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PHYSICAL CHEMISTRY OF
MACROMOLECULES
Macro to Nanoscales
This page intentionally left blank
PHYSICAL CHEMISTRY OF
MACROMOLECULES
Macro to Nanoscales

Edited by
Chin Han Chan, PhD, Chin Hua Chia, PhD,
and Sabu Thomas, PhD

Apple Academic Press

TORONTO NEW JERSEY
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ABOUT THE EDITORS

Chin Han Chan, PhD

Chin Han Chan is a registered chemist with research interests in physical proper-
ties of polymer blends. She has been elected as council member of the Malaysian
Institute of Chemistry and she has been appointed as the Chair of the Polymer
Committee of the Institute of Materials, Malaysia. After earning her doctorate
from Universiti Sains Malaysia (University of Science, Malaysia) in the field of
semicrystalline polymer blends, she spent one year for her postdoctorate on re-
active blends of themoplastic elastomers. Currently, she is an associate profes-
sor at the Faculty of Applied Sciences of Universiti Teknolgi MARA (MARA
University of Technology), Malaysia. She has been teaching elementary physical
chemistry, advanced physical chemistry, physical chemistry of macromolecular
systems, and general chemistry at undergraduate and graduate levels.
She has published more than 45 papers in international and national refereed
journals, more than 60 publications in conference proceedings, and more than
20 invited lectures for international conferences. She has been one of the editors
of Malaysian Journal of Chemistry, Berita IKM – Chemistry in Malaysia, and
books published by Royal Society of Chemistry entitled Natural Rubber Materi-
als, Volume 1: Blends and IPNs and Volume 2: Composites and Nanocomposites.
She peer-reviews a few international journals on polymer science. Her research
interest is devoted to modified natural rubber-based thermoplastic elastomers,
biodegradable polyester/polyether blends, and solid polymer electrolytes

Chin Hua Chia, PhD

Chin Hua Chia is currently an Associate Professor in the Materials Science Pro-
gramme, School of Applied Physics, Universiti Kebangsaan Malaysia (UKM)
(also known as National University of Malaysia). He obtained his PhD in 2007
in Materials Science (UKM, Malaysia). His core research interests include de-
veloping polymer nanocomposites, bio-polymers, magnetic nanomaterials, bio-
adsorbents for wastewater treatment, etc. He has published more than 50 research
vi About the Editors

articles and more than 60 publications in conference proceeding. He has recently

received the Best Young Scientist Award (2012) and the Excellent Service Award
(2013) from UKM.

Sabu Thomas, PhD

Sabu Thomas is the Director of the School of Chemical Sciences, Mahatma Gan-
dhi University, Kottayam, India. He is also a full professor of polymer science
and engineering and the Honorary Director of the Centre for Nanoscience and
Nanotechnology of the same university. He is a fellow of many professional bod-
ies. He has authored or co-authored many papers in international peer-reviewed
journals in the area of polymer processing. He has organized several international
conferences and has more than 420 publications, 11 books and two patents to his
credit. He has been involved in a number of books both as author and editor. He
is a reviewer to many international journals and has received many awards for
his excellent work in polymer processing. His h-index is 42. He is listed as the 5th
position in the list of Most Productive Researchers in India, in 2008.
CONTENTS

List of Contributors..................................................................................... ix
List of Abbreviations................................................................................... xi
Preface........................................................................................................xv
Part 1
Physical Chemistry of Macromolecules

1. Introduction................................................................................................. 3
Hans-Werner Kammer
2. Molecular Mass of Macromolecules and Its Distribution........................ 9
Hans-Werner Kammer
3. Macromolecules in Solution...................................................................... 25
Hans-Werner Kammer
4. Characterization of Polymers by Flowing Behavior.............................. 47
Hans-Werner Kammer
5. Transitions in Polymers............................................................................. 61
Hans-Werner Kammer
6. Crystallization and Melting of Polymers................................................. 93
Hans-Werner Kammer
7. Polymers in Non-Equilibrium................................................................ 119
Hans-Werner Kammer
8. Liquid-Crystalline Order in Polymers.................................................. 163
Hans-Werner Kammer
9. Surface Tension of Polymer Blends and Random Copolymers........... 181
Hans-Werner Kammer
10. Macromolecules in the Condensed State............................................... 201
Hans-Werner Kammer
11. Molecular Characterization of Synthetic Polymers by Means of
Liquid Chromatography......................................................................... 221
Dušan Berek
viii Contents

