Polymerization 1-5

Dr.
Hikmat Al-Hajaj Polymer Reaction Engineering 4th Stage
Classification of Polymerization Reaction

1- Step – growth (condensation) polymerization
2- Addition / Chain growth polymerization
3- Co-Polymerization
4- Ring-opening polymerizations, ROPs.
1- Step – growth (condensation) polymerization

Polymerization usually proceeds by the reactions between two different functional
groups, for example, hydroxyl and carboxyl groups, or isocyanate and hydroxyl groups.
All step polymerizations fall into two groups depending on the type of monomer(s)
employed. The first involves two different bifunctional and/or polyfunctional
monomers in which each monomer possesses only one type of functional group. (A
polyfunctional monomer is a monomer with more than one functional group per
molecule. A bifunctional monomer is one with two functional groups per molecule.)
The second involves a single monomer containing both types of functional groups.
The two groups of reactions can be represented in a general manner by the equations
The synthesis of polyamides (nylons) illustrates both groups of polymerization

reactions. Thus polyamides can be obtained from the reaction of diamines with diacids
Polyamides (nylons)
Or from the reaction of amino acids with themselves:
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Dr. Hikmat Al-Hajaj Polymer Reaction Engineering 4th Stage
Condations of Step – growth (condensation) polymerization

1- Monomer molecules consisting of at least two functional groups can undergo step-
growth polymerization
2- The two reacting functional groups can either be on the same monomer molecule, as
in Aminocaproic acid 𝑁𝐻2 − (𝐶𝐻2 )5 − 𝐶𝑂𝑂𝐻.
Or on two separate molecules, as in the reaction between ethylene glycol, 𝐻𝑂 −

(𝐶𝐻2 )2 − 𝑂𝐻 and adipic acid, 𝐶𝑂𝑂𝐻 − (𝐶𝐻2 )4 − 𝐶𝑂𝑂𝐻.
3- Some polymerization process accompanies the release of secondary molecules such

as the water molecule.
4- The moles of reactants should be equal.
Reactivity of Functional Groups

Step polymerization proceeds by a relatively slow increase in molecular weight of the
polymer.
The reaction mixture at any instance consists of various-sized diol, diacid, and hydroxy
acid molecules. Any HO-containing molecule can react with any COOH-containing
molecule. This is a general characteristic of step polymerization.
Kinetic analysis is greatly simplifies if one assumes that:

1- the reactivities of both functional groups of a bifunctional monomer (e.g., both
hydroxyls of a diol) are the same,
2- the reactivity of one functional group of a bifunctional reactant is the same

irrespective of whether the other functional group has reacted.
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3- the reactivity of a functional group is independent of the size of the molecule to

which it is attached (i.e., independent of the values of n and m).
These simplifying assumptions, often referred to as the concept of equal reactivity of

functional groups, make the kinetics of step polymerization identical to those for the
analogous small molecule reaction. As will be seen shortly, the kinetics of a
polyesterification, for example, become essentially the same as that for the esterification
of acetic acid with ethanol.
Consider the synthesis of a polyester from a diol and a diacid. The first step is the
reaction of the diol and diacid monomers to form dimer.
The polymerization proceeds in this stepwise manner with the molecular weight of the
polymer continuously increasing with time (conversion).
Step polymerizations are characterized by the disappearance of monomer early in the

reaction far before the production of any polymer of sufficiently high molecular weight
(approximately >5000–10,000) to be of practical utility.
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The rate of a step polymerization is the sum of the rates of reaction between molecules
of various sizes, such as :
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Table 1
Lists some typical polycondensation reactions.
Accessibility of Functional Groups

In order for a polymerization to yield high polymers the polymer must not precipitate
from the reaction mixture before the desired molecular weight is reached. Premature
precipitation effectively removes the growing polymer molecules from the reaction;
further growth is prevented because the polymer’s functional end groups are no longer
accessible to each other. The effect can be seen in Table 2 for the polymerization of
bis(4-isocyanatophenyl)- methane with ethylene glycol:
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The inherent viscosity 𝜂𝑖𝑛ℎ is a measure of the polymer molecular weight. Larger values
of 𝜂𝑖𝑛ℎ indicate higher molecular weights. Early precipitation of the polyurethane
occurs in xylene and chlorobenzene and limits the polymerization to a low molecular
weight. Higher molecular weights are obtained when the solvent for the reaction
becomes a better solvent for the polymer. The highest polymer molecular weight is
obtained in DMSO (dimethylsulfoxide), a highly polar aprotic solvent, in which the
polyurethane is completely soluble during the entire course of the polymerization.
Table 2
Effect of Solvent on Molecular Weight in Polymerization of
Bis(4-isocyanatophenyl)methane with Ethylene Glycol a, b
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Kinetics of Step Polymerization
Consider the polyesterification of a diacid and a diol to illustrate the general form of the
kinetics of a typical step polymerization. Simple esterification is a well-known acid
catalyzed reaction and polyesterification follows the same course. The reaction involves
protonation of the carboxylic acid,
followed by reaction of the protonated species I with the alcohol to yield the ester
Polyesterifications, like many other step polymerizations, are equilibrium reactions.

