Seminar Topic: Polymer Science

Presented By: Ajit Rokhade

M.Pharm. I

Department of Pharmaceutics
S.E.T’s College of Pharmacy
Dharwad
 Introduction

Polymers: Also known as macromolecules, are

giant molecules consisting of many repeat units &
are formed by the process known as
polymerization.
A-A-A-A-A-A-A-A-A-A-A-A-A-
Monomer: Low molecular weight compound that
can be connected together to give a polymer
Oligomer: Short polymer chain (Few monomers)
Structure of polymers
 Classification of polymerizations

(A) Chain Polymerizations: Also known as vinyl

polymerizations

These are divided into 4 types as:

1. Free radical
2. Anionic
3. Cationic
4. Ziegler Natta
Polymerization methods for chain polymerizations

i. Bulk Polymerizations

ii. Solution polymerizations

iii. Suspension polymerizations

iv. Emulsion polymerizations

(B) Step growth polymerizations:

Polymerizations for step growth polymerizations

i. Bulk Polymerizations

ii. Solution polymerizations

iii. Interfacial polycondensation

1. Free radical Polymerizations:
 This is perhaps the most well-known method of
polymerization
 As the name implies, it involves the continuous
addition of monomer units to a growing free radical
chain

Mechanism of free radical polymerization

Termination Process: It occurs by two methods

i. Coupling:
 
P-CH2CHR + R CHCH2P PCH2CHR-CHRCH2P

ii. Disproportionation:

 
P-CH2CHR + R CHCH2P PCH2CH2R + RCH=CH-P
2. Anionic Polymerization:

In this, the growing chain end is an anion & thus

associated with a positive counter ion.
 Only monomers that contain an electron withdrawing-
group on the double bond can stabilize an anion under go
this polymerizations

Eg: methyl cyano acrylate CN

CH2=C-COOCH3

Anionic polymerizations are commonly initiated with

organic bases such as organometallic compounds or with
electron transfer agents
Using base initiation as an example, initiation &
propagation occur as follows:

Initiation:

BM B- + M+

B- M+ + CH2=CHR B-CH2CHR- M+

Propagation:

B-CH2CHR- M+ + CH2=CHR B-CH2CHRCH2CHR- M+

To high MW polymer
 Anionic polymers do not have a built in termination
process. The polymer chains thus formed have active end
groups with long life times
 Such polymers are known as living polymers

This technique has several applications such as:

 (1) Ability to accurately control MW by controlling the
ratio of initiator to monomer, thus,
 Monomer  Grams of monomer
DP = C  Initiator  OR Mn = C  
 Moles of initiator 

Where, C = 1 for initiation by bases

C = ½ for initiation by electron transfer
(2) Ability to prepare polymers having an extremely
narrow MW distribution

(3) Ability to prepare polymers with specific end

groups

(4) Ability to prepare block copolymers

3. Cationic Polymerizations:
 In this polymerization, the active chain end is a cation &
the associated counter ion is a negative species

 Only monomers that contain an electron-donating group

on the double bond is capable of stabilizing a cation will
under go this polymerizations

 Example of a highly activated monomer are ketene

acetals, which contain 2 electron donors on double
bond
OR
CH2=C
OR
Cationic polymerizations are initiated with acids either
protonic or Lewis. In either case the initiating species is a
proton
 Using protonic acid as an example, initiation &
propagation occurs as follows:
 Cationic polymerizations often involve chain transfer
reactions, either to monomer or polymer

 X-
CH2R CHR
P-CH2-CH2 + CH2=CH
CH2R CH2R
P-CH2-CH X- + CH2=CH

CH2R CH2R
P-CH=CH + P-CH3CH X-
 Chain-transfer also occurs readily to polymer,
particularly when in the chain-transfer process a secondary
carbonium ion is converted to a tertiary carbonium ion

P-CH2-CH-CHR + P-CH2-CHR-CH2P PCH2CH2R +

 X-
P-CH2CR-CH2-P
 X-

 One facile termination reaction is disproportionation

CH2
CH3
P-CH2-C X- P-CH2-C + H X-
CH3
CH3
Ziegler Natta Polymerizations:

The combination of metal alkyls & transition metal

compound are known as Ziegler-Natta catalyst systems

 These catalyst systems are capable of polymerizing

olefins such as ethylene or propylene at atmospheric
pressures to a very high MW polymers

