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Synthesis of Polymers From Bio-Based Methacrylates Comprising Aromatic or Aliphatic Structures Using NIR-Mediated

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Near-infrared-mediated atom transfer radical polymerization (ATRP) synthesized polymethacrylates from bio-based monomers. Bio-based polymers showed broader dispersity and varied solubility compared to poly(methyl methacrylate).

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Area of Science:

  • Polymer Chemistry
  • Organic Synthesis
  • Materials Science

Background:

  • Developing sustainable polymers from bio-based resources is crucial for reducing reliance on petrochemicals.
  • Atom Transfer Radical Polymerization (ATRP) offers controlled synthesis of polymers with defined architectures.
  • Near-infrared (NIR) light can mediate ATRP, enabling polymerization under mild conditions.

Purpose of the Study:

  • To synthesize polymethacrylates using NIR-mediated ATRP from novel bio-based monomers.
  • To compare the properties of these bio-based polymers with poly(methyl methacrylate) (PMMA).
  • To investigate the synthesis and properties of block copolymers incorporating bio-based monomers.

Main Methods:

  • NIR-mediated ATRP was employed using a heptamethine cyanine sensitizer and a copper complex deactivator.
  • Polymerization was conducted at 790 nm excitation wavelength.
  • Synthesized homopolymers and block copolymers were characterized for yield, molecular weight, dispersity, glass transition temperature, and solubility.

Main Results:

  • Bio-based polymethacrylates exhibited broader dispersity than PMMA, suggesting increased chain termination.
  • All synthesized macroinitiators were chain extendable, forming block copolymers.
  • Block copolymers from bio-based monomers showed distinct solubility differences due to their unique ester structures, with lower initiation efficiency observed for one isomer mixture compared to methyl methacrylate.

Conclusions:

  • NIR-mediated ATRP is a viable method for synthesizing polymethacrylates from bio-based monomers.
  • The bio-based polymers present unique properties, including broader dispersity and varied solubility, offering potential for specialized applications.
  • Further research into initiation efficiency and structural influences is warranted for optimizing bio-based polymer synthesis.