However, to obtaining high yields of high-molecular-weight product such
polymerizations are run in a manner so as to continuously shift the equilibrium in the
direction of the polymer. In the case of a polysterification this is easily accomplished
by removal of the water that is a by-product of the reaction species II.
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The rate of a step polymerization is conveniently expressed in terms of the

concentrations of the reacting functional groups. The rate of polymerization Rp can then
𝒅 [ 𝑪𝑶𝑶𝑯]
be expressed as the rate of disappearance of carboxyl groups −
𝒅𝒕
− 𝒅 [𝑪𝑶𝑶𝑯] +
𝑹 = = 𝒌𝟑 [𝑪(𝑶𝑯)𝟐 ][𝑶𝑯] …𝟏
𝒅𝒕
+
where [COOH], [OH], and [𝐶 (𝑂𝐻)2 ] represent the concentrations of carboxyl,
hydroxyl, and protonated carboxyl (I) groups, respectively. The concentration terms are
in units of moles of the particular functional group per liter of solution.
+
𝒌𝟏 [𝑪(𝑶𝑯)𝟐 ]
𝑲= = …𝟐
𝒌𝟐 [𝑪𝑶𝑶𝑯][𝑯𝑨]
Combination of Eqs. 1 and 2 yields
− 𝒅[𝑪𝑶𝑶𝑯]
= 𝒌𝟑 𝑲[𝑪𝑶𝑶𝑯][𝑶𝑯][𝑯𝑨] …𝟑
𝒅𝒕
Two quite different kinetic situations arise from Eq.3 depending on the identity of HA,
that is, on whether a strong acid such as sulfuric acid or p-toluenesulfonic acid is added
as an external catalyst.
A. Self-Catalyzed Polymerization
In the absence of an externally added strong acid the diacid monomer acts as its own
catalyst for the esterification reaction. For this case [HA] is replaced by [COOH] and
Eq.3 can be written in the usual form
− 𝒅[𝑪𝑶𝑶𝑯]
= 𝒌[𝑪𝑶𝑶𝑯]𝟐[𝑶𝑯] … 𝟒
𝒅𝒕
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For most polymerizations the concentrations of the two functional groups are very
nearly equivalent, and Eq. 4 can be written as
𝒅[𝑴] 𝒅[𝑴]
− = 𝒌[𝑴]𝟑 … 𝟓 𝑜𝑟 − = 𝒌 𝒅𝒕 … 𝟔
𝒅𝒕 [𝑴]𝟑
where [M] is the concentration of hydroxyl groups or carboxyl groups. Integration of

Eq. 6 yields
𝟏 𝟏
𝟐𝒌𝒕 = – …𝟕
[𝑴]𝟐 [𝑴]𝟐𝟎
where [M]0 is the initial (at t = 0) concentration of hydroxyl or carboxyl groups.
The concentration [M] at time t of either hydroxyl or carboxyl groups is then given by
[𝑴] = [𝑴]𝟎 − [𝑴]𝟎 𝒑 = [𝑴]𝟎 (𝟏 − 𝒑) … 𝟖
Where Fraction of reaction p defined as the fraction of the hydroxyl or carboxyl

functional groups that has reacted at time t. p is also referred to as the extent or fraction
of conversion. (The value of p is calculated from a determination of the amount of
unreacted carboxyl groups.)
Combination of Eqs. 7 and 8 yields
𝟏
𝟐
= 𝟐[𝑴]𝟐𝟎 𝒌𝒕 + 𝟏 … 𝟗
(𝟏 − 𝒑 )
𝟏
Equation 9 indicates that a plot of (𝟏−𝒑) 𝟐
versus t should be linear. This behavior has
been generally observed in polyesterifications.
At first glance the plot does not appear to exactly follow the relationship. The
experimental points deviate from the third-order plot in the initial region below 80%
conversion and in the later stages above 93% conversion.
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Fig. 1
Third-order plot of the self-catalyzed polyesterification of adipic acid with diethylene
glycol at 166°C.
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Reasons for Nonlinearity in Third-Order Plot
a- Low-Conversion Region
The nonlinearity in the low conversion region attributed to the large changes that take
place in the reaction medium. The solvent for the reaction changes from an initial
mixture of carboxylic acid and alcohol to an ester. There is a large decrease in the
polarity of the reaction system as the polar alcohol and acid groups are replaced by the
less polar ester groups.
The direction of this change corresponds to that expected for a reaction involving a
charged substrate (protonated carboxyl) and neutral nucleophile (alcohol).
b- High-Conversion Region
The nonlinearity observed in the third-order plot in the final stages of the
polyesterification (Fig. 1) is probably due to the reaction system is fairly dilute and of
relatively low polarity.
Polyesterifications, like many step polymerizations, are carried out at moderate to high
temperatures not only to achieve fast reaction rates but also to aid in removal of the
small molecule by-product (often H2O). The polymerization is an equilibrium reaction
and the residue from each diol and each diacid (separately, not together) in the polymer
chain is termed a structural unit (or a monomer unit).
B. External Catalysis of Polymerization
The slow increase in molecular weight was mistakenly thought originally to be due to
the low reactivity of functional groups attached to large molecules.
The realization of this kinetic situation led to the achievement of high-molecular-weight

products in reasonable reaction times by employing small amounts of externally added
strong acids (such as sulfuric acid or p-toluenesulfonic acid) as catalysts. Under these
conditions, [HA] in Eq. 3 is the concentration of the catalyst. Since this remains constant
throughout the course of the polymerization, Eq. 3 can be written as
𝒅[𝑴]
− = 𝒌’ [𝑴]𝟐 … . 𝟏𝟏
𝒅𝒕
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Integration of Eq. 11 yields
𝟏 𝟏
𝑲’ 𝒕 = – … 𝟏𝟐
[𝑴] [𝑴]𝟎
Combining Eqs. 8 and 12 yields the dependence of the degree of polymerization on