 Also capable of producing stereo regular polymers

 For these reasons these catalysts are of enormous

industrial importance
Copolymerizations:

 A copolymer is a polymer chain that contains two or

more constituent monomers

 Depending on the arrangement of the monomers in the

copolymer, various types of copolymers can be identified as:

Random copolymer: A-B-B-A-A-B-A-B-A-B-

Alternating copolymer: A-B-A-B-A-B-A-B-A-B-A- B-A
Block copolymer: A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B
Graft copolymer: -A-A-A-A-A-A-A-A-A-A-A-A-A
B B
B B
B B
 Like homopolymerization copolymerization involves
initiation, propagation & termination steps

 Because in polymerizations leading to high MW

polymers, initiation & termination are rare events when
compared to propagation

 Only propagation step will be considered

 In the copolymerization of two monomers, the

following propagation step must be considered
  
P-M1 + M2 k11
P-M1M2
 
P-M1 + M2 k12
P-M1M2
 
P-M2 + M1 k21
P-M2M1
 
P-M2 + M2 k22
P-M2M2

Where M1& M2 are two monomers & k11, k12, k21 & k22
are four rate constants
These rate constants define r1 & r2, known as reactivity
ratios

r1 = k11/k12 & r2= k22/k21

 Reactivity ratio r1 is a measure of the rate with which

radical M1 reacts with monomer M1M2
 Reactivity ratio r2 is a measure of the rate with which
radical M2 reacts with monomer M2M1
 When the two radicals display same preferences for
either monomer, then

k /k = k /k OR r = 1/ r
 Because of this lack of preferences, a completely
random copolymer is obtained

(B) Step growth polymerizations:

 Unlike chain polymerizations, step growth

polymerizations do not have discrete initiation,
propagation & termination steps
 The condensation reaction must proceed in extremely
high yields as given by Carothers eqn.

DP = 1/1-P; where DP = degree of polymerization

& p = % conversion of functional groups (yield)
 According to above eqn. DP of 20 requires that 95%
of the functional groups react & a DP of 50 requires a 98%
conversion
 Condensation reactions can be carried out by
condensation of two monomers bearing two identical
functional groups on the same molecule or by the self
condensation of one monomer bearing two appropriate
functional groups

 Thus when two bifunctional monomers is used:

1+r Where r = ratio of two monomers

DP = in the reaction mixture
2r(1-p)+1-r
 For an exact equivalence of the two monomers r = 1 &
the eqn. reduces to the unmodified Carothers eqn.

 The Carothers eqn. can also be modified to take into

account of small amount of monofunctional reagents in
condensation reactions that use monomers having both
functional groups on one molecule. Thus,

Where No = number of
1+N1/No bifunctional molecules
DP = N1 = number of monofunctional
1-p + N1/No molecules
 Polymerization Methods

(A) Polymerization Methods for Chain

Polymerizations:

(i) Bulk polymerization:

 This method involves polymerization of neat monomers
& 2 situations arise. In one the polymer is not soluble in the
monomer so solid polymer precipitates as the
polymerization takes place
 In the other, polymer is soluble in monomer so the
viscosity of the polymer mass increases with time until
converted to solid polymer
 Very pure polymers can be prepared
 Highly exothermic, heat dissipation from the bulk
polymer solution is difficult
 Method suitable to small scale polymerizations

(ii) Solution polymerization:

 Monomer or monomers are dissolved in a suitable

solvent & then polymerized

The solvent should be solvent for both monomer &

polymer because the end product is a solution of polymer
in solvent, stirring throughout the process is possible

 Heat can be controlled by external cooling

 Polymer is isolated by either solvent evaporation or
precipitation of polymer in non-solvent

(iii) Suspension polymerization:

 The monomer is dispersed in a dispersing medium,

usually water is used
 When water is used as a dispersing medium, water
soluble monomers can’t be used unless a salting out
process is used
 Suspension polymerizations are used with free radical
polymerizations where initiator is dissolved in monomer,
which is then dispersed in water using an emulsifying
agent
 Each monomer droplet polymerizes by a bulk
polymerization process
 Heat dissipation is not a problem
 Polymer is insoluble in water
 Polymer obtained by this method are spheres, 0.01-0.5
cm in diameter

(iv) Emulsion polymerization:

