TOPIC:

CONDENSATION OR
STEP-GROWTH POLYMERIZATION

1
 Some definitions
Polymer
long chain molecule made from lots of small molecules joined together

Monomer
small molecules that join together in polymerisation

Addition Polymerisation
formation of long chain molecules from lots of small molecules
joining together – with no other product

Condensation Polymerisation
formation of long chain molecules from lots of small molecules
joining together – with a small molecule (e.g. water) released
 Condensation polymers

• Condensation polymers are polymers formed

from condensation reactions between monomers.
A small molecule (often water) is produced as
well as the polymer.
• Many natural polymers are condensation
polymers, e.g. silk, starch and DNA.
• The two main types are polyesters and
polyamides.
Comparing addition and condensation polymerisation

Identifying types of polymerisation

 For addition polymerisation, look out for:
 monomer has a double bond
 polymer backbone is continuous chain of C atoms

 For condensation polymerisation, look out for

 two monomers, each with two functional groups
 one monomer with two different reacting functional groups 4
 polymer contains ester or amide linkages
How are Polymers Really Formed?
Ball and socket depiction of
the polycondensation process.

Either a single building block

bearing a ball and a socket
(AB) or two different building
blocks, each bearing two balls
(BB) or two sockets (AA),
can link to form linear chains.

Rings could also be formed during such processes by the ball at one
end of the chain linking with the socket at the other.

Two other types of building blocks are also shown, which would5
lead to other interesting structures.
How are Polymers Really Formed?

Structures formed by
polycondensation of polyfunctional
monomers.

In the case of AB2 self-

condensation, high molecular
weight hyperbranched polymers
would be formed.

As they grow in size, these would

adopt a compact pseudospherical
structure that would carry a large
number of balls (B-type functional
groups) on their molecular
periphery.
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How are Polymers Really Formed?
On the other hand, A2B2 type
monomers would lead to an
insoluble, highly cross-linked
product.

Topologically cross-linked structures

would contain several ring subunits
because of the presence of a large
number of both A and B type
functionality that could react intra-
molecularly, whereas a
hyperbranched polymer could have
at the most a single ring because a
growing chain, at any time, can have
only a single A-type functional
group! 7
Some Important Commercial Polymers Prepared by Step-Growth
Polymerization

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 Polycondensation Reactions
Classification by Mechanism
 Step – Growth
 Chain – Growth

Classification by Type
 Condensation
 Addition

Classification by Bond
 Radical
 Ion 9
 What are differences between step and chain growth polymerizatoin?

A. Step Growth Polymerization

• The growing chains react with each other.
• Polymers grow to high Mw at a slow rate.
• High Mw is formed at the end of polymerization.
• Long reaction time is needed to obtain high Mw
and high conversion

B. Chain Growth Polymerization

• Monomer molecules add on to a growing polymer chain one at a time.
• Polymers grow to high Mw at a very fast rate
• High Mw is formed at the early stage.
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• Monomer adds on the growing polymer chain via reactive active center.
Step-Growth vs. Chain-Growth Polymerization.

Plot showing the variation of molecular

weight as a function of fractional
conversion (p) for simple step-growth and
chain-growth polymerizations.

As discussed, high molecular weight is

formed only at very high conversions in
the case of step- growth polymerizations
[curve depicts the variation: degree of
polymerization (DP) = 1/(1-p)].

However, for simple chain polymerizations, high molecular weight

polymer is formed even at very low conversions.

With increasing time, more monomers are converted to polymer without

affecting the overall average molecular weight of the polymer.
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 Characteristics of Step-Growth

Step-growth polymerization principle was used by Carothers in 1929.

Synthesis of Ester, RCOOR′
O
O
HO C CH2CH3 OH CH2CH3 CH3 CH2 C O CH2CH3

Carothers thought about following reaction.

It seemed to him likely that one would get long chainlike macromolecules like this

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Equal Functional Group Reactivity Concept

I. Thermodynamic Approach
“In order to for a polymerization to be thermo-
dynamically feasible, the Gibbs-Free Energy
change must be negative, that is, ΔGp < 0.”