12. Impedance Spectroscopy––Basic Concepts and Application

for Electrical Evaluation of Polymer Electrolytes................................ 333
Tan Winie and Abdul Kariem Arof
Part 2
Advanced Polymeric Materials––Macro to Nanoscales

13. Preparation of Chitin-Based Nano-Fibrous and Composite

Materials Using Ionic Liquids................................................................ 367
Jun-Ichi Kadokawa
14. Fire-Resist Bio-Based Polyurethane for Structural Foam
Application............................................................................................... 385
Khairiah Haji Badri and Amamer Musbah Omran Redwan
15. Graft Copolymers of Guar Gum vs Alginate––Drug
Delivery Applications and Implications................................................. 423
Animesh Ghosh and Tin Wui Wong
16. Thermal Properties of Polyhydroxyalkanoates.................................... 441
Yoga Sugama Salim, Chin Han Chan, K. Kumar Sudesh, and Seng Neon Gan
17. Replacing Petroleum-Based Tackifier in Tire Compounds
With Environmental Friendly Palm Oil-Based Resins........................ 475
Siang Yin Lee and Seng Neon Gan
18. Miscibility, Thermal Properties and Ion Conductivity of
Poly(Ethylene Oxide) and Polyacrylate................................................. 503
Lai Har Sim, Siti Rozana Bt. Abd. Karim, and Chin Han Chan
19. Poly(Trimethylene Terephthalate)––The New Generation of
Engineering Thermoplastic Polyester.................................................... 573
Sarathchandran C, Chin Han Chan, Siti Rozana Bt. Abd. Karim, and Sabu Thomas
Index......................................................................................................... 619
LIST OF CONTRIBUTORS

Abdul Kariem Arof

Centre for Ionics University of Malaya, Physics Department, Faculty of Science, University of Ma-
laya, 50603 Kuala Lumpur, Malaysia
Dušan Berek
Polymer Institute, Slovak Academy of Sciences, 84541 Bratislava, Slovakia

Khairiah Haji Badri

School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti
Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia
Chin Han Chan
Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Malaysia

Seng Neon Gan

Department of Chemistry, Universiti Malaya, 50603 Kuala Lumpur, Malaysia

Animesh Ghosh
Department of Pharmaceutical Sciences, Birla Institute of Technology, Mesra Ranchi-835215, India

Jun-Ichi Kadokawa
Graduate School of Science and Engineering, Kagoshima University, 1-21-40 Korimoto, Kagoshima
890-0065, Japan
Hans-Werner Kammer
Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Malaysia
SitiRozana Abdul Karim
Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Malaysia

K. Sudesh Kumar
School of Biological Sciences, Universiti Sains Malaysia, 11700 Penang, Malaysia

Siang Yin Lee

Pharmaceutical Chemistry Department, International Medical University, Bukit Jalil, 57000 Kuala
Lumpur, Malaysia

Amamer Musbah Omran Redwan

School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti
Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

Yoga Sugama Salim

Department of Chemistry, Universiti Malaya, 50603 Kuala Lumpur, Malaysia

C. Sarathchandran
Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India
x List of Contributors

Lai Har Sim

Centre of Foundation Studies, Universiti Teknologi MARA, 42300, PuncakAlam, Malaysia

Sabu Thomas
Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India

Tan Winie
Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Malaysia

Tin Wui Wong

Non-Destructive Biomedical and Pharmaceutical Research Centre, Universiti Teknologi MARA,
42300, Puncak Alam, Selangor, Malaysia
LIST OF ABBREVIATIONS

