POlymer

This name hints at

MT) a how polymers are
made

Latin: Plasticus, that

which can be molded
 ou(_ =
at Uy a
POly mer

co ce
The word, polymer, implies that polymers are constructed
from pieces (monomers) that can be easily connected into
long chains (polymer). When you look at the above shapes,
your mind should see that they cguld easily fit together.
Nylon was discovered in 1935. The name nylon is derived
from two cities where it was discovered namely New York
(NY) and London (LON).
Definition:
Polymers (poly : many; mers : units) are macro molecules (giant molecules or
large molecules) of high molecular masses built up by a repeated linking of a
large number of small molecules called monomers.

Eg: Polyethene is a polymer formed by linking together a large number of

ethene (CH,=CH,) molecules

HH
H H er
\ 7 Polymerisation |
n /
C=C \
C—C
H H Bh el
Pt. * Fy
Monomers: Small molecules which combine with each other to form
polymer molecules are called monomers. (repeating units).

Polymerization: The reaction by which monomers combine to form

polymers with or without elimination of simpler molecules is termed
as polymerization.

Degree of polymerisation: The number of repeating units (n) in a

polymer molecule (chain) is Known as the "degree of polymerisation"
(DP).

It indicates the length of polymer chain. The molecular weight of the

polymer is the product of the molecular weight of the repeating unit
and DP in case of addition polymers.
PVC (Polyvinyl chloride) with DP 1000

Molecular weight = 63x1000 = 63000

Most high polymers, useful for plastics rubbers or fibres have molecular weights
between 10,000 and 10,00,000.
(Low Polymers: 1000-20000 and High polymers > 20000).

The science of macromolecules is divided into biological and nonbiological

materials. Biological polymers form the very foundation of life and intelligence
and provide much of the food on which man exists.
Non biological polymers are synthetic materials used for plastics, fibres,
elastomers, with a few naturally occurring polymers such as rubber, wool,
cellulose.
Today these substances are essential for clothing, shelter, transportation,
communication as well as the conveniences of modern living.
 Few examples of monomers and its polymers

NAME OF THE POLYMER PARTIAL STRUCTURE OF

ek}
Poly(vinyl chloride ) po nh fi
(PVC) H.C—=C aa
—h —y “F,
H iH
Poly(propylene) Hs “ch
(PP) Ae = <a £ Cc ter ct,

Poly(vinyl alcohol) pH H Pp
(PVA) H,cC—=C ben
sae Le rat
H H H
 Poly(acrylonitrile) a Ht eh

iia H CN"
Poly(acrylic acid ) H 5 eB
ee, + c—ce
COOH / \—n
n COOH
methacrylate) 1.C==¢ Pie—cP
PMMA
( ) COOCH; H n
ee
Poly(methy! acrylate) } HM H
H.c=c ees /

COOCH; H boocH,
Poly(methacrylic acid) pus an CH3
H,C—C CcC—cC
= \ ley “
COOH H
 Poly(tetra fluoro ethene) [F ~~ a Bo oe sar
(Teflon) =< fo—<
F F F rE foe
Poly isoprene 7 Hs H Hs fi
(Natural rubber) H,>C—=C—C—cH é—c—c—é
2 —=CH2 i = —-
| ~- | 1 ot ny
H H H #H
Poly chloroprene 7 H . H
(Neoprene) H»C==C
2 —C==CH
= 2 +- c—c=
— c—c-
| | | Ln
H H H H

: fou-fonstl
Poly caprolactum HN--CH-C==0 7
(Nylon 6 )

5:-
Poly(hexa methylene Oo Oo
adipami
Pp de) , NHfCH2}NH miCFCH2}C
—
(Nylon 66) .
,
6 an
Poly carbonates
(PC)
Cc)
eet
foe

CH~ & “nA

Poly phenol — - ‘OH _

formaldehyde H.C CH CH3
(Novolac) = ; “A,

OH
Poly phenol : OH OH
formaldehyde
(Bakelite)

: ‘i . Re

“Hae a
Functionality: The number of reactive centres or functional groups present in a
monomer molecule.

Monomers are called bifunctional, trifunctional, etc, depending on the number of

functional groups or reactive centres present.

