Modification of Particle Surfaces by Grafting of Functional Polymers

Tsubokawa, Norio

doi:10.1533/9781845698591.36

Cited by 13 publications

(4 citation statements)

References 40 publications

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“…In general, the following principles (Scheme 1) may be applied to prepare polymer-grafted nanoparticles. [1][2][3][4][5][6] (1) ''Grafting onto'' process: graft polymerization of various vinyl monomers is carried out in the presence of nanoparticles using conventional initiators. The grafting of polymers onto the surface proceeds based on termination of growing polymer radicals, cations, and anions formed during the polymerization.…”

Section: Surface Grafting Of Polymers Onto Nanoparticles: Methodologymentioning

confidence: 99%

“…We have pointed out that the dispersibility of silica nanoparticles, carbon black, and carbon nanotubes is extremely improved by surface grafting of polymers, namely, chemical binding of polymers, onto silica nanoparticles, carbon black, and carbon nanotube surfaces. [1][2][3][4][5][6] We have reported grafting of various polymers, such as vinyl polymers, [7][8][9][10] polyesters, 11,12 polyethers, 13,14 poly(organophosphazene), 15 polyurethane, 16 and poly-(dimethylsiloxane), 17 onto the surface of silica nanoparticles and carbon black using surface functional groups as grafting sites. Furthermore, many other researchers have also attempted to graft polymers onto silica nanoparticle and carbon black surfaces.…”

mentioning

confidence: 99%

“…25,26 Polymer grafting onto a colloidal silica surface has been reported by Yoshinaga et al 27 We pointed out that polymer grafting onto nanoparticle surfaces is of interest for designing new functional organic-inorganic hybrid materials, which have excellent properties of both nanoparticles (as mentioned above) and grafted polymers, including photosensitivity, curing ability, bioactivity, and pharmacological activity. [1][2][3][4][5][6] However, scaled-up synthesis of polymer-grafted nanoparticles is difficult to achieve, because complicated reaction processes, such as centrifugation, filtration, and solvent extraction, are required for the synthesis of polymer-grafted nanoparticles, and large amounts of waste solvent are obtained.…”

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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: Surface Grafting Of Polymers Onto Nanoparticles: Methodologymentioning

confidence: 99%

mentioning

confidence: 99%

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confidence: 99%

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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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“…One versatile possibility to control surface properties purposefully and sustainably is to link polymers or block copolymers stably and permanently to surfaces. For a covalent linking mainly the “grafting from” and “grafting to” strategies are used. − Grafting from methods (Figure A) involve the covalent attachment of an initiating group followed by chain polymerization of suitable monomers. , Separately synthesized end-functionalized polymers can be attached to the surface by various grafting to methods (Figure B). Common approaches include the reaction of a terminally functionalized polymer that has native functional groups of the substrate surface with reactive groups of a monolayer or with functional groups of a primary polymer layer. , For the primary polymer layer approach a thin polymer (mono-) layer is applied, which serves both as initial surface layer and as reactive anchoring layer.…”

Section: Introductionmentioning

confidence: 99%

Tunable Hydrophilic or Amphiphilic Coatings: A “Reactive Layer Stack” Approach

Frenzel

Höhne

Hanzelmann

et al. 2015

ACS Appl. Mater. Interfaces

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Thin films with tunable properties are very interesting for potential applications as functional coatings with, for example, anti-icing or improved easy-to-clean properties. A novel "reactive layer stack" approach was developed to create covalently grafted mono- and multilayers of poly(glycidyl methacrylate)/poly(tert-butyl acrylate) diblock copolymers. Because these copolymers contain poly(glycidyl methacrylate) blocks they behave as self-cross-linking materials after creation of acrylic acid functionalities by splitting off the tert-butyl units. The ellipsometrically determined coating thickness of the resulting hydrophilic multilayers depended linearly on the number of applied layers. Amphiphilic films with tunable wettability were prepared using triblock terpolymers with an additional poly(methyl methacrylate) block. The mechanism of the formation of the (multi)layers was investigated in detail by studying the acidolysis of the surface-linked tert-butyl acrylate blocks by infrared reflection absorbance spectroscopy, accompanied by surface analysis using atomic force microscopy and contact angle measurements. In the case of the amphiphilic and switchable terpolymer layers this reaction was very sensitive to the used acidic reagent.

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Preparation and dispersibility of poly(L‐lactide)‐grafted silica nanoparticle

Takamura

Yamauchi

Tsubokawa

2011

J of Applied Polymer Sci

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To improve dispersibility of silica nanoparticle in organic solvents, the grafting of poly(L-lactide) (PLLA) onto silica nanoparticle surface by ring-opening polymerization of L-lactide (LA) was investigated in the presence of an amidine base catalyst. The ring-opening polymerization of LA successfully initiated in the presence of silica having amino groups (silica-NH 2 ) and an amidine base catalyst to give PLLA-grafted silica, but not in the presence of untreated silica (silica-OH). In the absence of the amidine base catalyst no ring-opening polymerization of LA even in the presence of silica-NH 2 and no grafting of PLLA onto silica were observed. It became apparent that the amidine base catalyst acts as an effective catalyst for the ring-opening graft polymerization of LA from the surface of silica-NH 2 . In addition, it was found that the percentage of PLLA grafting onto silica could be controlled according to the reaction conditions. The average particle size of PLLA-grafted silica was smaller than that of silica-NH 2 . Therefore, it was considered that the aggregation structure of silica nanoparticles was considerably destroyed by grafting of PLLA onto the surface. The PLLAgrafted silica gave a stable dispersion in polar solvents, which are good solvents for PLLA.

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Modification of Particle Surfaces by Grafting of Functional Polymers

Cited by 13 publications

References 40 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

Tunable Hydrophilic or Amphiphilic Coatings: A “Reactive Layer Stack” Approach

Preparation and dispersibility of poly(L‐lactide)‐grafted silica nanoparticle

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