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Sebastian Koltzenburg
Michael Maskos
Oskar Nuyken

Polymer
Chemistry
Polymer Chemistry
Sebastian Koltzenburg
Michael Maskos
Oskar Nuyken

Polymer Chemistry
Sebastian Koltzenburg Oskar Nuyken
Functional Biopolymers Garching, Germany
BASF SE, GMM/B - B001
Ludwigshafen, Germany

Michael Maskos
Fraunhofer ICT-IMM
Mainz, Germany

Translated by Karl Hughes

Forewords by Rolf Mülhaupt and Krzysztof Matyjaszewski

ISBN 978-3-662-49277-2    ISBN 978-3-662-49279-6 (eBook)

DOI 10.1007/978-3-662-49279-6

Library of Congress Control Number: 2016943641

© Springer-Verlag Berlin Heidelberg 2017

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of
the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or
information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar
methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publication does not imply, even in the absence of a specific statement, that such names are exempt
from the relevant protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this
book are believed to be true and accurate at the date of publication. Neither the publisher nor the
authors or the editors give a warranty, express or implied, with respect to the material contained herein
or for any errors or omissions that may have been made.

Cover illustration: With kind permission by Gurit

Printed on acid-free paper

This Springer imprint is published by Springer Nature

The registered company is Springer-Verlag GmbH Germany
The registered company address is: Heidelberger Platz 3, 14197 Berlin, Germany
 v

Foreword

Today, synthetic polymers can be found everywhere and are used in nearly every device.
All computer chips used in our desktops, laptops, smartphones, or tablets are enabled by
polymers used as photoresistors in microlithographic processes or as organic light-­
emitting diodes. Cutting-edge biomedical applications require polymers for tissue or
bone engineering, drug delivery, and tubing and containers for intravenous delivery of
medications. The interior of every automobile is almost entirely made from polymers,
and they are also used for automobile body parts and under-the-hood applications. New
lightweight and strong nanocomposite polymeric materials have enabled energy-­efficient
Dreamliner and A380 aircrafts. The construction industry uses polymers as insulating
materials, sealants, adhesives, and coatings. Many new applications require smart poly-
mers that respond to external stimuli, which can be used in sensors, shape memory
materials, and self-healing systems. Thus, polymers are perhaps the most important
materials in our society today, and their annual production exceeds 200 million tons.
Although approximately 50% of chemists in the USA, Japan, and Western Europe work
with polymers, polymer education has not yet reached the appropriate level, and many
of those chemists neither take advantage of the unique properties of polymeric materials
nor fully comprehend the synthetic pathways to control precisely macromolecular archi-
tecture.

Polymer Chemistry by Koltzenburg, Maskos, and Nuyken covers all aspects of polymer
science, starting with fundamental polymer physical chemistry and physics, including
all classical and modern synthetic techniques, and ending by reviewing various applica-
tions including more specialized uses in energy, environment, biomaterials, and other
advanced fields. The authors present the material in 22 chapters in a very lucid and
attractive way and identify the most important references for each chapter. This textbook
is expected to be very helpful for all beginners in polymer science and also for more
experienced polymer scientist.

I read the book with great interest and believe that it will become an excellent introductory
polymer science textbook for senior undergraduate and graduate students.

Krzysztof Matyjaszewski
J.C. Warner University Professor of Natural Sciences
Carnegie Mellon University,
Pittsburgh, PA, USA
Fall 2015
Foreword to the German Edition

Small molecules such as drugs and food ingredients prolong human life, whereas macro-
molecules as versatile structural and functional materials are essential for a high quality
of life, making “high tech” products available to all mankind. Originally developed as
substitutes for natural materials such as ivory, silk, and natural rubber, highly versatile
modern synthetic polymers can readily be tailored and processed to meet the diverse
needs of our society and our modern technologies. Nowadays polymeric materials and
systems are indispensable in modern life. The wide spectrum of polymer applications
spans from food packaging to construction, textiles, automotive and aerospace engi-
neering, rubbers, paints, adhesives, and system-integrated functional polymers indis-
pensable in electronics, flexible microsystems, and energy and medical technologies.
Their unique versatility in terms of tailored property profiles, ease of processing, applica-
tion range, and recycling, coupled with their outstanding resource, ecological, energy,
and cost efficiency, is not met by any other class of materials. Today polymeric materials
play an important role in sustainable development. The success of polymer development
and the high demand for polymer products by the rapidly growing world population are
reflected by the surging polymer production capacity, which today exceeds 300 million
tons per annum. Following the Stone Age, the Bronze Age, and the Iron Age, in the
twenty-first century we are now living in the Polymer Age.

