Article (Scientific journals)
Halato-Telechelic Polymers. 11. Viscoelastic Behavior of α,ω-Dicarboxylatopolybutadiene Based on Group 4 Metal Ions
Broze, Guy; Jérôme, Robert; Teyssié, Philippe et al.
1985In Macromolecules, 18 (7), p. 1376-1382
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Abstract :
[en] In nonpolar solvents, α,ω-alkaline and -alkaline-earth dicarboxylatopolybutadiene (M*n 4600) leads to gel formation at concentrations as low as 1.5 g dL-1. However, any polar additive, i.e., water or alcohol, has a depressive effect on the metal—carboxylate association and the resulting gelation. The use of group 4 metal ions is an efficient way to overcome this drawback. Cross-linking of the carboxy-telechelic polymer is then promoted by a group 4 metal (Ti, Zr, Ce) alkoxide used in excess vs. the acid end groups. When the unreacted alkoxide groups are hydrolyzed into metal oxoalkoxide groupings, the gelation occurs in the presence of the alcohol formed as a byproduct and the required humidity of the medium. Cross-linking efficiency depends on the size of the group 4 cation just like in the series of alkaline and alkaline-earth cations. The deformation mechanism is controlled by the stability of the metal—carboxylate bonds and by the mean number of chain ends attached to the metal oxide aggregates. In this respect, excess alkoxide is a key parameter to impart to the solutions a broader range of rheological properties. Viscous solutions are observed at a metal-to-chain molar ratio of 0.5, whereas increasing excess of metal alkoxide is responsible for a shear-thickening behavior and finally for elastic gels. © 1985, American Chemical Society. All rights reserved.
Disciplines :
Chemistry
Author, co-author :
Broze, Guy ;  Université de Liège - ULiège > Département de chimie (sciences) > Chimie des macromolécules et des matériaux organiques (CERM)
Jérôme, Robert ;  Laboratory of Macromolecular Chemistry and Organic Catalysis, University of Liége., Sart-Tilman, 4000 Liége, Belgium
Teyssié, Philippe ;  Université de Liège - ULiège > Relations académiques et scientifiques (Sciences)
Marco, Claude;  Laboratory of Materials Science, University of Mons, 7000 Mons, Belgium
Language :
English
Title :
Halato-Telechelic Polymers. 11. Viscoelastic Behavior of α,ω-Dicarboxylatopolybutadiene Based on Group 4 Metal Ions
Publication date :
1985
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
American Chemical Society, United States - District of Columbia
Volume :
18
Issue :
7
Pages :
1376-1382
Peer reviewed :
Peer Reviewed verified by ORBi
Available on ORBi :
since 05 December 2019

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