COPOLYMER

 A polymer made from two or more different

monomers
 The sequence of monomer units along a copolymer
chain can vary according to the method and
mechanism of synthesis
 Random Copolymers
 No definite sequence of monomer units exists
 Various monomers units occur randomly along the chain-
like structure

-A-A-B-B-B-B-A-B-A-A-B-B-B-A-A-A-A-B-A-
 The properties are usually different from the two related
homopolymers
 Often formed by free radical polymerization.

 Copolymerizations of equimolar mixtures of different

monomers give random copolymers.
 example: copolymerization of styrene and methyl
methacrylate (radical polymerization)
 Alternating Copolymers
 Contain a regular alternating sequence of two monomer units
 two monomer units distributed in alternating sequence.

-A-B-A-B-A-B-A-B-A-

 Often formed by ionic polymerization.

 The properties usually different from the two related
homopolymers.
 Formation of alternating copolymers is favored when the
monomers have different polar substituents (e.g. one
electron withdrawing and the other electron donating), and
both have similar reactivities toward radicals.
 example: copolymerization of acrylonitrile and butadiene
 Block Copolymers
 Contain a block of one monomer connected to a block of
another monomer
-A-A-A-A-A-A-A-B-B-B-B-B-B-B-A-A-A-A-A-A-A-
 Often formed by ionic polymerization and condensation
polymerization
 Block copolymers retain many of the physical characteristics
of the two homopolymers
 Eg: polystyrene-block-polybutadiene-block-polystyrene
or SBS rubber

H H
CH2 C CH2 CH2 CH2 C
x y z

HC CH

                                                                                                                                        
Block polymerization by living anionic polymerization

 the reactive site remain at the end of the polymer chain

 living polymer
 If a different suitable monomer is added, a block
copolymer will form
 Formation of block copolymers from condensation polymers
a) From 2 polymers with same reactive end groups

HOOC Ax COOH + H 2N By NH2

O O H H

C AX C N By N
n
 Example: High-impact polystyrene (HIPS)
 polystyrene backbone with chains of polybutadiene
grafted to the backbone
 Generally, can be synthesized by one of the following
techniques:
a) ‘Grafting-from’ Technique
 A polymer carrying active sites is used to initiate the
polymerization of a second monomer
 Advantage: very efficient
 Disadvantage: usually not possible to predict the
molecular structure of the graft copolymer and the
number of grafts formed
 Advantages:
 Allows structural characterization of the graft copolymer
formed because the backbone and the side-chain are both
synthesized separately
 If the molecular weight of each chains and their overall
compositions are known, it is possible to determine the
number of grafts per chain and the average distance
between two successive grafts on the backbone
a) ‘Grafting-through’ Technique
 In this technique, polymerization with a macromer is
involved.
 A macromer is a low-molecular weight polymer chain with
unsaturation on at least one end.
 A growing polymer chain can react with an unsaturated site,
resulting in the graft copolymer
 Stryrene-Butadiene Rubber (SBR)

 Styrene-Butadiene or Styrene-Butadiene-Rubber (SBR)

is a synthetic rubber copolymer consisting of styrene
and butadiene.

 Produced by free radical polymerization of styrene and

butadiene
 Butadiene can undergo either 1,2 or 1,4 polymerization
Polybutadiene :
 elastomeric material with good elastic properties and
outstanding toughness and resilience
 Poor resistance to oils, solvents, oxidation and
abrasion.

Polystyrene
 chemically inert and is quite resistant to alkali, halide
acids and oxidizing & reducing agents
 brittle at low temperature
 Commercial SBR is produced by either emulsion or
solution copolymerization
 Emulsion copolymerization is either a cold (41 oF) or
hot (122 oF).
 produced SBR with difference MW and MW
distribution, microstructure.
 The solution copolymerization process involves the use
of alkyllithium catalyst.
 Solution SBR generally has a higher MW, narrow MW
distribution, and higher cis-diene content than emulsion
SBR
It has good abrasion resistance and good aging stability
when protected by additives, and is widely used in car
tires, where it is blended with natural rubber.
 Styrene – Butadiene – Styrene Block Copolymer
(SBS rubber)

 Classified as thermoplastic elastomer (TPE)

 In the solid state, the SBS TPE has 2 phase:
 continuous polybutadiene rubber phase
 disperse glassy domains of polystyrene
 The styrene plastic end blocks (called domain), act
as cross-linking locking the rubber phase in place.
 Phase separation of SBS block copolymer.
(using Transmission Electron Microscope, TEM)
SBS block copolymer schematic microstructure
 In commercial SBS copolymer, the styrene-butadiene
(end-block-to-midblock) ratio in the range 15:85 to 40:60
on weight basis
 The useful temperature range is between the Tg of
polybutadiene and polystyrene
 At this T range, the hard styrene domains prevent
the flow of the soft elastomeric butadiene
midsegments through a network similar to
vulcanized rubber

Tg butadiene: < - 90 oC ; Tg polystyrene: ~ 95 oC

● The polymer is known as Kraton and is used for shoe

soles and adhesives.
 High Impact Polystyrene (HIPS)

 Pure polystyrene is brittle but polybutadiene is

elastomeric

 HIPS produced by free radical polymerization of styrene

in the presence of polybutadiene

 polystyrene backbone with chains of polybutadiene

grafted to the backbone

 Common applications of HIPS include toys and product

casings.