AA Acrylic acid
ABS Acrylonitrile-butadiene-styrene
AC Alternating current
AFM Atomic force microscopy
AMIMBr 1-Allyl-3-methylimidazolium bromide
ATHAS Advanced thermal analysis system
BA Butyl acrylate
BCF Bulk continuous fibers
BN Boron nitride
BR Butadiene rubber
CAP Critical adsorption point
CCD Charge coupled device
CFC Chlorofluorocarbon
CGF Chopped glass fiber
CNT Carbon nanotube
CPE Constant phase element
CPP Critical partition point
CR Chloroprene rubber
CT Cream time
CTCGs Content of terminal carboxyl groups
DBTO Dibutyl tin oxide
DC Direct current
DE Degree of esterification
DMA Dynamic mechanical analysis
DMP Dimethyl phthalate
DMT Dimethyl terephthalate
DNA Deoxyribonucleic acid
DRS Dielectric relaxation spectroscopy
DSC Differential Scanning Calorimetry
EBBA p-ethoxy benzylidene-bis-4-n-butylaniline
EC Ethylene carbonate
EDM Electric discharge machining
ENR Epoxidized natural rubber
EO Ethylene oxide
xii List of Abbreviations

EPDM Ethylene propylene diene monomer

EVAc Poly(ethylene-co-vinyl acetate)
EVOH Poly(ethylene-co-vinyl alcohol)
FFB Fresh fruit bunches
FR Fire retardant
FTIR Fourier transform infrared
FWHM Full width at half maximum
GPC Gel permeation chromatography
GPE Gelled polymer electrolytes
HDT Heat distortion temperature
2HEA 2-Hydroxy ethylacrylate
HFFR Halogen-free flame retardants
HIP Hot Isostatic Press
HPLC High-performance liquid chromatography
IBMA Isobutyl methacrylate
IDT Initial decomposition temperature
IR Isoprene rubber
IS Impedance Spectroscopy
it-PMMA isotactic poly(methyl methacrylate)
KWW Kohlrausch–Williams–Watts
LC Liquid crystalline
LCP Liquid crystal polymer
LCST Lower critical solution temperature
MBBA 4-Methyloxylbenzylidene – 4’-butylaniline
MMA Methyl methacrylate
MWCNT Multi-wall carbon nanotube
NBR Acrylonitrile butadiene rubber
NMR Nuclear magnetic resonance
NR Natural rubber
OMMT Organically modified montmorillonite
OPCs Organophosphorus compounds
PAN Poly(acrylonitrile)
PArM Poly(aryl methacrylate)
PBA Poly(butyl acrylate)
PBE Poly(bisphenol A-co-epichlorohydrin)
PBMA Poly(butyl methacrylate)
PBS Poly(butadiene-co-styrene)
PBT Poly(butylene terephthalate)
PBzMA Poly(benzyl methacrylate)
PCL Poly(e-caprolactone)
PCMA Poly(cyclohexyl methacrylate)
PEA Poly(ethyl acrylate)
List of Abbreviations xiii

PEAT Point of exclusion – adsorption transition

PEG Poly(ethylene glycol)
PEGMA Poly(ethylene glycol) methacrylate
PEGMe Poly(ethylene glycol) methyl ether
PEHA Poly-2-ethylhexyl acrylate
PEO Poly(ethylene oxide)
PER Polyester resins
PET Poly(ethylene terephthalate)
PHAs Polyhydroxyalkanoates
PHB Poly(hydroxy butyrate)
PHBV Poly(hydroxyl butyrate –co– hydroxyl valerate)
PHV Poly(hydroxyvalerate)
PiBMA Poly(iso-butyl methacrylate)
PKO Palm kernel oil
PLA Polylactide
PMA Poly(methy acrylate)
PMMA Poly(methyl methacrylate)
PMVE-Mac Poly(methyl vinyl ether-maleic acid)
PnBMA Poly(n-butyl methacrylate)
PNIPAM Poly(N-isopropylacrylamide)
PO Propylene oxide
POE Poly(oxyethylene)
POM Polarized optical microscopy
PPG Poly(propylene glycol)
PPhMA Poly(phenyl methacrylate)
PPMA Poly(propyl methacrylate)
PPO Poly(propylene oxide)
PPO-PU Polypropylene oxide-based polyurethane
PtBMA Poly(tert-butyl methacrylate)
PTMS Poly(tetramethylene succinate)
PTT Poly(trimethyleneterephthlate)
PUNL Polyurethane-nitrolignin
PVA Poly(vinyl alcohol)
PVDF Poly(vinylidene fluoride)
PVME Poly(vinyl methyl ether)
PVPh Poly(vinyl phenol)
RC Resistor-capacitor
RP Red phosphorus
RPA Random phase approximation
RT Rise time
SAN Poly(styrene-co-acrylonitrile)
SANS Small angle neutron scattering
xiv List of Abbreviations