 In this method initiator is insoluble in monomer &

soluble in water
 When a water-insoluble monomer is dispersed in water
containing water-soluble initiator & surfactant, the various
species present are shown in figure
A small portion of the surfactant molecules are dissolved
in water, to form colloidal clusters known as micelles

 Because the conc. of monomer dissolved in the aq. Phase

is too low & initiator is not soluble in the monomer
droplets, polymerization takes place in the micelles which
serve as the meeting point for water soluble initiator &
water insoluble monomer
Representation of stages of an ideal emulsion polymerization. (–O)
An emulsifier molecule; (M), a monomer molecule; (P) a polymer
molecule; and (R·) a free radical. (a) Prior to initiation; (b)
polymerization stage 1; shortly after initiation;
(c) polymerization stage 2; all emulsifier micelles consumed; (d)
polymerization stage 3; monomer droplets disappear
(e) end of polymerization
There are two important consequences of this unique
polymerization process
 First, due to the lower frequency of termination, chain
growth can continue for longer periods of time & hence
polymers prepared have very high MW
 Second, in conventional free radical polymerization the
propagation step is described by:


rP= kP [M][M ]

Where in emulsion polymerization the rate

Where, [M] = Conc. is described as:
of monomer
[M] = Conc. of radical ends
rP= kP [M][N/2] N = Number of micelles
(B) Polymerization Methods for Step-Growth
Polymerizations:

(i) Bulk polymerizations

 Because step-growth polymerizations are not

exothermic, heat dissipation is not a problem
 Bulk polymerization is an excellent method for
producing polymers by step-growth polymerizations

(ii) Solution polymerization:

 This is also an excellent polymerization method

 Because of the critical importance of exact
stoichiometry for achievement of high MW, the solvent
must be purified to remove impurities that might react
with monomer functional groups

(iii) Interfacial polycondensation:

 This is a specialized method using two mutually
immiscible solvents, each containing one monomer
 Polycondensation reaction occurs at the interface
between two solvents
 The method can only be applied to very rapid reactions
such as reaction between an acid chloride & an amine
 Thus polyamides can be readily formed by this process
by placing the amine in water & the diacid chloride in
CCl4
 Polymer Fabrication:
 Polymer fabrication involves the conversion of
monomers or bulk polymer into the desired useful form

(A) Molding:

 In this procedure the polymer is forced to flow into a

closed container having the desired shape by the
application of heat & pressure
 The closed container is known as mold
 These include; injection molding, compression molding,
transfer molding, blow molding, and extrusion
 Compression molding and transfer molding are used
mainly for thermosetting plastics
Injection molding, extrusion and blow molding are used
primarily with thermoplastics

Injection Molding :

This very common process for forming plastics involves

four steps:
(1) Powder or pelletized polymer is heated to the liquid state
(2) Under pressure, the liquid polymer is forced into a mold
through an opening, called a sprue. Gates control the
flow of material
(3) The pressurized material is held in the mold until it
solidifies
(4) The mold is opened and the part removed by ejector
pins
Injection Molding
 Advantages of injection molding include rapid
processing, little waste, and easy automation

Compression Molding:
 This type of molding was among the first to be used to
form plastics. It involves four steps:
(1) Pre-formed blanks, powders or pellets are placed in the
bottom section of a heated mold or die
(2) The other half of the mold is lowered and is pressure
applied
(3) The material softens under heat and pressure, flowing
to fill the mold. Excess is squeezed from the mold. If a
thermoset, cross-linking occurs in the mold
(4) The mold is opened and the part is removed
 For thermoplastics, the mold is cooled before removal so
the part will not lose its shape

 Thermosets may be ejected while they are hot and after

curing is complete

 This process is slow, but the material moves only a short

distance to the mold, and does not flow through gates or
runners

 Only one part is made from each mold

Transfer Molding:

This process is a modification of compression molding.

