Controlled Radical Polymerization of Vaporized Vinyl Monomers on Solid Surfaces under UV Irradiation

Abstract

Summary: In order to prepare well‐defined polymers on solid surfaces in the gas phase, a gas phase‐assisted surface polymerization (GASP) of vinyl monomers was carried out on solid surfaces pre‐coated with a photoiniferter, 2‐cyanoprop‐2‐yl N,N′‐dimethyldithiocarbamate, under UV irradiation. The GASP of methyl methacrylate (MMA) resulted in the formation of polymer on the surfaces and showed a proportional relationship between $\overline M _{\rm n}$ and polymer yield. Consecutive copolymerization of MMA and styrene led to the formation of a block copolymer, which was confirmed by a selective solvent fractionation method. These results demonstrate that controlled radical polymerization of vaporized monomer occurred on the solid surfaces.Expected mechanism of GASP under UV irradiation.magnified imageExpected mechanism of GASP under UV irradiation.

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

“…Endo and coworkers reported physically controlled radical polymerization of vapor-phase vinyl monomers by conventional free-radical initiators deposited onto solid surfaces, such as aluminum plate. [76][77][78][79] Deposition polymerization in monomer vapor of MMA and styrene was initiated from free radicals on the surface and high molecular weight polymers formed on the substrate surfaces. During polymerization, the number-average molecular weight was found to increase linearly with polymer yield.…”

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

“…For example, a broad singlet at 4.65 p.p.m. assigned to -COOCH 2 C 2 F 5 in the 1 H-NMR spectrum and characteristic FT-IR peaks at 1756 cm À1 assigned to n C¼O,ester , as well as 1170 and 1218 cm À1 assigned to n CÀF , 13 were all similar. These analytical results agree with previously reported values of PFMA.…”

Auto-Drawing and Functionalization by Vapor-Phase Assisted Polymerization on Solid Surface

“…This means that the product has totally a large PDI value. In a previous report [16], similar photo-VASP of St was carried out on a PMMA substrate pre-coated by a photo-iniferter: 2-cyanoprop-2-yl N,N'-dimethyldithiocarbamate at 40 ºC for 12 h, resulting in polystyrene production having M n 5230 and PDI 6.67. In this study, the obtained St-oligomer is considered to be due to the different conditions: photo-initiator, temperature, and polymerization time in comparison with the previous result.…”