Date of Award


Degree Type


Degree Name

Doctor of Philosophy (PhD)


Polymers and High Performance Materials

First Advisor

B.G. Bufkin

Advisor Department

Polymers and High Performance Materials


A feasibility study was conducted whereby the addition reaction between a maleimide acceptor and a nucleophilic donor was investigated as a means of developing crosslinkable emulsions. The suitability of using maleimide acceptors as a means of providing room temperature corsslinkable functionality was established by determining the second order rate constants (k(,2)) for the reaction of N-(n-heptyl)maleimide, N-(n-heptyl)citraconimide, N-(n-heptyl)-3-chloromaleimide, and N-(n-heptyl)-3,4-dichloromaleimide with conventional nucleophilic agents. While all of the maleimide model compounds displayed varying degrees of reactivity at room temperature (the k(,2) values varied from a minimum of 4.14 x 10('0) to a maximum of 2.78 x 10('-5) 1/mole-sec), the 3-chloromaleimido moeity was selected as the most auspicious candidate for the ensuing investigation since the chloro substituent provided a means of sterically protecting the double bond from excessive premature loss during free radical polymerization. In order to prepare an acrylate-type polymer containing pendent 3-chloromaleimido unsaturation, 6-(3-chloro-maleimido)hexyl acrylate (3-CMIHA) was selected as a reasonable candidate for the investigation. To reduce the residence time which 3-CMIHA experienced in the polymerization environment, the model emulsions were prepared using a two-step, delayed addition technique whereby the total amount of 3-CMIHA was added in the last 50 weight percent of the total 60/40-ethyl acrylate (EA)/methyl methacrylate (MMA) monomer feed. Unfortunately, in spite of the methodological and steric measures used to prevent premature loss of the 3-chloromaleimido double bond, analysis for the remaining unsaturation indicated that approximately 40 percent of the initial 3-chloromaleimido functionality was consumed during free radical polymerization. While films containing increasing amounts of 3-CMIHA (up to 12 mole percent) displayed reduced physical properties as a result of the premature crosslinking, coatings of the emulsion containing 2 mole percent (5.31 weight percent) 3-CMIHA demonstrated a 56.7 percent and 31 percent increase in tensile strength and 35 percent and 23.7 percent reduction in elongation with and without the use of an external cross-linking agent (1,6-hexanediamine), respectively; increased solvent resistance; and only moderate losses in impact resistance as compared to a 60/40-EA/MMA control which did not contain 3-CMIHA. When the emulsion containing 2 mole percent 3-CMIHA was combined with various chemically and structurally different curing agents, the coatings cured with m-phenylene-diamine displayed a 93 percent reduction in reverse impact strength, a 160 percent increase in solvent resistance, a 30 percent reduction in elongation, and a 54 percent increase in tensile strength as compared with identical coatings which did not contain a crosslinking agent. In juxtaposition with compositionally similar emulsions crosslinked with conventional types of functionality, 3-CMIHA was rated as being more effective than glycidyl methacrylate but inferior to either N-methylolacrylamide or N-(isobutoxymethyl)acrylamide in providing an overall enhancement of the physical properties of the system.