Anyone interested in sustainable development become increasingly confronted with

synthetic and natural macromolecules and their applications. In almost every facet of
modern technology and in innovative problem solutions, the development of engineer-
ing plastics and functional polymers plays a key role. In order to convert macromole-
cules into useful materials and sustainable products it is essential to understand the basic
correlations between molecular polymer design, polymer technology, processing, appli-
cations, and sustainability. Unlike most conventional textbooks with a rather narrow
focus on traditional chemistry and physics, this textbook clearly goes beyond the limits
of the individual disciplines and presents a fascinating view of the challenges and pros-
pects of modern interdisciplinary polymer sciences and engineering and their impact on
modern technologies. It is obvious that all three authors bring to bear their profound
experiences in teaching and research covering the broad field of polymer science and
engineering. Furthermore, they are highly skilled in didactics and have succeeded in
pointing out the relevance of tailoring polymers with respect to polymer applications.
This team of three authors has successfully merged their complementary skills, own
experiences, and different points of view. In 22 chapters the authors have impressively
managed to present a comprehensive view of the extensive and rapidly developing fields
of polymer sciences and technology in an appealing and easy-to-read format. In addition
to covering the fundamentals of polymer chemistry and physics, the book describes the
synthetic methods and polymer analytics as well as the technological aspects which are
essential for tailoring polymeric materials, including multicomponent and multiphase
polymer systems. Moreover, illustrated by carefully selected examples of specific applica-
tions, this text book gives an excellent view on the hot topics in polymer sciences as well
as on environmental aspects of polymers, recycling, bio-based polymers, and modern
research trends. The result of this remarkable and successful three-author co-production
 vii
Foreword to the German Edition

is a methodically well-conceived and easy-to-read textbook that serves as a desk book

reference for polymer scientists, engineers, educators, and students. This textbook repre-
sents a valuable source of information for those who are already familiar with science.
Because of its clear and didactic style, this textbook represents an excellent choice of
reading for those who are approaching the subject of polymer sciences and engineering
for the first time. The length of the book is more than adequate to cope with the complex-
ity and breadth of this highly diversified and interdisciplinary field. Despite its high den-
sity of valuable information, this textbook reads well and I am firmly convinced that it is
certain to become one of the key reference textbooks in the field of polymer sciences.

Rolf Mülhaupt
Freiburg
June 2013
Acknowledgement

The success of the German edition, the encouragement of colleagues in many countries,
and the honor of winning the 2015 prize (Literaturpreis der Chemischen Industrie) from
the Organization of German Chemical Industry (Verband der Chemischen Industrie
VCI) persuaded us to translate our textbook into English to make it more available to a
broader international audience.

The authors would like to thank the team of translators from the language department of
the TU Munich, led by Mr Karl Hughes, for their dependable cooperation and continu-
ous willingness to discuss suggestions for alteration.

The contribution of Dr Stephen Pask has been particularly valuable, both in terms of
language and his specialist knowledge. Thanks to his expertise and tireless unflagging
commitment and innumerable discussions in which Karl Hughes and his team were
constantly involved, we now have an English text which, we believe, contains numerous
improvements compared to the German edition.

We would like to thank Dr Kyriakos A. Eslahian, Dr Thomas Lang, and Jonas Schramm
for translating and redrawing the figures and for suggesting and making corrections
where necessary. We would like to express our special gratitude to Christoph Bantz who
read the final version of the entire document and provided patient and constructive
­criticism.

We also owe thanks to many interested and critical readers of the German edition who
have contacted us to point out typos and mistakes. In this respect we would specifically
like to name our colleagues Prof Dr André Laschewsky, University of Potsdam and Prof
Dr Ulrich Ziener, University of Ulm.

A special thank you goes to our sponsors for this translation project: the “Fonds der
Chemischen Industrie” and the group of macromolecular chemistry of the Gesellschaft
Deutscher Chemiker (GDCh).

Thanks are also expressed to Springer-Verlag, especially Ms Merlet Bencke-­Braunbeck

and Dr Tobias Wassermann, for their support during this project.

Finally, as with the German edition, we have enjoyed continued encouragement and sup-
port from our families, for which we can never thank them enough!

Sebastian Koltzenburg
Michael Maskos
Oskar Nuyken
January 2016
 ix

Contents

1 Introduction and Basic Concepts.........................................................................................   1

2 Polymers in Solution....................................................................................................................  17

3 Polymer Analysis: Molar Mass Determination............................................................  39

4 Polymers in Solid State...............................................................................................................  93

5 Partially Crystalline Polymers............................................................................................... 105

6 Amorphous Polymers.................................................................................................................. 119

7 Polymers as Materials................................................................................................................. 141

8 Step-Growth Polymerization................................................................................................. 163

9 Radical Polymerization.............................................................................................................. 205

10 Ionic Polymerization.................................................................................................................... 245

11 Coordination Polymerization................................................................................................. 293

12 Ring-Opening Polymerization............................................................................................... 321

13 Copolymerization.......................................................................................................................... 349

14 Important Polymers Produced by Chain-Growth Polymerization................ 381

15 Chemistry with Polymers.......................................................................................................... 407

16 Industrially Relevant Polymerization Processes....................................................... 425

17 The Basics of Plastics Processing......................................................................................... 439

18 Elastomers.......................................................................................................................................... 477

19 Functional Polymers.................................................................................................................... 493

x Contents

20 Liquid Crystalline Polymers.................................................................................................... 515

21 Polymers and the Environment............................................................................................ 533

22 Current Trends in Polymer Science..................................................................................... 551

