composition control of aromatic copolymers by using phase separation during polycondensation

176 Pages·2013·3.34 MB·English

by  Ichimori Toshimitsu

COMPOSITION CONTROL OF AROMATIC COPOLYMERS BY USING
PHASE SEPARATION DURING POLYCONDENSATION AND
APPLICATION FOR MORPHOLOGY FORMATION

March 2013

Toshimitsu Ichimori
DOCTORAL DISSERTATION

COMPOSITION CONTROL OF AROMATIC COPOLYMERS BY USING
PHASE SEPARATION DURING POLYCONDENSATION AND
APPLICATION FOR MORPHOLOGY FORMATION

March 2013

Toshimitsu Ichimori
The Graduate School of Environmental Science
(Doctoral Program)
OKAYAMA UNIVERSITY
JAPAN
CONTENTS

INTRODUCTION 1
AIM AND STRUTEGY OF THIS THESIS 8

CHAPTER 1
COMPOSITION CONTROL OF AROMATIC COPOLYESTERS BY SHEARING IN
HETEROGENEOUS POLYCONDENSATION

1-1 COMPOSITION CONTROL OF AROMATIC COPOLYESTERS BY SHEARING
1-1-1 INTRODUCTION 24
1-1-2 EXPERIMENTAL 26
1-1-2-1 Materials 26
1-1-2-2 Measurements 27
1-1-2-3 Polymerization 27
1-1-2-4 Determination of the Content of m-Oxybenzoyl Moiety in Precipitates 28
1-1-2-5 Kinetic Study 29
1-1-2-6 Preparation of Concentration - Temperature Phase Diagrams of Oligomer Model
Compounds 29
i
1-1-3 RESULTS AND DISCUSSION 30
1-1-4 CONCLUSION 44
1-1-5 REFERENCES 45

1-2 SECTIVE SYNTHESIS OF POLY(p-OXYBENZOYL) BY FRACTIONAL
POLYCONDENSATION: ENHANCEMENT OF SELECTIVITY BY SHEARING
1-2-1 INTRODUCTION 49
1-2-2 EXPERIMENTAL 51
1-2-2-1 Materials 51
1-2-2-2 Measurements 51
1-2-2-3 Polymerization 52
1-2-3 RESULTS AND DISCUSSION 53
1-2-4 CONCLUSION 61
1-2-5 REFERENCES 62

CHAPTER 2
HETEROGENEOUS POLYCONDENSATION FOR COMPOSITION CONTROL OF
POLY(p-MERCAPTOBENZOYL-co-p-BENZAMIDE) BY SHEARING

ii
2-1 INTRODUCTION 64
2-2 EXPERIMENTAL 66
2-2-1 Materials 66
2-2-2 Measurements 66
2-2-3 Polymerization 67
2-3 RESULTS AND DISCUSSION 68
2-3-1 Influence of Shearing on Composition 68
2-3-2 Mechanism of Composition Control by Shearing 75
2-4 CONCLUSION 83
2-5 REFERENCES 84

CHAPTER 3
MORPHOLOGICAL DIVERSITY AND NANOFIBER NETWORKS OF
POLY(p-OXYBENZOYL) GENERATED BY PHASE SEPARATION DURING
COPOLYMERIZATION

3-1 INTRODUCTION 86
3-2 EXPERIMENTAL 88
3-2-1 Materials 88
iii
3-2-2 Measurements 89
3-2-3 Polymerizations 90
3-3 RESULTS AND DISCUSSION 91
3-3-1 Influence of Trifunctional Comonomer on Morphology 91
3-3-2 Influence of Temperature and χ Value on Morphology 96
f
3-3-3 Control of Network Structure 101
3-3-4 Characterization of Networks 105
3-4 CONCLUSION 108
3-5 REFERENCES 109

