Gas‐Phase Assisted Surface Polymerization of Vinyl Monomers with Fe‐Based Initiating Systems

Abstract

Summary: Gas‐phase assisted surface polymerization (GASP) of methyl methacrylate (MMA) and styrene (St) was investigated with Fe‐based radical initiating systems, FeCl2/2,2′‐bipyridine (Bpy)/methyl α‐bromophenylacetate (MBPA), etc. GASP with these initiating systems proceeded to produce corresponding polymers on substrate surfaces. The resulting PMMA had very high PDI values, suggesting an uncontrolled reaction. In an attempt to control the GASP, polymerization with a simple initiating system, Fe(0)/MBPA, was examined on Fe(0)‐metal surfaces, resulting in significant polymerization activity to produce high‐molecular‐weight PMMA. The results of time‐course tests on GASP of MMA and St suggested that a change had taken place to produce physically controlled propagation sites on the Fe(0) powder surfaces.

Surface Grafting of Polymers onto Nanoparticles in a Solvent-Free Dry-System and Applications of Polymer-grafted Nanoparticles as Novel Functional Hybrid Materials

“…80,81 Solid-state grafting onto a carbon black surface has also been reported. Wu et al reported polymer grafting of natural rubber onto a carbon black surface via a solid-state method; this was achieved by trapping the natural rubber radicals formed in a Haake internal mixer.…”

Hydrophobic cellulose fiber surfaces modified with 2,2,3,3,3-pentafluoropropylmethacrylate (FMA) by vapor-phase-assisted photopolymerization

“…14 The molecular weight of the extracted polymers ranged from 28 600 to 1 160 000 in M w , with large polydispersity values of 2.6-4.9, consistent with the peculiar structural property of photo-VASP products as previously reported. 10,12,15 As listed in Table 1, PFMA production with HMPP gradually increased from 2.7 to 7.5 mg over a period of up to 5 h. Over 5 h, a significant increase in polymer accumulation (410.8 mg) was observed as shown in samples 1-5 (reaction time 6 h), with an extreme increase in molecular weight. This suggests that the propagation reaction was greatly accelerated once the reaction time exceeded 5 h. A similar phenomenon was observed in a previous study of VASP.…”

“…5-9 Previously, we reported physically controlled living radical polymerization using free radical initiators by the VASP method, enabling the preparation of block copolymers, 10 the design of fine patterns, application to surface coatings with a fluorinated polymer 11 and the development of a homogeneous coating of a fine Fe-powder surface. 12 In these studies, a small amount of organic solvent was used to precoat initiators on substrate surfaces.…”

Adhesion control of interface between cellulose and polypropylene by vapor‐phase assisted surface copolymerization

“…The homopolymerization of AA and BA indicated a more preferable accumulation of PAA than PBA. These contradictory findings may be induced by various uncontrollable factors, such as chain transfer reactions on the biomass surface and termination reactions which may have a tendency to occur on the CμC surface in the early stages during the induction period …”