Supplementary Information
Index......................................................................................................................................................... 577
 1 1

Introduction and Basic

Concepts

1.1 Polymers: Unique Materials – 2

1.2 Definition of Terminology and Basic Concepts – 4

1.2.1 Fundamentals – 4
1.2.2 Polyreactions – 5
1.2.3 Nomenclature of Polymers – 7

1.3 Polymer Architectures – 8

1.3.1 Linear and Branched Macromolecules – 8
1.3.2 Isomerism in Polymers – 10
1.3.3 Copolymers – 14

References – 16

© Springer-Verlag Berlin Heidelberg 2017

S. Koltzenburg et al., Polymer Chemistry, DOI 10.1007/978-3-662-49279-6_1
 2 Chapter 1 · Introduction and Basic Concepts

Among the many areas of chemistry, polymer science is a comparatively new field. The
1 empirical use of polymeric materials made from natural substances has been documented
for centuries; however, only the pioneering work of the late Hermann Staudinger (1926),
a Nobel laureate, in the 1920s provided the basis for a systematic understanding of this
class of materials. In the decades since then, polymer science has developed to become
both technically demanding and industrially extremely important. In particular, polymer
science is characterized by its interdisciplinary nature:
55 Most technologically relevant macromolecules1 are based on a carbon backbone and
thus belong in the realm of organic chemistry.
55 Approximately half of all polymers produced today are synthesized using organo-­
metallic catalysts.
55 A description of the behavior of both solid polymers and their solutions is now based
on well-established physical and physicochemical theories.
55 Because macromolecules are often used in the area of classical materials, processing
and molding of polymers is an essential step in the production of finished products.
Thus, engineering science is also important. In medical technologies, polymers are used
in highly specialized applications, such as artificial heart valves, eye lenses, or as
materials for medical devices.

Last but not least, as well as the vast and significant use of synthetic polymers, macro-
molecules are of crucial biological importance. Undoubtedly the most important polymer
in the world—without which human existence would not be possible—is DNA. Without its
polymeric nature, DNA could not fulfill its essential role as the memory molecule of living
systems. If the molecules were not linked to a polymeric strand, DNA would be nothing
more than a mixture of four different bases with no defined structure and therefore without
biological function. In addition to the millions of tons of natural rubber processed annu-
ally, further examples of biopolymers essential to life include proteins that catalyze chemi-
cal reactions as enzymes, form membranes, or act as antibodies differentiating between
friend and foe.
This chapter deals with the basic concepts and definitions of polymer science and
especially the most important question that a natural scientist can ask: “Why?” In particu-
lar, why should one take an interest in this field? It is shown that polymers constitute a
class of materials that not only make an essential contribution to the existence of life in the
form of biological macromolecules, but without which, thanks to their myriad technical
applications, our modern daily life would be no longer conceivable.

1.1 Polymers: Unique Materials

Even if we restrict ourselves to the field of non-biogenic, traditional materials, macro-

molecules are a material class of unparalleled versatility. However, the range of properties
covered by polymeric materials is much broader than that of traditional materials. Thus,
for example:

1 Originally, a distinction was made between macromolecular substances and polymers. This differentiation
has become unnecessary. In this book, these terms are used congruently.
1.1 · Polymers: Unique Materials
3 1
55 Glass fiber reinforced plastics can have tensile strengths that rival, e.g., steel, whereas
other polymers such as polyurethane foams can be used as soft cushions or mattresses.
55 Most plastics are electrical insulators, but highly conjugated polymers have also been
synthesized with specific conductivities of the same order of magnitude of those of
highly conductive metals (Naarmann and Theophilou 1987).
55 The density of porous polymeric materials can be varied across a very wide range. In
particular, from polymer foams such as Styrofoam®, extremely lightweight articles can
be produced.2
55 The melting point of polymers can also be greatly modified by varying the
macromolecular architecture. Some polymers can be physically described as highly
viscous melts even at room temperature, whereas other polymers have melting points
of several hundred degrees Celsius, and can be heated to red heat or sintered. Of course,
the temperature range of the melting or softening point is critical for the temperature at
which a material can be used or processed. On the one hand, a high melting point
allows a high service temperature but requires a lot of energy to process the molten
material into the final shape. For many materials in everyday life, which are only used
at room temperature, a low melting point is an advantage because they can be processed
much more resource-efficiently than materials with a high melting point. Here, too, the
unrivaled variability that polymers offer is often a decisive and advantageous factor.