reaction time as
𝟏
[𝑴]𝟎 𝒌’ 𝒕 = −𝟏 … 𝟏𝟑
𝟏−𝒑
The polymerization of diethylene glycol with adipic acid catalyzed by p-toluenesulfonic

acid are shown in Fig. 2. The plot follows Eq. 13 with the degree of polymerization
—
increasing linearly with reaction time. The much greater rate of increase of 𝑿𝒏 with
reaction time in the catalyzed polyesterification (Fig. 2) relative to the uncatalyzed
reaction (Fig. 1) is a general and most significant phenomenon. The polyesterification
becomes a much more economically feasible reaction when it is catalyzed by an external
acid. The self-catalyzed polymerization is not a useful reaction from the practical
viewpoint of producing high polymers in reasonable reaction times.
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Fig. 2
Polyesterification of adipic acid with diethylene glycol at 109°C catalyzed by 0.4

mol% p-toluenesulfonic acid
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Applications of step polymerization
1- Polyesters
2- Polycarbonates (PC)
Polycarbonates are polyesters, It has been synthesized by the reaction of the 2,2`-bis(4-
hydroxyphenyl)propane(bisphenol A) with phosgene or by ester interchange with
diphenyl carbonate
PC is commonly used for plastic lenses in eyewear, in medical devices, automotive

components, and Digital Disks (CDs, DVDs)
3- Polyamides
Polyamide is common in clothing and carpets and fishing line, electrical connectors.
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4- Phenolic Polymers
Phenolic polymers are obtained by the polymerization of phenol ( f ¼ 3) with

formaldehyde
The polymerization rate is pH-dependent, with the highest rates occurring at high and
low pH. The strong base-catalyzed polymerization yields resole prepolymers (resole
phenolics),
Crosslinking (curing) is carried out by heating at temperatures up to 180 °C. The

crosslinking process involves the same chemical reactions as for synthesizing the
prepolymer—the formation of methylene and ether bridges between benzene rings to
yield a network structure
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The strong acid-catalyzed polymerization yields novolac.
Curring occurs rapidly on heating with the formation of both methylene and
benzylamine crosslinking bridges between benzene rings
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5- Amino Plastics
The amino resins or plastics are obtained by the polymerization of formaldehyde with
urea or melamine
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6- Epoxy Resins
Epoxy resins or plastics are typically formed by the reaction of epichlorohydrin and
bisphenol A
A variety of amines are used as crosslinking agents
7- Polyurethanes
The synthesis of polyurethanes is usually presented as proceeding via the formation of

carbamate (urethane) linkages by the reaction of isocyanates and alcohols:
Water is often added in the production of flexible polyurethane foams. Isocyanate

groups react with water to form urea linkages in the polymer chain with the evolution
of carbon dioxide.
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8- Polysulfides
Polysulfide elastomers are produced by the reaction of an aliphatic dihalide, usually bis-
(2-chloroethyl)formal, with sodium polysulfide
Aircraft fuel tank sealants. Industrial tank liners. Corrosion protection of offshore
structures.
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LECTURE 2
2- Addition/ Chain growth Polymerization
Chain growth polymerization is also called addition polymerization and is

based on free radical, cationic and anionic reactions where a single initiating
species causes the growth of a polymer chain.
A. Cationic polymerization
B. Anionic polymerization
C. Free Radical Polymerization
Condations of addition/ Chain growth Polymerization

1- Only one monomer needed to start chain polymerization
2- The monomer shoud has duble bond
The kinetic chain reaction

Usually consists of at least three steps, namely:
(1) initiation,
compound I termed an initiator:
The reactive species, which may be a free radical, cation, or anion
(2) propagation,
Adds to a monomer molecule by opening the p-bond to form a new radical,
cation, or anion center, as the case may be. The process is repeated as many
more monomer molecules are successively added to continuously propagate
the reactive center.
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(3) termination
Polymer growth is terminated at some point by destruction of the reactive
center by an appropriate reaction depending on the type of reactive center
and the particular reaction conditions.
A. Cationic polymerization
The first species produced in cationic polymerizations are carbocations , by

using Lewis acids as initiators .Such as boron trifluoride and
aluminum chloride.
Lewis acids are not effective as initiators. A trace of a proton-containing

Lewis base, such as water, is also required. The Lewis base coordinates with
the electrophilic Lewis acid, and the proton is the actual initiator. Since
cations cannot exist alone, they are accompanied by a counterion, also called
a gegenion
Isobutylene (the first monomer to be polymerized commercially by ionic

initiators), vinyl ethers, and styrene have been polymerized by this technique.
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The initiation step
Propagation, or chain growth step

Propagation, or chain growth, takes place in a head-to-tail configuration as a
result of resonance stabilization and steric factors by carbocation (M+)
addition to another monomer molecule
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The termination step

