Atom transfer radical polymerization initiation techniques

Fristrup, C.J., K. Jankova, and S. Hvilsted. 2009. Surface-initiated atom transfer radical polymerization-a technique to develop biofunctional coatings. Soft Matter 5(23) 4623 634. 

Luo et al. [6] used a polydimethylsiloxane macro-initiator to initiate polymerization of methacrylate monomers with fluorinated side groups to prepare fluorosilicone polymers. To obtain diblock copolymers with a low surface energy, they designed poly(dimethylsiloxane)-block-poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate) (PDMS-1 -PHFBMA) diblock copolymers by atom transfer radical polymerization (ATRP) technique. To initiate 2,2,3,3,4,4, 4-heptafluorobutyl methacrylate polymerization, bromine end-capped polydimethylsiloxane (PDMS-Br) was used as the macro-initiator. Scheme 6.5 shows a schematic representation of the PDMS-fc-PHFBMA diblock copolymers. The system was strictly deoxygenated... 

While in most of the reports on SIP free radical polymerization is utihzed, the restricted synthetic possibihties and lack of control of the polymerization in terms of the achievable variation of the polymer brush architecture limited its use. The alternatives for the preparation of weU-defined brush systems were hving ionic polymerizations. Recently, controlled radical polymerization techniques has been developed and almost immediately apphed in SIP to prepare stracturally weU-de-fined brush systems. This includes living radical polymerization using nitroxide species such as 2,2,6,6-tetramethyl-4-piperidin-l-oxyl (TEMPO) [285], reversible addition fragmentation chain transfer (RAFT) polymerization mainly utilizing dithio-carbamates as iniferters (iniferter describes a molecule that functions as an initiator, chain transfer agent and terminator during polymerization) [286], as well as atom transfer radical polymerization (ATRP) were the free radical is formed by a reversible reduction-oxidation process of added metal complexes [287]. All techniques rely on the principle to drastically reduce the number of free radicals by the formation of a dormant species in equilibrium to an active free radical. By this the characteristic side reactions of free radicals are effectively suppressed. 

Initially, the polymerization of macromonomers was achieved by free radical polymerization reactions, which allowed only a limited control of the final properties. With the advent of ROMP and new free radical polymerization techniques, such as atom transfer radical polymerization (ATRP) the control of final properties became more facile (16). ATRP and ROMP techniques can be combined for the synthesis of macroinitiators (17). 

The need to better control surface-initiated polymerization recently led to the development of controlled radical polymerization techniques. The trick is to keep the concentration of free radicals low in order to decrease the number of side reactions. This is achieved by introducing a dormant species in equilibrium with the active free radical. Important reactions are the living radical polymerization with 2,2,4,4-methylpiperidine N-oxide (TEMPO) [439], reversible addition fragment chain transfer (RAFT) which utilizes so-called iniferters (a word formed from initiator, chain transfer and terminator) [440], and atom transfer radical polymerization (ATRP) [441-443]. The latter forms radicals by added metal complexes as copper halogenides which exhibit reversible reduction-oxidation processes. 

Atom transfer radical polymerization (ATRP) was selected as an exemplary CRP technique to systematically study the kinetics and gelation behavior during the concurrent copolymerization of monovinyl monomers and divinyl cross-linkers (Scheme 2). The effect of different parameters on the experimental gelation was studied, including the initial molar ratio of cross-linker to initiator, the concentrations of reagents, the reactivity of vinyl groups present in the cross-linker, the efficiency of initiation, and the polydispersity of primary chains. Experimental gel points based on the conversions of monomer and/or cross-linker at the moment of gelation, were determined and compared with each other in order to understand the influence of each parameter on the experimental gel points. 

As an illustration of the application of these techniques, the surface of poly(ethylene terephthalate) (PET) films has been modified via the grafting of polyacrylamide (PAM) by surface-initiated atom transfer radical polymerization (ATRP) and UV-initiated grafting in order to obtain a film of PET with a hydrophilic surface [15c],... 

A controlled free radical polymerization technique was also used, namely, atom transfer radical polymerization (ATRP), to synthesize ATE on the basis of ABA triblock copolymers (Fig. 11.3b) (Cui et al., 2004). The triblock copolymer was designed to have a rubbery midblock of poly(n-butyl acrylate) (PnBA) and two end blocks of poly 6-[4-(4-methoxyphenylazo)phenoxy]hexyl methacrylate) (PAzoMA) that is azo-SCLCP. For synthesis, a dibromo initiator, namely, l,l -biphenyl-4,4 -bis(2-bromoisobutyrate), can first be used to prepare the dibromo PnBA macroinitiator, which is then used to polymerize the azobenzene methacrylate monomer to yield the two end blocks of PAzoMA. This ATE is different from azo-SCLCP-grafted SBS. It is a thermoplastic elastomer, in which... 

In contrast, here a bifunctional initiator is employed and the polymerization order of the two blocks is inverted In a first step, the styrene block is synthesized by atom transfer radical polymerization (ATRP) followed by the addition of lactide via the recently developed organocatalytic ring-opening polymerization, as depicted in Fig. 3.1 [4, 5]. This synthesis route reduces the involved steps and enables a simplified and time-efficient preparation of copolymers with different block compositions. Importantly, both polymerization techniques offer precise and robust control over the copolymer composition, which is an essential requirement to reliably target the double-gyroid s narrow location in phase space [6]. 

Controlled radical polymerization techniques are suitable for synthesizing polymers with a high level of architectural control. Notably, they not only allow a copolymerization with functional monomers (as shown previously for free-radical polymerization), but also a simple functionalization of the chain end by the initiator. Miniemulsion systems were found suitable for conducting controlled radical polymerizations [58-61], including atom transfer radical polymerization (ATRP), RAFT, degenerative iodine transfer [58], and nitroxide-mediated polymerization (NMP). Recently, the details of ATRP in miniemulsion were described in several reviews [62, 63], while the kinetics of RAFT polymerization in miniemulsion was discussed by Tobita [64]. Consequently, no detailed descriptions of the process wiU be provided at this point. 

In recent years, focus has moved to the use of living radical polymerization techniques such as atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) for the production of well-defined polymer coatings. Both the grafting from and grafting to approaches have been explored for the attachment of MPC-based polymers onto a variety of substrates. Grafting from requires the incorporation of initiator sites onto the biomaterial surface prior to the polymerization reaction. This usually involves a series of... 

Recently, surface modification techniques for polymer chains have progressed a great deal with the development of a new polymer synthesis method. In particular, surface-initiated atom transfer radical polymerization (SI-ATRP) is one of the most effective modification methods for preparing a well-defined dense polymer brush structure, or polymer brush, on solid substrates. Thus, a self-oscillating polymer brush prepared by SI-ATRP can be expected to create a novel self-oscillating surface with autonomous function, which will lead to potential applications in transporting systems for nanomaterials of flow control in microfluidics. 

These results show that not only are novel radical-anions formed by interaction of Michael acceptors with I and related organometallics, but that the epr technique is an excellent method of ascertaining the basicity of the latter, as well as shedding light on the subtle aspects of the donor-acceptor interactions involved. The chemistry in Equation (1) is exactly analogous to that which occurs in initiation of Atom Transfer Radical Polymerization (ATRP) catalysis, Equation (2), where the same basic metal complexes and others are active (X = halide). 

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