Because of their great versatility and their resulting unique material properties, syn-
thetic polymeric materials have become indispensable in our daily lives. Many familiar
applications can only be realized using macromolecular materials:
55 The electrical and electronics industries in their current form are difficult to envisage
without polymers. This statement includes seemingly trivial applications such as the
sheathing for electric cables—no other non-polymeric substance class provides
materials that are both flexible and at the same time act as electrical insulators. Even in
technically much more demanding applications, such as the manufacture of solar cells,
LEDs, or integrated microchips, polymers play a crucial role, e.g., as etching masks,
protective coatings, dielectrics, or fiber optics.
55 The modern automobile would also be unthinkable without polymers. All motor
vehicles manufactured today are covered with a polymer layer—the so-called clearcoat.
In addition, polymers, from which, for example, the tires, dashboard, seat cushions,
and bumpers are constructed, make a major contribution to reducing the weight of the
vehicle, thus limiting the fuel consumption.
55 The construction industry has also benefited enormously from this relatively young
class of materials. Polymers in the form of insulating foams reduce the energy
consumption of buildings, serve as conduits for water supply and sanitation, and
provide a weather-resistant alternative to the use of exterior wood.
55 As packaging, polymers are now irreplaceable, especially for food packaging or as
shock absorbing material for goods in transit.

Polymers find applications not just as classical materials but also as, mostly soluble,
active ingredients and functional additives. As such, they often go unnoticed because

2 Low-density materials such as metal foams or ceramic aerosols can also be produced from non-polymeric
materials; these, however, do not have the same breadth of application in everyday life as polymers.
 4 Chapter 1 · Introduction and Basic Concepts

they are not the actual material but rather, often in relatively small amounts, responsible
1 for the appearance of something. Thus, polymers can be found in modern detergents,
cosmetics, or pharmaceutical products. They are also used in water treatment and paper
production. In the latter capacity, macromolecules as functional polymers are discussed
in detail in 7 Chap. 19.

1.2 Definition of Terminology and Basic Concepts

In the following section a brief introduction to the basic concepts of polymer science is
given.

1.2.1 Fundamentals

The term polymer refers by definition to molecules formed from a number of building
blocks, called monomers, usually connected by covalent bonds. The prefix “poly” comes
from the Greek word for “many” whereas the Greek prefix “mono” means “single” and
refers here to a single block. In the synthesis of many polymers, monomers are linked
together in the same manner to form a single chain consisting of covalently connected
repeating units (. see Fig. 1.1).
There is no definitive limit on the number of repeating units required to meet the
definition of the polymer. In general, it is stipulated that the number n, also referred to as
the degree of polymerization, must be sufficiently high that the physicochemical properties
of the resulting molecule no longer change significantly with each addition of a further
repeating unit. This definition is not exact. Macromolecules that are composed of rela-
tively few repeating units do not meet this definition and the term oligomers (“oligo” = “few”)
is used for such molecules.
One example of a polymerization reaction is the reaction of ethene to form polyethyl-
ene (. see Fig. 1.2). In this reaction, the C=C double bond of the ethylene is converted into
a single bond.
From the definition of the term polymer, it follows that in principle any chemical mol-
ecule that can form two (or more) bonds can be used as a monomer for the synthesis of
macromolecules. This allows a huge variety of accessible structures which barely set a limit
to the imagination of the synthetic chemist.

..Fig. 1.1 Schematic

structure of a polymer of n n
repeating units n

..Fig. 1.2 Polymerization of

ethene to polyethylene n H2C CH2
1.2 · Definition of Terminology and Basic Concepts
5 1
As already mentioned in the introduction to this chapter, the properties of polymers
can be varied within a broad range. For the control of these properties, a huge array of
adjustments is available to the polymer chemist. The most important are:
55 Type of monomers
55 The chemical bond between the repeating units—for example, ether vs amide bonds
55 Degree of polymerization
55 Architecture of the chain—for example, linear or cross-linked
55 Incorporation of chemically different monomers along the polymer chains
(copolymerization)
55 Sequence of monomers in a copolymerization—for example, alternately or in long
sequences which consist of only one type of monomer (7 see Sect. 1.3.3)
55 Specific interactions between the components of the polymer chain, e.g., hydrogen
bonding or dipole–dipole interactions

In addition to these essential questions, many other factors, such as admixtures (addi-
tives) and material processing, also have an influence on the properties of macromole-
cules. The aim of this book is to provide, against the background of an almost infinite
variety of possible polymer structures, an overview of the essential principles that can be
used for the selective synthesis of structures with desired properties.

1.2.2 Polyreactions

In the following, a brief overview of the basic possibilities for the synthesis of polymers
(polyreactions) is given. These can be classified according to various criteria.
Depending on the manner in which the polymer chains are constructed in the course
of the polyreaction of the monomers, a distinction can be made between step-growth and
chain-growth reactions.

 tep-Growth Reactions
S
This polymerization process can, in principle, be applied to all organic compounds which
have two functional groups capable of forming a chemical bond. Classic examples of this
are ester, amide, or urethane bonds (. see Fig. 1.3).
The resulting polymers here are referred to as polyesters, polyamides, or polyure-
thanes. Details on the nomenclature can be found in 7 Sect. 1.2.3.

 hain-Growth Reactions
C
In chain-growth reactions, the polymerization can ensue by an addition to a polymeriz-
able group, especially an olefinic double bond, or by the opening of a ring. The essential
criterion for chain growth is the existence of a (usually high energy and unstable) active
particle, which is able to add to a monomer unit and thereby transfers its active character
to the newly incorporated repeating unit. This leads—as with a falling row of dominoes—
to a chain reaction in which the growing chain continuously adds additional monomer
units until no more monomer is available or side reactions occur.
Vinyl compounds can often be polymerized by a chain-growth mechanism. Here, the
double bond is converted into two single bonds (. see Fig. 1.4). Because, in the case of car-
bon, two single bonds have less enthalpy than one double bond, the reaction is exothermic.
 6 Chapter 1 · Introduction and Basic Concepts