SAXS Small angle X-ray scattering

SBM Styrene-butadiene-maleic
SBR Styrene-butadiene rubber
SEC Size exclusion chromatograms
SEM Scanning electron microscope
SFG Short glass fiber
SPE Solid polymer electrolyte
sPS Syndiotactic poly(styrene)
TEM Transmission electron microscope
TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl radical
TFT Tack-free-time
TGA Thermal gravimetrical analysis
TGIC Temperature gradient interaction chromatography()
TMDSC Temperature-modulated differential scanning calorimetry
TMPSF Tetra methyl poly(sulfone)
TR-SAXS Temperature-resolved small-angle X-ray scattering
UCST Upper critical solution temperature
UM University of Malaya
VTF Vogel-Tamman-Fulcher
WAXS Wide-angle X-ray diffraction
XRD X-ray diffraction
PREFACE

The honor of this book shall be credited to Prof. Dr. Hans-Werner Kammer, who
served as the Senior Visiting Professor at Universiti Teknologi MARA, Shah
Alam, Malaysia (UiTM), from 2008 to 2012. Prof. Dr. Kammer was one of prime
driving forces in the initiation of compiling the lectures that are aimed at young
reseachers and practitioners. The first part of the book is an elaboration of keynote
lectures presented by him and the other authors during the Workshops on Macro-
molelcules I, II and III (2009, 2010 and 2011). These workshops were organized
by UiTM and co-organized by the Malaysian Institute of Chemistry. In this book,
Chapters 1 to 12 present a coherent view of a broad number of topics pertaining
to basic concepts of polymer science. These chapters comprise polymer charac-
terization, polymer thermodynamics, and the behavior of polymers (melts, so-
lutions, and solids). They emphasize basic science and terms and concepts that
are critical to polymer science and technology. These chapters provide a secure
ladder for young reseachers and practitioners to progress from the primary level
to an advanced level without much difficulty. We note here, physical chemistry
of polymer science does require a familiarity with mathematics. However, many
of the basic concepts are understandable to researchers who have experienced
elementary courses of physical chemistry for tertiary education. The mathematics
in these chapters is minimized, and hence, undergraduates and graduates should
be able to master the discussion in the chapters.
Nowadays, there is a growing tendency for researchers to attempt to ana-
lyze selected phenomena to the greatest depth with increased specialization. The
participants of the Workshops on Macromolelcules I, II and III were inspired and
have benefited from the keynote lectures, which provided broader perspective at
a given domain. The understanding of the basic principles on polymer science
resulted in thought-provoking impulses on the experimental design coupled with
the results and discussion of research. Some of the participants of the workshops
have subsequently presented their valuable research findings at the Internation-
al Symposium on Advanced Polymeric Materials 2012 (ISAPM 2012). ISAPM
2012 was a joint international symposium on polymeric materials between the
xvi Preface

Institute of Materials, Malaysia (IMM), Malaysia, and Mahatma Gandhi Univer-

sity (MGU), Kottayam, Kerala, India, under the auspices of the 8th International
Materials Technology Conference and Exhibition (IMTCE 2012) in Kuala Lum-
pur, Malaysia. The second part of the chapters are the collections of lectures
from the ISAPM 2012. Chapters 13 to 19 focus on application areas emphasizing
emerging trends and applications of polymeric materials, which cover the advanc-
es in the fields of polymer blends, micro- to nanocomposites, and biopolymers.
Finally, we wish to express our sincere gratitude and appreciation to the
contributors of the chapters. All criticism, comments, and additional infor-
mation from reviewers are gratefully appreciated. Special thanks are due to
Prof. Dr. Hans-Werner Kammer, the main contributor of the book, who made
valuable suggestions for the content of this book. This book is an outcome of the
initiative taken by Prof. Dr. Hans-Werner Kammer. We also would like to extend
our thanks to Siti Rozana Abdul Karim and Fatin Harun in formatting some of the
chapters.