Bifunctionality is the basic requirement for the formation of a polymer. All vinyl

Eg: Terphthalic acid, Hexamethylene diamine, Adipic Acid - Bifunctional.

oO
O ll
es ‘OH + H2N FOO gO gf NH2

OH Y oO
HO adipic acid hexamethylene diamine
Trimethylol phenol - trifunctional

Ethyne - tetrafunctional monomer

The final structure of polymer (whether linear, branched or cross-linked)

depends on the functionality of its monomer. Generally, bifunctional
monomers give rise to a linear polymer whereas trifunctional monomers
form a cross-linked polymer.
 What makes the polymers to have unique properties in comparison with monomer?

Length to diameter ratio of a polymer is very high compared to that of a simple

molecule. This characteristic difference affects their physical properties.

Due to their long lengths, molecules in a given sample of a polymer material

remain in a state of entanglement, both intermolecular and intramolecular.

High melting or softening temperature, high melt or solution viscosity arise as a

consequence of the big size and the entanglement of the molecular chains.
 Classification of Polymers

Classification on the basis of origin:

Natural Polymers:
They are available as such in nature. Examples of such polymers are natural
rubber, (1,4-cis-polyisoprene), natural silk, cellulose, starch, proteins etc.
(organic), silicates, glass, etc.,

Semi-synthetic Polymers:
They are chemically modified natural polymers such as_ hydrogenated,
halogenated or hydro halogenated natural rubber, cellulosics, i.e., esters and
ethers of cellulose such as cellulose nitrate, methyl cellulose, etc.

Synthetic Polymers:
They are manmade polymers prepared synthetically. Examples are PE, PS, PVC,
Bakelite resin, Polyesters, nylons (Organic) and silicones(Inorganic).
 Classification on the basis of thermal response
Thermoplastic Polymers:
They can be softened and plasticised repeatedly on application of thermal
energy without much change in properties, if treated with certain precautions. Eg.:
Polyolefins, PS, Nylons, Linear polyesters, PVC, Polyethers.

They normally remain soluble and fusible after many cycles of heating and
cooling. They consist of long chain linear (branch) structures with negligible cross-links.
They soften on heating readily because the secondary forces between the individual
chains can break easily by heat or pressure. NO Chemical changes occur Upon heating.
Temperature of use is limited to its softening temperature.

Thermosetting Polymers:
They are formed by condensation polymerisation and obtained in soluble and
fusible forms in early or intermediate stages of their synthesis. But they get set or
cured and become insoluble when further heated or thermally treated.
 The curing or setting process involves chemical reactions leading to further growth and
cross linking of the polymer chain molecules.

They have three dimensional network structure, joined by strong covalent bonds. They
retain their strength on heating and hence they do not soften on heating - so cannot be
reshaped and reused. On prolonged heating, however, charring of polymers is caused.
They are hard, strong and more brittle. They are insoluble in organic solvents.
It is clear that a thermo-set resin once moulded into plastic cannot be converted back
to the original resin.

Thermosetting polymers have higher Use temperature and dimensionally more stable
than thermoplastics.
Examples: Phenolic resins, urea/melamine resins, epoxy resins, unsaturated polyesters,
etc.
 Classification on the basis of mode of formation
Addition Polymers:
These polymers are formed by simple additions of monomers to each other in quick succession by a chain mechanism.
Eg: PVC, PE, PS, PMMA

Condensation polymers:
They are formed from inter molecular reactions between bi-functional or poly-functional (tri or tetra) monomer
molecules having reactive functional groups such as -OH, -COOH, -NH;, etc., by condensation polymerisation (step)
through elimination of simple Molecules like water, ammonia, ethanol, etc., as by products.

n nec) — nef angoc-Ccr)- -COOR———_—= fm cH) NH —co-fcH}—c oo} + (2n-1) HO

condensation potymeris.

Gamine adipic acid nylon-66 [poly(hexamethylene adipamice))

n HOE
tt VA
=e!
Y
Ufo
ft
a Ho—cH.—cHz-on SOD
- (2n -1)H20

condensation polymerisation
ethylene glycol
terpthalic acid
Linear Polymers:

They are formed from olefinic, vinyl or related polymerisation or by condensation

polymerisation of bifunctional monomers.

Linear molecules consist of monomers linked by primary covalent bonds but the
different chains are held together by secondary van der Waal's force of molecular
attractions.

This gives the possibility of chain movement in one direction.

