Gas‐phase‐assisted surface polymerization of methyl methacrylate with Fe(0)/TsCl initiator system

Andou, Yoshito; Yasutake, Mikio; Jeong, Jae-Mun; Kaneko, Masao; Nishida, Haruo; Endō, Takeshi

doi:10.1002/app.25270

Cited by 9 publications

(8 citation statements)

References 25 publications

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“…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.…”

Section: Discussionmentioning

confidence: 98%

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

Tsubokawa

2007

Polym J

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ABSTRACT:For the prevention of environmental pollution and simplification of reactions, scale-up synthesis of polymer-grafted inorganic nanoparticles in a solvent-free dry-system is reviewed. The grafting of polymers onto nanoparticles in a solvent-free dry-system was achieved by spraying monomers onto nanoparticles having initiating group. After the reaction, unreacted monomer and by-products were removed under high vacuum. For example, grafting of hyperbranched poly(amidoamine) (PAMAM) was successfully achieved using dendrimer synthesis methodology in a solvent-free dry-system. The percentage of PAMAM grafting onto the nanoparticle surface was 141% with repeated reaction cycles of 8-times. In addition, radical graft polymerization of vinyl monomers onto silica nanoparticles was achieved by spraying the monomers onto silica nanoparticles containing azo and peroxycarbonate groups in a solvent-free dry-system. The formation of ungrafted polymer was depressed in comparison with graft polymerization in solution: the grafting efficiency was 90-95%. PAMAM-grafted silica dispersed uniformly in epoxy resin and has an ability to cure the epoxy resin. Glass transition temperature of cured material was much higher than that of the material cured by conventional curing agents. The immobilization of norbornadiene, capsaicin, and flame retardant onto PAMAM-grafted nanoparticle and the properties of the resulting materials are also described.

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Section: Discussionmentioning

confidence: 98%

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

Tsubokawa

2007

Polym J

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“…The confinement of the free‐radical sites at the end of the chains also prevents termination through steric effects, which creates living chain ends that extend upon exposure to more monomer, and that can be used to form block copolymers 35, 37. The preapplication of initiator prior to placing the substrate in the vacuum chamber for exposure to monomer vapors was also used to perform living radical polymerizations based on ATRP by gas‐phase assisted surface polymerization (GASP)40, 41 and nitroxide‐mediated radical polymerization by surface‐initiated VDP 39…”

Section: Unifying Themesmentioning

confidence: 99%

“…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…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2010

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Chemical vapor deposition (CVD) polymerization utilizes the delivery of vapor-phase monomers to form chemically well-defined polymeric films directly on the surface of a substrate. CVD polymers are desirable as conformal surface modification layers exhibiting strong retention of organic functional groups, and, in some cases, are responsive to external stimuli. Traditional wet-chemical chain- and step-growth mechanisms guide the development of new heterogeneous CVD polymerization techniques. Commonality with inorganic CVD methods facilitates the fabrication of hybrid devices. CVD polymers bridge microfabrication technology with chemical, biological, and nanoparticle systems and assembly. Robust interfaces can be achieved through covalent grafting enabling high-resolution (60 nm) patterning, even on flexible substrates. Utilizing only low-energy input to drive selective chemistry, modest vacuum, and room-temperature substrates, CVD polymerization is compatible with thermally sensitive substrates, such as paper, textiles, and plastics. CVD methods are particularly valuable for insoluble and infusible films, including fluoropolymers, electrically conductive polymers, and controllably crosslinked networks and for the potential to reduce environmental, health, and safety impacts associated with solvents. Quantitative models aid the development of large-area and roll-to-roll CVD polymer reactors. Relevant background, fundamental principles, and selected applications are reviewed.

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“…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 .…”

Section: Introductionmentioning

confidence: 99%

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

Eksiler

Andou

Ariffin

et al. 2019

J. Polym. Sci. Part A: Polym. Chem.

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This study addresses the inherent issues surrounding surface modification methods of nanofibers and proposes an environmentally friendly and less toxic strategy for the surface modification of hydrophilic nanofiber. From the continuation of our previous work, which discussed the easy production of nanofiber (average size: 127 nm) from oil palm mesocarp fiber (OPMF), in this work, the surface of nanofibers (M‐IL‐OPMF) were modified through vapor‐phase‐assisted surface polymerization (VASP) to improve the affinity of interface between the polymer grafted M‐IL‐OPMF and non‐polar matrix. VASP of ε‐caprolactone was successfully proceeded from the [M‐IL‐OPMF] at 70 °C for 24 h and 72 h, and compositions were estimated to be 35.7% fiber/64.3% polymer and 27.8% fiber/72.2% polymer. To confirm the grafting of PCL, size‐exclusion chromatography (SEC) and Fourier transform infrared (FT‐IR) spectroscopy, thermogravimetry (TG), and dispersibility test in hydrophobic solvent were carried out. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2575–2580

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Gas‐phase‐assisted surface polymerization of methyl methacrylate with Fe(0)/TsCl initiator system

Cited by 9 publications

References 25 publications

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

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

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

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

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