Photo-Initiated Main-Chain Scission of Poly(methyl methacrylate) in Solution at Room Temperature
Year: 2026
Type: article
Abstract: Poly(methyl methacrylate) (PMMA), as a widely used transparent polymer material, is highly stable because of its all-carbon backbone, which makes its chain cleavage under mild conditions challenging. In this work, we report a photo-initiated solution reaction that induces main-chain scission of PMMA at room temperature, leading mainly to molecular-weight reduction and oligomer formation. This method requires no catalysts and does not need pre-introduction of specific groups. The degradation mechanism proposed according to DFT calculations involves the photolysis of trichloromethane to produce phosgene, which then reacts with ester groups on the side chains of PMMA to form acyl chloride groups. These acyl chloride groups further cleave under light or heat, generating radicals that trigger β-scission of the PMMA main chain through a side-chain-initiated pathway. The degradation mechanism was demonstrated experimentally, and the extent of chain scission can be regulated by temperature, O2 and an alcohol stabilizer.
Source: Polymers
Authors: Xiao Wang, Xiangze Meng, Zhiping Xu, Rui Yang
Institution: Tsinghua University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $3,258
OpenAlex ID: W7203723999