Polymers Bearing Pendent Adamantane: Effects On Synthesis and Thermal Properties

Date of Award


Degree Type


Degree Name

Doctor of Philosophy (PhD)


Polymers and High Performance Materials

First Advisor

Lon J. Mathias

Advisor Department

Polymers and High Performance Materials


Pendent adamantane-containing monomers were prepared and polymerized with comonomers to form new adamantane-containing poly(aryl ether)s, polyimides, polyamides, polyarylates, and polyesters. Incorporation of adamantyl groups into the polymers increased the glass transition temperature (T$\sb{\rm g})$ over the unsubstituted analogs. Comparisons were made between the rigidity of the different polymer backbones and the extent that the adamantyl group affected T$\sb{\rm g}.$ 4-Adamantyl resorcinol was prepared by alkylation of resorcinol with bromoadamantane. 1,3-(4-Aminophenoxy)-4-adamantyl-benzene was prepared from adamantyl resorcinol and 4-chloro-nitrobenzene using an NAS reaction followed by Palladium-catalyzed reduction to the diamine. The 5-adamantyl isophthalate was prepared from the alkylation of meta-xylene with bromoadamantane followed by oxidation to the diacid using a cobalt catalyst and O$\sb2.$ New adamantyl-substituted poly(ether ether ketone)s and poly(ether sulfone)s having intrinsic viscosities (IV) of 0.6-1.0 dL/g were prepared by nucleophilic aromatic substitution. Incorporation of pendent adamantyl groups into poly(ether ether ketone)s resulted in a polymer with a T$\sb{\rm g}$ of 225$\sp\circ$C, an increase of 100$\sp\circ$C over the unsubstituted analog. All the poly(aryl ether)s displayed good thermal stability by TGA in air and nitrogen, and were soluble in chlorinated and polar aprotic solvents. Poly(ether imide)s having intrinsic viscosities of 0.30-0.1.4 dL/g were prepared by a two-step synthesis using 1,3-(4-aminophenoxy)-4-adamantyl-benzene and aromatic dianhydrides. The polymers were generally more soluble than their unsubstituted analogs and had T$\sb{\rm g}$ values ranging from 231-296$\sp\circ$C. TGA showed 5% weight loss between 490-515$\sp\circ$C in nitrogen and 404-500$\sp\circ$C in air for the poly(ether imide)s. The polyamides were prepared by direct condensation using the Yamazaki phosporylation method and had IVs of 0.42-0.60 dL/g. Glass transition values ranged from 283-344$\sp\circ$C for the polyamides and TGA results showed 5% weight loss at 421-467$\sp\circ$C and 399-416 $\sp\circ$C in nitrogen and air, respectively. Adamantane-containing polyarylates were synthesized from two new pendent-adamantane monomers and 5-adamantyl isophthalic acid. The polyarylates from adamantyl resorcinol were prepared by interfacial polymerization and had intrinsic viscosities of 0.25-0.45 dL/g. The polyarylates were prepared by solution polymerization of the 5-adamantyl isophthaloyl chloride and had IVs of 0.60-0.85 dL/g. The T$\sb{\rm g}$ values for the polyarylates ranged from 175-274$\sp\circ$C. TGA showed 5% weight loss between 420-475$\sp\circ$C in nitrogen and 397-420$\sp\circ$C in air for these polymers. Polyesters were prepared by melt transesterification of 5-adamantyl dimethyl isophthalate with butanediol using titanium isopropoxide catalyst and had intrinsic viscosities of 0.2-0.40 dL/g. The T$\sb{\rm g}$ for the homopolymer was 117$\sp\circ$C. The 25:75 copolymer of 5-adamantyl resorcinol and terephthalic acia was crystalline as determined by WAXD and had a peak melting temperature of 156$\sp\circ$C.