2.

Condensation (Step-Growth) Polymerization

1
 2. Step-Growth Polymerization
• Condensation (Step-Growth) polymerizations, or simply step
polymerizations, are merely classical organic reactions that are used
to produce linear macromolecules starting from bifunctional
monomers or to produce polymer networks from mixtures of
bifunctional and multifunctional monomers having three or more
functional groups per molecule.
• The polymerization of bifunctional monomers may be described as a
stepwise or progressive conversion of monomers with two reactive
end groups to higher molecular-weight homologues, which
themselves retain two reactive end groups. It may take place either by
a polycondensation reaction, whereby a low-molecular-weight by-
product is formed along with the polymer, as is exemplified by
polyesterification.

2
 Cont…
 Step polymerization can therefore be expressed by the general reaction :
where n and m can have any value from 1 to very large number.
 Polyesterification reaction mixture of diacid and diol at any instance will
consist of various-sized diol, diacid, and hydroxyl acid molecules.

 Polyamidation and polyurethane-forming reactions can be written as

3
 Cont…
• Polymers such as polyamides, poly(ethylene terephthalate),
polycarbonates, polyurethanes, polysiloxanes, polyimides, phenol
polymers and resins, urea, and melamine- formaldehyde polymers can
be obtained by step-growth polymerization through different types of
reactions such as esterification, polyamidation, formylation,
substitution, and hydrolysis.
• Step polymerization reactions are always accompanied by elimination
of small groups.
• The poly condensation is brought about by monomers containing two
or more reactive functional groups such as hydroxyl, carboxyl and
amino groups condensing with each other.
• The mechanism of step-growth polymers is simply an extension of the
normal organic condensation reactions in which a small molecule i.e.
H2O or HCl are eliminated.

4
 2.1 Condensation Polymers
In Step polymerization or poly condensation proceed:
• The presence of two reactive functional groups in the monomer
• with step-wise condensation reaction between reactive functional
groups.
• only one type of reaction between two functional groups in the
polymerization.
• The polymer formed still contains both the reactive functional group
at its chain ends (as end groups) and hence is active and not dead.

5
 Features of step-growth polymerization
1. The group of polymer molecules proceeds by a stepwise
intermolecular reaction only and only one reaction type in involved in
the polymerization.
2. Monomer units can react with each other or polymers of any size.
3. The functional group at the end of a monomer is usually assumed to
have the same reactivity as that on a polymer of any size.
4. A high conversion of functional groups is required in order to produce
high-molecular mass product.
5. Many step-growth polymerization reactions are reversible.
6. Condensation polymerization is usually produced by step-growth
polymerization but not all step-growth polymerization are condensation
reactions. There is no elimination product in polyurethane synthesis from
a diol and di-isocyanate.

6
 Cont…
• A step-growth polymerization reaction between bi-functional or
multifunctional monomers in which a high-molecular-weight polymer
is formed after a large number of steps. Many naturally and synthetic
polymers are produced by step-growth polymerization including
polyesters, polyethers, urethanes, epoxies, and polyamides.
• Examples of Step-Growth polymerization:

7
 Cont…
• The reaction of dicarboxylic acids with diamines to form polyamides
(Nylon) and the reaction of organic diacids with alcohols to form
polyesters, like polyethylene terephthalate (PET) are examples of
step-growth.
• Due to the nature of the polymerization mechanism, the reaction has
to proceed for a long time to achieve high molecular weight polymers.
• The mechanism is generally referred to as AAC2 (Acidcatalyzed, acyl-
oxygen cleavage, bimolecular).

8
 Comparison of Chain- and Step Polymerization Mechanisms
Step Polymerizations
• Any two molecular species can react.
• Monomer disappears early.
• Polymer MW rises throughout.
• Growth of chains is usually slow
(minutes to days).
• Long reaction times increase MW, but
yield of polymer hardly changes.
• All molecular species are present
throughout.
• Usually (but not always) polymer repeat
unit has Fewer atoms than had the
monomer.
• Growth occurs only by addition of monomer
to active chain end.
• Monomer is present throughout, but its
concentration decreases.
• Polymer begins to form immediately.
• Chain growth is usually very rapid (second to
microseconds).
• MW and yield depend on mechanism details.
• Only monomer and polymer are present
during reaction.
• Usually (but not always) polymer repeat unit
has the same atoms as had the monomer
9
 2.2 Kinetics of Step - Growth Polymerization
• Step-growth polymerizations are condensation reactions that usually
occur in equilibrium, a fact that intrinsically leads to a high degree of
reversibility.
• For example polyester and polyamide formation, the value of the rate
constant, k, can be considered independent of the polymer chain
length, which is equivalent to assuming that the polymerization
mechanism is the same throughout the entire reaction. The reaction is
assumed first order.
A + B + calayst --------------------- -AB- + catalyst.
Rate=[A] [B] [catalyst]
• In etherification reaction acid (H+) is the catalyst and if the
stoichiometry of the functional group A‘ and B‘ is assumed, [A] =[B]
Rate= -𝑑(𝐴)/dt = 𝑘[𝐴]2[𝐻+]

10
 Cont…
• The rate of a step polymerization is most conveniently expressed in
terms of the rate of disappearance of the reacting functional groups.
Thus, the rate of polyesterification, Rp, can be expressed as the rate of
disappearance of carboxyl groups.

where [COOH] represents the concentration of unreacted carboxyl

groups. The progress of a polyesterification reaction can thus be
followed experimentally by titrating the unreacted carboxyl groups with
a base during the reaction.

