Initiators for atom transfer radical polymerization

Nakagawa, Y., Miller, P. J., and Matyjaszewski, K. (1998). Development of novel attachable initiators for atom transfer radical polymerization. Synthesis of block and graft copolymers from poly(dimethylsiloxane) macroinitiators. Polymer, 39(21) 5163-5170. 

Measurement of reactivity ratios under normal free-radical and CCT polymerization conditions indicates that CCT is a modified free-radical polymerization as expected.434 The reactivity ratios for MMA and butyl methacrylate were used as a mechanistic probe. Reactivity ratios were 1.04 and 0.81 for classical anionic polymerization, 1.10 and 0.72 for alkyllithium/trialkylaluminum initiated polymerization, 1.76 and 0.67 for group transfer polymerization, 0.98 and 1.26 for atom transfer radical polymerization, 0.75 and 0.98 for CCT, and 0.93 and 1.22 for classical free-radical polymerization. These ratios suggest that ATRP and CCT proceed via radical propagation. 

H) Atom transfer radical polymerization Numerous reports have been published regarding the synthesis of star polymers using multifunctional initiators capable of initiating the atom transfer radical polymerization (ATRP) of certain monomers, mainly styrene, methacrylates, and acrylates. The living character of the growing chain ends provides the possibility for the synthesis of star-block copolymers. 

Doerffler, E. M., and Patten, T. E. (2000). Benzyl acetate and benzyl ether groups as latent initiator sites for atom transfer radical polymerization. Macromolecules, 55(24) 8911 8914. 

Block copolymers were synthesized by a combination of fipase-catalyzed polymerization and atom transfer radical polymerization (ATRE). " " At first, the polymerization of 10-hydroxydecanoic acid was carried out by using lipase CA as catalyst. The terminal hydroxy group was modified by the reaction with a-bromopropionyl bromide, followed by ATRP of styrene using CuCE2,2 -bipyridine as catalyst system to give the polyester-polystyrene block copolymer. Trichloromethyl-terminated poly(e-CL), which was synthesized by lipase CA-catalyzed polymerization with 2,2,2-trichloroethanol initiator, was used as initiator for ATRP of styrene. 

Novel catalytic systems, initially used for atom transfer radical additions in organic chemistry, have been employed in polymer science and referred to as atom transfer radical polymerization, ATRP [62-65]. Among the different systems developed, two have been widely used. The first involves the use of ruthenium catalysts [e.g. RuCl2(PPh3)2] in the presence of CC14 as the initiator and aluminum alkoxides as the activators. The second employs the catalytic system CuX/bpy (X = halogen) in the presence of alkyl halides as the initiators. Bpy is a 4,4/-dialkyl-substituted bipyridine, which acts as the catalyst s ligand. 

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. 

The last decades have witnessed the emergence of new living Vcontrolled polymerizations based on radical chemistry [81, 82]. Two main approaches have been investigated the first involves mediation of the free radical process by stable nitroxyl radicals, such as TEMPO while the second relies upon a Kharash-type reaction mediated by metal complexes such as copper(I) bromide ligated with 2,2 -bipyridine. In the latter case, the polymerization is initiated by alkyl halides or arenesulfonyl halides. Nitroxide-based initiators are efficient for styrene and styrene derivatives, while the metal-mediated polymerization system, the so called ATRP (Atom Transfer Radical Polymerization) seems the most robust since it can be successfully applied to the living Vcontrolled polymerization of styrenes, acrylates, methacrylates, acrylonitrile, and isobutene. Significantly, both TEMPO and metal-mediated polymerization systems allow molec-... 

SIP-driven polymer brush library fabrication leverages the fact that the polymerization initiation species are permanently bound to the substrate. Since the initiators are tethered, controlled delivery of monomer solution to different areas of the substrate results in a grafted polymer library. In NIST work, initiators bound via chlorosilane SAMs to silicon substrates were suitable for conducting controlled atom transfer radical polymerization (ATRP) [53] and traditional UV free radical polymerization [54, 55]. Suitable monomers are delivered in solution to the surface via microfluidic channels, which enables control over both the monomer solution composition and the time in which the solution is in contact with the initiating groups. After the polymerization is complete, the microchannel is removed from the substrate (or vice versa). This fabrication scheme, termed microchannel confined SIP ([t-SIP), is shown in Fig. 10. In these illustrations, and in the examples discussed below, the microchannels above the substrate are approximately 1 cm wide, 5 cm long, and 300-500 [tm high. 

