Exfoliated polymer/clay nanocomposites with high clay contents were facilely constructed by the vapor-phase assisted surface polymerization of methyl methacrylate (MMA) with montmorillonite premodified with a trimethylstearyl ammonium salt and a free radical initiator: 2,2′-azobis(isobutyronitrile). This method required only premodified MMT and vaporized vinyl monomer without any prehomogenizing and postpolymerization processes. The exfoliated structure of the nanocomposites, which was confirmed by X-ray diffraction analysis, was retained even after melt processing.

Summary: Gas‐phase assisted surface polymerization (GASP) of β‐propiolactone (βPL) was investigated using substrate‐supported anionic initiators to produce a strongly bonded poly(β‐propiolactone) (PPL)/CaO composite and a novel PPL crystalline deposit with a high melting point value on Al plates. The polymerization of βPL smoothly proceeded in the gas phase to give high‐molecular‐weight PPLs having high PDI values. An almost linear relationship between $\overline M _{\rm n}$ value and incremental increase in the deposit suggested the living nature of the GASP of βPL. The obtained polymer‐coated substrates, especially PPL/CaO composite, showed strong interaction at the organic/inorganic interface. Moreover, the thermal and structural analyses of deposits revealed that some specific conformations were formed on CaO powder and Al plate surfaces to give highly crystallized deposits. These results demonstrate that the GASP is an effective method for coating any substrate that has a complex shape and a surface morphology.

Cover: Gas-phase assisted surface polymerization (GASP) of methyl methacrylate (MMA) with a simple initiating system, Fe(0)/abromophenylacetate (MBPA), produced high molecular weight PMMA on Fe(0)-metal surfaces, suggesting a physically controlled propagation process on the surfaces. Further details can be found in the Full Paper by

We report a simple method to produce a hydrophobic surface created by continual vapor-phase-assisted surface photopolymerization (photo-VASP) of 2,2,3,3,3-pentafluoropropylmethacrylate (FMA), which affords control over the chemical and physical properties of unique substrate surfaces without inducing any morphological changes. The photo-VASP approach was able to modify the surface of cellulose fiber substrates such as a typical, complicated, flexible and soft substrate while maintaining their original properties, imparting superior water repellency without compromising the original tactile nature of the material. The substrate surface was consecutively exposed to the vaporized initiator and monomer FMA under ultraviolet irradiation to start photopolymerization, resulting in selective coating of the irradiated surface with polymer chains. The cellulose fibers coated by the thin polymer layer retained their original tactile nature and demonstrated superior water repellency, with a controlled static contact angle 41301.

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.

To obtain a high polymer coated Fe(0) surface, gas-phase-assisted surface polymerization (GASP) of methyl methacrylate (MMA) was investigated using a zerovalent iron (Fe(0))/p-toluene sulfonylchloride (TsCl) initiator system, resulting in successful high polymer production on the solid surface. GASP was found to be initiated by radical species that might have been generated via redox reactions with Fe(0), Fe(II), Fe(III), and TsCl. From 1 H-NMR analysis, the p-toluene sulfonyl group was found at one end of the polymer chain. The molecular weight of obtained PMMA drastically decreased with increase in the composition ratio of Fe(0) in the initiator system, and increased with increase in polymer yield. From the results, it was assumed that the physically controlled polymerization of MMA proceeded by immobilized active species at gas-solid interfaces.

Polystyrene (PSt)-based copolymer/montmorillonite (MMT) nanocomposites were prepared by an in situ vapor-phase-assisted surface polymerization (VASP) as a solventless method using an organically modified MMT and a free radical initiator. Simultaneous and consecutive VASP of styrene (St) and methyl methacrylate (MMA) on the premodified MMT induced the accumulation of poly(MMAran-St) and poly(MMA-block-St) on the MMT surface, resulting in effective intercalation and exfoliation of silicate layers. The homogeneously dispersed silicate platelets in the polymer matrices were confirmed by X-ray diffraction and transmission electron microscope analyses. An important contributor to this phenomenon must be the particular interaction between a small amount of MMA units and silicate surfaces. This approach allows the nanocomposites with accompanying intercalation and exfoliation of silicate layers to be applied to a wide range of vaporizable monomers which in the absence of this technique would be otherwise difficult to individually prepare.

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