A Novel Visible Light Initiatiating System for Cationic Polymerization

Yaǧcı, Yusuf; Hepuzer, Yeşi̇m

doi:10.1021/ma990508q

Cited by 90 publications

(76 citation statements)

References 23 publications

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“…) as a novel initiating system for visible light-induced cationic polymerization [ 49 ] prompted us to employ the same redox process for the mechanistic transformation. Accordingly, block copolymers were obtained by two discrete steps.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Block Copolymers by Combination of Atom Transfer Radical Polymerization and Visible Light‐Induced Free Radical Promoted Cationic Polymerization

Kahveci

Açık

Yaǧcı

2012

Macromol. Rapid Commun.

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A new synthetic approach for the preparation of block copolymers by mechanistic transformation from atom transfer radical polymerization (ATRP) to visible light-induced free radical promoted cationic polymerization is described. A series of halide end-functionalized polystyrenes with different molecular weights synthesized by ATRP were utilized as macro-coinitiators in dimanganese decacarbonyl [Mn(2) (CO)(10) ] mediated free radical promoted cationic photopolymerization of cyclohexene oxide or isobutyl vinyl ether. Precursor polymers and corresponding block copolymers were characterized by spectral, chromatographic, and thermal analyses.

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Section: Resultsmentioning

confidence: 99%

Synthesis of Block Copolymers by Combination of Atom Transfer Radical Polymerization and Visible Light‐Induced Free Radical Promoted Cationic Polymerization

Kahveci

Açık

Yaǧcı

2012

Macromol. Rapid Commun.

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“…Upon increasing the irradiation time, the absorption band of EO 2-is progressively collapsing, however we fail to observe the formation of silver nanoparticles. The same photolysis experiment is performed with a solution of acetonitrile containing eosin dye, AgNO 3 [55][56][57][58][59]. For instance, it has been reported that the photogenerated alkoxy benzyl radicals [33] or ketyl radicals [60] can convert efficiently Ag + to Ag 0 .…”

Section: Mechanistic Aspect Of Ag Nanoparticles Photogeneration In Somentioning

confidence: 99%

In-situ fabrication of polyacrylate–silver nanocomposite through photoinduced tandem reactions involving eosin dye

Balan

Malval

Schneider

et al. 2010

Polymer

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. In-situ fabrication of polyacrylate-silver nanocomposite through photoinduced tandem reactions involving eosin dye. Polymer, Elsevier, 2010, 51 (6) ABSTRACTA silver-acrylate nanocomposite was prepared using a novel one-pot strategy involving eosin dye as visible sensitizer and an amine derivative as radicals source. The mechanism highlighted by steady state photolysis and time resolved absorption spectroscopy lies on the initial formation of a strong ion pair complex between eosin and Ag + . Upon visible irradiation, the excited triplet state of the metal complex efficiently abstracts a hydrogen atom from the amine and produces a -aminoalkyl radical. In acrylate monomer matrix, such a strong reactive species initiates a free radical photopolymerization and also provides the reduction of the silver cation. Through this "in-situ" fabrication method, the kinetics formation of the nanocomposite and its detailed structural analysis are characterized by UV-Visible, real-time FTIR absorption spectroscopy and by transmission electron microscopy.

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“…2) starts with the derivatization of 3-APSG with trichloroacetyl isocyanate to generate the activated silica with surface-linked R-NH-CO-NH-COCCl 3 moieties (R 5 propyl, 3-APSG-COCCl 3 ) which, under irradiation with a mercury (Hg) lamp in the presence of Mn 2 (CO) 10 , initiates the co-polymerization of the chiral diacrylamide [(R,R)-DACH-ACR or (R,R)-DPDEA-ACR] directly from the silica surface, yielding the final CSP1 and CSP2, respectively, containing the covalently grafted chiral polymers [5]. A plausible mechanism of photoinitiation involves a preliminary decomposition of Mn 2 (CO) 10 into Mn(CO) 5 species that react with trichloroacetyl groups, yielding carbon-centered, surface-confined radicals [12,13]. The latter, in the presence of chiral vinyl monomers, initiate the polymerization yielding the final surface-grafted chiral polymeric stationary phase [15,16].…”

Section: Outcome Of the Polymerization And Characterization Of The Nementioning

confidence: 99%

“…For instance, radicals formed by the irradiation of systems containing a xanthene dye and an aromatic amine, were oxidized by a Istituto di Chimica Farmaceutica, Università di Urbino ''Carlo Bo'', Urbino, Italy diphenyliodonium salt [11]. Similarly, the dimanganese decacarbonyl Mn 2 (CO) 10 -organic halides combination is an efficient co-initiator for visible light cationic polymerization, when used in conjunction with onium salts [12,13]. Polymerization of vinyl monomers, such as methyl methacrylate, styrene, and glycidyl methacrylate, was successfully initiated by the system consisting of molibdenum hexacarbonyl Mo(CO) 6 and surface-linked trichloroacetyl groups as well [13,14].…”

Section: Introductionmentioning

confidence: 99%

Hybrid polyacrylamide chiral stationary phases for HPLC prepared by surface‐initiated photopolymerization

Ciogli

D’Acquarica

Gasparrini

et al. 2010

J of Separation Science

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Two hybrid polyacrylamide chiral stationary phases (CSPs) for HPLC have been synthesized by a new surface-initiated photo-induced radical polymerization approach of enantiopure N,N'-diacryloyl derivatives of (1R,2R)-diaminocyclohexane (CSP1) and (1R,2R)-diphenylethylenediamine (CSP2). This system is based on the activation of mesoporous silica microparticles by chemically bonded trichloroacetyl groups and dimanganese decacarbonyl as catalyst. UV irradiation was performed using a lab-made quartz photochemical reactor, ad hoc designed for the photo-induced polymerization process on the surface of microparticles. The two phases were evaluated and compared as chromatographic supports for the enantioselective HPLC of model chiral compounds. Their physico-chemical properties and chromatographic performances were also evaluated in comparison with those exhibited by the homologue CSPs obtained by the grafting-from thermal-induced process (CSP3 and CSP4). The new photopolymerization approach yielded higher grafting density than the thermal-induced one, especially in the case of the less reactive monomer (the diacryloyl derivative of (1R,2R)-diphenylethylenediamine), good chromatographic efficiency and a broad application field under normal phase and polar organic mode conditions.

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A Novel Visible Light Initiatiating System for Cationic Polymerization

Cited by 90 publications

References 23 publications

Synthesis of Block Copolymers by Combination of Atom Transfer Radical Polymerization and Visible Light‐Induced Free Radical Promoted Cationic Polymerization

Synthesis of Block Copolymers by Combination of Atom Transfer Radical Polymerization and Visible Light‐Induced Free Radical Promoted Cationic Polymerization

In-situ fabrication of polyacrylate–silver nanocomposite through photoinduced tandem reactions involving eosin dye

Hybrid polyacrylamide chiral stationary phases for HPLC prepared by surface‐initiated photopolymerization

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