Homo and statistical copolymerization reactions of ethylene glycol dicyclopentenyl ether methacrylate (EGDEMA) and a vegetable‐oil based methacrylic ester C13MA (average alkyl chain length = 13) are studied via activator regenerated electron transfer polymerization (ARGET ATRP) using only trace amounts of copper catalyst. Poly(EGDEMA) and poly(C13MA) homopolymers and statistical poly(EGDEMA‐stat‐C13MA) copolymers are cleanly synthesized with monomodal molecular weight distribution and dispersities Đ = Mw/Mn = 1.39–1.76 and Mn ~ 12 kg/mol. Chain end fidelity is confirmed by chain extension from poly(C13MA) macroinitiator with EGDEMA to make poly(C13MA‐b‐EGDEMA) diblock copolymers, which exhibit two distinct glass transition temperatures (Tgs), one for the poly(C13MA) block (−39°C) and the other for the poly(EGDEMA) block (23.9°C), suggesting microphase separation. Due to the relatively low Tg of poly(EGDEMA‐stat‐C13MA), terpene‐derived isobornyl methacrylate (IBOMA) is copolymerized with EGDEMA forming poly(EGDEMA‐stat‐IBOMA) statistical copolymers with Tgs ranging from 22.9–113°C. Additionally, crosslinking of the poly(EGDEMA) homopolymer and poly(EGDEMA‐stat‐C13MA) and poly(EGDEMA‐stat‐IBOMA) copolymers is achieved by UV thiol‐ene clicking of the pendent double bonds of EGDEMA units with suitable dithiols at 365 nm. For poly(EGDEMA), conversion of the thiol‐ene click reaction reaches 70%; where as the conversion of the clicking reactions is higher in the copolymers with a conversion up to 92% for poly(EGDEMA‐stat‐C13MA) and 97% for poly(EGDEMA‐stat‐IBOMA).
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