Synthesis of poly(methyl methacrylate‐g‐glycidyl azide) graft copolymers using N, N‐dithiocarbamate‐mediated iniferters

Abstract

A glycidyl azide polymer with pendent N, N-diethyl dithiocarbamate groups (GAP-DDC) was prepared by the reaction of poly(epichlorohydrin) (PECH) with pendent N, N-diethyl dithiocarbamate groups (PECH-DDC) and sodium azide (NaN 3 ) in dimethylformamide (DMF). It was then used as a macro-photoinitiator for the graft polymerization of methyl methacrylate (MMA). Photopolymerization was carried out in a photochemical reactor at a wavelength greater than 300 nm. Conversion was determined gravimetrically and first-order time conversion plot for the polymerization system showed linear increase with the polymerization time indicating that polymerization proceed in controlled fashion. The molecular weight distribution (M w /M n ) was in the range of 1.4-1.6 during polymerization. The formation of poly(methyl methacrylate-g-glycidyl azide) (PMMA-g-GAP) graft copolymer was characterized by gel permeation chromatography, FT-IR spectroscopy, Thermogravimetric analysis, and differential scanning calorimetry.

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“…Al-Kaabi et al synthesized GAP carrying pendant N, N-diethyl dithiocarbamate groups and used as macro-photoinitiator for grafting of methylmethacrylate onto the polyether main chain. 29 Submarian reported the synthesis and characterization of an energetic triblock copolymer, hydroxyl-terminated poly (azidomethyl ethylene oxide-b-butadiene-b-azidomethyl ethylene oxide) (GAP-PBD-GAP). A detiled structural characterization was performed.…”

Online monitoring of reaction temperature during cationic ring opening polymerization of epichlorohydrin in presence of BF3 and 1,4‐butanediol

“…Polyepichlorohydrin (PECH) and ECH copolymers are major functional polymeric materials with reactive pendent chloromethyl groups for modification via nucleophilic substitution and have been utilized in applications such as energetic polymeric binders, catalyst contained binders for solid propellants, and liquid crystal alignment layers …”

Synthesis and characterization of poly(vinyl 2,4,6‐trinitrophenylacetal) as a new energetic binder

“…During the past 4 decades, a large number of energetic binders that can, or might, find applications in propellants or plastic‐bonded explosives have been synthesized and examined. They include azido polymers,3–14 nitrate ester polymers,15–20 and aliphatic and aromatic nitro polymers 21, 22. Nevertheless, almost all of the efforts have been in the investigation of azido polymers and nitrate ester polymers.…”