Atom‐Transfer Radical Polymerization: A Strategy for the Synthesis of Halogen‐Free Amino‐Functionalized Poly(methyl methacrylate) in a One‐Pot Reaction

Abstract

Summary: An initiator containing an alkyl bromide unit and a protected amine functional group is used with CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA), in a 1:2 molar ratio with respect to initiator concentration, in order to obtain amino‐group terminated as well as halogen‐free poly(methyl methacrylate) (PMMA) in a one‐pot atom‐transfer radical polymerization (ATRP). The terminal bromines are replaced by hydrogen atoms of the PMDETA ligand, which acts as a transfer agent. However, terminating side reactions like disproportionation or dehydrobromination occur from the beginning of the polymerization. Kinetic studies by in‐line Raman spectroscopy and off‐line 1H NMR spectroscopy revealed that the controlled character of the ATRP is lost under these conditions. The measured molecular weights were consistently higher than the theoretical ones and the molecular weight distributions are relatively broad. Thermal analysis of the obtained poly(methyl methacrylate) shows two main degradation steps, one starting from unsaturated end groups (depolymerization), and one caused by main‐chain scission, a further proof for the occurrence of terminating side reactions.Structural analysis of PMMA by matrix‐assisted laser desorption‐ionization mass spectrometry.magnified imageStructural analysis of PMMA by matrix‐assisted laser desorption‐ionization mass spectrometry.

Spatiotemporally Controlled Formation of Two‐Component Counterpropagating Lateral Graft Density Gradients of Mixed Polymer Brushes on Planar Au Surfaces

“…Although most of the terminal bromine atoms on the initiator were removed during the polymerization of the PNIPAAm polymer-brush stage using CuBr/1,1,4,7,7-pentamethyldiethylenetriamine (PMDETA), [45] the remaining initiator sites were deactivated by treating the as-formed PNIPAAm gradients with 0.2 M sodium acetate in 60 % dimethyl sulfoxide (DMSO), and 40 % H 2 O for 30 min to ensure complete inactivation. [46] Secondary-ion mass spectroscopy (SIMS) imaging experiments (data not shown) reveal no detectable Br -after treatment, suggesting complete removal of active sites.…”

Synthesis, copolymer composition, and rheological behavior of functionalized polystyrene with isocyanate and amine side groups

“…[22][23][24][25] FPs, especially, with amine group have been widely investigated recently because of their great reactivity and potential uses in such applications as adhesion, surface science, compatibilizer of polymer blends and so forth. [26][27][28][29] As reported in the literature, amine endgroup polymers have been obtained by conventional radical polymerization, atom transfer radical polymerization, [30][31][32][33] anionic polymerization, [34][35][36][37] and reversible addition fragmentation chain transfer (RAFT) polymerization. [38,39] Postma et al [40] have successfully synthesized the end-functional polymers by RAFT polymerization.…”

Atom Transfer Radical Polymerization (ATRP) of Methyl Methacrylate using a Functional Initiator Bearing an Amino‐Adamantane

“…[1] Amine substituted adamantane derivatives (amantadines) are important functional groups in the physical, organic, and medicinal chemistry. This multiple use of amantadine creates a special interest in the study of its physiological activity as well as of efficient method of preparation of amantadine containing materials.…”

“…[3,4] Polymers bearing drug molecules are being used in polymer therapeutics. [5] Another interesting advantage of adamantane containing polymers is that they have high thermal stability, because of the presence of tricyclic adamantane molecule (tricycle [3.3.1.1 1,2 ] decane) which is a thermodynamically stable hydrocarbon. [6] One of the main goals in modern synthetic polymer chemistry is to synthesize polymers with predetermined molecular weights, narrow molecular weight distribution and well-defined end functionality and architecture.…”

“…[8,11] It is known that the choice of initiator is critically important in ATRP. There have been a number of recent reports describing the use of ATRP to prepare polymer with several functional initiators having different functional groups like amide, [12] alanine, [13] N-carboxy anhydride, [14] polypeptide, [15] ÀCOOH, [16] amino acid, [17] binol ester-based bifunctional initiator, [18] halogen-free amine, [1] norbornenyl [19] etc. It was found that different functional groups had different effects on the ATRP.…”