1 a
n HO R OH + n HOOC R' COOH O R O R'
- (2n-1) H2O O O n
Polyester
b H H
N R N R'
n H2N R NH2 + n HOOC R' COOH
- (2n-1) H2O O O n
Polyamide

c H H
n HO R OH + n OCN R' NCO O R O N R' N
O O n
Polyurethane

..Fig. 1.3 Creation of (a) polyester, (b) polyamide, and (c) polyurethane

..Fig. 1.4 Polymerization of an

olefinically unsaturated
compound
n R
R
n

..Fig. 1.5 Ring-opening

polymerization using the
example of ethylene oxide O O
n
n

Ring-opening polymerizations also generally involve a chain-growth mechanism

(. see Fig. 1.5). Here, the driving force is the release of the ring strain. Thus, for instance,
three membered rings, such as ethylene oxide (oxirane), undergo facile polymerization.
As with small molecule organic chemistry, chain-growth reactions are classified accord-
ing to whether they involve radical, positively, or negatively charged reactive species. In these
cases, one refers to a radical, cationic, or anionic polymerization, respectively. Another
important class of chain-growth polymerizations are those involving transition metal com-
pounds, referred to as transition-metal catalyzed (catalytic) or coordinative polymerizations.
It follows from . Figs. 1.3–1.5 that there are three basic possibilities for the formation
of a covalent chemical bond as the result of a polyreaction:
55 Addition to a multiple bond
55 Elimination of (mostly low-molecular) fragments
55 Opening of a ring

These are referred to as polyaddition, polycondensation, or ring-opening polymeriza-

tion, respectively.
1.2 · Definition of Terminology and Basic Concepts
7 1
The latter differentiation makes a stringent subdivision of the different types of polym-
erizations difficult, in particular in the field of chain reactions. Thus, for example,
­ring-­opening polymerization is possible by both catalytic and ionic mechanisms. Likewise,
they can occur both via step-growth reactions and chain-growth reactions. However,
there is little value in making this distinction between polycondensation and polyaddition
and this is not being pursued further here.
This difficulty has been accounted for in this book by the inclusion of a separate chap-
ter on ring-opening polymerization (7 see Chap. 12), and the basic mechanisms are dis-
cussed in the preceding chapters.
A detailed overview of methods for synthesizing macromolecules can be found in
7 Chaps. 8–12.

1.2.3 Nomenclature of Polymers

The basic principle of polymer nomenclature rests on the designation of the monomer or
repeating unit set in brackets, in conjunction with the prefix “poly.” For example,
poly(styrene) is produced from styrene. Whether one uses the name of the monomer or
the repeating unit is rather arbitrary. Thus, for example, the polymerization product of
styrene is mostly referred to as poly(styrene), whereas that of ethene, after the repeating
unit, usually as poly(ethylene). For reasons of clarity, the brackets are generally omitted
with polymers that consist only of a single monomer type (so-called homopolymers), and
are only used with copolymers, i.e., polymers composed of at least two chemically different
monomers (7 see Sect. 1.3.3).
In the formula, the repeating unit is placed in square brackets (. see Fig. 1.6). For more
complex structures it has also become common practice to indicate with dotted lines that
the molecule is further extended (. see Fig. 1.9).
If the repeating unit is further altered after polymerization by a chemical reaction
(7 see Chap. 15), the resulting polymer is often designated according to a formal mono-
mer, but one that was not used in the polymerization. For example, the product of hydro-
lysis of polyvinyl acetate is referred to as polyvinyl alcohol, even though it is not accessible
via the direct polymerization of the (unstable) vinyl alcohol (. see Fig. 1.7).

..Fig. 1.6 Polymerization of

styrene to polystyrene
n
n

..Fig. 1.7 Synthesis of

polyvinyl alcohol from polyvinyl OH-
acetate n
O n - n CH3COO- n
O O O OH
 8 Chapter 1 · Introduction and Basic Concepts

..Fig. 1.8 Synthesis of

1 polyethylene terephthalate
OH + n HOOC
(PET) from ethylene glycol n HO COOH
and terephthalic acid

- (2n-1) H2O

n
O
O
O

For polymers resulting from a reaction of a dicarboxylic acid with a diol, common
names, based on the name of the corresponding ester, have become usual. For example,
the polyester resulting from the complete esterification of ethylene glycol with terephthalic
acid (. see Fig. 1.8) is referred to as polyethylene terephthalate (abbreviated PET).