11
 2.2.1. Step-Reaction Polymerization - Kinetics
Step-Reaction Polymerization

12
Cont…

13
Rate of polymerization

14
Rate of Polymerization

15
Degree of polymerization

Acid-catalyzed condensation of ethylene

glycol with terephthalic acid producing PET.

16
 2.2.2. Stoichiometric Imbalance
Carothers developed a simple method of analysis for predicting the molar mass of
polymers prepared by step polymerization. He recognized that the number-average
degree of polymerization with respect to monomer units is given by the relation.

where N0 is the number of molecules present initially

N is the number of molecules remaining after a time t of polymerization
Assuming that there are equal numbers of mutually-reactive functional groups, can be
related to the extent of reaction p at time t which is given by

• Applicable to stoichiometric balance in the numbers of mutually-reactive functional

groups and highlight high extent of polymerization. 17
 Cont…

Slight stoichiometric imbalances significantly limit the attainable values

of x¯n . Consider a RA2+RB2 polymerization in which RB2 is present in
excess. The ratio of the numbers of the two different types of functional
group (A and B) present initially is known as the reactant ratio r, and for
linear step polymerization is always defined so that it is less than or
equal to one. Thus for the reaction under consideration.

18
 Cont…

where NA and NB are, respectively, the numbers of A and B functional groups present
initially. Since there are two functional groups per molecule.
substitution for NA

It is common practice to define the extent of reaction p in terms of the functional

groups present in minority (i.e. A groups in this case). On this basis

Substitution of Equations 3.5 and 3.6 into Equation 3.1 yields the more general Carothers
equation.

19
 Cont…
Equation 3.3 is the special case for r=1. X- = 1/1-p
Table 3.3 gives values of x¯n calculated using Equation 3.7 and reveals the dramatic
reduction in x¯n when r is less than unity.
Thus only very slight stoichiometric imbalances can be tolerated if useful polymers are
to be formed, the corollary of which is that r must be controlled with great accuracy. It
is now absolutely clear that, in order to control r with the necessary precision, the
monomers used in linear step polymerizations must be of very high purity and that the
linking reactions must be clean.

20
 Cont…
• Assuming these criteria are satisfied, Equation 3.7 can be used to exert
control of molar mass by using slight imbalances in stoichiometry to
place an upper limit on x¯n for reactions taken to very high
conversions of functional groups.
• Equation 3.7 also is applicable to reactions in which a monofunctional
compound is included to control x¯n, e.g. RA2+RB2+RB or ARB+RB. All
that is required is to re-define the reactant ratio

• where NA and NB are, respectively, the initial numbers of A and B

functional groups from the difunctional monomer(s) NRB is the
number of molecules of RB present initially.

21
 Extent of reaction and degree of polymerization
•To produce a relatively high-molecular-weight polymer (Xn > 100), it
is necessary to allow the reaction to proceed to a very high degree of
conversion p > 0.98 or, in other words, to a product that contains a
very small number of chain ends.

22
 Limiting step-polymerization

•These are polyethers that are processed to an oligomer stage and are subsequently
converted to network polymer by appropriate reactions of terminal epoxyide groups.
•With polyimides for fiber applications, molecular weight must often be limited
because too high a viscosity is detrimental to extrusion of filaments through the
fine holes of a spinneret.

Three ways to limit M. W. in step polymerization

23
 2.2.3. Network Step-Polymerization : Theory of Gelation
•If monomers containing a functionality greater than two are used in
step polymerization, chain branching results.
•If the reaction is carried to a high enough conversion, gelation occurs.
•The onset of gelation, or gel point, is accompanied by a sudden
increase in viscosity such that the polymer undergoes an almost
instantaneous change from a liquid to a gel.