CONCLUDING REMARKS 112

LIST OF PUBLICATIONS 118

ACKNOWLEDGEMENTS 120
iv
INTRODUCTION AND THE AIM OF THIS STUDY

INTRODUCTION

Since the early 1930’s, many kinds of polymers have been artificially synthesized. At the
beginning, nylons were synthesized by W. H. Carothers et al in the USA and vinyl plastics
were synthesized by the German company. At the same time, the fundamental studies on the
polymer science have been also begun. Since 1926, Staudinger studied about the relation
between molecular weight and viscosity of polymers. Furthermore, he proposed the existence
of macromolecule and proved it by the organic chemical method, which is called as the
polymer reaction without degradation. After that, W. H. Carothers classified polymers into
two groups, which are condensation polymers and addition polymers.[1-16] Flory classified
them again based on their formation mechanisms.[17-25] Condensation polymers are formed
by the step-growth polymerization, which proceeds in incremental steps by the condensation
reaction between functional groups of monomers with eliminating small molecules. Addition
polymers are formed by the chain-growth polymerization, which proceeds by the chain attack
of monomers to the active center formed by the polymerization initiator. There are clear
differences in the polymerization mechanism between the step-growth polymerization and the
chain-growth polymerization. For example, as for the relation between molecular weight and
1
reaction rate, polymers with high molecular weight are immediately formed and the molecular
weight does not change with the increase in the reaction rate in the chain-growth
polymerization. On the other hand, the monomer concentration immediately decreases and the
polymers with high molecular weight can be obtained by the high reactivity (> 98%) in the
step-growth polymerization.
The demand for new polymeric materials with high functionality has been increased and
the precision polymerizations have been developed. In the early 1950’s, living anionic
polymerization was first discovered. Living polymerization is named as a specific
chain-growth polymerization defined as that comprised of only initiation and propagation
reaction, in other words, it does not contain termination and chain transfer reaction. Based on
the characteristic polymerization mechanism, the living polymerization can precisely control
the composition, sequence regularity, molecular weight and its polydispersity. However, this
precision polymerization method is limited only to synthesize addition polymers.
The step-growth polymerization contains polycondensation, polyaddition and
addition-condensation polymerization. Precise control of polycondensation reaction is of great
importance to create new materials. As the polymerization mechanism by two kinds of AB
type condensative monomer is depicted in Figure 1, polycondensation is the step-type
polymerization obeying the stochastic process. Further, exchange reactions such as the
ester-ester exchange reaction and amide-amide exchange reaction occur so rapidly, leading to
2
r
me
ra n
t o
Te ti
u
ol
r s rs
me me on
mer Oligo copoly r soluti
Tri ndom olyme mer.
a P
R o
n
o
m
n ss pe
atio roce B ty
meriz – stic p of A
go ha ds
Oli Stoc on ction o kin
ti a w
tion Polymeriza Exchange re nsation by t
u e
mer r sol ond
e c
Di m ly
go po
g Oli of
n n
di o
med bon ution ustrati
or sol ill
wly f on mer ual
Neeaving group Oligomerizati – AB type monomer II Poly FIGURE 1 Concept
L
n
o r
uti me
mer I mer sol zation ng poly
mono Mono ymeri – rnati
pe Pol Alte
y
t
B
A
3
the reshuffling of the sequence regularity. Recently, large progress has been made in the
precision polycondensation, and many attractive procedures have been reported, such as
synthesis of sequence-defined polymers,[26-35] condensative chain polymerization,[36-41]
solid-state polycondensation,[42-47] nucleation-elongation polymerization,[48,49]
non-stoichiometric polycondensation,[50-52] and so forth. However, most of them were
carried out in the homogeneous phase like solution state and molten state. It has not been
established in the homogeneous polycondensation to control of molecular weight,
polydispersity, composition, sequence regularity and so on, which have been done in the
nature.
It is well known that polymeric materials and their assembling systems in the nature have
been initially born in the primitive sea for long time. Generally, they possess precise
structures from primary to higher-ordered structure such as composition, sequence regularity,
molecular weight, its diversity, morphology and so on, and these structures are precisely
controlled. Therefore, the polymers exhibit high performance and functionality in the nature
attributed to the precisely defined structures. They can be divided into polysaccharides,
proteins and nucleic acids. Biological polymers of plants are mainly comprised of
polysaccharides and those of animals are mainly comprised of proteins. Especially, with
respect to the biological polymers of animals including our body, proteins have been
synthesized by the combination of twenty kinds of α-amino acids connected via amide
4