Chain polymerization of ester functionalized monomers.

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Doctoral Dissertations 1896 - February 2014
1-1-2001
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Tao, Xie
University of Massachusetts Amherst
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31E0bb D27S 6514
CHAIN POLYMERIZATION OF ESTER FUNCTIONALIZED MONOMERS
A
Dissertation Presented
by
TAO
XIE
Submitted to the Graduate School ofthe
University ofMassachusetts Amherst in partial fulfillment
ofthe requirements for the degree of
DOCTOR OF PHILOSOPHY
September 2001
Polymer Science and Engineering
©
Copyright by Tao Xie 2001
All Rights Reserved
CHAIN POLYMERIZATION OF ESTER FUNCTIONALIZED MONOMERS
A
Dissertation Presented
by
TAO
XIE
Approved as to style and content by:
Jacques Penelle, Chair
"^V^
Thomas McCarthy Department Head
J.
Polymer Science and Engineering
ACKNOWLEDGMENTS
I would like to thank my advisor, Prof. Jacques Penelle, for his thoughtful guidance
and support throughout my Ph.D. research work. His knowledge and scientific attitude
have benefited me the most. My committee members, Prof. Shaw L. Hsu and Prof. Paul
M. Lahti, earned my gratitude for their helpful suggestions and criticisms, which
I
consider invaluable to the learning process in graduate school.
During the course of this research, I have received generous help from people around
me, in particular the members of CJJVIA lab at the University of Louvain in Belgium and
members of the Penelle group at the University of Massachusetts. Mere words cannot
adequately describe the benefit I have received from working in their intellectual
environment.
owe
I particular gratitude to Herion Hugues whose initial work on the ring-opening
polymerization of diethyl cyclopropane- 1,1-dicarboxylate was incorporated into Chapter
2 of this dissertation. I am especially indebted to Prof. Shaw L. Hsu and Dr. Andre
Stolov for their collaboration in the second part of this thesis.
My my
deepest appreciation is extended to all friends for the memorable years inside
and outside the lab in both Amherst and Louvain-la-Neuve in Belgium.
my
Finally, I appreciate parents for their love and support throughout the years.
iv
ABSTRACT
CHAIN POLYMERIZATION OF ESTER FUNCTIONALIZED MONOMERS
SEPTEMBER
2001
TAO
XIE, B.S., ZHEJIANG UNIVERRSITY, P.R. CHINA
M.S., ZHEJIANG UNIVERSITY, P.R. CHINA
D.E.A., UNIVERSITY OF LOUVAIN, BELGIUM
Ph.D., UNIVERSITY OF MASSACHUSETTS AMHERST
Directed by: Professor Jacques Penelle
The overall purpose ofthis dissertation is to develop new polymer materials
containing ester functionalities. This document will be separated into two sections
covering two synthetic research projects that I have worked on for my Ph.D. dissertation.
A
Both projects involved chain polymerizations of ester-functionalized monomers. key
feature ofthis thesis was to gain an in-depth understanding ofthe individual chain
polymerizations employed, namely, anionic ring-opening polymerization of dialkyl
cyclopropane-1,1-dicarboxylates and radical polymerization ofmultifunctional
captodative monomers.
Part I focuses on developing a new synthetic methodology based on anionic ring-
opening polymerizations ofcyclopropanes geminally substituted on the cycle. The goal
was to obtain carbon-chain polymers with ester substituents located on every third-carbon
atom ofthe backbone, a substitution pattern that cannot be achieved by any other
synthetic method. Ester groups are chosen not only because oftheir electron-
withdrawing nature that ensures enough activation but also because the structural
versatility offered by ester groups allows to tailor polymer properties in a very easy way.
v
Conditions allowing this ring-opening polymerization to proceed in a living way arc
By
identified. taking advantage of the living character of the anionic polymerization, a
control over the polymer end-groups, molecular weight and molecular weight distributiion
of the polymers can be achieved. Tailoring the polymer properties is also possible by
varying the ester groups. Chemical modification of the polymer offers another way to
obtain new polymers such as polyelectrolyte having the same substitution pattern.
In part II, a possible answer is proposed to the environmental issues the coating
industry is currently facing which include the toxicity of acrylic monomers used and
generation of volatile organic compounds during the process. New functionalized bis(a-
substituted acrylate)s were developed that can be assumed non/less toxic based on
previous literature. The new functionalities introduced in the monomers are crucial in
affecting not only their reactivity toward the photopolymerization involved in the coating
production but also some properties of the final coatings. Both of these aspects are
covered in the research.
vi
TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS
iv
ABSTRACT
v
;
LIST OF TABLES
xiii
LIST OF FIGURES
x v
i
LIST OF SCHEMES
xv
ii
PART ONE: RING-OPENING POLYMERIZATION OF
CYCLOPROPANE- -DICARBOXYLATES
1 ,1
CHAPTER
INTRODUCTION
1 2
.
Background
1.1 2
1.2 General Goal and Specific Objectives ofthis Project 3
1.3 Design ofa Synthetic Route to Polymers with Substitution Pattern d 7
1.3.1 Theoretical Considerations on the Ring-Opening Polymerization of
Cyclopropanes 7
1.3.2 Polymerization of Cyclopropanes Reported in the Literature 10
1.3.2.1 Radical Polymerizations 10
1.3.2.2 Cationic Polymerizations 15
1.3.2.3 Coordination Polymerizations 17
1.3.2.4 Anionic Polymerizations 18
1 .4 Dissertation Plan 21
1.5 References 22
ANIONIC RING-OPENING POLYMERIZATION OF DIETHYL
2.
CYCLOPROPANE- -DICARBOXYLATE 25
1 ,1
25
2.1 Introduction
26
2.2 Experimental Part
26
2.2.1 Materials
2.2.2 Synthesis ofDiethyl Cyclopropane-1,1-Dicarboxylate 1 26
vii
2.2.3 Synthesis of Sodium Thiophenolate (PhSNa)
..27
2.2.4 Synthesis of Sodium Diethyl Methylmalonate (SDEM)
28
2.2.5 Polymerization Procedure
28
2.2.6 Measurements
29
2.3 Results and Discussion
29
2.3.1 Previous Study on the Ring-Opening Polymerization of 29
1
2.3.1.1 Synthesis ofthe Pure Monomer
1 29
2.3.1.2 Synthesis ofthe Initiator PhSNa 30
2.3.1.3 Polymerization Kinetics of 1 Initiated
by Sodium Thiophenolate
31
2.3.1.4 Characterization of Poly(l) 34
2.3.2 Complementary Study on the Ring-Opening
Polymerization in this Work 36
PhSNa
2.3.2.1 Initiator 36
2.3.2.2 Other Factors Affecting the Polymerization of 1 38
2.4 Conclusions 42
2.5 References 43
ANIONIC RING-OPENING POLYMERIZATION OF DIISOPROPYL
3.
CYCLOPROPANE- ARBOXYLATE
-DIC 44
1 ,1
3.1 Introduction 44
3.2 Experimental Section 45
3.2.1 Materials 45
3.2.2 Synthesis of Potassium Thiophenolate (PhSK) 46
3.2.3 Synthesis ofthe Monomer 1 46
3.2.4 Polymerization Procedure 47
3.2.5 Measurements 48
3.3 Results 48
3.3.1 Polymerization Kinetics 48
3.3.2 Polymer Characterization 52
3.3.3 Physical Properties 55
3.4 Discussion 55
3.4. Polymerization Mechanism 55
1
3.4.2 Influence ofTemperature on the Polymerization 57
viii