Gas‐Phase Assisted Surface Polymerization Behavior of β‐Propiolactone on Inorganic and Organic Substrates and Consequent Composite Production

Abstract

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.

Chemical Vapor Deposition of Conformal, Functional, and Responsive Polymer Films

“…c) Dispersed multi‐wall carbon nanotubes (MWCNTs) have been coated with poly(glycidyl methacrylate) (PGMA) by iCVD, showing that each individual tube is coated conformally. Reproduced with permission from a) 36, b) 42, c) 59. a) Copyright 2009 American Chemical Society.…”

“…As compared to the continuous introduction of volatile initiators by iCVD and piCVD, preapplication of initiator fixes the available supply for film growth. Methods for CVD polymerization involving preapplication of the initiator include vapor‐phase assisted surface polymerization (VASP),35–38 living free‐radical polymerization methods such as nitroxide‐mediated polymerization (surface initiated vapor deposition polymerization (SI‐VDP))39 and atom transfer radical polymerization (ATRP) (also categorized as a form of gas‐phase assisted surface polymerization (GASP)),40, 41 anionic42 and cationic43–45 ring‐opening polymerization, cationic polymerization of acetylene derivatives,46 photoinitiated cationic polymerization of vinyl monomers,47 and ring‐opening metathesis polymerization (ROMP) (sometimes termed solventless polymerization) 46, 48, 49…”

Surface modification for nano‐lignocellulose fiber through vapor‐phase‐assisted surface polymerization

“…The vapor phase‐assisted surface polymerization (VASP) method has been developed to coat many substrate surfaces with polymers, resulting in the prominent achievements of hydrophobic/hydrophilic controlling and surface grafting . It is an excellent method to preserve the delicate surfaces of materials due to the advantages of VASP process .…”

“…The vapor phase-assisted surface polymerization (VASP) method has been developed to coat many substrate surfaces with polymers, resulting in the prominent achievements of hydrophobic/hydrophilic controlling and surface grafting. [18][19][20][21][22][23][24][25] It is an excellent method to preserve the delicate surfaces of materials due to the advantages of VASP process. 26 Basically, this polymerization procedure is a solvent-free method, taking place by gas-solid interface interaction, and provides higher grafting rate when compared to the commonly used liquid processes.…”

Melt-Processable Nanocomposites Grafting-From Platelet Surfaces by Vapor-Assisted Surface Polymerization

“…One attractive feature of the VASP method is that gaseous monomers can diffuse and penetrate interstitially within the fine gaps and spaces of the solid substrates, allowing the construction of fine structured composites [26] and coatings [27,28]. After the diffusion and adsorption on the interstitial surfaces, the monomers polymerize in a manner of "pseudografting from" the substrate surfaces.…”