Termination may also occur by chain transfer, where a proton is transferred to a
monomer molecule, leaving a cation which can serve as an initiator
Chain transfer to counterion, also called spontaneous termination, involves transfer of a

b-proton to the counterion
The rate of addition to aliphatic monomers is of the order of
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B. Anionic polymerization
Anionic polymerization is initiated by compounds that release anions in the reaction
mass. Cationic and anionic polymerization are very similar in nature
Initiation in Anionic Polymerization
A variety of basic (nucleophilic) initiators have been used to initiate anionic

polymerization. These include covalent or ionic metal amides such as NaNH2 and
LiN(C2H5)2, alkoxides, hydroxides, cyanides, phosphines, amines, and organometallic
compounds such as n-C4H9Li and fMgBr. Initiation involves the addition to monomer
of a nucleophile (base), either a neutral (B:) or negative (B:_) species. Alkyllithium
compounds are probably the most useful of these initiators, employed commerically in
the polymerizations of 1,3-butadiene and isoprene. Initiation proceeds by addition of
the metal alkyl to monomer.
Followed by propagation:
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Termination
1- Termination by Impurities.
Trace impurities lead to termination . Any moisture present terminates
propagating carbanions by proton transfer:
2- Spontaneous Termination
The mechanism for the decay of carbanions, referred to as spontaneous
termination
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C. Radical polymerization
Since many synthetic plastics and elastomers and some fibers are prepared by free
radical polymerization, free radical polymerization is a rapid reaction which consists of
the characteristic steps of initiation, propagation, and termination.
Free radical initiation can occur through application of heat (thermal), ultraviolet and
visible light (photochemical), ionizing light, redox reagents, electricity
(electrochemical), etc., i.e., any process that creates the essential free radicals. Thus,
diphenylketone decomposes on exposure of ultraviolet radiation of the appropriate
wavelength forming two free radicals
Radical polymerization kinetically, three steps ; initiation, propagation, and termination
Initiation
1- Primary radical generation
2. Combination of these primary radicals with a single monomer molecule
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Propagation step
The propagation reaction is defined as the addition of monomer molecules to the
growing polymer radicals.
Termination step
The termination reaction is the one in which polymer chain radicals are destroyed. This
can occur only when a polymer radical reacts with another polymer radical or with a
primary radical.
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LECTURE 3
3. Co-Polymerization
1- Step Co-Polymerization
A copolymer is defined in step polymerization as one having more than one kind of
repeating unit.
A polyester 5 prepared from terephthalic acid and ethylene glycol is a homopolymer,

but a polyester 6 made with a 1:1:2 mixture of terephthalic acid, isophthalic acid, and
ethylene glycol is a copolymer. In synthesizing copolymers such as 6, the distribution
of monomer units is random because the two dicarboxylic acids have virtually equal
reactivity.
A polymer has two different repeat units and is referred to as a copolymer, the process
by which it is synthesized is referred to as a copolymerization. Such as:
A Polymers with structures XXXIII and XXXIV, each containing a single repeat unit,
may be referred to as homopolymers to distinguish them from copolymers.
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Types of Copolymers
1-Random or statistical Copolymers
Random Copolymers in which there is an irregular (statistical) distribution of R and R=

groups as well as R - and R= - groups along the copolymer chain.
Method of Synthesis Random Copolymers:

The copolymerization of a mixture of monomers offers a route to statistical copolymers;
For instance, a copolymer of overall composition XXXV is synthesized by

copolymerizing a mixture of the four monomers
The overall composition of the copolymer obtained in a step polymerization will almost
always be the same as the composition of the monomer mixture since these reactions
are carried out to essentially 100% conversion (a necessity for obtaining high -
molecular-weight polymer). Further, for step copolymerizations of monomer mixtures
such as in Eq. 2-192 one often observes the formation of random copolymers. This
occurs either because there are no differences in the reactivities of the various monomers
or the polymerization proceeds under reaction conditions where there is extensive
interchange . Statistical copolymers containing repeating units each with a different
functional group can be obtained using appropriate mixture of monomers.
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2- Alternating Copolymers
Alternating Copolymers in which there is an alternate distribution of monomers
It is possible to synthesize an alternating copolymer by using a two-stage process. In the

first stage, a diamine is reacted with an excess of diacid to form a trimer
The trimer is then reacted with an equimolar amount of a second diamine in the second
stage.
Block Copolymers
where A and B represent two different repeating units. Different block copolymers are
distinguished by the number of blocks per molecule, for example
which are referred to as AB diblock, ABA triblock, ABAB tetrablock, and AB

multiblock copolymers, respectively. For the various block copolymers the values of m
and p as well as n are average values; thus, there is a distribution of block lengths and
number of blocks along the copolymer chain.
The specific type of copolymer is noted by insertng -alt-, or -ran- in between the names
of the two repeating units; -co- is used when the type of copolymer is not specified:
poly(A-co-B), poly(A-alt-B, poly(A-ran-B).
Block copolymers are named by inserting -block- in between the names of

the homopolymers corresponding to each of the blocks. The di-, tri-, tetra-,
and multiblock copolymers are named as polyA-block-polyB, PolyA-block-polyB-
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block-polyA, polyAblock-polyB-block-polyA-block-polyB, and poly(polyA-block-

polyB), respectively. Adoption in the literature of some of these IUPAC
recommendations for naming copolymers has been slow.
There are two general methods for synthesizing block copolymers

The two methods, referred to here as the one-prepolymer and two-prepolymer
methods, are described below for block copolymers containing different functional
groups in the two repeat units.
The two-prepolymer method involves the separate synthesis of two different

prepolymers, each containing appropriate end groups, followed by polymerization of
the two prepolymers via reaction of their end groups.
The one-prepolymer method involves one of the above prepolymers with two ‘‘small’’
reactants. The macrodiol is reacted with a diol and diisocyanate.
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Utility of Copolymerization
Copolymer synthesis offers the ability to alter the properties of a homopolymer in a
desired direction by the introduction of an appropriately chosen second repeating unit.
Copolymerization is used to alter such polymer properties as crystallinity, flexibility,