— Chin Han Chan, PhD, Chin Hua Chia, PhD,

and Sabu Thomas, PhD
Part 1: Physical Chemistry of
Macromolecules
This page intentionally left blank
CHAPTER 1

INTRODUCTION
HANS-WERNER KAMMER

CONTENTS

1.1 Global Structure of Macromolecules............................................................ 4

1.2 Chemical Structure of Macromolecules ....................................................... 5
Keywords............................................................................................................... 8
References.............................................................................................................. 8
4 Physical Chemistry of Macromolecules: Macro to Nanoscales

The high molecular mass compounds or polymers consist of large molecules hav-
ing molecular masses in the order of 104 to 106 g/mol. The molecules of these
compounds are formed by low-molecular units of identical chemical structure,
called monomers. Monomers are covalently linked to build up a polymer mol-
ecule or a macromolecule, frequently like a chain. Therefore, macromolecules are
also termed chain molecules. The combination of a large number of monomers to
a polymer molecule generates completely new properties, such as elasticity or the
ability to form fibers or films. The large molecules also display flexibility.
In the beginning of 20th Century, it was believed that molecular masses of
many thousand dalton are impossible and macromolecules were seen as physi-
cally bounded associates or colloids. Indeed for a stable macromolecule the bond-
ing energy RT must exceed approximately 2.48 kJ/mol at room temperature. The
measurements of vapor or osmotic pressure provide strong arguments for exis-
tence of chemically bounded large molecules. If macromolecules would exist just
as colloids or associates one could find conditions in increasingly diluted solutions
where they decay into their constituents, that is one would find lower molecular
masses. However, this was not observed. Historically, Staudinger (around 1930)
proved by so-called polymer analogue reactions, where only side groups change
not the backbone that macromolecules really exist. Hydrogenation of natural rub-
ber removed double bonds that were seen as source of intermolecular attraction
leading to associates. Hence, again lowering of molecular mass should result.
This effect was not observed giving rise to Staudinger’s famous conclusion about
the structure of chain molecules.
We may distinguish natural and synthetic or man-made polymers. Examples
for natural systems are proteins, polysaccharides, and natural rubber whereas
polyethylene, polystyrene, and polyamide are examples for synthetic polymers.
A polymer molecule consists of monomer units A of its low-molecular ana-
logues linked covalently N times. It might be symbolized by –(A)N–, where N is
called degree of polymerization. It is for high molar mass polymers in the order
of 1000, N ≈ 1000.

1.1 GLOBAL STRUCTURE OF MACROMOLECULES

The macromolecules may form linear, branched, cross-linked, and network-

like structures (see Figure 1). Usually, a chain is seen as linear, if it comprises
per 1000 C atoms in the backbone less than 10 branches whereas a branched
Introduction 5

macromolecule contains more than 40 branches. For three-dimensional network

polymers, the concept of molecules loses its meaning.

FIGURE 1 Linear, branched, cross-linked, and network-like structures of macromolecules.

1.2 CHEMICAL STRUCTURE OF MACROMOLECULES

The polymers are classified with respect to chemical structure of their main chain
(or backbone). Organic polymers form the most important class, their chain con-
sists of carbon atoms. In inorganic polymers the chain does not contain carbon.
The organoelement macromolecules comprise silicon or phosphorus in the back-
bone.
When the backbone consists of chemically identical units, the compound is
called homopolymer or polymer, in short. The copolymers comprise two or more
chemically different monomers in the main chain. They are symbolized by –
(AxB1-x)N–, where x gives the content of monomers A in the chain. Also sequence
distribution of A and B along the chain determines properties of copolymers.
Hence, two more degrees of freedom exist, composition x and sequence distribu-
tion. For the latter, we may distinguish four arrangements:
• Random -AABBBBABBABAA-
• Alternating -ABABAB-
• Block -AAAAAABBBB-
• Graft main chain formed by monomers A, side chains formed by monomer
B
6 Physical Chemistry of Macromolecules: Macro to Nanoscales

The structure of a macromolecule as a whole is characterized by its configu-

ration and conformation. Configuration is the definite spatial arrangement of the
atoms in the molecule. It does not change in the course of thermal motion. Altera-
tion of configuration needs breaking of chemical bonds. The different kinds of
configurations are called isomers of a molecule. The arrangements of substituents
relative to double bond are called cis-, when chemically equal side groups are on
one side to the double bond, and called trans-, when they alternate at different
sides. As an example, it mention here 1,4-polybutadiene, which exists in cis- and
trans- configuration (Figure 2).