1.3 Polymer Architectures

An overview of the different structural principles according to which a polymer can be

built is provided below. Several structural variants need to be distinguished:
55 Unbranched (linear) and branched polymers
55 Isomerism of the repeating units
55 Copolymers

1.3.1 Linear and Branched Macromolecules

In addition to their chemical diversity, polymers can also differ substantially from each
other in their molecular architecture. The result, as can be readily seen, of the above-­
discussed polycondensation of ethylene glycol and terephthalic acid (7 see Sect. 1.2.3), is a
linear, unbranched macromolecule with exactly two ends.3 However, if one was to add, for
example, a small amount of trifunctional acid to the monomer mixture, a branching
point can develop at those locations where this molecule is incorporated into the polymer
(. see Fig. 1.9). When an excess of one functional group, for example the OH function, is
used, a molecule is produced after the complete reaction of the other functional group
which has only alcohol functions as terminal groups which cannot sustain further poly-
condensation—that is, the polymerization comes to a halt.
In this quite simple architecture it already becomes clear that there are limits to a plain
formula for polymers and that, for an exact description of the molecule, one requires more
accurate information than just the name(s) of the monomer(s).

3 To a lesser extent, macrocyclic rings can form when one terminal acid group reacts with the terminal
alcohol group of the same molecule.
1.3 · Polymer Architectures
9 1
..Fig. 1.9 Schematic
representation of (a) a linear a b
polymer chain and
(b) a branched macromolecule

= Trifunctional monomer

..Fig. 1.10 Coexistence of

linear, terminal and branched Branched
segments in a highly branched
polymer (schematic)

Terminal

Linear

If the number of branches in the macromolecule is increased, one eventually

reaches a class of so-called highly branched polymers. These molecules can be notion-
ally divided into linear segments, branches, and so-called terminal end segments
(. see Fig. 1.10). An example of such a highly branched polymer is polyethyleneimine,
discussed in 7 Chap. 19.
The greater the ratio of branched to linear segments, the greater the degree of branching
of the material. Ideally, there is a perfectly branched, symmetrical macromolecule which
grows outward from a central point, resembling a family tree, until the spatial density of
branches on the surface of the (generally in good approximation, spherical) molecule is so
high that further growth is no longer possible (. see Fig. 1.11 ). Because of the similarity
with trees, such molecules are referred to, after the Greek word “dendron” for “tree,” as
dendrimers (Buhleier et al. 1978).
Because of the branched polymer’s strong outward increase in segment density, its
interior contains cavities which can be used for the storage of guest molecules such as dyes
or agents. However, the loading density is quite low because of the small number of these
cavities. In addition, the synthesis of such perfectly branched systems is only possible in
multistep reaction sequences and therefore very time consuming, so dendrimers have, up
to now, achieved only limited technical significance (7 see Chap. 8).
Although highly branched or dendritic polymers represent individual, discrete macro-
molecules, the synthesis of polymer networks leads to the formation of a covalent, branched
network within which all of the molecules available in the system are incorporated.
 10 Chapter 1 · Introduction and Basic Concepts

1 NH 2 NH 2 NH 2
NH 2 NH 2 NH 2
NH 2 NH
NH 2 NH 2
2 NH 2
NH 2
NH 2
H 2N
N N N NH 2
H 2N N N
N NH 2
H 2N N
N NH 2
H 2N N
N NH 2
N N
H 2N N N NH 2
H 2N N
N N N NH 2
N
H 2N N
N NH 2
H 2N N N
N N N
N N NH 2
N
H 2N N
NH 2
H 2N N
N NH 2
H 2N N
NH 2
N N N
H 2N N N
N
N N NH 2
H 2N N
N N NH 2
N N N
H 2N
N NH 2
H 2N N N NH 2
N N N
H 2N N NH 2
N
H 2N N NH 2
N
H 2N N N NH 2
N N
H 2N N
NH 2
H 2N NH 2
NH 2 NH NH 2 NH 2
2 NH 2 NH NH NH NH 2 NH 2 NH 2
2 2 2

..Fig. 1.11 Schematic representation of a dendrimer

Such a network emerges, for example, if higher-functional monomers (i.e., those with
more than two reactive groups) are caused to react and the reaction exceeds a certain level
of monomer conversion (7 see Sect. 8.3.4). Such a network can be described as a single
molecule which occupies the entire reaction space (. see Fig. 1.12).

1.3.2 Isomerism in Polymers

As with small molecules, macromolecules can also exist as isomers. Here, the following
cases, which are particularly important from the viewpoint of the polymer chemist, are
structural-, stereo-, and conformational isomerism.

Structural Isomerism
With structural isomerism (also referred to as constitutional isomerism), the nature of the
covalent linkage of the atoms with each other differs, similar to the low-molecular isomers
acetone and propionaldehyde. For example, polyvinyl alcohol and polyethylene oxide
(. see Fig. 1.13) are structurally isomeric polymers.
1.3 · Polymer Architectures
11 1
..Fig. 1.12 Schematic
representation of a polymer
network

..Fig. 1.13 Structural

isomerism using the example a b
of (a) polyvinyl alcohol and
(b) polyethylene glycol O
n
n
OH

An important case of structural isomerism occurs in the polymerization of conjugated

dienes such as isoprene (2-methylbut-1,3-diene). During the polymerization of this
monomer, as discussed in more detail in 7 Sect. 14.10, each monomer unit can be added
to the macromolecule in different ways. These are shown in . Fig. 1.14.
The isomers shown rarely occur as pure forms in practice. Most often the polymers formed
are composed of different structural variations within the same polymer chain. In addition to
the isomers shown here, 1,4-polyisoprene also exists as cis and trans isomers (see below).