Tm, and Tg The crystallinity of statistical copolymers is lower than that of either of the
respective homopolymers (i.e., the homopolymers corresponding to the two different
repeating units) because of the decrease in structural regularity. The melting temperature
of any crystalline material formed is usually lower than that of either homopolymer. The
Tg value will be in between those for the two homopolymers. Alternating copolymers
have a regular structure, and their crystallinity may not be significantly affected unless
one of the repeating units contains rigid, bulky, or excessively flexible chain segments.
The Tm and Tg values of an alternating copolymer are in between the corresponding
values for the homopolymers. Block copolymers often show significantly different
behavior compared to alternating and statistical copolymers.
CHAIN COPOLYMERIZATION
Chain copolymerization is important from several considerations. Copolymerization is
also very important from the technological viewpoint. It greatly increases the ability of
the polymer scientist to tailor-make a polymer product with specifically desired
properties.
For example
Polystyrene is a brittle plastic with low impact strength and low solvent resistance
Copolymerization as well as blending greatly increase the usefulness of

polystyrene. Styrene copolymers and blends of copolymers are useful not only as
plastics but also as elastomers. Thus copolymerization of styrene with acrylonitrile leads
to increased impact and solvent resistance, while copolymerization with 1,3-butadiene
leads to elastomeric properties. Combinations of styrene, acrylonitrile, and 1,3-
butadiene improve all three properties simultaneously.
Types of Copolymers:
1-random copolymer
the two monomer units distributed randomly
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The two monomers enter into the copolymer in overall amounts determined by their
relative concentrations and reactivities. The simultaneous chain polymerization of
different monomers can also be carried out with mixtures of three or more monomers.
Such polymerizations are generally referred to as multicomponent copolymerizations;
the term terpolymerization is specifically used for systems of three monomers.
2- alternating copolymer
The alternating copolymer contains the two monomer units in equimolar amounts in a
regular alternating distribution:
3- Block copolymer
A block copolymer is a linear copolymer with one or more long uninterrupted sequences
of each polymeric species
4- Graft copolymer
Graft copolymer is a branched copolymer with a backbone of one monomer to which

are attached one or more side chains of another monomer
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COPOLYMER COMPOSITION
Copolymerization of the two monomers leads to two types of propagating
species—one with M1 at the propagating end and the other with M2. These can be
represented by M1* and M2* where the asterisk represents either a radical, a
carbocation, or a carbanion as the propagating species depending on the particular case.
If it is assumed that the reactivity of the propagating species is dependent only on the
monomer unit at the end of the chain (referred to as the end or ultimate unit), four
propagation reactions
are then possible. Monomers M1 and M2 can each add either to a propagating chain
ending in M1 or to one ending in M2, that is,
where k11 is the rate constant for a propagating chain ending in M1 adding to monomer
M1, k12 that for a propagating chain ending in M1 adding to monomer M2.
The propagation of a reactive center by addition of the same monomer (i.e., Reactions
6-2 and 6-5) is often referred to as homopropagation or self-propagation; propagation
of a reactive center by addition of the other monomer (Reactions 6-3 and 6-4) is referred
to as crosspropagation or a crossover reaction. All propagation reactions are assumed to
be irreversible. Monomer M1 disappears by Reactions 6-2 and 6-4, while monomer M2
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disappears by Reactions 6-3 and 6-5. The rates of disappearance of the two monomers,
which are synonymous with their rates of entry into the copolymer, are given by
In order to remove the concentration terms in M1* and M2 * from Eq. 6-8, a steady-
state concentration is assumed for each of the reactive species M1* and M2* separately.
For the concentrations of M1* and M2* remain constant, their rates of must be equal.
In other words, the rates of Reactions 6-3 and 6-4 must be equal:
Equation 6-12 is known as the copolymerization equation or the copolymer composition

equation.
The copolymer composition, d[M1]/d[M2] , is the molar ratio of the two monomer units
in the copolymer. d[M1] / d[M2] is expressed by Eq. 6-12 as being related to the
concentrations of the two monomers in the feed, [M1] and [M2], and the parameters r1
and r2.
The parameters r1 and r2 are termed the monomer reactivity ratios. Each r as defined
above in Eq. 6-11 is the ratio of the rate constant for a reactive propagating species
adding tis own type of monomer to the rate constant for its additon of the other
monomer.
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Types of Copolymerization Behavior

Different types of copolymerization behavior are observed depending on the values of
the monomer reactivity ratios. Copolymerizations can be classified into three types
based on whether the product of the two monomer reactivity ratios r1r2 is unity, less
than unity, or greater than unity
1- Ideal Copolymerization: r1 r2 = 1
A copolymerization is termed ideal when the r1r2 product is unity. Ideal
copolymerization occurs when the two types of propagating species M1* and M2* show
the same preference for adding one or the other of the two monomers. Under these
conditions
When r1 = r2 = 1, the two monomers show equal reactivities toward both propagating
species. The copolymer composition is the same as the comonomer feed with a random
placement of the two monomers along the copolymer chain.
Such behavior is referred to as random or . For the case where the two monomer
reactivity ratios are different, that is, r1 > 1 and r2 < 1 or r1 < 1 and r2 > 1, one of the
monomers is more reactive than the other toward both propagating species. The
copolymer will contain a larger proportion of the more reactive monomer in random
placement. Figure 6-1 shows the variation in the copolymer composition as a function
of the comonomer feed composition for different values of r1. The term ideal The
copolymer is richer in M1 when r1 > 1 and is poorer in M1 when r1 < 1. One can
distinguish between extreme and moderate ideal behavior depending on the difference
between r1 and r2. Extreme ideal behavior occurs when r1 and r2 are very different
(e.g., 10 and 0.1). Moderate ideal behavior occurs when r1 and r2 are not too different,
(e.g., 0.5 and 2). The term ideal copolymerization does not in any sense connote a
desirable process. An important consequence of ideal copolymerizations is that it
becomes progressively more difficult to produce copolymers containing appreciable
amounts of both monomers as the difference in r1 and r2 increases, that is, as one
progresses from moderate to extreme ideal behavior. When, for example, r1 = 10 and
r2= 0.1, copolymers containing appreciable amounts of M2 cannot be obtained.
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2- Alternating Copolymerization: r1r 2 = 0