FIGURE 2 Cis- and trans- configuration of 1,4-polybutadiene.

The stereoregular polymers occur due to asymmetric carbon atoms in the main
chain. The isotactic structures have side groups on one side of the plane through
chain axis, in syndiotactic molecules attached substituents alternate regularly at
different sides and in atactic molecules there is an irregular arrangement of side
groups (Figure 3 and Figure 4).

FIGURE 3 Isotactic and syndiotactic molecular structures.

Introduction 7

FIGURE 4 1,2-isotactic and syndiotactic polybutadiene.

The mutual repulsion between substituents may cause some displacement. As a

result, the plane of symmetry is bent in the form of a helix. This occurs also in bio-
polymers (double-helix of deoxyribonucleic acid (DNA)). Different stereoisomers
have different mechanical and thermal properties. For example, atactic polystyrene
is an amorphous polymer whereas syndiotactic polystyrene is a crystalline sub-
stance. The chemical design of macromolecules determines their properties as extent
of crystallization, melting point, softening (glass transition temperature), and chain
flexibility which in turn strongly influence mechanical properties of the materials.
The conformation of a macromolecule is its shape in space that alters as a
result of thermal motion without breaking of bonds.
The complementary to Staudinger’s covalently linked chain molecules we
mention here briefly supramolecular polymers (Lehn, 1995). These polymers
are designed from low or high molar mass molecules that are capable of strong
unidirectional association. As a result, chains develop by reversibly self-assem-
bled molecules through unidirectional noncovalent interactions.
In covalently bound macromolecules units are irreversibly linked with high
bonding energy, C–C bond amounts to 360 kJ/mol. The elements in supramo-
lecular polymers are reversibly linked with bonding energy of more than one
order of magnitude lower as in covalently linked chains, H bonds vary in the
range from 10 to 20 kJ/mol. Owing to reversibility of intermolecular interac-
tions, these systems are always in equilibrium. They mention here three classes
of supramolecular polymers:
8 Physical Chemistry of Macromolecules: Macro to Nanoscales

1. Coordination polymers formed by complexation

2. π-π interactions lead to assembling of low molecular units into polymers
in solution
3. Hydrogen bonded polymers with multiple unidirectional interactions
All these intermolecular interactions are weaker than covalent bonds. An ex-
ample of a dimer is shown in Figure 8. The association constant was found to be
Ka = 6.107 (mol)-1. This corresponds to ∆Go = –45 kJ/mol or 1/8 of the energy of
C–C bond.

FIGURE 5 Quadrupole hydrogen bonding dimer of 2-ureido-4-pyrimidone groups.

KEYWORDS

•• Global structure
•• Chemical structure
•• Configuration
•• Conformation
•• Stereoregularity

REFERENCES
1. Lehn, J. M. Supramolecular Chemistry: Concepts and Perspectives, VCH, Weinheim
(1995).
CHAPTER 2

MOLECULAR MASS OF
MACROMOLECULES AND ITS
DISTRIBUTION
HANS-WERNER KAMMER

CONTENTS

2.1 Averages of Molecular Mass....................................................................... 10

2.2 Molecular Mass Distributions..................................................................... 11
Appendix A.......................................................................................................... 22
Appendix B.......................................................................................................... 22
Keywords............................................................................................................. 24
References............................................................................................................ 24
10 Physical Chemistry of Macromolecules: Macro to Nanoscales

2.1 AVERAGES OF MOLECULAR MASS

In naive approximation, one could say the degree of polymerization, N, deter-

mines the molecular mass of a polymer sample.

