NPTEL – Biotechnology – Cell Biology

Module 16 Polymers
Lecture 39 Polymers I

16.1 Introduction
A polymer is a macromolecule, made up of many smaller repeating units called
monomer. Polymers have high molecular weight in the range of several thousand or even
higher. The first synthetic organic polymer polyvinylchloride was synthesized in 1838 by
accidentally. Later, polystyrene was discovered in 1839.
16.2 Classification
Polymers can be classified into a number of ways which are described below.

CLASSIFICATION OF POLYMER

Based on structure Based on molecular Based on source

forces
Natural
Linear
Thermoplastic
Cyclic Synthetic
Thermosetting
Branched Addition
Elastomers
Network Condensation
Fibers

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Polymers can be divided into four types depending on its skeletal structure.

• A linear polymer is represented by a chain with two ends.

• A cyclic polymer have no chain ends and show properties that are entirely
different from their linear counterparts.

linear

cyclic

o Branched polymers have side chains, or branches, of significant length which are
bonded to the main chain at branch points, and are characterized in terms of the
number and size of the branches.

branched

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o Network polymer or cross-linked polymer have three dimensional structures in

which each chain is connected to all others by a sequence of junction points and
other chains. But it does not contain any main chain when compare with branched
polymer.

network

Similarly, polymers can be classified into four categories based on the forces of attraction
between polymer chains are thermoplastic polymers, thermosetting polymers and
elastomers.

Thermoplastic Polymers: The individual chains of thermoplastic polymer are held

together by van der Waals forces. They are strong if the polymer chains are lined up in an
ordered, closely packed array. This region is called crystallites and the other where
polymer chains are oriented randomly is called amorphous. Thermoplastic polymers have
both ordered crystalline regions and amorphous noncrystalline regions. Thermoplastic
polymers are hard at room temperature, but become soft when heated, because on heating
individual polymer chains slip from one another. Polyethylene, polystyrene, polypropene
and teflon are some examples for thermoplastic polymer.

F F

C C
n
F F
Teflon

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Thermosetting Polymers: The greater the degree of cross-linking makes the polymer
more rigid. Such cross-linked polymers are called thermosetting polymers. Thermosetting
polymers are generally stronger than thermoplastic polymers due to strong covalent
linkage (cross-linking) between polymer chains not by weak intermolecular van der
Waals forces. They are more brittle in nature and their shape is permanent. Once it is
hardened they cannot be recycled. Melmac®, a highly cross-linked thermosetting
polymer of melamine and formaldehyde, used to make lightweight dishes. Bakelite and
polyurethanes are examples for thermosetting polymers.
H
N N NH2
H2N N NH
N N
N N
H2N N NH2 O -H2O HN
NH
N N H H
NH N NH
NH2 H2N N NH
f ormaldehyde N N
melamine
N N
NH2
NH2
melmac®

Elastomers: An elastomer is a randomly oriented amorphous polymer, which stretches

and then reverts back to its original shape. To avoid slipping of polymer chains it must
have some cross-linking. When elastomers are stretched, the random chains stretch out
where as the van der Waals forces are not strong enough to maintain them in that
arrangement and retains its original shape when the stress is removed. Rubber is an
example of an elastomer.
Fibers: These are thread like polymers which can be used as fabrics. The strong
intermolecular forces like hydrogen bond provide high tensile strength and high modulus
to fibers. A few examples are cotton, wool, silk, nylon etc.

Generally, polymers can be divided into two broad groups depending on the source,
either natural polymers or synthetic polymers.

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16.3 Natural Polymers

Polymers are naturally available. A few examples are:
Polysaccharides: Polysaccharides are important class of biopolymers which are made up
of long chains of monosaccharide units bound together by glycosidic bonds.
Polysaccharides contain more than ten monosaccharide units. Starch and glycogen are
very common examples for storage polysaccharides. Similarly, cellulose and chitin are
examples for structural polysaccharides.

HOH2C HOH2C HOH2C

O O O O
O O
O
HO OH
HO OH HO OH

three subunits of cellulose

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Nucleic Acids: Nucleic acids, such as DNA (deoxyribonucleic acid) and RNA
(ribonucleic acid), are made from nucleotide monomers. Nucleic acids are found in all
living things, where they function in encoding, transmitting and expressing genetic
information.

