Methyl acrylate atom transfer radical

To promote a polymerization, the newly formed carbon-halogen bond must be capable of being reactivated and the new radical must be able to add another alkene. This was accomplished for the radical polymerizations of St and methyl acrylate (MA), which were initiated by 1-phenylethyl bromide and catalyzed by a Cu(I)/2,2 -bipyridine (bpy) complex [42,79-81]. The process was called Atom Transfer Radical Polymerization (ATRP) to reflect its origins in ATRA. A successful ATRP relies on fast initiation, where all the initiator is consumed quickly, and fast deactivation of the active species by the higher oxidation state metal. The resulting polymers are well defined and have predictable molecular weights and low polydispersities. Other reports used different initiator or catalyst systems, but obtained similar results [43,82]. Numerous examples of using ATRP to prepare well-defined polymers can now be found [44-47,49]. Scheme 4 illustrates the concepts of ATRA and ATRP. To simplify schemes 3,4 and 5, termination was omitted. 

Another type of bJock-copolymer was obtained by conversion of living ROMP into controlled atom-transfer radical polymerization (ATRP). The approach involves the termination of a living ROMP polymer with a />bromomethylbenzaldehyde. This prepolymer may be Initiated using CuBr/2,2-dipyridyl and used for bJock-copolymer formation with styrene and methyl acrylate (Scheme 48). Finally, the preparation of 7-oxabicyclo[2.2.1]hept-2-ene-5,6-dimetha-nol-derived ROMP polymers and their use for the preparation of 7V-alkyl-3-aza-8-oxabicyclo[3.2.1]octane-... 

AYD Aydin, S., Erdogan, T., Sakar, D., Hizal, G., Cankurtaran, O., Tunca, U., and Karaman, F., Detection of microphase separation in poly(tert-butyl acrylate-Z>-methyl methacrylate) synthesized via atom transfer radical polymerization by inverse gas chromatography, Eur. Polym. J., 44, 2115, 2008. 

ATRP, atom transfer radical polymerization PIB, polyisobutylene PSt, polystyrene PMMA, poly(methyl methacrylate) POOP, polydioxapane PMVE, poly(methyl vinyl ether) PfBA, poly(/-hutyl acrylate) PAA, poly(acrylic acid) PTHF, poly(tetrahydrofuran) PTMO, poly(trimethylene oxide) MMT, montmorillonite. 

Yuan, J.Y. and Pan, C.Y. (2002) Synthesis of block copolymer from 5,6-benzo-2-methylene-13-dioxepane and methyl acrylate via atom transfer radical polymerization. Chin. J. Polym. Sci., 20 (2),... 

Luo, Z.-H. Yu, H.-J. He, T.-Y., Synthesis and Characterization of the Hydro-phobic Diblock Copolymers of Poly(dimethylxiloxane)-block-poly(eth)d methyl acrylate) Through Atom Transfer Radical Polymerization. J. Appl. Polym. Sci. 2008,107,1201-1208. 

Ma, Q., and Wooley, K. L. (2000). The preparation of t-butyl acrylate, methyl acrylate, and styrene block copolymers by atom transfer radical polymerization precursors to amphiphilic and hydrophilic block copolymers and conversion to complex nanostructured materials. /. Polym. Sci., Part A Polym. Chem., 3 (Suppl.) 4805-4820. 

Roos, S. G., Mueller, A. H. E., and Mat jaszewski, K. (1999). Copolymerization of n-butyl acrylate with methyl methacrylate and PMMA macromonomers comparison of reactivity ratios in conventional and atom transfer radical copolymerization. Macromolecules, 32(25) 8331-8335. 

Woodworth, B. E., Metzner, Z., and Matyjaszewski, K. (1998). Copper triflate as a catalyst in atom transfer radical pol5merization of styrene and methyl acrylate. Macromolecules, 31(23) 7999-8004. 

Lacerda et al. [63] prepared novel nanostructured composite materials from bacterial cellulose membranes (BC) and acrylate polymers by in-situ atom transfer radical polymerization (ATRP). The BC membranes were first functionalized with initiating sites by reaction with 2-bromoisobutyryl bromide (BiBBr), and then polymerization of methyl methacrylate (MMA) and n-butylacrylate (n-BA) was carried out in presence of catalysts copper (I) bromide and N, N, N, N", N"-pentamethyldiethylenetriamine (PMDETA), shown in Figure 5.8. 

Although ROMP or ADMET reactions hold a prominent position among polymerisation processes initiated by NHC-Ru complexes, other catalytic paths leading to macromolecular products were also investigated. The activity of compounds 30 and other similar monometallic [(NHQRuCl2(p-cymene)] complexes was tested in the atom transfer radical polymerisation (ATRP) of vinyl monomers by Delaude and Demonceau, along with 32. These complexes led to the controlled polymerisation of methyl methacrylate at 85 °C (Equation (7.8)). Attempts to polymerise n-butyl acrylate and styrene turned out to be more challenging, because of difficulties to control the acrylate polymerisation and of competition with the self-metathesis of styrene. 

Kavitha, A.A. and Singha, N.K. (2009) Tailor-made poly(methyl acrylate) bearing amantadine functionality (amino adamanty 1) via atom transfer radical polymerization (ATRP). A precursor of a supramolecular cross-linked polymer. Macromolecules, 42,5499-5508. 

By this chemistry, polymers with one amine end group as well as a,co-diamine-functionalized polymers can be used to prepare AB or ABA copolymers, respectively. The method gives copolymers with well-controlled polypeptide segments. Furthermore, no unreacted homopolymers or homopolypeptides could be detected. Several examples of the polymer B block have been reported poly(octenamer) prepared by acylic diene metathesis polymerization [67], poly(methyl acrylate) prepared by atom transfer radical polymerization (ATRP) [70], poly(ethylene glykol) PEG, and PDMS [68]. The method was expanded for the synthesis of... 

Karesoia, M., Jokinen, H., Karalainen, E., Pulkkinen, P., Torkkeli, M., Soiuinen, A. et al. (2009) Grafting of montmorillonite nano-clay with butyl acrylate and methyl methacrylate by atom transfer radical polymerization blends with poly(BuA-co-MMA). Journal of Polymer Science Part A Polymer Chemistry, 47, 3086-3097. 

Liu, S., Sen, A. Syntheses of syndiotactic-polystyrene-graft-poly(methyl methacrylate), syndiotactic-polystyrene-graft-poly(methyl acrylate), and syndiotactic-poly-styrene-graft-atactic-polystyrene with defined structures by atom transfer radical polymerization. Macromolecules, 33,5106-5110 (2000). 

Boyes S. G., Brittain W. J., Weng X., and Cheng S. Z. D., Synthesis, characterization, and properties of ABA type triblock copolymer brushes of st5rene and methyl acrylate prepared by atom transfer radical polymerization . Macromolecules, 2002 35(13) 4960 967. 

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