C H A P T E R
18
Polymer Chemistry
18.1 INTRODUCTION AND TYPES
OF POLYMERS
Introduction
This chapter is an introduction to polymer
chemistry with emphasis on topics related to
pulp and paper. Polymers are very important
to many aspects of pulp and paper, including
wet end chemistry, surface sizing, and coating.
Of course, the principal constituents of pulp
fibers are all polymers. Like other chapters in
this book, many of the introductory details are
not included; for further information, one should
consult a textbook on polymer science.
History of Polymers
One of the earliest industrial developments
was the use of natural, soft rubber (poly-cis-
isoprene) in the early 1800s; the development of
the vulcanization process (reaction of the carbon
double bonds with sulfur to form cross-linked
chains) by Goodyear in 1839 led to hard rubber.
The first human-made plastic may be consid-
ered to be cellulose nitrate, which was discov-
ered in 1846 by Schonbein of Switzerland by
the action of a mixture of nitric and sulfuric acids
on cotton. Cellulose nitrate was used as a propel-
lant/explosive by the Austrian army in 1852
(now called guncotton or smokeless powder),
with amyl acetate solvent as the first modern
lacquer in the United States in 1882, and in early
Biermann's Handbook of Pulp and Paper: Paper and Board Making
https://doi.org/10.1016/B978-0-12-814238-7.00018-0
photographic films (plasticized with camphor to
form Celluloid, and as the first artificial silk
by Count de Chardonnet in France in 1884.
Cellulose acetate (discovered in 1865), being
much safer, as it is less flammable, soon replaced
cellulose nitrate for most uses. Regenerated cel-
lulose (see cellulose xanthate) was invented by
Cross and Bevan in 1892; this is the viscose rayon
process and was used by Brandenberger to make
cellophane, marking the beginning of modern
packaging with transparent, plastic films in
1924 when the first cellophane plant started
operation in Buffalo, New York. Indeed the
cellulose-based plastics dominated the synthetic
plastics field for about 50 years.
The development of purely synthetic poly-
mers began with the discovery of the phenol-
formaldehyde resins by Baekeland with the
trade name of Bakelite, small-scale production
of which began in 1907. Other developments
included the use of styrene in synthetic rubbers
in the 1930s, the appearance of nylon (invented
by Carothers) in 1939, and the appearance of
Teflon in 1941.
Polymers
Polymers are high-molecular-weight chemi-
cals made of repeating units, called monomers,
which are linked by covalent bonds. The phys-
ical properties of polymers depend on (1) the
chemical composition of the monomeric units,
373 Copyright © 2018 Elsevier Inc. All rights reserved.
374 18. POLYMER CHEMISTRY

(2) stereochemistry, if present, between the mono- diblock or A(A)nB(B)nBA(A)nA if it is triblock.

meric units, (3) the mechanical configuration of
the polymer chain (that is, is it coiled or linear),
and (4) the chain length of the polymer, that is,
the number of monomers, known as the degree
of polymerization (DP), of the polymer. Typical
DP values of commercial polymers range from
several hundred to many tens of thousands.
Polymers may be grouped according to their
component monomers. The simplest type of poly-
mer is the homopolymer, a polymer containing
only one type of monomer (Fig. 18.1). For conve-
nience, letters of the alphabet are assigned to
different types of monomers, so that a homopoly-
mer may be described as one having the configu-
ration of: A-A-A-A-A-A-A-A-A-A. This can also
be written as: A-(A)n-A; if n ¼ 8 the DP of these
polymers is 10. A simple example of this is
polyethylene, made from the ethylene monomer
CH2]CH2; the structure of the polymer is
CH3e(CH2eCH2)neCH3. Copolymers are poly-
mers containing two types of monomer, and
terpolymers contain three types of monomers. A
copolymer with an alternating structure is of the
form ABABABABABABABABABABABABA; a
copolymer with a random structure is ABBAAA-
BAABBABBBABABAABBBABA; a block copol-
ymer has the structure A(A)nAB(B)n if it is
Block copolymers are made by anionic polymer-
ization techniques because monomers can be
added consecutively with this method, as the
anion is stable indefinitely. The structure of a
graft copolymer is shown in Fig. 18.1.
A branched homopolymer is like a graft copol-
ymer, except all of the monomer units are identical.
Polymers may be cross-linked to give additional
strength and rigidity. A cross-linked homopoly-
mer is depicted in Fig. 18.1.
Many plastics or adhesives form cross-links
during their manufacture or curing phase. These
plastics are called thermosets because once set
in position they will not soften with heating.
Epoxy resins, phenol-formaldehyde resin, and
polystyrene cross-linked with divinyl benzene
are several examples of thermosetting materials.
Other polymers consisting of linear chains or
linear chains with little or no branching are called
thermoplastics, which soften when heated and
harden when cooled to ambient temperatures.
18.2 ADDITION POLYMERS
There are two categories for types of polymer-
ization reactions used to form polymers:

FIGURE 18.1 Representative structures of HOMOPOLYMER: A-A-A-A-A-A-A-A-A-A or AAAAAAAAAA or A(A)nA

various classes of polymers.
COPOLYMERS: ABABABAB ABBAAABAABBABBBABABAABBBABBA

alternating random

A(A)nAB(B)nB A(A)nAB(B)nBA(A)nA

block (diblock) triblock

GRAFT -AAAAAAAAAAAAAAAAAAAAAAAAAA-
COPOLYMER: B B B
B B B
B B B
B B B
B B

CROSS-LINKED -AAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAA-
HOMOPOLYMER: A A A
A A A
A A A
A A A
-AAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAA-
A A
A A
A A
-AAAAAAAAAAAAAAAAAAA- etc. in all directions....
 18.2 ADDITION POLYMERS
condensation and addition mechanisms to form
condensation and addition polymers, respectively.
The addition mechanism is used to make poly-
mers from monomers with ring structures or
double bonds by a chain reaction. The “extra”
bond of the monomer is used to form the bond
between monomers; this means that no mole-
cules are lost during polymerization, that is,
there is no change in the molecular weight of
the monomer incorporated into the polymer.
These polymers are usually formed by free
radical reactions; however, anionic and cationic
mechanisms may also be used but require special
solvents and reaction conditions. Free radical re-
actions are started using initiators. Initiators are
compounds that form free radicals, such as perox-
ides, to start the reaction. The free radical is al-
ways carried by the terminal carbon atom
between propagation steps. Initiation may also
375
be carried out with high-energy radiation, photol-
ysis, or thermal energy. The reaction of a vinyl
monomer, which has the form CH2]CHR, is
shown in Fig. 18.2. Monomers almost invariably
add head to head, eCH2CHReCH2CHRe, as
opposed to head to tail, which is
eCH2CHReCHRCH2e. Head to head addition
can form three types of polymers, which differ
in rotation around a carbonecarbon single
bond: in atactic polymers the R groups are
randomly oriented around the longitudinal axis
of the polymer; in isotactic polymers the R groups
branch out on one side of the polymer chain; and
in syndiotactic polymers the R groups alternate
from one side of the axis to the opposite side of
the axis. Atactic polymers are usually amorphous
and less dense than their often crystalline syndio-
tactic or isotactic counterparts. Their structures
are:

R R R R
CH2 CH2 CH2 CH2
ISOTACTIC H H H H
R H R H
CH2 CH2 CH2 CH2
H R H R
SYNDIOTACTIC

STEP EXAMPLE REACTION DESCRIPTION

Initiation: I2→2I∙ The initiator forms two free radi-

cals.
R
I∙ + H2C=CHR→ICH2C∙ The free radical reacts with the
H first monomer.

Propagation: I(CH2CHR)nCH2CHR∙ + H2C=CHR Monomers are added to the growing

chain.
→ I(CH2CHR)n+1CH2CHR∙

Chain transfer: -CH2CHR∙ + H2C=CHR'

H
→ -CH=CHR + CH3C; One possibility.
R

Termination: 2 -CH2CHR∙ → -CH2CHRCHRCH2- Termination by coupling or

combination.
2 -CH2CHR∙ → -CH2CH2R + -CH=CHR Termination by disproportionation.

FIGURE 18.2 The steps involved in polymerization by the addition mechanism.

