감마선 동시조사법을 이용한 Styrene의 RAFT 중합 거동 연구
RAFT Polymerization of Styrene by γ-Ray Simultaneous Irradiation
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Reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene was carried outusing the γ-ray simultaneous irradiation method, which enables radical generation without chemical initiators. Theeffects of RAFT agent type, solvent, monomer content, and [M]/[CTA] ratio were systematically examined. Amongthe RAFT agents tested, the trithiocarbonate-based CTA (2-cyano-2-propyl dodecyl trithiocarbonate, CPDTC)showed superior control compared to dithioester-based CTAs, producing higher molecular weights and narrowermolecular weight distributions. Solvent studies revealed that dioxane provided the best control, while acetone andTHF generated radiolysis by-products that disturbed the RAFT equilibrium. Increasing monomer content resulted inhigher Mn without significant changes in PDI, whereas larger [M]/[CTA] ratios led to linear increases in Mnbut alsobroader PDIs, indicating a trade-off between molecular weight growth and control efficiency. These results confirmthat γ-ray-induced RAFT polymerization is an effective route for synthesizing well-defined polystyrene withoutinitiators and highlight its potential for extending radiation-assisted RAFT techniques to advanced applications infunctional polymers, electronic materials, and biomedical systems.
Abstract
Reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene was carried outusing the γ-ray simultaneous irradiation method, which enables radical generation without chemical initiators. Theeffects of RAFT agent type, solvent, monomer content, and [M]/[CTA] ratio were systematically examined. Amongthe RAFT agents tested, the trithiocarbonate-based CTA (2-cyano-2-propyl dodecyl trithiocarbonate, CPDTC)showed superior control compared to dithioester-based CTAs, producing higher molecular weights and narrowermolecular weight distributions. Solvent studies revealed that dioxane provided the best control, while acetone andTHF generated radiolysis by-products that disturbed the RAFT equilibrium. Increasing monomer content resulted inhigher Mn without significant changes in PDI, whereas larger [M]/[CTA] ratios led to linear increases in Mnbut alsobroader PDIs, indicating a trade-off between molecular weight growth and control efficiency. These results confirmthat γ-ray-induced RAFT polymerization is an effective route for synthesizing well-defined polystyrene withoutinitiators and highlight its potential for extending radiation-assisted RAFT techniques to advanced applications infunctional polymers, electronic materials, and biomedical systems.