G = HTS

GP = HPTSP : this equation is the basic of un-

derstanding about polymerization, depoly-
merzation equilibrium 13
Equal Functional Group Reactivity Concept
GP = Gpolymer  Gmonomer

= (HP – Hm) – T(SP – Sm)

= HP – TSP

Where HP : enthalpy change per monomer unit

SP : entropy change per monomer unit

GP < 0  Polymerization is spontaneous

GP > 0  Polymerization is not possible

GP = 0  monomer polymer

at this temperature is ceiling temperature.

(for both step and chain growth) 14

Equal Functional Group Reactivity Concept

II. Kinetic Approach

“A negative GP does not necessarily mean that polymerization occurs under a par-
ticular set of reaction conditions and reaction sites”

e.g) should have

 functional group
 proper initiator
 temperature etc.

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Carother’s Equation

The number of funtional groups used 2( N  N )

P  The number of funtional groups used  2( N00  N )  (1)
P  Number of functional groups initially  N f  (1)
Number of functional groups initially N 0f
0

Initial number of monomers N0

DPn  Initial number of monomers  N  ( 2)
DPn  Number of moles of molecules after reaction  N  ( 2)
0
Number of moles of molecules after reaction N
f = number of average functional group per monomer
N0 = number of initial monomers

N0f = number of initial functional group

N = number of final molecules (monomer, dimer,  polymer)

From eqn (1) (2)

From eqn (1) (2)
2 2
P 2  2
P  f  DPn  f
f DPn  f
2 1 Generalized Carother's Eq.
 DPn  2  1 if f  2
 DPn  2  fP  1  P if f  2
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2  fP 1  P
Kinetics

A. Types of monomer

  a. AB type
HO COOH

 b. AA and BB type

HOOC COOH HOCH2CH2OH

 c. Three functional groups for crosslinked polymers

HOCH2CHCH2OH
17
OH
Kinetics

B. Condensation of difunctional monomers.

 
a. O

H+ O
HOCH2CH2OH
(-H2O)
* OCH 2CH 2 *

O
 b.
NH
∆ O
H2NCH2CH2CH2CO2H
(-H2O)
* NHCH 2CH 2 CH 2C *

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  Network Step Polymerization

A. Greater than two functionality polymers.

  OH
a. Alkyd-type polyester :   HOCH2CHCH2OH
 

OH

b. Phenol-formaldehyde resin : 
 

NH2

c. Melamine-formaldehyde resin :  N N

H2N N NH2
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COMMON TYPES OF CONDENSATION
POLYMERS

1. Polyesters
2. Polycarbonates
3. Polyurethanes
4. Polyamides
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1. Polyesters

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1. FUNDAMENTALS OF ESTERIFICATION

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1.1 TRANSESTERIFICATION

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 1.2 Linear Polymers: Polyesters
• Polymer formation begins with one diacid molecule reacting with one
dialcohol molecule to eliminate a water molecule and form an ester.

• The ester unit has an alcohol on one end and acid on the other, which are
available for further reactions.

• The eventual result is a polyester called poly(ethylene terephthalate) or

more commonly, PET.

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 1.3 LINEAR POLYMERS: POLYESTERS
Polymer from terephthalic acid and ethylene glycol

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 1.3 LINEAR POLYMERS: POLYESTERS
Made by the transesterification of the methyl ester

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 1.3 LINEAR POLYMERS: POLYESTERS
Made by the transesterification of the methyl ester

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ANHYDRIDE + DIOL

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DIPHENOL + DIACID

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 1.4 POLYESTER FILMS:
PROPERTIES & PRODUCTS

• strong, tough, brilliant and clear

• ease of converting
• excellent temperature resistance
• strong tear-initiation and puncture resistance
• excellent oil, grease, or moisture resistance

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 1.4 POLYESTER FILMS:
PROPERTIES & PRODUCTS

• excellent chemical resistance

• office supplies
(e.g. book jackets, carbon ribbons)
• solar film
• microfilm jackets
• laminates
• food packaging
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2. Polycarbonates

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 2. POLYCARBONATES

• polyesters of carbonic acid (fictive compound)

• derivatives of carbonic acid are commercially
available:

– phosgene
– urea
– carbonates 33
 2. POLYCARBONATES
• Esters of carbonic acid.
• Carbonic acid is in equilibrium with CO2 and water, but esters
are stable.
• React phosgene with bisphenol A to obtain Lexan® for
bulletproof windows.