Alternating copolymerization is characterized by r1r2 = 0, where neither r1 nor r2 is
greater than one. As with ideal behavior, there are two types of alternating behavior—
extreme and moderate alternating behavior. Both r1 and r2 are zero in extreme
alternating behavior.
Each of the two types of propagating species preferentially adds the other monomer,
that is, M1* adds only M2 and M2* adds only M1.
Moderate alternating behavior occurs when

(1) both r1 and r2 are small (r1r2 = very small , close to 0)
(2) one r value is small and the other r is zero (r1r2 =0).
The copolymer composition tends toward alternation but is not the perfectly alternating
structure I . As the r1r2 product decreases from one toward zero, there is an
increasing tendency toward alternation. Perfect alternation occurs when r1
and r2 are both zero.
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The tendency toward alternation and the tendency away from ideal behavior increases
as r1 and r2 become progressivley less than unity. The range of behaviors can be seen
by considering the situation where r2 remains constant at 0.5 and r1 varies between 2
and 0.
Figure 6-2 shows the copolymer composition as a function of the feed composition in
these cases. The curve for r1 = 2 shows the ideal type of behavior described previously.
As r1 decreases below 2, there is an increasing tendency toward the alternating behavior
with each type of propagating species preferring to add the other monomer .The
increasing alternation tendency is measured by the tendency of the product r1r2 to
approach zero.
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3- Block Copolymerization: r 1 > 1; r 2 > 1

If both r1 and r2 are greater than unity (and therefore, also r1r2 > 1) there is a tendency
to form a block copolymer in which there are blocks of both monomers in the chain.
This type of behavior is rarely encountered.
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LECTURE 4
4- Ring-Opening Polymerization (ROP)
The ring-opening polymerization (ROP) of cyclic monomers such as cyclic ethers,

acetals, amides (lactams), esters (lactones), and siloxanes. Ring-opening polymerization
is of commercial interest in a number of systems, including the polymerizations of
ethylene oxide, trioxane, E-caprolactam and octamethylcyclotetrasiloxane.
Whether cyclization is competitive with linear polymerization for a particular reactant

or pair of reactants depends on thermodynamic and kinetic considerations of the size of
the ring structure that may be formed.
The thermodynamics stability of different sized ring structures. Some of the most
useful data on the effect of ring size on thermodynamic stability is that on the heats of
combustion of cycloalkanes (Table 2-7) (1 kJ = 0.2388 kcal). A comparison of the heats
of combustion per methylene group in these ring compounds with that in an open-chain
alkane yields a general measure of the thermodynamic stabilities of different-sized
rings. More precisely, thermodynamic stability decreases with increasing strain in
the ring structure as measured by the differences in the heats of combustion per
methylene group of the cycloalkane and the n-alkane. The strain in cyclic structures
is very high for the 3- and 4-membered rings, decreases sharply for 5-, 6-, and 7-
membered rings, increases for 8–13-membered rings, and then decreases again for
larger rings.
The general order of thermodynamic stability of different-sized rings is given by:

3, 4 << 5, 7–13 < 6, 14 and larger.
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Polymerization Mechanism and Kinetics

Ring-opening polymerizations are generally initiated by the same types of ionic
initiators.
Ring-opening polymerization (ROP) is a chain polymerization, consisting of a sequence

of initiation, propagation, and termination. Only monomer adds to the growing chains
in propagation.
Most cationic ring-opening polymerizations involve the formation and propagation of

oxonium ion centers. Reaction involves the nucleophilic attack of monomer on the
oxonium ion:
The typical anionic ring-opening polymerization involves the formation and

propagation of anionic centers. Reaction proceeds by nucleophilic attack of the
propagating anion on monomer:
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CYCLIC ETHERS
Cyclic ethers can be named simply as oxacycloalkanes, such as oxacyclopropane,
oxacyclobutane, oxacyclopentane, and oxacyclohexane, where the prefix oxa indicates
the replacement of CH2 by O in corresponding cycloalkanes. Most cyclic ethers,
however, are known by other names.
The 3-, 4-, 5-, and 6-membered rings are oxirane, oxetane, oxolane, and oxane,
respectively, or ethylene oxide (or epoxide), trimethylene oxide, tetrahydrofuran, and
tetrahydropyran.
The carbon–oxygen bond in ethers is a strong bond, and the ether oxygen is basic in the
Lewis sense.
The result is that ring-opening polymerization of cyclic ethers is generally initiated only
by cationic species except for epoxides. Epoxides are polymerized by both anionic and
cationic initiators because of the high degree of strain in the 3-membered ring .
The polymerization of simple cyclic ethers (i.e., those with a single ether linkage) has
been generally limited to those of 3, 4 and 5 members
Cyclic ethers of less than 5 members or more than 6 members are relatively easily
polymerized.
The 5-memebered cyclic ethers polymerize with more difficulty.

