Intrinsic Sulfur-Containing Thermoplastic Cyclic Olefin Polymers with High Refractive Index, Colorless Transparency, and Thermal Stability

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High-refractive-index polymers are essential materials for advanced optical applications. Cyclic olefin polymers (COPs) are particularly attractive optical materials; however, conventional COPs typically exhibit refractive indices below 1.55, and achieving higher values without sacrificing transparency remains challenging. Here we report a series of intrinsic sulfur-containing COPs prepared by ring-opening metathesis polymerization followed by hydrogenation using a sulfur-containing heteroaromatic monomer (HSM) and rigid cycloolefin comonomers. Without external sulfur-rich additives, the resulting polymers exhibit high refractive indices ( n 589 = 1.612–1.673), relatively high Abbe numbers (ν d = 20.4–30.6), and colorless optical transparency (visible-light transmittance of >90%). In addition, the polymers show good thermal stability, with T g values ranging from 132 to 175 °C and T d5% values above 300 °C. This work presents an effective molecular design strategy for colorless, high-refractive-index, and thermally robust thermoplastic COPs.

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