Synthesis and characterization of liquid crystalline polyrotaxanes based on poly(azomethine)s

TR Number



Journal Title

Journal ISSN

Volume Title


Virginia Tech


Polyrotaxanes are new polymers. Macrocyclic molecules, such as crown ethers, are threaded by linear or branched polymer chains. There is no covalent bond between the crown ethers and the polymer backbone. After the crown ethers are threaded onto the polymer backbone, both ends of the polymer can be blocked by large end groups. Polyrotaxanes are the topological isomers of blends of crown ethers and polymers. This architectural modification will produce interesting chemical and physical property changes in the polymer such as Tg and Tm, solubility, tensile strength, flexibility of the polymer.

The study include crown ethers, blocking groups, poly(azomethine)s A and B, poly(azomethine)rotaxanes A and B synthesis, characterization, and property research.

Crown ethers, 21-crown-7, 30-crown-10, 42-crown-14, and 60-crown-20, were synthesized from oligo(ethylene glycol)s and oligo(ethylene glycol) ditosylates with 22-40% yield. The high temperature synthetic method was developed so that the percentage yield of large crown and the small crowns in the same reaction could be controlled. A new purification method, low temperature recrystallization method was developed. The crown ethers properties included melting points, decomposition temperature, chemical shift on NMR spectra were studied.

A series of blocking groups were synthesized and characterized. Several synthetic routes were studied, and the best route was the Grignard synthesis. The purification method was improved by recrystallization in cyclohexane or carbon tetrachloride. A by-product, bis(p-t-butylphenyl)methanol, was obtained. The new compounds, p-tri(p-t-butylphenyl)methylaniline and p-tri{(p-t-butylphenyl)methylphenol, were identified by ¹H NMR, FTIR, and elemental analysis.

Poly(azomethine)s A and B are liquid crystalline polymers. They are rigid and strong. They have high Tm's and do not dissolve in general solvents. To check the reported information, the synthesis and characterization of these polymers were repeated. They precipitated from the reaction solution when their degree of polymerization reached 3-5. They were not thermally stable and were easily hydrolyzed in strong acids and in GPC column.

In order to establish the effectiveness of the blocking groups, a monomeric rotaxane, a di(azomethine)rotaxane, was designed and synthesized. The compound was successfully isolated by multiple reprecipitations and recrystallizations. A 12% yield of this compound was obtained. The largest crown ether that the blocking group could block was 42-crown-14.