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Vulcanization on Polymer Film Surfaces With Elemental Sulfur.

Shang-Yu Tsai¹, Yue-Sheng Lai¹, Ying-Ling Liu¹

¹Department of Chemical Engineering, National Tsing Hua University, Hsinchu, Taiwan.

Macromolecular Rapid Communications

|May 5, 2026

Summary

This study introduces a novel surface vulcanization technique for polymer films using elemental sulfur. This method creates asymmetric, crosslinked polymer structures, paving the way for new sulfur-containing materials.

Keywords:

benzoxazine elemental sulfur functional polymer film surface modification vulcanization

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Area of Science:

Materials Science
Polymer Chemistry
Surface Chemistry

Background:

Elemental sulfur is a sustainable feedstock for sulfur-rich polymers.
Existing sulfur chemistry primarily focuses on bulk polymer synthesis.
There is a need for methods to modify polymer surfaces with sulfur.

Purpose of the Study:

To develop a surface vulcanization method for polymer films using molten sulfur.
To create asymmetric, sulfur-modified polymer structures.
To explore the application of this technique to polybenzoxazine (PBz) films.

Main Methods:

Infiltration of molten sulfur into polymer films.
In situ vulcanization of the infiltrated sulfur within the polymer matrix.
Characterization using Scanning Electron Microscopy with Energy-Dispersive X-ray (SEM-EDX), X-ray Photoelectron Spectroscopy (XPS), and Fourier Transform Infrared Spectroscopy (FTIR).

Main Results:

Successful surface vulcanization of polybenzoxazine (PBz) films was achieved.
An asymmetric structure with a vulcanized layer on the film surface was formed.
Characterization confirmed the presence of sulfur and crosslinking on the film surface.

Conclusions:

Surface vulcanization using elemental sulfur is a viable strategy for modifying polymer films.
This method enables the creation of asymmetric, sulfur-containing materials.
The developed technique offers a new platform for advanced sulfur-based polymer materials.