Reversible addition–fragmentation chain transfer graft copolymerization of styrene and m‐isopropenyl‐α,α′‐dimethylbenzyl isocyanate from polypropylene lanterns: Solid phases for scavenging applications

Abstract

The γ‐initiated reversible addition–fragmentation chain transfer mediated free‐radical graft copolymerization of styrene and m‐isopropenyl‐α,α′‐dimethylbenzyl isocyanate (TMI) from a polypropylene (PP) solid phase was performed with cumyl phenyldithioacetate (CPDA) as the chain‐transfer agent. The initial CPDA concentration was 8 × 10−3 mol L−1. Polymerizations were performed with a dose rate of 0.18 kGy h−1 at the ambient temperature. Initial comonomer mixtures with 15, 30, and 50 mol % TMI were used. Depending on the amount of TMI in the initial comonomer mixture, the plot of the grafting ratio versus the time showed two grafting regimes (for 15 and 50 mol % TMI) or one (for 30 mol % TMI). Scavenger lanterns with 15 and 50 mol % TMI featured two isocyanate loading regimes, the second with higher loading capacities. The scavenger lanterns with 30 mol % TMI showed a linear loading capacity over the full grafting ratio. A maximum loading capacity of 110 μmol per scavenger lantern was achieved with 50 mol % TMI at a grafting ratio of approximately 60 wt %. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 857–864, 2006

Synthesis of Functional Polymers by Post‐Polymerization Modification

“…[11] Smith et al observed that the extent of grafting of an RGD peptide onto polyNAS decreased with increasing pH value and temperature owing to promotion of hydrolysis. [11] Cline and Hanna have noted that the reactivity of various amines towards aminolysis of p-nitrobenzoyl-Nhydroxysuccinimide in anhydrous dioxane correlated strongly with the basicity of the amino group, though steric hindrance within the investigated set of amines caused certain deviations [11,16] diNAS [8] NAS [18] NMAS [9,15,19] NAS [20] NSVB [20] NAS [4,13] NMAS [21,22] NSVB [23] NNHS [24] PFA [6] PFMA [6] PFVB [25] PFMA [26] NPF [7] NPA [27] NPMA [28] NPA [29] NPMA [30] MAPTT [10] 3 MA [17] MA [31] MA [32] MVI [17,33] VI [33] TMI [34] VDM [35,36] VDM [37] VDM [38] VPDMO [38] IDMO [38] GMA [39] GMA [40] 4-ES [41] GMA [42] GA [43] GMA …”

Living Radical Polymerization by the RAFT Process—A First Update

“…[238] Other papers cover RAFT polymerization of AA/65 from a PVDF surface previously irradiated with an electron beam [115] and graft copolymerization from a PP surface was achieved by gamma-irradiation of a solution of styrene and 1-(2-isocyanatopropan-2-yl)-3-(propen-2-yl)benzene and 38 in the presence of a PP 'lantern'. [239] Several papers report the use of RAFT polymerization to prepare a backbone polymers/macroinitiator for comb polymer synthesis. Poly(N-phenyl maleimide-co-(4-chloromethylstyrene)) was prepared by RAFT copolymerization with 7 and used as a macroinitiator for ATRP of styrene (CuCl/2,2 -bipyridine catalyst) to form poly(N -phenyl maleimide-co-4-chloromethylstyrene)-combpolystyrene.…”

Complex Macromolecular Architectures by Reversible Addition Fragmentation Chain Transfer Chemistry: Theory and Practice

“…We applied ginitiation and RAFT [103] to graft low polydispersity polymers (styrene and m-isopropenyl-a,a 0 -dimethyl benzyl isocyanate) from poly(propylene) lanterns. [104,105] These studies demonstrate that two distinct regimes of grafting exist: i) the grafting layer regime, in which the surface is not yet completely covered with polymer chains, and ii) a regime in which a second polymer layer is formed. In this second regime, the surface is effectively covered with polymer chains (of well-defined length) and new polymer chains are started by PS radicals from already grafted chains.…”