376 18. POLYMER CHEMISTRY

Addition polymers are characterized by high- H COOR COOR COOR

molecular-weight averages, rubbery or brittle n C C CH2 CH2
solids, and, usually, amorphous structures. The H R' R' R'
chain reaction goes very quickly, and the entire
polymer is built in a matter of seconds. It should R' R Polymer Name
be noted that polymerization proceeds until
H CH3 Poly(methacrylate)
all of the monomer is removed or the free radi-
H CH2CH3 Poly(ethacrylate)
cals are all terminated. It is quite possible that
CH3 CH3 Poly(methyl methacrylate)
residual monomer will be present after (Lucite, Plexiglas)
polymerization.
Fig. 18.3 shows a variety of vinyl diene struc- FIGURE 18.5 Acrylic ester structures.
tures. Fig. 18.4 shows a variety of vinyl poly-
mers, and Fig. 18.5 shows a variety of acrylic
polymers, all of which are usually formed by include eCH2CCI2e [poly(vinylidene chloride),
the addition mechanism. Two other polymers Saran] and eCF2CF2e [poly(tetrafluoroethy-
lene), Teflon]. The diene polymers are very
elastic because the double bonds cause the back-
H H R H H H R H
bone to assume a kinked, random coil shape;
n C C C C C C C C
these are rubber materials. Tensile forces allow
H H H H n
these coils to be partially straightened; relaxation
of the forces allows the original structure to be
R Polymer Name
assumed. Another type of acrylic polymer is
Poly(butadiene) (synthetic rubber)
polyacrylic acid, where both R and R0 in
H
CH3 Poly(isoprene) (natural rubber, cis config∙) Fig. 18.5 consist of H atoms. The so-called super-
CI Poly(chloroprene) (Neoprene) absorbent polymers that are used in diapers and
FIGURE 18.3 Polymerization of dienes. The position of
incontinence products are based on polyacrylic
the double bond is variable; it may be a side group. acid, where some of the carboxylic acids occur
as the sodium salt. Sometimes the polyacrylic
acid polymers are reacted with starch to form
the superabsorbent polymers.
H R
Another type of addition polymerization is
n C C –CH2–CHR–CH2–CHR–CH2–CHR–
the ring opening reaction. One example is the
H H polymerization of ethylene oxide used to form
R Polymer Name
polyethylene glycols and ethoxylated molecules
used as surfactants.
H Polyethylene, PE
CH3 Poly(propylene), PPE
CI Poly(vinyl chloride), PVC 18.3 CONDENSATION POLYMERS
OH Poly(vinyl alcohol), PVA
OAc Poly(vinyl acetate), PVAc The condensation mechanism is used to
C N Poly(acrylonitrile), PAN
make polymers from monomers with two (or
CONH2 Poly(acrylamide), PAM
more for cross-linked polymers) reactive func-
COOH Poly(acrylic acid)
tional groups by a step-wise reaction. Each reac-
Polystyrene, PS
tion step between two monomers produces a
FIGURE 18.4 Vinyl polymer structures. simple molecule, often water, but sometimes
 18.3 CONDENSATION POLYMERS
NH3 or another molecule, as a side product.
These reactions are common, well-known
organic chemistry reactions. They are easily
controlled reactions, unlike free radical reac-
tions. The most common reactions of synthetic
polymers are esterification (formation of ester
linkages) and amidation (formation of amide
linkages). Fig. 18.6 gives an example of each.
In the case of nylon 6,6 (6 is the number of
carbon atoms in each of the two monomers if
a dicarboxylic acid and diamine were used to
form it), it is possible to use a single compound
to make the polymer, that is, H2N(CH2)5COOH.
It is apparent that monomers will react together
initially and small polymers (oligomers) will
react later. This means that after a short time
essentially all of the monomers will be gone
and oligomers will exist. These oligomers will
then react to form short-chain polymers, then
the short-chained polymers will react to form
moderately long-chain polymers. The number
average DP can be predicted as a function of
the extent of reaction. The extent of reaction is
the fraction of functional groups, which have
participated in the polymerization reaction.
For bifunctional reactants present in equal pro-
portions, such as in Fig. 18.6, the DPn ¼ 1/
(1-p). For example, if 50% of the functional
groups reacted p ¼ 0.5, then DPn ¼ 2; this
would occur if each monomer reacted with
one other monomer so that only dimers were
left. If p ¼ 75% (if these dimers reacted to form
tetramers), then DPn ¼ 4. It is apparent that if
O O
HOCH2CH2OH + HOC COH
ETHYLENE GLYCOL TEREPHTHALIC ACID
H2N(CH2)6NH2 + HOOC(CH2)4COOH
1,6–HEXANEDIAMINE ADIPIC ACID
FIGURE 18.6 Formation of polyester and polyamide polymers.
377
p ¼ 99%, DPn ¼ 100; if p ¼ 99.9%, DPn ¼ 1000;
and if p ¼ 99.99%, DPn ¼ 10,000. It is very diffi-
cult to obtain such high extent of reactions;
therefore, condensation polymers tend to have
relatively low molecular weights unless the
monomers have, on the average, more than two
functional groups each. Two other useful relation-
ships include DPw ¼ (1 þ p)/(1-p) and DPw /DPn
¼ 1 þ p; consequently, for high extents of reaction
the polydispersity approaches 2.
Condensation polymers are characterized by
polar linkages, relatively low-molecular-number
averages, unless cross-linking agents are used,
and, often, crystalline polymers. Other examples
of condensation polymers include polysaccha-
rides (Chapter 17, Vol. 2), proteins, and polyure-
thanes. Proteins are made from amino acids,
which have the structure HOOCeCHReNH2,
and are joined by amide linkages to form:
COCHRNH  COCHRNH  COCHRNH
Polyurethanes are formed by the reaction of dii-
socyanates (O]C]N-R-N]C]O) and glycols
with the linkage eNHeCOee by the reaction:
OCNCH2 CH2 CNO þ HOCH2 CH2 OH/