N N
O O O
O

O O H
OH
O P O- N O P O- N
O O O
O

O O H
OH
O P O- O P O-
N O N
O O
O

O O H
OH
O P O- O P O-
N O N
O O
O

O O H
OH
O P O- O P O-
O O

a short segment of RNA a short segment of DNA

Proteins: Proteins are large biological molecules, made up of the smallest units called α-
amino acids. They are building blocks of plant and animal cells. Many proteins are
enzymes that catalyze biochemical reactions and are essential to metabolic functions.

Natural Rubber: Natural rubber is the polymer of isoprene. This is mainly harvested as a
sticky milky colloidal form called latex from the bark of the rubber tree.

natural rubber

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16.4 Synthetic Polymers

The polymers which are synthesized in the laboratory are called as synthetic polymers,
based on the method of its preparation they can be further classified into addition
polymers and condensation polymers.
Addition polymers: Addition polymers are formed by the sequential addition of the
monomer units with the help of a reactive intermediate such as free radicals, cation or
anions without loss of small molecules. The addition polymerization generally involves
three steps called initiation, propagation and termination. These steps apply to all types of
addition polymerization such as free-radical, cation and anion. In this process alkenes are
typically used as monomers and polymerization results by successive additions across the
double bonds.
 Radical polymerization results when a suitable alkene is heated with a radical
initiator.
 Initiation step: On heating the initiator molecule decomposes into a radical which
combines with the monomer and forms a new radical for the chain propagation.

O
O
O
O
benzyl radical
phenyl radical
benzoylperoxide

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 Propagation step: The formed radical reacts with another monomer and generate
a new radical which propagates the chain. The chain propagation process
determines the length of a polymer chain.

 Termination step: There are three ways to terminate the propagating chain either
by coupling with another monomer radical or by disproportionation reaction or by
reaction with an impurity (such as oxygen).
chain combination

n n n n

disproportionation
H
n n n
2

reaction with an impurity

impurity
n n
impurity

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 In cationic polymerization, a cation intermediate is generated by the addition of a

Lewis acid such as BF3, AlCl3, etc. with the monomer typically alkene. The cation
formed in the initiation step reacts with another monomer and generate a new
cation, this process is repeated until chain termination occurs.
initiation

BF3
F3B

propagation

F3B F3B F3B

 Chain propagation can be affected by three ways either by loss of a proton or by

addition of a nucleophile or by reacting with the solvent molecule.
termination
loss of a proton

H
F3B F3B

reaction with a nucleophile

Nu
F3B F3B Nu
chain transf er reaction with the solvent

XY Y
F3B F3B

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 Anionic polymerization occurs by the addition of a nucleophile initiator with the

monomer alkene and generates a new anions, this process occurs only when the
nucleophilicity of the initiator nucleophiles are strong enough to attack the
electron rich olefins. Similarly, if electron withdrawing substituents are attached
to the olefin bond increases the rate of addition. Here the chain propagation step
was terminated by reaction of generated nucleophiles with impurity or solvent
molecules.

initiation

Cl Cl
Bu Li
Bu

propagation
Cl Cl Cl
Cl Cl
Bu Cl
Bu Bu

termination
reaction with an impurity
Cl Cl
Cl impurity Cl
Bu Cl Cl
Bu
impurity

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Condensation Polymers: This type of polymers is generated by the condensation of two

monomer units with the loss of small molecules such as H2O, HCl, and NH3 etc. Here the
monomer units must have two functional groups in order to condensation reaction took
place. Dacron®, nylon 6 and nylon 66 are few examples for condensation polymers.

O O
H2 H2
H3C O C C O CH3 HO C C OH

dimethy terephthalate ethelene glycol

O O H2 H2 O O H2 H2
H3C O C C O C C O C C O C C OH 2n CH3OH
n

Dacron® polyester

Copolymer: If the polymer chain is formed from only one type of monomer units are
called homopolymers. Alternatively, two of more different monomer units can combine
to form a polymer chain is called copolymers.

