Doctoral Dissertations

Abstract

"A study has been made on the anionic polymerization of a series of 5-membered cyclocarbosiloxanes with methyl and/or phenyl substituents. The polymerization was initiated by lithium n-butyldiphenylsilanolate in the presence of tetrahydrofuran. Six 5-membered cyclocarbosiloxanes (2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane; 2,2,5- trimethyl-5-phenyl-1-oxa-2,5-disilacyclopentane; 2,5-dimethyl-2,5-diphenyl- 1-oxa-2,5-disilacyclopentane; 2,2-dimethyl-5 ·,5-diphenyl-1-oxa- 2,5-disilacyclopentane; 2-methyl-2,5,5-triphenyl-1-oxa-2,5-disilacyclopentane; 2,2,5,5-tetraphenyl-1-oxa-2,5-disilacyclopentane) were synthesized. Since the chemical shifts of the protons of the cyclic monomers and the polymers formed were different, the rate of polymerization of the cyclic monomers was measured utilizing an NMR spectrometer. The effects of tetrahydrofuran concentration, initiator concentration and water concentration on the rate of polymer formation and on the molecular weight of the polymer formed are reported for a cyclocarbosiloxane 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane. Both monomodal and bimodal distributions of molecular weights were obtained on the polymers depending on the relative concentrations of initiator and water. The formation of this type of molecular weight distribution is explained. The rate of polymerization of phenyl substituted cyclocarbosiloxanes is also reported. This study shows that the structure of the growing chain end is important in determining the rate of polymerization. The apparent activation energy of polymerization for the cyclocarbosiloxanes studied was found to be in the range 10 - 14 kcal/mole"--Abstract, page ii.

Advisor(s)

Mayhan, Kenneth G.

Committee Member(s)

Almond, Carl A.
James, William Joseph
Stoffer, James O.
Kardos, J. S.
Webb, William H.

Department(s)

Chemistry

Degree Name

Ph. D. in Chemistry

Sponsor(s)

University of Missouri--Rolla. Graduate Center for Materials Research
University of Missouri--Rolla. Department of Chemistry
University of Missouri--Rolla. Department of Chemical Engineering

Publisher

University of Missouri--Rolla

Publication Date

1973

Journal article titles appearing in thesis/dissertation

  • The exchange of chloro and ethoxy groups upon the addition of dimethylchlorosilane to vinyldimethylethoxysilane

Pagination

xiv, 178 pages

Note about bibliography

Includes bibliographical references.

Rights

© 1973 Balaraman Suryanarayanan, All rights reserved.

Document Type

Dissertation - Restricted Access

File Type

text

Language

English

Library of Congress Subject Headings

Addition polymerization
Carbanions
Polymerization

Thesis Number

T 2815

Print OCLC #

6027168

Electronic OCLC #

914277523

Link to Catalog Record

Electronic access to the full-text of this document is restricted to Missouri S&T users. Otherwise, request this publication directly from Missouri S&T Library or contact your local library.

http://laurel.lso.missouri.edu/record=b1066800~S5

Comments

This work was supported in part by USPH-1-ROl-HL-13999-01 and by the Graduate Center for Materials Research, University of Missouri-Rolla

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