property under the drying condition, excellent degradability and biocompatibility, and is widely applied to the fields of medicines, food packaging and the like. However, since PGA is degraded at a high rate, the mechanical strength is suddenly reduced in a short time, which is disadvantageous for long-term use of the material, and PGA is insoluble in most organic solvents, and is only dissolved in fluorine-containing solvents such as Hexafluoroisopropanol (HFIP) at room temperature, the PGA is rapidly precipitated in a low molecular weight state in solution polymerization, and the product has poor performance. For example, literature （Zhang, P.; Ladelta, V.; Hadjichristidis, N. Living/controlled anionic polymerization of glycolide in fluoroalcohols: Toward sustainable bioplastics. J. Am. Chem. Soc. 2023, 145, 14756-14765） screens out a series of fluoridation reagents with proper acid-base property and strong hydrogen bonding function as reaction cosolvent for solution polymerization, and the fluoridation reagents and organic base together catalyze the active polymerization of glycolide. The glycolide is connected with other monomers through a copolymerization way, so that the mutual complementation of the glycolide and other monomers is hopeful to be realized. However, most of the presently disclosed comonomers are cyclic lactones such as lactide, caprolactone, trimethylene cyclic carbonate, and the like, with little extension for other types of monomers. The synthesis of penta-crystalline pentablock five-membered copolymer PE-PEO-PCL-PLLA-PGA containing a polyglycolide block is achieved by combining a fluoroalcohol assisted catalytic method with an organo-metal catalyst switch as in literature （Zhang, P.; Ladelta, V.; Abou-hamad, E.; Müller, A. J.; Hadjichristidis, N. Catalyst switch strategy enabled a single polymer with five different crystalline phases. Nat. Commun. 2023, 14, 7559）. In such systems, the fluorination reagents are unusual and expensive, the procedure for preparing the copolymer is complex, and the molecular weight of the resulting PGA is low. Disclosure of Invention Aiming at the problems, the invention discloses a polyglycolide-polyether-polycarbonate copolymer and a preparation method thereof, and the copolymer has the characteristics of higher relative molecular mass, higher melting point, adjustable component composition and excellent mechanical property. The preparation method has the advantages of low cost of raw materials, simple operation, mild conditions, no need of complicated post-treatment purification process and more contribution to industrialization. The specific technical scheme is as follows: The number average molecular weight of the poly glycolide-polyether-polycarbonate copolymer is 3-185 kg/mol, the molecular weight distribution is 1.4-6.8, and the content of glycolide chain links in the copolymer is 0.1-90%. The copolymer disclosed by the invention simultaneously comprises a polyglycolide chain link, a polyether chain link and a polycarbonate chain link, the content of each chain link is adjustable, and the copolymer with different mechanical properties is obtained by adjusting the content of each chain link so as to adapt to different application fields. Optionally, the number average molecular weight of the polyglycolide-polyether-polycarbonate copolymer can be specifically selected from 3 kg/mol、10 kg/mol、15 kg/mol、20 kg/mol、30 kg/mol、40 kg/mol、50 kg/mol、60 kg/mol、80 kg/mol、100 kg/mol、120 kg/mol、150 kg/mol、180 kg/mol、185 kg/mol or any value in the range, further optionally 50-185 kg/mol, and further optionally 150-185 kg/mol. Optionally, the molecular weight distribution of the polyglycolide-polyether-polycarbonate copolymer may be specifically selected from 1.4, 1.8, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.8 or any value within the above range, and further optionally 1.4 to 5.0. The glycolide mer content of the polyglycolide-polyether-polycarbonate copolymer may be subjected to a wide range of conditions, and may specifically be selected from 0.1%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70%, 80%, 90% or any value within the above range. Op