Substituted 5-membered cyclic ethers are usually unreactive.
The 6-membered cyclic ethers such as tetrahydropyran (III) and 1,4-dioxane (IV) are
unreactive under a wide range of reaction conditions, but the 6-membered cyclic acetal,
trioxane (V), undergoes polymerization.
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Anionic Polymerization of Epoxides

The anionic polymerization of epoxides such as ethylene and propylene oxides can be
initiated by metal hydroxides, alkoxides, oxides, and amides
Thus the polymerization of ethylene oxide by M+A-involves initiation
followed by propagation
Cationic Polymerization
The polymerization of 3,3-bis(chloromethyl) oxetane (R = CH2Cl)
A variety of initiator systems, of the types used in the cationic polymerization of alkenes
can be used to generate the tertiary oxonium ion–propagating species . Strong protonic
acids such as trifluoroacetic, fluorosulfonic, and trifluoromethanesulfonic (triflic) acids
initiate polymerization via the initial formation of a secondary oxonium ion
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Cyclic Acetals
A variety of cyclic acetals undergo facile cationic polymerization
This includes various 1,3-dioxacycloalkanes such as 1,3-dioxolane (m = 2), 1,3-

dioxepane (m =4), and 1,3-dioxocane (m = 5)
LACTAMS
Anionic initiation is also practiced, especially polymerization in molds to directly

produce objects from monomer. Cationic initiation is not useful because the conversions
and polymer molecular weights are considerably lower
Nylon 6, Nylons 11 and 12 are specialty polyamides.
LACTONES
Lactones (cyclic esters) undergo anionic and cationic polymerization to form polyesters
Sulfur heterocyclics
The 3- and 4-membered cyclic sulfides are easily polymerized by both cationic and
anionic initiators, such as
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CYCLOALKENES
Cycloalkenes undergo ring-opening polymerization in the presence of coordination

initiators, based on transition metals to yield polymers containing a double bond, for
instance, cyclopentene yields polypentenamer.
Coordination Polymerization
The coordination polymerization is invented by two Italian scientists: Karl Ziegler and
Giulio Natta. They shared the nobel prize in chemistry in 1963 using Ziegler–Natta
catalysts to polymerize nonpolar monomers: 1-alkene, cycloalkenes, dienes, and
alkynes through coordination mechanism instead of common chain or step
polymerization.
The polymers can exhibit stereo specificity if the monomer contains unsymmetrical
carbon atom.
Both heterogeneous and homogeneous Ziegler–Natta catalysts have been developed.

The heterogeneous catalysts consist of transition metal compound (e.g., titanium
chloride) and organometallic compounds (e.g., aluminum alkyl halide) as cocatalyst.
The homogeneous catalystsare made from transition metal metallocene and aluminum
alkyl halide.
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Reaction Mechanisms
The polymer chain grows from the catalyst surface by successive insertion reactions of
complexed monomer and the R group originally present in the organometallic cocatalyst
ends up as the terminal group of the chain.
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Monomer activity decreases with increasing steric hindrance about the double bond as
shown below:
Tacticity
If the R groups on successive stereocenters are randomly distributed on the two sides of
the planar zigzag polymer chain, the polymer does not have order and is termed atactic.
An isotactic structure occurs when the stereocenter in each repeating unit in the polymer
chain has the same configuration
All the R groups will be located on one side of the plane of the carbon–carbon polymer
chain—either all above or all below the plane of the chain.
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A syndiotactic polymer structure occurs when the configurations of the stereocenters

alternate from one repeating unit to the next with the R groups located alternately on
the opposite sides of the plane of the polymer chain.
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LECTURE 5
Polymerization techniques
Processes for Chain-Growth Polymerization
1. Solution Polymerization: is a method of industrial polymerization. In this

procedure, a monomer is dissolved in a non-reactive solvent that contains
a catalyst or initiator.
The reaction results in a polymer which is also soluble in the chosen solvent.
Polymerization of a monomer in a solvent. The solvent acts as diluent and aids in the
transfer of the heat of polymerization. The solvent also allows easier stirring.
For polymerization in solution good solvents have to be used to dissolve the monomer
and also the polymer formed. The solvent should be chemically inert and easy to recover
after polymerization. The advantage of polymerization in solution is the lower viscosity
of reaction mixture.
Vinyl acetate, acrylonitrile, and esters of acrylic acid, 1,4-cis-polybutadiene and

polystyrene and high density Polyethylene (HDPE) are polymerized in solution. The
polymer produced is characterized by relatively low molecular weight and narrow
molecular weight distribution.
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Figure : Solution polymerization of ethylene, using Ziegler-Natta catalysts. Gaseous ethylene is

pumped under pressure into a reactor vessel, where it polymerizes under the influence of a Ziegler -
Natta catalyst in the presence of a solvent.
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2. Suspension Polymerization: is a water-cooled bulk polymerization. Liquid

monomer with dissolved initiator is dispersed in water by vigorous stirring.
The droplets formed are transformed during polymerization into sticky, highly viscous
particles, which become rigid and have diameters in the range of 100 to 1000µm.
Suspension polymerization is applied in industry for production of poly(vinyl chloride),

expandable polystyrene, and high impact polystyrene. The major process for poly(vinyl
chloride) production is suspension polymerization .
The size of the particles formed is affected by the physical properties of the
monomer/water emulsion (surface tension, viscosities, densities), by the polymerization
conditions (stirring speed, temperature, concentration of chemicals), and by the
geometries of the reactor and stirrer used.
Figure : Suspension polymerization vessel
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3. Emulsion Polymerization: refers to a unique process employed for some radical

chain polymerizations. It involves the polymerization of monomers in the form of
emulsions (i.e., colloidal dispersions).
Emulsion polymerization is presently the predominant process for the commercial

polymerizations of vinyl acetate, chloroprene, various acrylate copolymerizations, and
copolymerizations of butadiene with styrene and acrylonitrile. It is also used for
methacrylates, vinyl chloride, acrylamide, and some fluorinated ethylenes.
Emulsion polymerization is a unique process in that it affords the means of increasing

the polymer molecular weight without decreasing the polymerization rate.
The advantages of emulsion polymerization are:
▪ Low viscosity of the reaction mixture during the polymerization.

