ARGET ATRP of ethylene glycol dicyclopentenyl ether methacrylate with vegetable oil and terpene‐derived methacrylic monomers

Abstract

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).

Syntheses and polymerization of monoterpene-based (meth)acrylates: IBO(M)A as a relevant monomer for industrial applications

“…100 In 2011, the polymerization of L-menthyl methacrylate (MA5) using ATRP was explored, employing bis[2-(2-bromoisobutyrooxy)ethyl]disulfide as the ATRP agent. 39 Maric et al 105 published the use of an ATRP technique for the copolymerization of the biobased methacrylate IBOMA (MA9) and C13MA (similar to lauryl methacrylate) with ethylene glycol dicy-clopentenyl ether methacrylate (EGDEMA). Specifically, they utilized ARGET ATRP, a method where the activator is continuously regenerated through electron transfer.…”

Sustainable Microcrystalline Cellulose-graft-Diblock Bottlebrush Copolymer Elastomers Derived from All Biomass Sources

“…Kim et al have successfully synthesized an amphiphilic supercapacitor composed of hydrophobic PIBOMA and hydrophilic poly­(ethylene glycol) methyl ether methacrylate (PEGMA), exhibiting sufficient mechanical strength . Furthermore, many studies have been reported to choose biobased PIBOMA as the hard segments instead of PS or PMMA to prepare triblock-type elastomers , for applications in drug delivery and optical devices. − In comparison, as a polymer with low crystallinity, poly­(lauryl methacrylate) (PLMA) with long alkyl side chains is much flexible and can play the role as the soft segments and also as a compatibilizer for nonpolar polymer blends on account of its low glass transition temperature ( T g = −65 °C) and low melting temperature ( T m = −33 °C). , Malmström et al have conducted surface-initiated atom transfer radical polymerization (SI-ATRP) of LMA from modified Al 2 O 3 nanoparticles (NPs) and have found that they are more embedded in the low-density polyethylene (LDPE) matrix than the naked NPs . Sakakibara and Tsujii et al have also employed the PLMA-adsorbed cellulose nanofibers (CNFs) to disperse in high-density polyethylene (HDPE) to prepare the green nanocomposite materials, demonstrating homogeneous dispersion with an obvious mechanical property reinforcement .…”