Kinetically Enhanced Access to a Dynamic Polyester Platform via Sequence Selective Terpolymerisation of Elemental...

Area of Science:

• Polymer Chemistry
• Materials Science
• Organic Chemistry

Background:

• Elemental sulfur, a byproduct of oil refining, possesses dynamic sulfur-sulfur bonds with potential for creating dynamic polymers.
• Existing methods for synthesizing linear polymers from elemental sulfur with tunable properties and functionality are limited.

Purpose of the Study:

• To develop robust methodologies for synthesizing linear polymers from elemental sulfur.
• To enable the creation of polymers with tuneable properties and functionality using elemental sulfur.

Main Methods:

• Sequence selective terpolymerization of elemental sulfur with aromatic thioanhydrides and epoxides.
• Utilized simple lithium alkoxide catalysis.
• Investigated reaction mechanisms including rate acceleration and post-polymerization modification.

Main Results:

• Successfully synthesized semi-aromatic poly(ester-alt-Sx) terpolymers.
• Enabled the use of a wider range of epoxide comonomers, including flexible, rigid, functional, and natural product-derived variants.
• Achieved a broad tuning of glass transition temperatures (Tg) over a range of >150 °C.
• Demonstrated post-polymerization modification via sulfur-sulfur bond metathesis for creating crosslinked, reprocessable, and acid-degradable adhesives.

Conclusions:

• Developed a novel terpolymerization method for incorporating elemental sulfur into polymer backbones.
• The new method allows for precise control over polymer properties and functionality.
• The resulting polymers show promise for applications in advanced materials, such as recyclable adhesives.