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Example of condensation polymerization
I. Polycarbonate

O
Cl C Cl
+ HO OH

O
* O O C n * + HCl

Lexan from GE
Tm = 270°C, Tg=150°C
high impact resistance, transparency, packaging, phone dial ring,
process similar to polyester synthesis
2stage,
①vaccum at 200°C
35

②300°C
 2.3 POLYCARBONATE RESIN:
PROPERTIES & PRODUCTS

• one of the most versatile engineering plastics

• 200 times impact resistance of glass
• long-term durability
• optical clarity
• corrective eyewear and sunwear lenses
• CD and DVD
• automotive windows

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3. Polyurethanes

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3. POLYURETHANES (POLYCARBAMATES)
FORMATION

38
3.1 POLYURETHANE

39
Example of condensation polymerization
Polyurethane
HO(CH2)nOH + O C N (CH2)6 N C O

diol HMDI (hexamethylene diisocyanate)

diol + CH2 NCO

OCN

4,4'-diphenylmethane diisocyanate

or

diol + NCO

NCO

CH3
40
TDI (tolylene diisocyanate)
3.2 POLYURETHANE FOAM APPLICATIONS

Flexible foam:
• insulators
• automobile crash panels
• bedding
• carpet underlays
• synthetic sponges
Rigid foam:
• lightweight furniture
• construction panels
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4. Polyamides

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 4. POLYAMIDES FORMATION

Basic Amide Chemistry

• Acid chlorides react with ammonia and amines to give amides.

• A base (NaOH or pyridine) is added to remove HCl by-product.

43
BASIC AMIDE CHEMISTRY

44
Usually made from reaction of diacids with diamines,
but may also be made from a single monomer with an
amino group at one end and acid group at other.

45
Example of condensation polymerization
Aromatic Polyamide

Kevlar poly(p-phenylene terephthalamide)

-high strength

H2N NH2 + HOOC COOH

O O

HN NHC C

46
Example of condensation polymerization
Nomex poly(m-phenylene isophthalamide)
-very good high temperature resistance
H2N NH2 HOOC COOH -HCl
-H2 O
+
CH2Cl2
DMAc
The electron density of NH2 is reduced by aromatic ring. So, the nuclephilicity of aromatic
amine is reduced by –COOH.
High temperature is needed.
\ For faster reaction, diacid chloride is used.

47
Example of condensation polymerization
Aromatic Polyimides
O O

n O O + n H2 N NH2
DMAc
O O DMF
DMSO
Pyromellitic dianhydride p-aminoaniline
(PMDA)

O
O
-H2O
[ C NH N ]
H n

HOOC COOH
polyamic acid
(amidatoin) soluble

O O

C C
[ N N ]
n poly(pyromellitimido,-1,4 phenylene)
C C
insoluble
O O
48
Example of condensation polymerization
Polybenzimidazole (PBI)

H2N HOOC COOH

NH2 -H2 O
+
H2N NH2

N N
* n *
N N
H H

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 4 PROPERTIES & PRODUCTS

• extreme high tenacity

• high heat resistance
• high impact resistance
• low weight
• high chemical resistance

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 PROPERTIES & PRODUCTS

• vehicles
• tires
• protective clothing
• impact-resistant materials
• asbestos replacement

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 SOME EXAMPLE OF
CONDENSATION REACTIONS

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 TYPES OF CONDENSATION REACTIONS

1. Polyesters

O O O
H2O -n H2O
O HO (CH2)5 C OH (CH2)5 C O
trace

-n H2O
HO R OH +

O O O O O O
O HO R O OH * R O O *
n

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 TYPES OF CONDENSATION REACTIONS

2. Polyamides
O O
O O - n H2O H
H2N R NH2 + R' * R N R' N *
HO OH H n

O O
O O - n HCl H
H2N R NH2 + R' * R N R' N *
Cl Cl H n

O O O
H2O -n H2O
NH H2N (CH2)5 C OH (CH2)5 C N
trace H
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POLYAMIDES VIA CONDENSATION -- NYLON 66
H O O O O
O C-(CH2)4-C O C-(CH2)4-C
H O -
O-
+ NH3+ NH3+
NH2 CH2-(CH2)4-CH2 NH2 CH2 CH2
(CH2)4
slight excess
Nylon Salt