Mpolymer = NMmonomer (1)

This relationship simplifies largely the real situation. In contrast to low mo-
lecular substances that have well-defined molecular masses, macromolecular sub-
stances do not have. Due to the statistical nature of polymerization processes, it
is impossible to obtain polymer samples comprising macromolecules of identical
size or chain length. Samples are produced that are non-uniform with respect to
molecular mass. Therefore, polymers have molecular mass distributions and one
characterizes the molecular mass of a polymer by suitable averages.
Let us consider an example. A polymer sample was separated by fractionation
into 12 fractions having the amounts and molecular masses as given in Table 1.
Using the data of Table 1, we may formulate two different averages of mo-
lecular mass:

12 12
M w = ∑ Wi M i M n = ∑ XiMi (2)
i =1 i =1

TABLE 1 Molecular mass distribution of a polymer sample

Relative amount 5.3 12.3 15.3 15.4 13.7 10.7 8.5 6.3 4.8 3.5 2.4 1.8
in wt%
Molecular mass in 1 2 3 4 5 6 7 8 9 10 11 12
104 g/mol

The quantities Wi and Xi symbolize mass fraction and mole fraction of fraction
i. The molecular masses M w and M n are called weight average and number aver-
age molecular mass, respectively. If the sample has a sharp molecular mass, we
get Mw = Mn . The second equation of Equation (2) can be easily recast in mass
fraction. It is:
Molecular Mass of Macromolecules and Its Distribution 11

-1
 12  (3)
M n =  ∑ Wi M i 
 i =1 
With data of Table 1, we get according to Equation (2), M w = 50620 g/mol and
M n ≅ 35490 g/mol. The first equation for Equation (2) can be recast in averages
of Mn. It follows:

1 M n2
M w = ∑ Wi M i = ∑ X i M i2 = > Mn (4)
i Mn i Mn

For the average of the scatter around the average, we have with Equation (4):

( )
2 2
Mn - Mn = M n2 - M n , (5)

2
M n2 - M n Mw (6)
2
= -1
Mn Mn

The ratio M w / M n serves usually as measure of fluctuation of molecular mass

around the average or as measure of polydispersity of the polymer sample. In
example, the polydispersity amounts to 1.4.

2.2 MOLECULAR MASS DISTRIBUTIONS

We consider an ensemble of similar molecules, having certain properties, and we

ask for the average of a property over the ensemble. In generalization of Equation
(2), we have for property p the average.

n
mi n
p = ∑ pi = ∑ pi wi
m i =1
with ∑w =1
i
i
(7)
i =1

where wi is the probability for occurrence of property pi in the ensemble under

discussion. The Equation (7) is called normalization condition of probability
12 Physical Chemistry of Macromolecules: Macro to Nanoscales

since we find any property with certainty. Equation (7) holds true for a discrete
spectrum of properties pi. If the property p is continuously distributed over the
ensemble, we have to replace the summation in Equation (7) by integration. It is:

∞ ∞
p = ∫ dwp = ∫ dpρ ( p ) p with ∫ dpρ ( p ) = 1 (8)
0 0

The function ρ(p) is called distribution function of property p. It tells us the

probability for occurrence of a certain value of property p. One may also formu-
late an integral distribution of property p.
pp (9)
( ) ∫
Φo p = dπρ (π )
0

If π = M, the molecular mass, quantity Φo(M) represents the integral molecular

mass distribution. It is the fraction of molecules having a molecular mass between
0 and M in the sample.
The average or expectation value of a quantity is the value of that property we
expect after carrying out a series of trials or a series of measurements on similar
objects. In addition to the average, calculated after Equations (7) or (8), we are
interested in the quality of that average or to what extent the individual values de-
viate from average. Hence, a measure of the quality of average or of the variability
of the individual events or their scatter around the average is called the variance or
fluctuation <∆p2> of property p. It is defined by the average of (positive) deviation
of individual events from average

( )
2 2
∆p 2 ≡ p - p = p2 - p ≥ 0 (10)

Probability distributions are characterized by two quantities, average and

variance. It is precisely what we did as we calculated average M n and variance
2 2
<∆Mn2> = Mnn - M n (compare Equation (6)) for the molecular mass distribu-
tion given in Table 1.
Let us start with a very important distribution function in analysis of random
events, the Gaussian or normal distribution. They mention this distribution here
just for illustration. It is not suitable for comprehension of molecular mass distri-
butions in synthetic polymers. The Gaussian distribution function reads:
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