Date of Award

Spring 2013

Degree Type

Masters Thesis

Degree Name

Master of Science (MS)


Polymers and High Performance Materials

Committee Chair

Robson Storey

Committee Chair Department

Polymers and High Performance Materials

Committee Member 2

Daniel Savin

Committee Member 2 Department

Chemistry and Biochemistry

Committee Member 3

Jeffrey Wiggins

Committee Member 3 Department

Polymers and High Performance Materials


This volume describes efforts toward the synthesis and employment of phenoxyalkyl (meth)acrylates, which were used to end-quench 1sobutylene polymers m1tiated from 2-chloro-2,4,4-tnmethylpentane (TMPCl), and 5-tert-butyl-1 ,3-d1(1-chlorol- methylethyl)benzene (bDCC), respectively, at -70 °C in 40/60 (v/v) hexane/methyl chlonde. The quencher/cham end molar rat10s typically ranged from 2.5-4, while the ratio of Lewis ac1d/cham end was vaned from approximately 3 5-6 In all cases, alkylation occurred exclusively at the para position of the quencher and no cham degradat10n was observed, even at high concentrations of TiC14 and long reaction times. Prellmmary qualitative studies mvolved the reaction of quenchers of varymg alkyl tether length, with pre-synthesized, tert-chlonde monofunct10nal poly1sobutylenes (Pills) and large excesses of TiC14, m order to establish proof of concept. Subsequent quant1tat1ve studies ensued, ut1lizmg bDCC as an mternal NMR reference, which enabled the momtonng of quenchmg kmetics and the extent of side reactions, 1f any, for each quencher It was determmed that quenchers with 2 and 3 carbon tether lengths alkylated too slowly to be of practical use, despite thelf low cost. However, quenchers with tether lengths of 4 carbons or greater, proved highly effective, with the longer tethers yieldmg faster kmetics Finally, selected quenchmg reactions were performed in situ, 1rnrnediately followmg polymenzat1on, after FTIR spectroscopic measurements md1cated that all of the isobutylene monomer had been consumed. All difunct10nal, telechehc macromonomers obtamed were charactenzed by proton (1H) and carbon (13C) NMR, GPC and MALDI-TOF MS This study represents a novel method of generatmg telechehc polyisobutylene (meth)acrylate-functional macromonomers ma "one-pot, one step" synthesis.