Stereoisomerism
In analogy to small molecule organic substances, constitutionally identically macromole-
cules may differ in their spatial form. Notably relevant for polymers are cis-trans isomers
and enantiomers.
The cis-trans isomerism is particularly important for polymers with a double bond in the
main chain. The simplest example of this are cis- and trans-1,4-polybutadiene (. Fig. 1.15).
As in the field of low-molecular organic chemistry, they differ in their physicochem-
ical properties. This effect is generally very pronounced in macromolecules. cis-1,4-­
 12 Chapter 1 · Introduction and Basic Concepts

..Fig. 1.14 Structural

1 isomers of polyisoprene 1
1,2-Polyisoprene
2 n

4
3
n 3,4-Polyisoprene
2 4
1 3

4
1,4-Polyisoprene
1 n

..Fig. 1.15 cis-trans

isomerism using the example
of (a) cis-1,4-polybutadiene and
(b) trans-1,4-polybutadiene n

..Fig. 1.16 Stereoisomerism

using the example of
polypropylene: isotactic, Polypropylene
syndiotactic, and atactic n
polypropylene

Isotactic

Syndiotactic

Atactic

Polybutadiene (butadiene rubber), for example, is an amorphous, sticky material,

whereas the trans isomer is a (partially) crystalline material with a high melting point.
The situation is similar for the cis and trans isomers of isoprene (7 see Sect. 14.10.3). The
cis isomer is a soft and, in its non-vulcanized state, sticky material which is known as
natural rubber, whereas the trans isomer, which is referred to as gutta-percha, is a non-
sticky and much harder material.
A technically very important case of a polymer exhibiting enantiomerism is
­polypropylene (PP). In the polymerization of propene (7 see Chap. 11) a macromolecule is
created whose main chain—the so-called polymer backbone—could formally be placed in
a plane, whereas the methyl groups of the C3 carbon point upwards or downwards ­relative
to this plane (. see Fig. 1.16). Depending on whether the stereochemistry at the C2 atom
1.3 · Polymer Architectures
13 1
..Fig. 1.17 Pseudo-asymmetry
using the example of a * b *
CH2 CH CH2 CH O
(a) polypropylene compared n n
to optical activity in CH3 CH3
(b) polypropylene oxide
H H
CH CH2 *C CH2 CH O CH2 *C O CH2
CH3 CH3 CH3 CH3

is regularly (stereoregular) or statistically configured, different stereoisomers result, which

are referred to as isotactic, syndiotactic, or atactic polypropylene.
Polypropylene is referred to as isotactic polypropylene (it-PP) if all of its tertiary car-
bon atoms are configured identically. Syndiotactic polypropylene (st-PP) has an alternating
configuration of its methyl groups along the chain, whereas in atactic polypropylene
(at-PP) the spatial orientation of the methyl groups is irregular.
The three types of polypropylene mentioned above are diastereomers. Whereas it-PP
is a highly crystalline material with a melting point of ca. 160 °C, at-PP cannot crystallize
because of its irregular structure and it is an amorphous, sticky material. The control of
stereochemistry is thus of considerable importance (7 see Chap. 11).
However, in contrast to substances composed of small molecules, stereoregular poly-
olefins are usually not optically active. This is because the two polymeric chains attached
to the chiral center are very large and thus indistinguishable from a physicochemical point
of view. A mirror plane can thus be placed approximately through the chiral center. This
is also referred to as pseudo-asymmetry. In contrast to this, no mirror plane can be placed
through the molecule of polypropylene oxide (. see Fig. 1.17) because of the additional
oxygen atom. Therefore, this macromolecule can exhibit optical activity if one succeeds in
producing a stereoregular product and separating the stereoisomers.

Conformational Isomerism
Even with macromolecules, individual molecular groups can rotate around a single bond.
Consider the case of polyethylene as the simplest organic polymer. The trans conformation
is approximately 4 kJ/mol more favorable than the gauche conformation. Therefore, the all-
trans conformation is the enthalpically most favorable conformation. However, the number
of possible trans and gauche conformations of n single bonds is 3n, i.e., a very large number
for polymers. For this reason, an all-trans conformation is enthalpically favorable, but
extremely unlikely, with the result that this conformation is entropically unfavorable. In
addition, the enthalpy difference of 4 kJ/mol, which corresponds to about 1.5 times kBT (kB:
Boltzmann constant, T: absolute temperature) at room temperature, is not particularly
large. From simple considerations, it follows that at room temperature the trans configura-
tion is only approximately 1.6 times more likely than the gauche configuration. A signifi-
cant number of bonds therefore exist in the gauche configuration, and the molecule adopts
a spatial arrangement quite different from the extended form, which resembles rather a ball
of wool (. see Fig. 1.18).4 Details of this are discussed further in 7 Chap. 2.