It is used primarily to produce thermosetting plastics. Its
steps are:
(1) A partially polymerized material is placed in a heated
chamber
(2) A plunger forces the flowing material into molds
(3) The material flows through sprues, runners and gates
(4) The temperature and pressure inside the mold are
higher than in the heated chamber, which induces
cross-linking
(5) The plastic cures, is hardened, the mold opened, and
the part removed
Blow Molding:

Blow molding produces bottles, globe light fixtures,

tubs, automobile gasoline tanks, and drums.
It involves:
1.A softened plastic tube is extruded
2.The tube is clamped at one end and inflated to fill
a mold.
3.Solid shell plastics are removed from the mold.
This process is rapid and relatively inexpensive
(B) Extrusion:

 In this process, polymer is propelled continuously

along a screw through regions of high temperature &
pressure where it is melted compacted & finally forced
through a die to give the final object

 The procedure is useful for preparing rods, tubes,

channels & sheets.
(C) Preparation of Films

1. Melt Fabrication:

 Films can be produced by extrusion through a suitably

shaped die or by first extruding a tube & then
expanding the hot tube by compressed gas into a tube
of thin film
Calendering:
 In this procedure the polymer is squeezed into a
thin film between heated rollers
Melt Pressing:

 In this method the polymer is placed between two

metal plates & the plates then placed between two heated
platens in a press

2. Solution Casting:

 In this procedure the polymer is dissolved in a suitable

solvent to form a viscous solution that is then spread on a
flat, non-adhesive surface; then slowly the solvent
evaporates. The resultant polymer film is then peeled
from the surface
3. In situ Polymerization

 In this procedure, a liquid polymer or prepolymer is

polymerized inside a suitable mold. This procedure is
useful for preparing sheets of rigid polymers & is
particularly useful for preparing sheets of crosslinked
polymer
Use of Additives:
 Many polymers in their pure form have properties that
make them unsuitable for certain applications
 Hence, by use of fillers, plasticizers & stabilizers, these
properties can be substantially enhanced

1. Fillers:

 These improve dimensional stability, impact

resistance, tensile & compressive strength, abrasion
resistance & thermal stability
 These can be subdivided into two, namely particulate
& fibrous
 Particulate fillers are carbon black, short glassfibres,
asbestos, mica, wood & flour
 Fibrous fillers are cellulosic fibers, synthetic fibers
(nylon or polyesters), carbon fibers & boron filaments

2. Plasticizers:

 These additives lower Tg of a polymer & improve flow

property & brittleness
 Typical plasticizers used are phthalate esters, adipates,
fatty acid esters & glycol derivatives

3. Stabilizers

 Used against polymer degradation. Antioxidants such as

phenols & aromatic amines are commonly used
Polymer Properties:

A. MW & MW Distribution:
 MW of polymers are described in terms of average MW
 Polymer MW can be defined in many ways:
(1) Number average MW, which is given as:
Where w = NiMi
Mn 
w

N M
i i
Ni = No. of molecules
 Ni N i W = mass of molecule
Mi = MW of molecule
(2) Weight average MW is given as:

 w M N M
2
i i i i
Mw  
w N M i i
(3) Viscosity average MW:

 Ni M i
1/ a
1 a

M    For a = 1, M   Mw
  N i M i 

B. Polymer Hydrophobicity:
 When a polymer is placed in an aqueous environment, it
gradually absorbs water & the amount of water absorbed
depends upon the nature of polymer

 Since the polymeric controlled release device is exposed

to an aqueous environment, its interaction with water is of
considerable importance
 According to the nature of polymer-water interactions,
polymers can be broadly classified into:

1. Hydrophobic Polymers:
 These polymers are essentially water impermeable &
when placed in water , will absorb very little water
(<5%)

 Structural parameters that contribute to hydrophobicity

are chain stiffness, high degree of crystallinity &
presence of highly hydrophobic groups
2. Hydrophilic Polymers:
 These polymers absorb > 5% of water
 Structural parameters contribute to hydrophilicity are
chain flexibility, absence of crystallinity & presence of
groups like amino, carboxyl & hydroxyl etc

3. Water-soluble Polymers:
 Some polymers are highly water soluble even though
are of very high MW. Polymers such as PVA, PAA,
PVP, PAAm & PEO

3. Hydrogels:
 These are highly hydrophilic or water soluble
polymers, which are crosslinked by covalent bonds.
 Because of crosslinks, these polymers are water
insoluble & can absorb very high amounts of waters
 Because of this property, hydrogels have a lot of bio-
medical & drug delivery applications
References:

 Controlled Drug Delivery Systems by Robinson

J.R., Lee V.H.L (P.No: 141-177)

 Polymer Science & Technology by R.O. Ebewele

(P.No: 269)

 Internet Sources (www.google.com)