In a recent report, new nanocomposites of Au NPs and poly(4-vinylpyridine) were obtained through surface-initiated atom-transfer radical polymerization (SI-ATRP). The citrate-stabilized gold nanoparticles were first modified by the disulfide initiator [BrC(CH3)2COO(CH2)iiS]2 for ATRP initiation, and the subsequent polymerization of 4-vinylpyridine occurred on the surface of the gold particles. The assembled Au PVP nanocomposites are pH-responsive because of the pyridyl groups, which are facially protonated and positively charged. The micrographs show Au N Ps of around 15 nm size [92] (Scheme 3.14). 

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 synthesis of A2B miktoarm star polymers has been discussed and exemplified using PIB as a component. The synthesis involves a quasi living cationic polymerization of isobutylene from a monofunctional cationic initiator. This initiator also contains a blocked hydroxyl group. Eventually, the blocked hydroxyl group of the initiator is deblocked, and functionalized with a branching agent. This activated reagent is then used for an atom transfer radical polymerization process of /erf-butyl acrylate (18). 

The synthesis of mixed peroxides formed from /-butyl hydroperoxide and carbon-centred radicals has been studied. The reactions were strongly effected by solvents as well as catalytic amounts of Cun/Fem. The kinetic data suggest that the conditions for the Ingold-Fischer persistent radical effect are fulfilled in these cases.191 The use of Cu /Cu" redox couples in mediating living radical polymerization continues to be of interest. The kinetics of atom-transfer radical polymerization (ATRP) of styrene with CuBr and bipyridine have been investigated. The polymer reactions were found to be first order with respect to monomer, initiator and CuBr concentration, with the optimum CuBr Bipy ratio found to be 2 1.192 In related work using CuBr-A-pentyl-2-... 

Controlled free-radical polymerization methods, like atom-transfer radical polymerization (ATRP), can yield polymer chains that have a very narrow molecular-weight distribution and allow the synthesis of block copolymers. In a collaboration between Matyjaszewski and DeSimone (Xia et al., 1999), ATRP was performed in C02 for the first time. PFOMA-/)-PMMA, PFOMA-fr-PDMAEMA [DMAEMA = 2-(dimethylamino)ethyl methacrylate], and PMMA-/)-PFOA-/)-PM M A copolymers were synthesized in C02 using Cu(0), CuCl, a functionalized bipyridine ligand, and an alkyl halide initiator. The ATRP method was also conducted as a dispersion polymerization of MMA in C02 with PFOA as the stabilizer, generating a kine-... 

Thermally responsive polymers, such as poly( V-isopropyl acrylamide) (NI-PAm), have also been studied extensively for applications related to those previously discussed [112], De las Heras et al. described the synthesis and patterning of NIPAm brushes on SAMs and their subsequent performance during temperature-dependent adhesion assays of BSA and Streptococcus mutans (Fig. 7). The authors employed p.CP to pattern features of hydrophobic hexadecanethiol and backfilled the surface with an initiator-functionalized alkanethiol. Polymer brushes were grown via surface-initiated atom transfer radical polymerization (ATRP). FITC-BSA was then... 

Frechet and coworkers recently described how living free radical polymerization can be used to make dendrigrafts. Either 2,2,6,6-tetramethylpiperidine oxide (TEMPO) modified polymerization or atom transfer radical polymerization (ATRP) can be used [96] (see Scheme 10). The method requires two alternating steps. In each polymerization step a copolymer is formed that contains some benzyl chloride functionality introduced by copolymerization with a small amount of p-(4-chloromethylbenzyloxymethyl) styrene. This unit is transformed into a TEMPO derivative. The TEMPO derivative initiates the polymerization of the next generation monomer or comonomer mixture. Alternatively, the chloromethyl groups on the polymer initiate an ATRP polymerization in the presence of CulCl or CuICl-4,4T dipyridyl complex. This was shown to be the case for styrene and n-butylmethacrylate. SEC shows clearly the increase in molecu-... 

The patterned organosilane monolayers introducing organolsilane molecule with a polymerization initiating unit are useful as template surfaces for site-specific polymerization. Atom transfer radical polymerization (ATRP) unit was immobilized as a monolayer component. Since ATRP is one of the most successful methods for polymerizing a variety of monomers in a controlled fashion [44, 45], tailor-made surface topography is possible. Several reports have described the formation of polymer thin film by the radical polymerization from the immobilized ATRP initiator [46, 47],... 

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