an alternating copolymer ABABABABABABABABABABABAB

a block copolymer AAAABBBBAAAABBBBAAAABBBB

a random copolymer AABABABBAABAAABBAABABBBA

a graft copolymer AAAAAAAAAAAAAAAAAAAAAAAA

B B B
B B B
B B B
B B B
B B B
B B B
B B B
B B B

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There are four types of copolymers are known. First, alternate arrangement of monomer
units results alternating copolymer. Secondly, block arrangement of monomer units result
block copolymers. Thirdly, a random arrangement of monomer units results random
copolymers and finally, a graft copolymers results by one type of monomer units are
arranged at the branches of the chain and the another type of monomer units still reside at
the main chain.
Polyamides: This type of polymers is formed by the result of generation of amide bonds
in the polymerization reaction. Nylon 6 and nylon 66 are important examples for this type
of polymers nylon 6 is synthesized from ϵ-caprolactam, which on heating decomposes
into 6-aminohexanoic acid that polymerizes into nylon 6. Here the number 6 represents
the number of carbon atoms present in the monomer unit.
O
O
NH H+, H2O H3N
OH
6-am no
i h exanoic acid
e-caprolactam

-H2O

O O
H H
N N
N
5 H 5 5
O n

nylon 6

a polyamide

Nylon 66 is produced by the condensation reaction between two monomer units adipic
acid and 1,6-hexanediamine in the presence of heat. This is formed from a six-carbon
diacid and a six-carbon diamine.

O O O O O O
H2N NH2
HO OH N N N N
4 6 -H2O 4 H 6H 4 H 6H
n
adipic acid 1,6-hexanediamine
nylon 66

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Polyesters: This type of polymers is generated by the result of formation of ester bonds in
the polymer chain by the condensation reaction between two monomer units. Dacron® is
a well-known polyester, synthesized by the transesterification of dimethyl terephthalate
with ethylene glycol.
O O
H2 H2
H3C O C C O CH3 HO C C OH

dimethy terephthalate ethelene glycol

O O H2 H2 O O H2 H2
H3C O C C O C C O C C O C C OH 2n CH3OH
n

Dacron polyester

Similarly, trans esterification of dimethyl terephthalate with 1,4-

di(hydroxymethyl)cyclohexane results Kodel® polyester.

O O H2 H2
H3C O C C O CH3 HO C C OH -CH3OH
dimethy terephthalate 1,4-di(hydroxymethyl)cyclohexane

O O H2 O O H2
O C C O CH2 C O C C O CH2 C
n

Kodel®

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Polycarbonates: This is an example for condensation of step-growth polymer. Here the

polymer chain is linked together by carbonate bonds. Lexan®, a polycarbonate formed by
the condensation reaction between the two monomers phosgene and bisphenol A. This is
used for manufacturing bulletproof windows.

O CH3 -HCl
Cl C Cl HO C OH
CH3
phosgene s eno
bi ph lA

CH3 O CH3 O CH3

C O C O C O C O C O
CH3 CH3 CH3
n
Lexan®
a polycarbonate
Polyurethane: A carbamate functional group is synthesized by the addition reaction of an
alcohol with an isocyanate molecule. This is also called as urethane. If a polymer chain is
linked together by urethane bonds are called as polyurethane. Typically, polyurethanes
are prepared by the addition reaction of diol monomers with diisocyanate monomers.
Polyurethane in the form of foams has been used for furniture stuffing, carpet backings
and insulations.

O
H
R N C O ROH R N C OR
isocyanate alcohol urethane

CH3
O C N N C O
H2 H2
HO C C OH
toluene-2,6-diisocyanate ethylene glycol

O CH3 O H2 H2 O CH3 O H2 H2 O
H H H H
C N N C O C C O C N N C O C C O C

n
a polyurethane

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Module 16 Polymers
Lecture 40 Polymers II

16.5 Application of Synthetic Polymers in Catalysis

Recently, polymer supported catalysts have received much attention in organic synthesis.
The polymer support provides potential advantages such as easy separation and recovery
of the expensive catalyst from the reaction mixture by simple filtration and allows it for
subsequent reuse. The reduced toxicity and odor of polymer supported species are
another advantage over conventional solution-phase reactions. Typically, polymer
supported catalyst show higher activity as compared with the monomer catalyst; this is
due to the increase in the number of reactive centers in the polymer catalysts. Generally
Lewis acids can be immobilized to polymer support by covalent bonding or ionic
bonding or coordination of polymeric ligands with metal species.

Hodge and coworkers have synthesized polymer supported oxazaborolidines with α,α-
diaryl-β-aminoalcohol by Suzuki coupling of α,α-diphenyl-L-prolinol derivatives with
cross-linked polystyrene containing phenylboronic acid residue.1,2 This supported catalyst
shows high level of enantioselectivity up to 97% ee for the reduction of ketone to alcohol
(Scheme 1).

