Microstructure and Physical Properties of Hydrochlorinated 1,4-Polyisoprene Prepared by Butyllithium in Nonpolar Solvent

Nanodroplets of polyisoprene fluid contained within poly(acrylic acid‐co‐acrylamide) shells

“…For 1 , the PI repeat units remained intact, giving 3 . However, approximately 30% of the double bonds along the PI backbone of 2 underwent hydrochlorination,51 giving partially hydrochlorinated 4 . The number‐average molecular weights and the number of repeat units for 3 and 4 were measured by 1 H NMR spectroscopy with end‐group analysis, with a single diphenylethylene (DPE) unit52 as an internal reference.…”

Thermal shaping of shell-crosslinked (SCK) nanoparticles, facilitated by nanoconfinement of fluid-like cores

“…NMRP afforded a PI-containing diblock copolymer with a subambient T g , 3, that could be increased to higher temperature through chemical modification. As depicted in Scheme 3, treatment of 3 with HCl (g) resulted in partial hydrochlorination 20 of double bonds in the PI block as well as deprotection of the tert-butyl groups to produce PI(HCl)-b-PAA (5). 1 H NMR spectroscopy indicated 90% hydrochlorination, as observed by the decreased intensity of the olefinic proton resonance at 5.2 ppm.…”

“…Moreover, nitroxidemediated radical polymerization (NMRP), as described by Hawker et al 19 for the preparation of PI of narrow molecular weight distribution and consisting predominantly of cis-4,1microstructure (T g y 270 uC), is used in place of previously employed anionic polymerization 17a,b as the starting point for preparing SCK nanoparticles containing PI cores expected to range in T g from 270 uC to 40 uC. 20 The syntheses of the amphiphilic diblock copolymer, PAA-b-PI, by NMRP, supramolecular assembly into polymer micelles, and intramicellar crosslinking within the shell layers are discussed in detail. Preparation of SCKs having PI cores with T g values above room temperature, by partial hydrochlorination of the double bonds of the PI, in the PAA-b-PI diblock copolymer precursor followed by micellization and shell crosslinking is also described.…”

Reactions of Polymers

“…Hydrochlorination, usually carried out at about 10 C, proceeds by electrophilic addition to give the Markownikoff product with chlorine on the tertiary carbon (Eq. 9-33) [Golub and Heller, 1964;Tran and Prud'homme, 1977]. Some cyclization of the intermediate carbocation (XXVI) also takes place (Sec.…”