Optimization of the synthesis of poly(octadecyl acrylate) by atom transfer radical polymerization and the preparation of all comblike amphiphilic diblock copolymers

Abstract

The atom transfer radical polymerization of octadecyl acrylate (ODA) has been investigated and optimized to produce polymers with predetermined molecular weights and narrow polydispersities (Ͻ1.2). The poor solubility of the catalytic system formed with conventional ligands such as the N-(n-propyl)-2-pyridylmethanimine and 2,2Ј-bipyridine with Cu(I)Br in nonpolar reaction conditions gave poor control over molecular weight characteristics in ODA polymerizations. The use of N-(n-octyl)-2pyridylmethanimine in combination with Cu(I)Br yielded a more soluble catalyst that improved control over the polymerization. The products from the polymerizations were further improved when an initiator, octadecyl 2-bromo-2-methyl-propanoate, similar in structure to the monomer, was used. Together, these modifications produced polymerizations that showed true controlled character as well as products with predetermined molecular weights and narrow polydispersities. Diblock copolymers of PODA were prepared with methyl methacrylate (MMA) and olig(oethylene glycol) methyl ether methacrylate (OEGMA). The PODA-block-POEGMA copolymers are the first examples of all comblike amphiphilic block copolymers. One of PODA-block-POEGMA copolymer samples has been shown to self-assemble as micelles in a dilute aqueous solution.

Semicrystalline Macromolecular Design by Nitroxide‐Mediated Polymerization

“…methyl ether methacrylate) by ATRP. [25] Moreover, Matyjaszewski et al demonstrated the synthesis of poly[(octadecyl methacrylate)-co-(ethylene glycol methyl ether methacrylate)] random and gradient copolymers by ATRP. [26] Recently, our group was interested in synthesizing gradient copolymers by batch and semi-batch nitroxidemediated radical polymerization, demonstrating the effect of the synthetic methodology on the molecular architecture.…”

Modification of Chlorinated Poly(propylene) via Atom Transfer Radical Graft Copolymerization of 2‐Ethylhexyl Acrylate: A Brush‐like Graft Copolymer

“…[20][21][22][23] ATRP is used to prepare block and graft copolymers with different architecture with well controlled molecular weight, and well-defined end group. [24][25][26][27][28] These block copolymers are also used for the stabilization for the gold nanoparticles. [29] Recently there are reports on the surface initiated graft copolymerization on PP.…”

Novel polymers based on atom transfer radical polymerization of 2‐methoxyethyl acrylate

“…In recent years, numerous different acrylate monomers have also been homo-and block copolymerized by ATRP. [16][17][18][19][20] The purpose of this work is to study the controlled radical homopolymerization of 2-MEA and the possible block copolymerization with methyl methacrylate (MMA) to expand the PMEA material versatility and provide guidelines for the design of novel materials with tailor-made medical device properties.…”