4 Recent work shows that for isolated chains this picture becomes even more complex: additional forces
such as dispersion forces have to be considered, leading to substantial chain-length-dependent influence
on the chain architecture; see, e.g., Lüttschwager NOB, Wassermann TN, Mata RA, Suhm MA (2013) The
Last Globally Stable Extended Alkane. Angew. Chem. Int. Ed. 52:463–466.
 14 Chapter 1 · Introduction and Basic Concepts

..Fig. 1.18 All-trans

1 conformation a
(a) and “ball of wool”
conformation
(b) of polyethylene

M1 + M2

M1 M2 M2 M1 M1 M2 M1 M2 M1 M1 M2

..Fig. 1.19 Statistical copolymer consisting of two monomers M1 and M2

1.3.3 Copolymers
Copolymers are polymers composed of at least two chemically different monomers. In
principle, with copolymerization of different monomers in various quantities, an infinite
variety of different macromolecules can be synthesized. This chemical diversity is increased
by the various possibilities available for incorporating the comonomers into the chain as
well as their sequences. These are discussed below.

Statistical Copolymers
If two chemically different monomers M1 and M2 are polymerized in a random, statisti-
cally determined sequence to each macromolecule, this is referred to as a statistical copo-
lymer (. see Fig. 1.19).
Here, the incorporation of the monomers into the polymer main chain is determined
by the relative reactivity of the monomers and obeys statistical laws (7 see Chap. 13). The
copolymer is referred to as poly(M1-stat-M2)5.

5 The expression of random copolymers (used mostly incorrectly) is often found instead of statistical
copolymers. The term statistical copolymer should, however, be preferred.
1.3 · Polymer Architectures
15 1

M1 + M2 M1 M2 M1 M2 M1 M2 M1

..Fig. 1.20 Alternating copolymer consisting of two monomers M1 and M2

M1 + M2 M1 M1 M1 M2 M2 M2

..Fig. 1.21 Block copolymer consisting of two monomers M1 and M2

Alternating Copolymers
With alternating copolymers, two monomers M1 and M2 are built into the polymer main
chain in regular alternation. This results in the structure shown in . Fig. 1.20.
These polymers are referred to as poly(M1-alt-M2). Such polymers result from the
polymerization of monomers that can react with one another but not with themselves.
One example is the polycondensation of a diol and a diacid (. see Fig. 1.3). Alternating
copolymers result from vinyl polymerizations only when the reactivity of the individual
monomers with the other monomer is much greater than with itself. Details are discussed
in 7 Sect. 13.3.

Block Copolymers
In block copolymers, the comonomers are arranged along the polymer backbone in blocks
of consecutive identical monomers (. see Fig. 1.21).
Depending on the number of blocks in the polymer backbone, one refers to, for exam-
ple, di-, tri-, or multiblock copolymers. The nomenclature for these macromolecules is
PolyM1-block-PolyM2, as, for example, in polystyrene-block-polybutadiene. Colloquially,
the designation Poly(M1-block-M2) has become common; e.g., poly(styrene-block-­
butadiene).

Graft Copolymers
Polymers in which a side chain of M2 is linked to the main chain of M1 are called graft
copolymers of the monomers M1 and M2 (. see Fig. 1.22). These macromolecules are
referred to as PolyM1-graft-PolyB. Here, PolyM1 is the main chain, the so-called graft
stock, and PolyM2 is the grafted side chain.
Copolymers for which only the monomers are to be designated but in whose name no
particular copolymer architecture is to be specified are generally referred to as Poly(M1-co-­M2).
The following chapters present a deeper discussion of the properties and the synthesis
of polymeric materials. This is structured as follows:
55 7 Chapters 2 and 3 present the size and shape of polymers, as well as methods for
determining their molar mass
55 In 7 Chapters 4–7, the properties of solid polymeric materials are discussed
55 7 Chapters 8–13 are devoted to the synthesis of polymers
55 7 Chapters 14–17 deal with important classes of polymers, chemical reactions of
polymers, and procedures for the manufacture and processing of macromolecules
 16 Chapter 1 · Introduction and Basic Concepts

1 M1 + M2 M1 M1 M1 M1 M1 M1

M2

M2

M2

M2

..Fig. 1.22 Graft copolymer consisting of two monomers M1 and M2

55 7 Chapters 18–20 are dedicated to special classes of materials (elastomers, functional

polymers, and liquid crystalline polymers)
55 The textbook concludes with some environmental aspects of synthetic macromolecules
(7 see Chap. 21) and a brief presentation of current trends in polymer chemistry (7 see
Chap. 22)

References
Staudinger H (1926) Die Chemie der hochmolekularen organischen Stoffe im Sinne der Kekuléschen
Strukturlehre. Ber Dtsch Chem Ges 59:3019–3043
Naarmann H, Theophilou N (1987) New process for the production of metal-like, stable polyacetylene.
Synth Met 22:1–8
Buhleier E, Wehner W, Vögtle F (1978) “Cascade”- and “nonskid-chain-like” syntheses of molecular cavity
topologies. Synthesis 1978:155–158
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