scholarly journals In Situ Surface-Initiated Atom-Transfer Radical Polymerization Utilizing the Nonvolatile Nature of Ionic Liquids: A First Attempt

Polymers ◽  
2020 ◽  
Vol 13 (1) ◽  
pp. 61
Author(s):  
Ryo Satoh ◽  
Saika Honma ◽  
Hiroyuki Arafune ◽  
Ryo Shomura ◽  
Toshio Kamijo ◽  
...  

In this paper, in situ surface-initiated atom-transfer radical polymerization (SI-ATRP) based on both an open and a coated system, without using volatile reagents, was developed to overcome the limited usage of ATRP due to the necessity of sealing. Nonvolatile ionic liquid (IL)-type components were used, specifically N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide as the polymerizable monomer and N,N-diethylmethyl(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imide as the polymerization solvent. In the experiment, the reversible-deactivation radical polymerization characteristics are properly ensured in nonvolatile ATRP solution coated on silicon wafer as thin liquid film, to form concentrated polymer brushes (CPBs). The average molecular weight and molecular-weight distribution of the polymer produced in the liquid film and formed on silicon wafer were measured by gel permeation chromatography, which confirms that the polymerization reaction occurred as designed. Furthermore, it is clarified that the surface of the polymer brush synthesized in situ swollen by IL also exhibited low friction characteristics, comparable to that synthesized in a typical immersion process. This paper is the first to establish the effectiveness of in situ preparation for CPBs by using the coating technique.

2008 ◽  
Vol 23 (12) ◽  
pp. 3316-3322 ◽  
Author(s):  
Ayhan Oral ◽  
Talal Shahwan ◽  
Çetin Güler

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.


e-Polymers ◽  
2005 ◽  
Vol 5 (1) ◽  
Author(s):  
Gang Wang ◽  
Xiulin Zhu ◽  
Cheng Zhengping ◽  
Jian Zhu

AbstractHeterogeneous atom transfer radical polymerization (ATRP) of styrene initiated by 2-bromo-2-nitropropane in bulk was carried out with CuCl/2,2′-bipyridine as the catalyst. The kinetics was first order in monomer and the numberaverage molecular weight of the polymer increased linearly with monomer conversion, indicating the ‘living’/controlled nature of the polymerization. However, the number-average molecular weight was usually higher than the theoretical one. The nitro group might react with the Cu complex, resulting in insufficient initiation. The amount of catalyst has no effect on the controllability of this catalyst system for the ATRP of styrene. The presence of a halide end group in the obtained polymer was confirmed by both 1H NMR and chain-extension reaction.


e-Polymers ◽  
2004 ◽  
Vol 4 (1) ◽  
Author(s):  
Stefko B. Iliev ◽  
George S. Georgiev

Abstract A more than twofold increase in the rate of 2-hydroxyethyl methacrylate atom transfer radical polymerization in methanol at 20°C was observed under the action of a pulsatile magnetic field. At the same time, the average molecular weight of the produced polymers decreased while the polydispersity increased slightly. The results are explained by assuming a shift of the equilibrium from the dormant species to the active propagating radicals under the action of the magnetic field.


2009 ◽  
Vol 24 (5) ◽  
pp. 1880-1885 ◽  
Author(s):  
Hou Chen ◽  
Yanfeng Meng ◽  
Ying Liang ◽  
Zixuan Lu ◽  
Pingli Lv

Reverse atom transfer radical polymerization of methacrylonitrile (MAN) initiated by azobisisobutyronitrile (AIBN) was approached for the first time in the absence of any ligand in four novel ionic liquids, 1-methylimidazolium acetate ([mim][AT]), 1-methylimidazolium butyrate ([mim][BT]), 1-methylimidazolium caproate ([mim][CT]), and 1-methylimidazolium heptylate ([mim][HT]). The polymerization in [mim][AT] not only showed the best control of molecular weight and its distribution but also provided a more rapid reaction rate with the ratio of [MAN]:[FeCl3]:[AIBN] at 300:2:1. The block copolymer PMAN-b-PSt was obtained via a conventional ATRP process in [mim][AT] by using the resulting PMAN as a macroinitiator. After simple purification, [mim][AT] and FeCl3 could be easily recycled and reused and had no effect on the living nature of reverse atom transfer radical polymerization of MAN.


2018 ◽  
Vol 3 (3) ◽  
pp. 496-508 ◽  
Author(s):  
Haichen Li ◽  
Christopher R. Collins ◽  
Thomas G. Ribelli ◽  
Krzysztof Matyjaszewski ◽  
Geoffrey J. Gordon ◽  
...  

Combination of deep reinforcement learning and atom transfer radical polymerization gives precise in silico control on polymer molecular weight distributions.


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