Br

B(OH)2
N N OH
OH H
H
1
Crosslinked polystyrene

O OH
1, BH3
*

Scheme 1

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Itsuno et al. has reported cross-linked polymer supported chiral oxazaborolidinone

catalyst for Mukiayama-aldol type reaction between aldehyde and silyl enol ether that
provided β-hydroxyketone in >90% ee (Scheme 2). Further, this catalyst was used for
asymmetric Mannich reaction and asymmetric allylation reaction.3

CF3
O OH O
F3C
OSiEt3 2
O
Ph S
EtCN, -78 °C N O
O 2
99%, 91% ee
O

HN
Scheme 2

Shibasaki and coworkers have developed a bifunctional chiral catalyst consisting Lewis
acid (aluminium metal) and the Lewis base (phosphine oxide), which was successfully
applied to asymmetric Reisser-type reaction of trimethysilylcyanide with quinolone and
2-furoyl chloride (Scheme 3). This catalyst afforded high activity and nearly similar
enantioselectivity as compared with the monomer.4,5

O
P(O)Ar2 P(O)Ar2
O Al Cl O Al Cl
O O
P(O)Ar2 P(O)Ar2
Janda JELTM
4 3
Ar = o-tol
R
R
Cl TMsCN, -40 °C
O CH2Cl2-toluene R N CN
O
R N O
R = H, Cl O
3 R =H, 91%, 85% ee
3 R = Cl, 80%, 96% ee
4 R = Cl, 92%, 86%
Scheme 3

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Kobayashi et al. has developed hydrophobic polymer supported scandium catalyst for
allylation reaction of ketone with tetra-allyltin in water (Scheme 4).6 The same catalyst 5
showed high activity in Mukaiyama-aldol reaction also and the reactions proceeded much
faster in water than in other organic solvents.7

5 5
SO3Sc(OTf )2
5
Crosslinked Spacer
polystyrene

O OH
n 5, (3.2 mol %)
4S Ph
Ph solvent, 12 h
H2O, 95%
benzene, 28%

SO3ScX2

OTMS OH O
O 0.16 mmol Sc/g
Ph SEt
Ph H SEt H2O, 30 °C, 12 h

97%

Scheme 4

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Nanostructured polymer supported Sc(III) catalyst was prepared by cross-linking inverted

hexagona (HII) monomer containing sodium sulfonate head group with divinylbenzene,
followed by exchanging sodium with scandium(III) nitrate (Scheme 5).8 This catalyst was
tested for Mukiyama aldol and Mannich type reactions.
O
SO3 Na
N
H
O

HII phase of SO3

SO3 O3S
DVB Photo-crosslink Sc(NO3)3 Sc3+
SO3 O3S
H2O Sc3+
H2O SO3 O3S
SO3

NP-Sc 6
N anost tured polymer
ruc
supported Sc(III) catalyst

O OTMS OH O
6
Ph H Ph Ph Ph
H2O, 14 h, rt

88%, syn/anti = 64/36

O 6 PhHN O
OTMS
PhNH2 H2O, 24 h, rt
Ph H Ph Ph
Ph

72%, syn/anti = 62/38

Scheme 5

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Polymer supported Ti(IV) catalyst was explored for some carbon-carbon bond forming
reactions including allylation, cyanation and ene reactions (Scheme 6).9

O
TiCl4, toluene O
OH
HO O
18 h O
7 Ti
Crosslinked
Cl Cl
polystyrene

O OH
7
n
Ph H 4S 25 °C, CH3CN Ph
89%

O 7 OH
TMS
Ph H 25 °C, CH2CL2 Ph CN
71%

7 OH
OHC CO2Et
Ph 25 °C, toluene, CH2Cl2 Ph CO2Et
70%
Scheme 6

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Seebach and co-workers have developed polymer supported Ti-TADDOLate for

enantioselective diethyl zinc addition to aldehydes.10 It showed high activity as well as
enantioselectivity (Scheme 7).

