Poly styrene, synthesis

Scheme 12.10 Cyclic poly(styrene) synthesis using the combination of ATRP and click cyclization [40].

N. Carretta, V. TricoU, E. Picchioni, lonomeric membranes based on partially sulfonated poly(styrene) Synthesis, proton conduction and methanol permeation. J. Membr. Sci. 166, 189-197 (2000). 

MO calculations, 2, 99 in photography, 1, 389 reactions with poly(styrene), 1, 309 structure, 2, 102 Bipyrimidines synthesis, 3, 103... 

A combination of TEMPO living free radical (LFRP) and anionic polymerization was used for the synthesis of block-graft, block-brush, and graft-block-graft copolymers of styrene and isoprene [201]. The block-graft copolymers were synthesized by preparing a PS-fo-poly(styrene-co-p-chloromethylstyrene) by LFRP [Scheme 110 (1)], and the subsequent re-... 

ATRP and grafting from methods led to the synthesis of poly(styrene-g-tert-butyl acrylate)-fr-poly(ethylene-co-butylene)-fr-poly(styrene-g-ferf-butyl acrylate) block-graft copolymer [203]. ATRP initiating sites were produced along the PS blocks by chloromethylation as shown in Scheme 112. These sites then served to polymerize the ferf-butyl acrylate. The poly(ferf-butyl acrylate) grafts were hydrolyzed to result in the corresponding poly(acrylic... 

Sherrington et al. were the first to attempt the synthesis of chiral polymeric metal complexes by the chemical modification route,78,177,178 whereby the [Mn(salen)Cl] units are attached in a pendant fashion, by only one of the aromatic rings, to poly(styrene) or poly(methacrylate) resin beads of various morphology. Epoxidation of 1-phenylcyclohexene gave enantioselectivity values between 61% and 91%. 

A method for microwave-assisted transesterifications has been described by Van-den Eynde and Rutot [73], The authors investigated the microwave-mediated deriva-tization of poly(styrene-co-allyl alcohol) as a key step in the polymer-assisted synthesis of heterocycles. Several /i-ketoesters were employed in this procedure and multigram quantities of products were obtained when neat mixtures of the reagents in open vessels were subjected to microwave irradiation utilizing a domestic micro-wave oven (Scheme 7.65). The successful derivatization of the polymer was confirmed by IR, 1H NMR, and 13C NMR spectroscopic analyses. The soluble supports... 

It should be noted that the Hantzsch-1,4-DHP synthesis can be conducted with a soluble polymer. Successful derivatization of poly(styrene-co-allyl alcohol) under the action of microwave irradiation with a variety of ethyl oxopropanoates and ethyl 3-aminobut-2-enoates were reported by Vanden Eynde s group [27]. 

CH2CpCo(C0)2 3 and CpCo(C0)2 were prepared utilizing the procedures of Grubbs et al. for the syntheses of poly-styrene-bound cyclopentadiene (25) and Rausch and Genetti for the synthesis of CpCo(C0)2 (26 ). Thus, for 3, commercially available (P)CH2C1 (1% DVB, microporous, 1.48 mmol Cl/g. resin) was treated with excess NaCp to form CH2CpH 2. This was then exposed to Co2(C0)e to form desired compound 3 (0.3-0.5 mmol Co/g. resin,... 

A regiospecific solid-phase synthesis of 3-methylthiazolo[3,2-c][l,2,3]triazole 105 has been achieved using poly-styrene-sulfonyl hyrazide resin (PS-Ts-NHNH2) 287. The reaction of resin 287 with l-thiazol-2-yl-ethanone in 5% TiCU/MeOH provides hydrazone 288 and subsequent treatment of this latter compound with morpholine at 95 °C gave fused triazole 105 in 60% yield (Scheme 29) <2004TL6129>. 

Postsulfonation of polymers to form PEMs can lead to undesirable side reactions and may be hard to control on a repeatable basis. Synthesis of sulfonated macromolecules for use in PEMs by the direct reaction of sulfonated comonomers has gained attention as a rigorous method of controlling the chemical structure, acid content, and even molecular weight of these materials. While more challenging synthetically than postsulfonation, the control of the chemical nature of the polymer afforded by direct copolymerization of sulfonated monomers and the repeatability of the reactions allows researchers to gain a more systematic understanding of these materials properties. Sulfonated poly(arylene ether)s, sulfonated poly-(imide)s, and sulfonated poly(styrene) derivatives have been the most prevalent of the directly copolymerized materials. 

In this review, synthesis of block copolymer brushes will be Hmited to the grafting-from method. Hussemann and coworkers [35] were one of the first groups to report copolymer brushes. They prepared the brushes on siUcate substrates using surface-initiated TEMPO-mediated radical polymerization. However, the copolymer brushes were not diblock copolymer brushes in a strict definition. The first block was PS, while the second block was a 1 1 random copolymer of styrene/MMA. Another early report was that of Maty-jaszewski and coworkers [36] who reported the synthesis of poly(styrene-h-ferf-butyl acrylate) brushes by atom transfer radical polymerization (ATRP). 

The solution phase synthesis of peptides often results in mixtures of labelled, unlabelled compounds along with other impurities and requires extensive purification. A route using a solid phase approach [polyethylene glycol-poly-styrene PEG-PS derivatised with a xanthen-2-oxovalerate (XAL) linker] was recently developed [193] (Scheme 44). 

Recently, Scialdone and colleagues have employed phosgenated />-nitrophenyl(poly-styrene) ketoxime (Phoxime, 76) resin in the synthesis (via 77 and 78) of acyclic and heterocyclic amino-acid-derived ureas 79 too (Scheme 42). Resin 75 was first reacted with an amino acid and TMSCl in pyridine, and the resulting carbamate acid resin 77 was then coupled with an amine under standard carbodiimide protocol (HOBt/DIC in DMF) to obtain the carbamate amide resin 79. 

Becer CR, Paulus RM, Hoppener S et al. (2008) Synthesis of poly(2-ethyl-2-oxazoline)-h-poly(styrene) copolymers via a dual initiator route combining cationic ring opening polymerization and atom transfer radical polymerization. Macromolecules 41 5210-5215... 

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