½OCONHCH2 CH2 NHCOOCH2 CH2 n
Epoxies are polyethers but retain the name
of one of the reactants. The most common
epoxies involve reaction of excess epichlorohy-
drin with bisphenol A; the excess epoxide
groups are cured by reacting with polyamines,
as shown in Fig. 18.7. Epichlorohydrin is used
O O O O
C COCH2CH2 OC COCH2CH2O– + n H2O
POLY(ETHYLENE TEREPHTHALATE)
–NH(CH2)6NH–CO(CH2)4CO– + n H2O
NYLON 6,6
378
O CH3
H 2C CHCH2CI + HO
EPICHLORDHYDRIN
O OH
RHC CH2 + R'NH2
in numerous resins supplied to the pulp and
paper industry.
18.4 MOLECULAR WEIGHTS OF
POLYMERS
Synthetic polymers consist of individual
polymers with varying molecular weights.
The properties of the polymers depend not
only on the average molecular weight but
also on the distribution of molecular weights
as well. An example of a molecular weight dis-
tribution typical of free radical reactions is
shown in Fig. 18.8. Many of the methods
used to characterize polymers give average
molecular weights that depend on the molecu-
lar weight distribution as well as the number
average molecular weight. It becomes useful,
NUMBER OF MOLECULES
Mn
MOLECULAR WEIGHT
FIGURE 18.8 Typical distribution of molecular weights
in polymers produced by free radical polymerization.
18. POLYMER CHEMISTRY
CH3
O O
NaOH
H2C CH—CH2–O C OCH2 –HC CH2
C OH
CH3 + n HCI
CH3
bisPHENOL A (DIPHENYL PROPANE) LINEAR POLYMER WITH EPOXIDE GROUPS
R CHCH2NHR' (CURING STEP)
FIGURE 18.7 Formation of epoxy resins.
as will be demonstrated shortly, to define several
types of molecular weight distributions.
The first is a simple average where each
molecule contributes equally to the average (a
number average molecular weight depicted as
Mn ). Let Ni equal the number of the molecules
(or moles or other measure of number of mole-
cules) with mass Mi (or a measure of mass such
as DP). Using summation terminology for each
fraction from i ¼ 1 to N, abbreviated here as S,
the number of molecules in each fraction multi-
plied by the molecular weight (or other measure
of molecular weight such as DP) for each fraction
are summed and the entire sum is divided by
the total number of molecules, as shown in
Eq. (18.1).
P P
N i  Mi Ni  DPi
Mn ¼ P ; DPn ¼ P (18.1)
Ni Ni
A number average molecular weight is
obtained by methods that depend on the colliga-
tive properties of polymer solutions. One such
method is vapor phase osmometry that indirectly
MW
measures vapor pressures of polymer solutions.
Such methods are limited to low-molecular-
weight polymers (several thousand grams per
mole or less). This method has the drawback
that it does not represent the behavior of polymer
mixtures very well.
Consider an extreme, hypothetical example;
suppose during kraft pulping that 10 individual
glucose units are cleaved from a cellulose chain
with a DP of 1000. We now have 11 “polymers,”
 18.4 MOLECULAR WEIGHTS OF POLYMERS 379
1 with a DP of 990 and 10 with a DP of 1. The DP and one part of 4000 DP. Calculate DPn ,

number average DP is (1  990 þ 10  1)/ DPw , and DPw DPn in each of the two cases.
(10 þ 1) ¼ 90.9; in reality, however, the only
effect one would notice is a slight loss of yield Solution
(1%) with identical strength properties. In fact,
Case A: DPn ¼ ð2  2500Þ=2 ¼ 2500
if every cellulose chain had a DP of 91, the 

pulp would be useless for structural papers. DPw ¼ 2  25002 ð2  2500Þ ¼ 2500

A second type of average gets around these DPw DPn ¼ 2500=2500 ¼ 1
difficulties; it is the weight average, Mw , where
the weight of each molecule is considered impor- Case B: DPn ¼ ð1000 þ 4000Þ=2 ¼ 2500
tant, not the number. We introduce the term Wi, 