O
O
O
O
O

O OH Suspension polymerization
O OH

TADDOL-styrene copolymer

O
O
O
O Ti(Oi Pr)4
Polymer-supported
O O Ti-TADDOLate
8

Polymer-supported
O OH
Ti-TADDOLate
Et2Zn
Ph H 8 Ph
89%
Scheme 7

Chiral amino alcohol immobilized polyethylene (PE) fibers has been synthesized by
electron beam induced perirradiation graft copolymerization method (Scheme 8).11 This

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more stable fibrous catalyst was used in phenylacetylene addition to benzaldehyde with
Zn(OTf)2.

PE fiber HO

1.1 equiv Zn(OTf)2

O OH
1.2 equiv Et3N
H *
Ph 1.2 equiv 9 Ph
Toluene, 48 h
45%, 91% ee

Scheme 8

Cross-linked polymer supported Ti(OiPr)2.BINOLate complex was reported for

enantioselective diethyl zinc and trimethylsilyl cyanide addition reaction with aldehydes
(Scheme 9).12

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O O
O

O
O
O
Suspension
Polymerizaion
BINOL
O
Deprotection copolymer

OTIPS
OTIPS

O
O
O Ti(Oi Pr)4
Ti(Oi Pr)2.EBINOLate
O 10

O
O

O OH
0.2 equiv 10
H Et2ZN
1.3 equiv Ti(Oi Pr)4
toluene, -20 °C
66%, 82% ee

O OH
H TMSCN 0.2 equiv 10
CN

72% ee

Scheme 9

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Polymeric monolith containing TI-TADDOLate has been synthesized by thermally

induced radical solution polymerization of a monomeric mixture containing TADDOL
monomer, styrene and divinylbenzene, using azobisisobutyronitril (AIBN) as the radical
initiator (Scheme 10). This catalyst was used for Diels-Alder reaction and diethyl zinc
addition to benzaldehyde.13

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Ar Ar Ar Ar
O OH O OH

O OH O OH
O Ar O Ar Ar
Ar

Polymeric monoliths

Ar Ar
O O Cl
Ti
O O Cl
O Ar Ar

11

Polymeric monoliths

O O
11
N
O
O N
O
O
exo/endo = 2.3,25%, 25% ee

O OH
11
H Et2ZN
-30 °C, 2.5 h

60%, 99% ee

Scheme 10

Modified poly(ethylene glycol) (MeOPEG) supported chiral bisoxazoline ligand was

synthesized for enantioselective carbon-carbon bond forming reactions such as Diels-
Alder reaction, cyclopropanation and ene reaction in the presence of Cu(OTf)2 (Scheme
11).14

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O (CH3)3 O
O
O
N N
R
12
R

O O
Cu(OTf )2
N
O 12
O N
O
O
R = t -Bu, 83%, 45% ee

Cu(OTf )2 Ph
COOEt
Ph Ph N2CHCOOEt
12 Ph
R = t -Bu, 45%, 93% ee

OH
Cu(OTf )2
Ph OHCCOOEt Ph COOEt
12
R = Ph, 96%, 95% ee

Scheme 11

Umani-Ronchi and coworkers have synthesized polymer supported indium(III) catalyst

from Amberlyst-15 for ring opening reaction of enantiopure epoxides with N-
methylindole as well as thiophenol derivatives (Scheme 12).15

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SO3H SO3 Na SO3

NaSO4(sat) In(OTf)3
SO3H SO3 Na SO3 In3+
H2O EtOH, rt
SO3H SO3 SO3
Na

Amberlyst-15 Amberlyst-In
13
OH
Ph

O 13
Ph
N Et2O, wet N

64%, > 98% ee

Ph OH OH

SH O 13 S S
Ph Ph
Et2O, wet

> 49 : 1
90% ee
Scheme 12

Janda and coworkers developed a new method for the synthesis of cross-linked
copolymer witj Yb(OTf)3 (Scheme 12). The immobilized catalyst was tested for Mannich
as well as Diels-Alder reaction.16

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(BzO)2, PhCl
N acacia gum/NaCl in H2O
O O
85 °C, 6-12 h

(Yb(OTf)3
Yb
N CH3OH/CH2CL2 (1:1)
O O rt, 24 h 14

Crosslinked poly(4-vinylpyridine/styrene)

Ph Ph
N HN
OTMS
14 X : Y : Z = 10 : 90 : 1
Ph
O Ph
98%

Ph 14 X : Y : Z = 10 : 90 : 1 OEt
Ph OEt
CH3CN/CH2Cl2 (3:1)

N Ph
H
93% trans/cis = 13/87
Scheme 13

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