Grafting of methacrylates and styrene on to polystyrene backbone via a “grafting from” ATRP process at ambient temperature

Abstract

Well defined graft copolymers are prepared by “grafting from” atom transfer radical polymerization (ATRP) at room temperature (30 °C). The experiments were aimed at grafting methacrylates and styrene at latent initiating sites of polystyrene. For this purpose, the benzylic hydrogen in polystyrene was subjected to allylic bromination with N‐bromosuccinimide and azobisisobutrylnitirle to generate tertiary bromide ATRP initiating sites (BrCPS). The use of BrCPS with lesser mol % of bromide initiating groups results in better control and successful graft copolymerization. This was used to synthesize a series of new graft copolymers such as PS‐g‐PBnMA, PS‐g‐PBMA, PS‐g‐GMA, and PS‐g‐(PMMA‐b‐PtBA) catalyzed by CuBr/PMDETA system, in bulk, at room temperature. The polymers are characterized by GPC, NMR, FTIR, TEM, and TGA. Graft copolymerization followed by block polymerization enabled the synthesis of highly branched polymer brush, in which the grafting density can be adjusted by appropriate choice of bromide concentration in the polystyrene. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3818–3832, 2007

Modified syndiotactic polystyrene/montmorillonite nanocomposite: Synthesis, characterization, and properties

“…The bromination takes place in the aliphatic chain and not in the aromatic ring. 32 The grafting parameters such as grafting yield, grafting efficiency, and weight gain were calculated, based on gravimetric measurements, according to the following equations: grafting yield (%G)=(W g -W 0 )/W g ×100; grafting efficiency (%GE)=W g /(W m +W 0 )×100; weight gain (%WG)=(W g -W 0 )/ (W m +W 0 )×100; where W g is the mass of the grafting copolymer, W 0 is the mass of polymeric initiator, and W m is the mass of the monomer taken for the reaction. The grafting parameters for sPS-g-PS, sPS-g-(PS-b-PMS) and [sPS-g-(PS-b-PMS)]-g-PMMA were calculated and summarized in Table I.…”

Synthesis of Microspheres as Versatile Functional Scaffolds for Materials Science Applications

“…The ''grafting from'' technique can be coupled with living/ controlled free radical polymerization techniques (e.g. nitroxidemediated polymerization (NMP), [23][24][25] ATRP, [26][27][28] and RAFT [29,30] ) leading to grafts consisting of well-defined and narrow-disperse polymers.…”

Amphiphilic polystyrene-graft-poly(N,N-dimethylamino-2-ethyl methacrylate) hydrogels synthesized via room temperature ATRP: Studies on swelling behaviour and dye sorption

“…In this paper, water soluble DMAEMA [22][23][24][25] functional monomer has been used for controlled graft polymerization from the polystyrene backbone in conjunction with CuBr/PMDETA catalyst system, at room temperature [26]. The controlled radical polymerization of DMAEMA would enable the control of the composition of the DMAEMA graft (through the reaction time/monomer conversion) and in addition should produce polymers with reproducible variation in size, in response to a stimulus.…”