Initiation Mechanisms in Radical Polymerization: Reaction of t-Butoxy radicals with Allyl methacrylate

1985 ◽  
Vol 38 (5) ◽  
pp. 689 ◽  
Author(s):  
WK Busfield ◽  
ID Jenkins ◽  
SH Thang ◽  
E Rizzardo ◽  
DH Solomon
Keyword(s):  
Radical Polymerization ◽  
Hydrogen Abstraction ◽  
Unusual Feature ◽  
Polymerization Reaction ◽  
Double Bonds ◽  
Radical Trapping ◽  
Allyl Methacrylate

The radical-trapping technique employing 1,1,3,3-tetramethylisoindolin- 2-yloxyl (1) as scavenger has been used to study the reactions of t-butoxy radicals with allyl methacrylate (2). Extensive hydrogen abstraction as well as addition to both allyl and acryloyl double bonds was observed. One unusual feature of the reaction, the formation of considerably more (Z)- alkene than (E)- alkene from trapping of radicals derived from the allyloxy moiety, is also discussed.

Preparation of a phosphorous-free terpolymer as a decalcifying agent for removing calcium from crude oil

RSC Advances ◽  
2016 ◽  
Vol 6 (63) ◽  
pp. 58426-58433 ◽  
Author(s):  
Shuaishuai Ma ◽  
Zhilan Cai ◽  
Yuming Zhou ◽  
Shiwei Li ◽  
Shuang Liang
Keyword(s):  
Free Radical ◽  
Acrylic Acid ◽  
Crude Oil ◽  
Radical Polymerization ◽  
Free Radical Polymerization ◽  
Polymerization Reaction

A novel phosphorous-free terpolymer, used as a decalcifying agent for removing calcium from crude oil, was prepared through a free-radical polymerization reaction of acrylic acid, allylpolyethoxy amino carboxylate, and 2-hydroxyethyl acrylate.

The Reaction of Organophosphorus Radicals With Vinyl Acetate and Acrylonitrile in the Presence of an Aminoxyl Radical Scavenger

1995 ◽  
Vol 48 (3) ◽  
pp. 625 ◽  
Author(s):  
WK Busfield ◽  
ID Grice ◽  
ID Jenkins
Keyword(s):  
Vinyl Acetate ◽  
Hydrogen Abstraction ◽  
Phosphate Esters ◽  
Radical Scavenger ◽  
Diphenylphosphine Oxide ◽  
Dimethyl Phosphite ◽  
Radical Trapping ◽  
Diffusion Controlled ◽  
Order Of Magnitude

The radical-trapping technique employing 1,1,3,3-tetramethyl-1,3-dihydro-2H-isoindol-2-yloxyl (1) as a radical scavenger has been used to study the reaction of diphenylphosphinoyl (2) and dimethoxyphosphinoyl (3) radicals with vinyl acetate and acrylonitrile. The phosphorus- centred radicals were generated by hydrogen abstraction from diphenylphosphine oxide and dimethyl phosphite respectively. Diphenylphosphine oxide was approximately three times as reactive as dimethyl phosphite towards hydrogen abstraction by t- butoxyl radicals and four times as reactive as tetrahydrofuran (towards abstraction of an α-hydrogen). Diphenylphosphinoyl radicals were found to be relatively nucleophilic and, in competition experiments, reacted about an order of magnitude faster with acrylonitrile than with vinyl acetate. Dimethoxyphosphinoyl radicals were rather less nucleophilic and reacted only twice as fast with acrylonitrile as they did with vinyl acetate. In the presence of excess aminoxyl (1), both diphenylphosphinoyl and dimethoxyphosphinoyl radicals were efficiently scavenged to produce stable phosphinic and phosphate esters respectively. The rate of scavenging was close to diffusion-controlled (c. 1.8×109 1. mol-1 s-1).