▪ Polymers with high molecular weight are formed at high rates of polymerization.
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4. Bulk or mass polymerizations: is carried out by usinng pure monomer in liquid

state. The catalyst should dissolve in the monomer. The reaction is initiated by heating
or exposing to radiation. As the reaction proceeds the mixture becomes more viscous.
Bulk polymerization is carried out in the absence of any solvent or dispersant and is thus
the simplest in terms of formulation.
Bulk or mass polymerizations is the simplest process for step polymerizations. This is
often used to synthesize cross-linked and thermosetting polymers such as Phenolic
resins are polycondensation products of phenol and formaldehyde.
And it is used for many types of chain-growth polymers such as , for ethylene, styrene,
methyl methacrylate.
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5. Interfacial Polymerization : is a type of step-growth polymerization in

which polymerization occurs at the interface between two immiscible phases
(generally two liquids), resulting in a polymer that is constrained to the interface.
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Solution Polymerization
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Polymer Architecture
In terms of their architecture, polymers can be classified as linear, branched and cross-
linked polymers (Table 1). In the linear polymers, the structural units are arranged in a
linear sequence. Branched polymers may have short and long branches. Branched
polymers include comblike and star polymers. Extensive branching may lead to a
dendritic structure.
Table 1 polymer architectures
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Dr.

Hikmat Al-Hajaj Polymer Reaction Engineering 4th Stage

Classification of Polymerization Reaction

1- Step – growth (condensation) polymerization

The synthesis of polyamides (nylons) illustrates both groups of polymerization

Or from the reaction of amino acids with themselves:

Condations of Step – growth (condensation) polymerization

Or on two separate molecules, as in the reaction between ethylene glycol, 𝐻𝑂 −

3- Some polymerization process accompanies the release of secondary molecules such

4- The moles of reactants should be equal.

Reactivity of Functional Groups

Kinetic analysis is greatly simplifies if one assumes that:

2- the reactivity of one functional group of a bifunctional reactant is the same

3- the reactivity of a functional group is independent of the size of the molecule to

These simplifying assumptions, often referred to as the concept of equal reactivity of

Step polymerizations are characterized by the disappearance of monomer early in the

Accessibility of Functional Groups

Kinetics of Step Polymerization

Polyesterifications, like many other step polymerizations, are equilibrium reactions.

The rate of a step polymerization is conveniently expressed in terms of the

Combination of Eqs. 1 and 2 yields

where [M] is the concentration of hydroxyl groups or carboxyl groups. Integration of

where [M]0 is the initial (at t = 0) concentration of hydroxyl or carboxyl groups.

[𝑴] = [𝑴]𝟎 − [𝑴]𝟎 𝒑 = [𝑴]𝟎 (𝟏 − 𝒑) … 𝟖

Where Fraction of reaction p defined as the fraction of the hydroxyl or carboxyl

Combination of Eqs. 7 and 8 yields

Reasons for Nonlinearity in Third-Order Plot

B. External Catalysis of Polymerization

The realization of this kinetic situation led to the achievement of high-molecular-weight

Integration of Eq. 11 yields

Combining Eqs. 8 and 12 yields the dependence of the degree of polymerization on

The polymerization of diethylene glycol with adipic acid catalyzed by p-toluenesulfonic

Polyesterification of adipic acid with diethylene glycol at 109°C catalyzed by 0.4

Applications of step polymerization

PC is commonly used for plastic lenses in eyewear, in medical devices, automotive

Phenolic polymers are obtained by the polymerization of phenol ( f ¼ 3) with

Crosslinking (curing) is carried out by heating at temperatures up to 180 °C. The

The strong acid-catalyzed polymerization yields novolac.

A variety of amines are used as crosslinking agents

The synthesis of polyurethanes is usually presented as proceeding via the formation of

Water is often added in the production of flexible polyurethane foams. Isocyanate

Chain growth polymerization is also called addition polymerization and is

Condations of addition/ Chain growth Polymerization

The kinetic chain reaction

The first species produced in cationic polymerizations are carbocations , by

Lewis acids are not effective as initiators. A trace of a proton-containing

Isobutylene (the first monomer to be polymerized commercially by ionic

The initiation step

Propagation, or chain growth step

The termination step

Chain transfer to counterion, also called spontaneous termination, involves transfer of a

The rate of addition to aliphatic monomers is of the order of

Initiation in Anionic Polymerization

A variety of basic (nucleophilic) initiators have been used to initiate anionic

Radical polymerization kinetically, three steps ; initiation, propagation, and termination

2. Combination of these primary radicals with a single monomer molecule

A polyester 5 prepared from terephthalic acid and ethylene glycol is a homopolymer,

Random Copolymers in which there is an irregular (statistical) distribution of R and R=