Table Of ContentRING-FORMING
POLYMERIZA TIONS
ROBERT J. COTTER and MARKUS MATZNER
RESEARCH AND DEVELOPMENT DEPARTMENT
CHEMICALS AND PLASTICS
UNION CARBIDE CORPORATION
BOUND BROOK, NEW JERSEY
PART B, 2
Heterocyclic Rings
1972
È
ACADEMIC PRESS New York and London
COPYRIGHT © 1972, BY ACADEMIC PRESS, INC.
ALL RIGHTS RESERVED
NO PART OF THIS BOOK MAY BE REPRODUCED IN ANY FORM,
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PRINTED IN THE UNITED STATES OF AMERICA
To our wives, Barbara and Debora, and children, Patricia,
Robert, Jr., Katherine, and Stella. Their patient understanding,
interest, and encouragement have contributed immeasurably to
the writing of this book.
Preface
These volumes comprise a comprehensive review and compilation of ring-
forming polymerization reactions that proceed with heterocyclic ring
formation. The phenomenal growth of research and commercial development
efforts in this area of polymer chemistry is readily apparent from even the
most cursory glance at the table of contents herein. That this growth appears
to be continuing unabated is evident from the size of the updated supple
mentary reference lists at the end of the volumes.
These books are designed to fill the need of polymer and organic chemists
for a rapid, easy-to-use key to the available literature on these new materials.
Because of the presence of heterocyclic rings of various types in biological
macromolecules, the contents of these works will also be of interest to those
concerned with the polymer chemistry of living systems.
The large number of heterocyclic ring-containing polymers that have been
investigated has resulted in a need for an orderly and systematic presentation
of their synthesis and properties. The emphasis in these works is on polymer
ization reactions that yield polymers containing a ring that is not present in
any of the monomers. Additionally, polymerizations leading to linear, high
molecular weight products are stressed, although some information on cross-
linked materials is included. Polymerizations which propagate via double
bond (containing heteroatoms) formation, "a two-membered ring," are
discussed initially. Subsequent chapters are arranged according to the number
of carbon atoms in the ring that are formed during polymerization. This is
followed up through rings containing four carbon atoms. Intra-intermolecular
ring-forming polymerizations and á,/3-unsaturated aldehyde polymerizations
are treated in separate chapters. Both of these classes generally lead to rings
containing five carbon atoms in keeping with the content outline of the other
chapters.
The tables of polymers that have been assembled and presented stand alone
as a handy index to polymers that have been prepared by ring-forming
polymerizations. In most instances they are complete bibliographies for the
individual polymers since many have not been prepared by other routes. The
monomers from which the polymers in the tables have been prepared are also
xiii
XIV PREFACE
listed in the Subject Index. Quickly locating a reference wherein the polymer
ization of a particular monomer has been studied can be a valuable time-saver
for those faced with choosing one synthetic path from among several for that
particular monomer.
The use of these volumes in conjunction with Part A of this work provides
ready access to information about literally hundreds of monomers and
polymers. No other source comparable in convenience and scope is presently
available.
As mentioned in the Preface to Part A of this endeavor, the continued
interest and efforts of many people have eased the task of writing this book.
Our sincere appreciation is again extended to those same professional
colleagues who have been of invaluable assistance. In addition, we acknow
ledge the skillful assistance of Rita Matts, who typed most of the manuscript
for these two volumes. The aid of Patricia Kralovich and Mary Lou Peters
who provided supplementary secretarial help is sincerely appreciated. Anneli
DePaolis provided an invaluable assist by redrawing many of the chemical
formulas for the manuscript. Finally, we wish to acknowledge and extend our
appreciative thanks to the personnel of Academic Press for their thoughtful
assistance and cooperation at many points during production.
ROBERT J. COTTER
MARKUS MATZNER
Contents of Part A
Introduction
CHAPTER I. Carbon-Carbon Double Bond-Forming Polymerizations
CHAPTER ii. Intra-Intermolecular Polymerizations Leading to
Homocyclic Carbon Rings
CHAPTER in. Diels-Alder Polymerizations
CHAPTER iv. Polymerization of Diisopropenyl Monomers and Other
Carbocyclic Ring-Forming Polymerizations
CHAPTER v. Metallorganic Ring-Containing Polymers of Unsaturated
Carbon Compounds
CHAPTER vi. Metallorganic Ring Polymers from Nitrogen Chelate Ligands
CHAPTER VII. Metallorganic Ring Polymers from Nitrogen: Oxygen
Chelate Ligands
CHAPTER VIII. Metallorganic Ring Polymers from Nitrogen: Sulfur
Chelate Ligands
CHAPTER ix. Metallorganic Ring Polymers from Oxygen Chelate Ligands
CHAPTER x. Metallorganic Ring Polymers from Sulfur Chelate Ligands
CHAPTER xi. Polysiloxanes, Polysilazanes, and Polymetalloxanes from
Ring-Forming Polymerizations
Supplementary Reference List
Author Index—Subject Index
xv
Contents of Part B, 1
Introduction
CHAPTER i. Multiple Bond-Forming Polymerizations
CHAPTER ii. Rings Containing Two Carbon Atoms
CHAPTER in. Rings Containing Three Carbon Atoms
Supplementary Reference List
Author Index—Subject Index
XVI
Introduction
This book is organized according to the specific heterocyclic ring structure
that is formed in a ring-forming polymerization. This arrangement was chosen
to be of maximum aid to synthetic polymer chemists who are interested in
tailormaking polymer repeat units. By classifying his proposed new repeat
unit according to the types of rings present in it, he will be able to consult
this book to ascertain whether any ring-forming polymerizations are of
interest to him. Each chapter is further arranged according to polymer type
and the various methods that have been used to prepare that type. The
emphasis is on synthetic methods, with the numbers assigned to the methods
also being used in the tables to indicate how the tabulated polymers were
made. Although the considerations that result in a number being assigned to
a method may seem arbitrary at times, they were often necessary to aid in the
codification of the data.
