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Reactive blending via coordination chemistry—extraordinary mechanical response for atactic 1,2‐polybutadiene complexed with palladium chloride
Author(s) -
Belfiore Laurence A.,
Bossé Francis,
Das Pronab
Publication year - 1995
Publication title -
polymer international
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.592
H-Index - 105
eISSN - 1097-0126
pISSN - 0959-8103
DOI - 10.1002/pi.1995.210360207
Subject(s) - polybutadiene , palladium , polymer chemistry , dynamic mechanical analysis , materials science , tetrahydrofuran , glass transition , chemistry , polymer , solvent , copolymer , organic chemistry , catalysis
Experimental evidence in solution and in the solid state suggests that atactic 1,2‐polybutadiene and palladium chloride form coordination complexes with unusual mechanical properties. Ternary phase diagrams with tetrahydrofuran as the solvent highlight regions where gelation is favored relative to precipitation. The strongest evidence for a network structure is based on the facts that (i) solid films swell in heptane, and (ii) infrared spectroscopy identifies a new absorption characteristics of three‐membered rings and dihapto coordination of the olefinic sidegroup in 1,2‐polybutadiene to the metal center in palladium chloride‐bis(acetonitrile). Carbon‐13 solid state NMR spectroscopy suggests that the polymeric palladium complex is a glass when the salt concentration is 4 mol%. NMR linewidth data together with the pulse sequence parameters suggest that the chain backbone of the polymeric palladium complex experiences a significant reduction in molecular mobility which is consistent with diamagnetic glassy materials. Most importantly, the elastic modulus of polybutadiene increases by three orders of magnitude during the transition from rubbery to glassy behavior. This type of mechanical response cannot be explained by a filler effect, crystallite reinforcement, or antiplasticization. Transition‐metal coordination concepts applied to polymeric materials suggest that the enhancement in mechanical properties is a direct consequence of ‘coordination crosslinks’ where the palladium salt bridges different polymer chains. However, palladium‐catalyzed rections of the olefinic sidegroup, generating a chemically crosslinked network, represent a second explanation of the significantly enhanced macroscopic physical properties of 1,2‐polybutadiene in the presence of the transition‐metal salt. Reactive blending via metal‐ligand coordination represents a new mechanism to compatibilize polymeric mixtures that would otherwise exhibit phase separation.