scholarly journals Mapping the multi-step mechanism of a photoredox catalyzed atom-transfer radical polymerization reaction by direct observation of the reactive intermediates

2020 ◽  
Vol 11 (17) ◽  
pp. 4475-4481 ◽  
Author(s):  
Luke Lewis-Borrell ◽  
Mahima Sneha ◽  
Aditi Bhattacherjee ◽  
Ian P. Clark ◽  
Andrew J. Orr-Ewing
Keyword(s):  
Atom Transfer Radical Polymerization ◽  
Real Time ◽  
Radical Polymerization ◽  
Absorption Spectroscopy ◽  
Direct Observation ◽  
Transient Absorption ◽  
Reactive Intermediates ◽  
Transient Absorption Spectroscopy ◽  
Polymerization Reaction ◽  
Step Mechanism

Short-lived intermediates are tracked in real-time by transient absorption spectroscopy during a multi-step photoredox catalysed polymerization reaction.

Efficient synthesis of narrowly dispersed amphiphilic double-brush copolymers through the polymerization reaction of macromonomer micelle emulsifiers at the oil–water interface

2016 ◽  
Vol 7 (27) ◽  
pp. 4476-4485 ◽  
Author(s):  
Heng Li ◽  
Han Miao ◽  
Yong Gao ◽  
Huaming Li ◽  
Daoyong Chen
Keyword(s):  
Molecular Weight ◽  
High Molecular Weight ◽  
Radical Polymerization ◽  
Pickering Emulsion ◽  
Polymerization Reaction ◽  
Water Interface ◽  
Efficient Synthesis ◽  
Oil Water

Narrowly dispersed amphiphilic PMA-g-PMMA/PDMA DBCs with high molecular weight were efficiently synthesized by Pickering emulsion template directed radical polymerization of macromonomer micelles.

Radical Polymerization Reaction of Styrene-Based Monomers Catalyzed by Iron Complexes Bearing β-Aminoketonato Ligand

2015 ◽  
Vol 72 (5) ◽  
pp. 306-317 ◽  
Author(s):  
Takafumi SAKAYORI ◽  
Takashi SATO ◽  
Makoto NAGAYA ◽  
Takamichi YAMAGUCHI ◽  
Shinji ISHIHARA ◽  
...  
Keyword(s):  
Radical Polymerization ◽  
Iron Complexes ◽  
Polymerization Reaction

Synthesis of poly-2-hydroxyethyl methacrylate–montmorillonite nanocomposite via in situ atom transfer radical polymerization

2008 ◽  
Vol 23 (12) ◽  
pp. 3316-3322 ◽  
Author(s):  
Ayhan Oral ◽  
Talal Shahwan ◽  
Çetin Güler
Keyword(s):  
Atom Transfer Radical Polymerization ◽  
Radical Polymerization ◽  
Interlayer Spacing ◽  
Solvent System ◽  
Polymerization Reaction ◽  
Atom Transfer ◽  
Scanning Calorimetry ◽  
Copper Bromide ◽  
Transmission Electron

The poly-2-hyroxyethyl methacrylate (PHEMA)/clay nanocomposite was synthesized by in situ atom transfer radical polymerization (ATRP) from initiator moieties immobilized within the silicate galleries of the clay particles. To produce organically modified montmorillonite (MMT) that has ATRP initiator moiety, a new catalyst that consists of quaternary ammonium salt moiety and an initiator moiety was synthesized. This initiator was intercalated into the interlayer spacing of the MMT. The polymerization reaction was carried out in a mixed solvent system consisting of methyl ethyl ketone and 1-propanol at 50 °C, using the initiator that has been already synthesized with a copper bromide catalyst. The 2, 2′-bipyridyl (bpy) complex was used as ligand. The products were characterized via Fourier transform infrared, nuclear magnetic resonance (1H NMR, 12C NMR), transmission electron microscopy, x-ray diffraction, thermogravimetric analysis, and differential scanning calorimetry.

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