60% Slurry

200 C, 15 Atm. 1 hr

O O
-
NH3+(CH2)6-NH-C-(CH2)4-C-NH-(CH2)6-NH-C-(CH2)4-C O
O 8-10 O

270-300 C, 1hr
- H2O

O
NH-(CH2)6-NH-C-(CH2)4-C 55
O
Nylon 6 6
 TYPES OF CONDENSATION POLYMERS

O O O O
R O C R' C O R' C O C
n n

Polyesters Polyanhydrides

O O O
O n
O R
n

Polyacetals
Polycarbonates 56
 LEXAN POLYCARBONATE
Interfacial Process
-O - Aq NaOH
O + Cl-C-Cl
Na+ Na+ CHCl2
O
CH3 CH3

O O + NaCl
C
CH3 CH3 O
x
Lexan
Ester Interchange

O O OH
C
O 1) 200 C/20mm
Lexan +
+
2) 300 C. <1mm
H
O O
H
CH3 CH3 57
 TYPES OF CONDENSATION POLYMERS
CH3
O
H
R O N R' N O O
C H
O CH3

polyurethanes polyphenylene oxide

O Ar O

S
R O O
polyarylenes
polyarylene ether sulfones 58
 LOW TEMPERATURE CONDENSATION POLYMERIZATION

• Interfacial or Solution in Polar Aprotic Solvents

Parameter Low Temp High Temp

Intermediates
Purity Moderate High
Stoichiometry Not Essential Essential
Heat Stability Not Essential Essential
Structure Highly Reactive Thermally stable
Cost High Moderate

59
INTERFACIAL OR SOLUTION POLYMERIZATION
IN POLAR APROTIC SOLVENTS (CON’T)

Conditions Low Temp High Temp

Time Minutes to hours Hours to days
Temperature 0 – 150 C >250 C
Pressure Atmospheric High to vacuum
Yield Low to moderate Quantitative
By-products Salts Volatiles
Solvents Required None

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APPLICATIONS OF LOW TEMPERATURE CONDENSATIONS

• Prep. of Infusible Thermally Stable Polymers

• Prep. of Thermally Unstable Polymers

Prep. of Polymers Containing Functional Groups with

Differing Reactivity

Formation of Block or Ordered Polymers

(No equilibration of polymer in melt allowed)

Direct Production of Polymer Solutions for Coatings,

Spinning into Fibers, Solvent Blending to form
Composites
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 TYPES OF CONDENSATION POLYMERS

O O
O O
H
R N C R' C N N N
H
O O
polyamides polyimides

O O S S
Ar Ar
N N N N

polybenzoxazoles polybenzthiazoles
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 AROMATIC POLYAMIDES “ARAMIDS”

NH2 C-Cl
M-isomers favor formation of
O
+
soluble polymers
NH2 C-Cl
O

Unique solvent combination

DMF, LiCl
S
O O Can be Dry Spun to Fiber
O As Spun:
O NH-C NH-C Elongation, 23-34%,
C-NH O Tenacity, 4.6-5.3 g/Denier

C-NH
C-NH O
O

Nomex M.p. > 350 C 70% Strength Retained in Ionizing63

Radiation
 POLYIMIDES FOR ELECTRONIC APPLICATIONS
O O
O O
2 (CH3)2CHOH
HO-C C-O
O O

O O O-C C-OH
O O
PMDA
O syn and anti isomers
Cl-C-C-Cl
O O
O
Cl-C C-O

O-C C-Cl NH2 O

O O
DMAC
ODA
NH2

O O
NH-C C-O

O-C C-NH O
O O
Fabricate in soluble form
soluble
O heat or
O
amine catalyst
N O
N
Post treat to final form
O O
insoluble 64

Kevlar
 POLYETHERSULFONES

HO K2CO3
K+-O Bis-nucleophile

Bis-Phenol-A OH O- K+

K+-O O
Cl S
+
O
O- K +
Cl
DMSO/Toluene
160 C

2) CH Cl
3
CH3O
O
S
O
O

Molecular Weight = 65,000 - 250,000 65

Amorphous Material, Tg  200C, Films pressed at 280C

66