Although the term polymer can mean different things to many people, this
book is about linear polymers that were made intentionally. Tars, distillation
residues, or glops from reactions that "went bad" (unintentional polymer
izations) are not included. Ring-forming polymerizations that were planned
to be such by their experimenters are what have been considered. The qualita
tive description of the molecular weight of a polymer can be ambiguous. In
this book, the term "high molecular weight" is used to mean that a level has
been attained that imparts mechanical properties to the polymer. That is, it
is either film- or fiber-forming and mechanical property evaluation is possible.
Another way to look at the use of this term is that the polymer is high enough
in molecular weight so that further increases do not appreciably change its
mechanical properties. "Low molecular weight" is used to designate oligomers,
and "moderate molecular weight" describes polymer samples with molecular
weights up to the threshold level for property appearance. Since definite
molecular weight numbers associated with these various criteria differ from
class to class, and, moreover, are generally not available anyway, these
qualitative terms were found to be useful and meaningful.
xvii
XV111 INTRODUCTION
Whether or not a high molecular weight, linear polymer was obtainable
from a particular ring-forming polymerization was used as the main criterion
for judging the merits of the method. The data in the tables were also selected
to indicate at a glance if the polymer was obtained at a high molecular weight.
However, being well aware of how fickle polymerizations can be with respect
to whether high, moderately high, or low molecular weight products are
obtained, all ring-forming polymerizations that were found have been
included. Too many examples exist in the authors' experiences of "unsuccess
ful" polymerizations that were made to work when greater attention was paid
to experimental techniques, monomer purification procedures, or other details.
Finally, a word of warning is in order to those who may be uninitiated in the
difficulties attendant to proving the structure of a polymer. The structures
reported for the polymers described in this book are those suggested by the
workers whose research is cited. In some cases, the evidence presented for the
assigned structures hinged mainly on the reactants employed and an elemental
analysis of the product. Of course, where evidence was found that disputed an
assigned structure, it is included and discussed. The newer, non-destructive,
spectrophotometric methods for structure determination have been used on
many ring-containing polymers, and their wider use is to be encouraged. In
any event, we hope this alert will serve those who may not be aware of this
problem.
EXPLANATION OF TABLES
The tables of polymers that have been assembled and presented in this book
stand alone as a handy index to those polymers that have been prepared by
ring-forming polymerizations. In most instances, they are complete biblio
graphies for the individual polymers, since many have not been prepared by
other routes. The general guidelines that were used in assembling these tables
from the literature data are given below.
Number
The first column in every table contains an arabic number that has been
assigned to each polymer or entry in the table. The first entry in a table is
No. 1, with the following ones being numbered consecutively.
Structure
The tables contain the structure of the repeating unit of the polymer in the
second column. Within a table, the polymers are arranged according to
increasing complexity and/or empirical formula of the repeat unit. In general,
the arrangement that has been employed allows one to readily compare the
effect of changes in structure on polymer properties. Some guidelines that
were used are illustrated by the following examples. Polymer classes such as
polyazines which have a constant structural feature are written with this
INTRODUCTION XIX
feature at the left, viz., =§N—N = CH— R—CH=J= . The examples are then
n
tabulated in order of increasing complexity of R according to the general
guidelines given below. A polymer class that possesses a variable "constant
structural feature" such as poly(Schiff Bases) is listed similarly, viz.,
=f=N— R — N = CH—R—CH^ . The polymers are then listed with R' held
n
constant according to increasing R complexity. Then R' is changed according
to the same guidelines used for R, and the polymers listed again according to
increasing R complexity.
The guidelines employed to adjudge increasing complexity of R and R'
radicals are as follows.
1. Alkylene.
2. Alkylene-containing heteroatoms ({-CH -)- 0-(-CH )- ) follow the all
2 2 2 2
carbon-containing alkylene (-(-CH -)- ). Oxygen precedes nitrogen
2 5
precedes sulfur heteroatoms.
3. Cycloalkylene.
4. Aralkylene, e.g. xylylene, —CH —C H —CH —.
2 6 4 2
5. Aromatic Radicals.
i. One Ring. Para precedes meta precedes ortho substitution.
ii. One Heteroaromatic Ring. Para precedes meta precedes ortho
substitution.
iii. Two Rings. Para substituted rings first. If connected by other
atoms, carbon atoms precede heteroatoms. One connecting atom
precedes two, etc.
After both para substituted rings; one para—one meta, one
para—one ortho; two meta; one meta—one ortho; etc.
iv. Naphthalene Rings. 1,4-Substituted precedes 1,5 precedes 2,7, etc.
v. Three Rings. Similar hierarchy as outlined above.
vi. Fused Three-Ring Systems.
vii. Four Rings, etc.
Copolymers are listed under the homopolymers to which they are most
closely related. In some instances, the name of the monomer from which the
polymer was prepared is given under the repeat unit structure. If a structure
has been presented in the text preceding the table, only a reference to that
page and structure number may be listed. Abbreviations that are used in the
structural formulas are always explained under the structure. The symbol
-H ^—£ ^rhr denotes a copolymer, not necessarily a block copolymer.
Method
The tables all contain a Method column which contains at least one number
for each entry. This number refers to the synthetic method described in the