24
Cont…

25
Step-Reaction Copolymerization

26
Step Polymerization Techniques

27
Cont…

28
Step Polymerization Techniques

29
Step Polymerization Techniques

30
Step Polymerization Techniques

31
Dendritic Polymers

32
Dendritic Polymers

33
Dendritic Polymers

34
Dendritic Polymers

35
Dendritic Polymers

36
Dendritic Polymers

37
Dendritic Polymers

38
 Carbonyl Addition-Elimination Step Polymerization : I. Polyester
Mechanism : Structure-property relationships:

I. Polyester
Synthesis :
 Carbonyl Addition-Elimination Step Polymerization : I. Polyester
I. Polyester
Other commercially important polyester:
PBT

PEN

PET
 Carbonyl Addition-Elimination Step Polymerization
II. Polycarbonates

III. Polyamides
 Carbonyl Addition-Elimination Step Polymerization
IV. Polyimide
 Aromatic Addition-Elimination Polymerization
This reaction is analogous to carbonyl addition-elimination, in that it
Mechanism : is a two step process where the negative charge is accomodated by an
electron withdrawing group. To emphasize the simularity, this example
uses a ketone:

Monomers : Bisphenols are most often used as the nucleophillic components. The chemistry begins when
a base like NaOH or K2CO3 deprotonatea the bisphenol, as in this example for Bisphenol A:
 Aromatic Addition-Elimination Polymerization

I. Poly(etheretherketone), ‘’PEEK’’

The most common form of PEEK is the one shown, derived from Bisphenol A. This polymer is a
remarkable material, highly crystalline, thermally stable, resistant to many chemicals, very tough. It
can be melt-processed at very high temperatures (>300 °C), and is useful for special applications like
pipes in oil refineries and chemical plants, and parts for aerospace, where high price is not a
limitation.
 Aromatic Addition-Elimination Polymerization

II. Polysulfone, ‘’PSF’’

Like polycarbonate, many other polysulfones could be synthesized, but the particular one shown here is
by far the most common commercially, so that the general term "polysulfone" usually refers to this
particular one. Worse, it is seldom called "poly(etherethersulfone)," despite its close structural similarity
to PEEK
Unlike PEEK, poly(etherethersulfone) is completely amorphous, probably a result of the relatively
large size of the sulfonyl group, and the kink in the polymer backbone caused by the narrow C-S-C
bond angle (close to 100°). Therefore, it can be processed at lower temperature than PEEK, but the
material is not as resistant to heat and chemicals.
 Carbonyl Addition-Condensation Polymerization

III. Phenol-Formaldehyde Polymers IV. Polymeric Heterocycles

 Carbonyl Addition-Condensation Polymerization

•The phenol-formaldehyde polymers are the oldest commercial synthetic polymers, first introduced around
100 years ago. Their inventor, Leo Bakeland, had no idea what was happening in his reaction kettles, but he
was able to work out conditions to produce a tough, light, rigid, chemically resistant solid from two
inexpensive ingredients. He soon became a rich man, in the same class as the famous industrialists of the
time like Alfred Nobel, Henry Ford, Andrew Carnegie, George Eastman, etc.
•The actual chemistry is complicated, and still not completely understood. The polymers are usually
thermosetting (i.e., crosslinked), and their insolubility limits the analytical techniques that can be brought to
bear. The main reaction is the production of methylene bridges between aromatic rings, as shown below.
Many side reactions also occur, and some of these give phenol-formaldehyde polymer its dark color.
•Of course, these crosslinked polymers cannot be melted or dissolved, so their synthesis must be conducted
in molds for the actual product. In practice, the polymerization is usually carried out to somewhere below
the gel point in a separate reactor, and then the "pre-polymer" is transferred to the mold, where the reaction
is completed.
Urea or melamine can be substituted for phenol. Methylene bridges can also be formed between the nitrogen
atoms, giving rise to chemical relatives of the phenol-formaldehyde polymers. The urea and melamine based
materials have much less color, and so are useful for decorative applications such as dinner plates and
countertop materials (FormicaTM).
 Addition to Multiple Bonds or Epoxides

Mechanism :

The urethane linkage (often called carbamate) is usually made by adding an OH across the
C=N of an isocyanate.
The reaction is catalyzed by bases such as tertiary amines or by certain tin salts.

I. Polyurethanes Polyurethanes are synthesized by the reaction of diols with diisocyanates:

Many different polyurethanes have been synthesized, giving rise to materials with widely varying
properties. For example, rubbery polyurethanes are used for Spandex fiber and for seat cushions in
furniture and cars, while hard polyurethanes are used for wheels on roller skates, for bowling balls, and for
paints and varnishes. The hydrogen bonds between the NH and CO groups provide toughness to the
polymers.
 Addition to Multiple Bonds or Epoxides
II. Epoxy Polymers
These polymers are best known as two component thermosetting adhesives, although linear polymers
can be prepared. The term "epoxy" polymers is something of a misnomer, because the epoxy groups are in
the monomer, not in the polymer. To form the actual polymer, one reacts a multifunctional epoxide with a
multifunctional nucleophile. Epoxy monomers based on Bisphenol A are by far the most common
substrates, although others can be used. The nucleophiles are most often amines or phenoxides. The
number of reactive functional groups on the components governs whether the polymer is linear or cross-
linked.

Epoxy Adhesive Chemistry

The resulting network will not dissolve in any solvents,
and resists all but the strongest chemical reagents.
 Addition to Multiple Bonds or Epoxides

Other Epoxy Polymer

The polarity of OH groups provides hydrogen

bonding, useful for adhesion to polar surfaces
like glass, wood, etc. Epoxy polymers are often
used to form composite structures filled with
glass or carbon fiber.