scholarly journals Polymerization of organized monomers

2004 ◽  
Vol 58 (11) ◽  
pp. 479-486 ◽  
Author(s):  
Dragoslav Stoiljkovic ◽  
Branka Pilic ◽  
Radmila Radicevic ◽  
Ivana Bakocevic ◽  
Slobodan Jovanovic ◽  
...  

The current explanations of olefin and vinyl monomer polymerization propose that monomer molecules are successively added one by one to the growing polymer chain. This may be true if the monomer molecules exist as individual species in a polymerizing system, e.g. in dilute solutions of monomer. There are cases, however, in which monomer molecules are organized: bulk liquid monomer, solid monomer, a monomer monolayer adsorbed on a support, etc. Various supra-molecular species and particles of monomer exist in such cases. In the 1960-ties, Semenov, Kargin and Kabanov proposed a theory of organized monomer polymerization. In the last 25 years, our research group has further developed and applied that theory to various polymerizing systems: the radical polymerization of compressed ethene gas, the radical polymerization of liquid methyl methacrylate, olefin polymerization by transition metals and by Al-based catalysts. An outline of the main achievements are presented in this article.

2013 ◽  
Vol 85 (4) ◽  
pp. 835-842 ◽  
Author(s):  
Yasuhito Koyama ◽  
Takahiro Yoshii ◽  
Yasuhiro Kohsaka ◽  
Toshikazu Takata

A new concept for photodegradable cross-linked polymers utilizing characteristics of rotaxane cross-links and aromatic disulfides is proposed. The cross-linked polymer is obtained by the radical polymerization of a vinyl monomer in the presence of a [3]rotaxane-type cross-linker having two radically polymerizable groups. The [3]rotaxane-type cross-linker was prepared in 93 % yield by the typical rotaxane-forming reaction using a dumbbell-shaped aromatic disulfide possessing a bis(ammonium salt) moiety and a crown ether wheel tethered by a hydroxymethyl group (96 %) and the subsequent vinyl group-endowment (80 %). The radical polymerization of methyl methacrylate (MMA) in the presence of the cross-linker (0.1 mol %) at 60 °C afforded solvent-insoluble polymer in 90 % yield. When the polymer was swollen to a gel in dimethylformamide (DMF) and a small part of the gel was UV-irradiated, the gel was promptly solubilized, probably via the photochemical scission of the S–S linkage of the interlocked aromatic disulfide, causing the efficient decomposition of the rotaxane cross-links. The recovered poly(methyl methacrylate) bearing a small amount of crown ether moiety has a molecular weight of Mn 170 kg/mol (Mw/Mn 2.1) that indicated the occurrence of the site-selective photodegradation.


Polymer ◽  
2002 ◽  
Vol 43 (26) ◽  
pp. 7231-7241 ◽  
Author(s):  
Sophie Viala ◽  
Klaus Tauer ◽  
Markus Antonietti ◽  
R.-P Krüger ◽  
Wolfgang Bremser

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