DPw ¼ 1  10002 þ 1  40002
which is the weight of the fraction with molecu-
ð1000 þ 4000Þ ¼ 3400
lar weight Mi. The weight of fraction i can be 
substituted as: Wi ¼ Ni  Mi . Using this substi- DPw DPn ¼ 3400=2500 ¼ 1:36
tution, the following relationships are obtained:
P P
W  Mi N  M2i
Mw ¼ Pi ¼ P i
Wi N i  Mi
P (18.2) EXAMPLE 2
N  DP2i
DPw ¼ P i What is Mn and Mw for a polymer mixture
Ni  DPi containing 0.5 mol of each of three polymers
A weight average molecular weight is deter- where M ¼ 20,000; 40,000 and 50,000 respectively.
mined by light scattering methods but is limited
to relatively high molecular weights, above Solution
several tens of 1000 g/mol. One can calculate
Mn ¼ ð0:5  20; 000 þ 0:5  40; 000 þ 0:5
the weight average DP in the example above,
 50; 000Þ=ð0:5 þ 0:5 þ 0:5Þ ¼ 36; 700
where the number average DP was 91. The 
DPw ¼ (1  9902þ10  12)/(1000) ¼ 980.1: Mw ¼ 0:5  20; 0002 þ 0:5  40; 0002


Mw Mn is a measure of the polydispersity, that is, þ 0:5  50; 0002 ð0:5  20; 000 þ 0:5
how disperse the molecular weight distribution  40; 000 þ 0:5  50; 000Þ ¼ 37; 500
is. Because the weight average molecular weight
is always higher than the number average molec-
ular weight, except for the special case when
they are equal if all of the polymers have the
exact same molecular weight (a monodisperse
sample), the ratio is greater than one. The poly- EXAMPLE 3
dispersity of this hypothetical example is Repeat Example 2, except instead of 0.5 mol
extremely high. It is 980.1/91 ¼ 10.8 than small each, assume you have 0.5 parts by weight of
molecules of similar structure. each component.

Solution
EXAMPLE 1 Use Eq. (18.2) directly and find:
Imagine a cellulose that has a DP of 5000. In
case “A” it is split into two equal parts of 2500 Mw ¼ ð0:5  20; 000 þ 0:5  40; 000 þ 0:5
each. In case “B” it is split into one part of 1000  50; 000Þ=ð0:5 þ 0:5 þ 0:5Þ ¼ 36; 700
380 18. POLYMER CHEMISTRY
To solve for the number average, we need a
relative measure of moles of the different materials.
Assume we have 0.5 kg of each polymer:
500 g=20; 000 g=mol ¼ 0:025 mol;
500 g=40; 000 g=mol ¼ 0:0125 mol; and
500 g=50; 000 g=mol ¼ 0:01 mol.
Now:
Mn ¼ ð0:25  20; 000 þ 0:0125  40; 000
þ 0:01  50; 000Þ=0:0475 mol ¼ 31; 600
A molecular weight profile of soluble polymers
may be obtained by a chromatographic method
known as size exclusion chromatography (SEC),
which is also known as gel permeation chroma-
tography (GPC). The chromatography column
consists of a “gel” such as polystyrene cross-
linked with divinyl benzene. The gel effectively
has “tunnels” of various sizes on the order of the
size of the molecules to be separated. Large mole-
cules cannot enter these tunnels, whereas small
molecules can. Therefore the volume of the chro-
matography column is effectively larger for the
small molecules. The large molecules come off
the column in the solvent first, and the smallest
molecules come off last. The fact that large mol-
ecules of similar structure come off the column
first is unique to this method that separates by
size. In all other forms of chromatography, large
compounds elute later. The mechanical proper-
ties of polymers and polymer solutions are
greatly dependent on their molecular weights.
Fig. 18.9 shows the effect of the DP on plasticity,
strength properties, and solution viscosity.
Solution viscosity
Strength
Property
Plasticity
Degree of polymerization
FIGURE 18.9 Properties of polymers as a function of
average degree of polymerization (DP).
EXERCISES
1. Describe the mechanism whereby GPC
separates compounds and indicates the
unique characteristic, in regard to the
order of elution of similar compounds,
of GPC.
2. A polymer contains 1 mol with DP 200 and
1 mol with DP 400. What are the number
average and weight average DPs? If the
polymer is polystyrene, what is the number
average molecular weight?
3. What are some differences between addition
polymers and condensation polymers?
4. Draw the general structure of vinyl polymers
and show the structures of three.
5. A polymer has an average molecular weight
of 6  106 and is monodisperse. How was it
made?