Date of Award

Fall 1998

Document Type

Dissertation - Restricted

Degree Name

Doctor of Philosophy (PhD)



First Advisor

Wilkie, Charles A.

Second Advisor

Adair, Paul C.

Third Advisor

Donaldson, William A.


This work consists of three parts.

In Part I , the graft copolymerization of methyl methacrylate, methyl acrylate, methacylic acid and acrylic acid onto polybutadiene and its copolymers by benzoyl peroxide, BPO, or 2, 2'azobis(2-methylpropionitrile), AIBN, initiation were explored. The results show that these monomers can be grafted onto butadiene region of butadiene-containing polymers. The extent of both graft copolymerization and homopolymerization are dependent on the time and temperature of the reaction and the concentration of all of the reactants. One must specify the monomer, initiator and solvent for the efficient graft copolymerization. The methyl methacrylate adds directly to the radical sites which are formed on the backbone by the interaction of the polymer and the primary radical form the initiator, while for the other three monomers, the graft copolymerization occurs by addition of macro-radical to the double bonds.

In Part II , the cross-linking of polybutadiene, butadiene-styrene copolymers, and polystyrene by irradiation, thermal and chemical processes, and Friedel-Crafts chemistry and the effect of cross-linking on the thermal stability were investigated. The proof of cross-linking of the polymer comes from the insolubility of the product after the cross-linking reaction and is characterized by gel content and swelling ratio. The results show that the thermal stability of the polymer can be improved by cross-linking.

In Part III , the thermal degradation of three vinyl polymers, poly(vinylsulfonic acid) and its sodium salt and poly(vinylphosphonic acid) were studied by combination technique: TGA/FTIR. The results show that TGA/FTIR combined with analysis of residues provides an excellent opportunity to understand the degradation pathway of the compounds. The observation of foaming indicates that the char which is formed contains carbon as well as the inorganic salts which have been observed. The carbon is in a partially graphitized form. The salts produce a very large amount of char and may prove useful to impart increased flame retardance to other polymers if they can be incorporated in a convenient manner into these polymers.