Anionic Synthesis of Aromatic Carboxyl Functionalized Polymers. Chain-End Functionalization of Poly(styryl)lithium with 4,5-Dihydro-4,4-dimethyl-2- [4-(1-phenylethenyl)phenyl]oxazole

Synthesis of aromatic carboxyl functionalized polymers by atom transfer radical polymerization

“…TLC analysis of the aromatic carboxyl functionalized polystyrene ( 2 ), ( R f = 0, toluene) shows only one spot on the chromatogram, which corresponds to the formation of aromatic carboxyl functionalized polymer in quantitative yield 18. The size exclusion chromatographic (SEC) analysis of the aromatic carboxyl functionalized polystyrene ( 2 ) shows a monomodal molecular weight distribution (Fig 1) with M w / M n = 1.22 and M n = 3 040 g mol −1 .…”

“…Styrene (Aldrich Chemical Co) was purified by drying over calcium hydride followed by vacuum distillation and drying over molecular sieves before use. Tetrahydrofuran (THF) (Aldrich Chemical Co) was purified as described previously 18. 19 α‐Bromo‐ p ‐toluic acid (Aldrich Chemical Co) and CuBr (Aldrich Chemical Co) were used as received.…”

Synthesis of well-defined functionalized polymers and star branched polymers by means of living anionic polymerization using specially designed 1,1-diphenylethylene derivatives

“…Both 1-{4-[N,N-bis(trimethylsilyl)amino]phenyl}-1-phenylethylene (3) and 4,5-dihydro-4,4-dimethyl-2- [4-(1-phenylethenyl)-phenyl]oxazole (4) were employed for these polymer syntheses. [11,12] The degree of end-functionalization was ca. 100% in both cases.…”

“…Two d-glucose residues were also introduced quantitatively to the polyisoprene chain end by addition reaction of poly(isoprenyllithium) to 11. In order to introduce three d-glucose residues to the chain end, poly(styryllithium) was first functionalized with 11, followed by treatment with 3-(49-chloromethylbenzyl)-1,2 : 5,6-di-Oisopropylidene-a-D-glucofuranose (12). Two d-glucose and one d-galactose residues could be introduced to the chain end by using 6-(49-chloromethylbenzyl)-1,2 :…”

Adducts of Polymeric Organolithiums with 1,1‐Diphenylethylene. Rates of Formation and Crossover to Styrene and Diene Monomers

“…The addition reaction of polymeric organolithium compounds with 1,1‐diphenylethylene and its derivatives is an integral component of many recently developed procedures for the synthesis of well‐defined, chain‐end functionalized polymers, block copolymers, macromonomers, as well as heteroarm and regular star‐branched polymers 1–7. For example, a general functionalization methodology has been developed based on the addition of polymeric organolithium compounds with substituted 1,1‐diphenylethylenes as shown in Scheme , where X and Y represent functional groups 1,5,8–17…”