Synthesis and Styrene Copolymerization of Chloro and Fluoro Ring-substituted Isopropyl 2-cyano-3-phenyl-2-propenoates

Author

Alessandra Cimino, DePaul UniversityFollow

Date of Award

Winter 3-20-2020

Degree Type

Thesis

Department

Chemistry

First Advisor

Kyle Grice, PhD

Second Advisor

Ruben Perez, PhD

Abstract

Novel trisubstituted ethylenes (TSE), chloro and fluoro 2-cyano-3-phenyl-2-propenoic propenoates (XPhCH=C(CN)CO₂CH(CH₃)₂) were prepared and copolymerized with styrene (ST). The monomers were synthesized by modified crossed aldol condensation reaction (Knoevenagel condensation) of chloro and fluoro ring-substituted benzaldehydes with isopropyl cyanoacetate using piperidine as catalyst. They were subsequently characterized by IR, ¹H and ¹³C-NMR and CHN analysis as well. The novel TSE monomers formed were then copolymerized with styrene (ST) in solution at 70 °C and 1,1′-Azobis(cyclohexanecarbonitrile) (ABCN) was used as radical initiator of the reaction. The composition of the novel copolymers was calculated from nitrogen analysis and their structures were analyzed by IR, ¹H and ¹³C-NMR. The order of relative reactivity (1/r₁) for the TSE monomers was calculated to be: 2,3,5,6-tetrafluoro (1.30) > 2,3,6-trichloro (1.21) > 2,3,4-trifluoro (1.20) > 3,4,5-trifluoro (1.17) > 2,3,4,5,6-pentafluoro (1.16) > 2,4,5-trifluoro (0.99) > 2,4,6-trifluoro (0.81). Thermogravimetric analysis (TGA) showed that decomposition of the synthesized copolymers in nitrogen occurred in two steps.

Recommended Citation

Cimino, Alessandra, "Synthesis and Styrene Copolymerization of Chloro and Fluoro Ring-substituted Isopropyl 2-cyano-3-phenyl-2-propenoates" (2020). College of Science and Health Theses and Dissertations. 362.
https://via.library.depaul.edu/csh_etd/362

SLP Collection

no