They have higher molecular slippage, higher molecular mobility and less
dimensional stability
Branched Polymers:

The branches appear as a consequence of uncontrolled side reactions occurring during

polymerisation or while design of polymerisation.

Branched polymers are usually more readily soluble and fusible than linear molecules of
comparable chain length and molecular weight (because of lower crystallinity and lower
density).

In this type of polymers, the movement of polymer chain is more restricted than that of
simple linear chain molecules.

Branched polymers are also obtained when trifunctional monomer is mixed with
bifunctional monomer in small amounts during polymerisation.
Cross-linked/network Polymers:
They can be represented by network structure, planar network (as in graphite), and space-
network (as in diamond).
Polymerization of poly-functional monomers.

Here, monomer molecules are connected to each other by covalent bonds resulting in a
formation of a three dimensional network.

In such molecules, the movement of individual molecules is prevented by strong cross-links.

Cross linked polymers are insoluble and infusible as the molecules in them are giant
molecules with high molecular weight. Depending on nature and frequency of cross links,
such polymers may show different orders of swelling in solvents. They are strong and tough
since the movement of intermolecular chains is totally restricted.
Also the plastic deformation does not occur on heating due to the presence of primary
covalent bonds and no slipping between the molecules is possible.

Examples: Phenol-formaldehyde resins, epoxy resins, vulcanised rubber, urea formaldehyde

resins, etc.
 Lecture-2

CY 110:POLYMER SCIENCE

ClassifiCatiOni.cessscscissseeses
Classification based on application and physical properties:
Rubbers (Elastomers):
These are polymers which have elastic properties in excess of 300%.
Their structure is in the form of a coil and hence they can be stretched like a spring.
Their chains get reverted back to the original coiled state as the deforming stress is
released.
The unstretched rubber is amorphous and stretched rubber is partly crystalline. They are
formed by addition polymerization.
Elastomers exhibit tensile strength in the range of 300-3000 psi and elongation at break
ranging between 300-1000%.

They become useful, if cross-linked to the desired extent by sulphur which is known as
vulcanization.

Examples: Natural rubber, Buna-S, Nitril rubber, Silicone rubber

To sum up:

(i) Rubbers stretches rapidly and considerably under tension reaching high

elongation (~ 500 %) with low damping (little loss of energy or heat)

(ii) They exhibit high tensile strength and high modulus when fully stretched

(iii) They retract rapidly exhibiting the phenomenon of snap or rebound

(iv) They recover their original dimensions fully on the release of stress, exhibiting

the phenomenon of resilience and low permanent set

(v) They have high local segment mobility (low gross mobility)

(vi) They have their use temperature above Tg, (low cohesive energy)
Plastics:
In general, the properties of plastics are intermediate between those of fibres and
elastomers.
Some plastics are hard, rigid, stiff and dimensionally stable, while others may be soft and
flexible.

Plastics exhibit tensile strength ranging between 4000-15000 psi and elongation at break
usually from 20-200% or even higher.
They are stronger than rubbers. They are partly crystalline. They have cohesive energy in
the range of 2 - 5 kcal/g. mole per 50nm chain length, which is higher than those of
elastomers but lower than those of fibres.

Examples: PE, PP, PS, PVC, poly amides, phenol-formaldehyde resins,

poly carbonates etc.

They include both thermoplastics and thermosets.

 Fibres:
They are the strongest of the 3 different types of polymers. They have very high mechanical strength
(tensile strength in the range of 20,000 - 150,000 psi), good thermal insulation, softness and flexibility.

They exhibit molar cohesion energy in the range of 4-10 kcal/g.mole per 50nm chain length).

High tensile strength and modulus characteristics of fibres are

generally obtained by utilising the combination of molecular symmetry and high degree of crystallinity.

Their crystalline melting point is in the range of 200 — 300 °C (well below the decomposition temperature
of the polymer). Their Tg is not too high and not too low.

Linear polymers with high symmetry and high intermolecular forces resulting from the presence of polar
groups in the chain, high molecular weight (to impart tensile strength) with no branching (detrimental to Is
crystallinity) and cross linking, are the best fibres.

Examples: Wood, Silk, Cotton, Jute — Natural Fibres

Nylon 66, Nylon 6, Terhlene, Orlox — Synthetic Fibres
 Resins:
Resins are low molecular weight polymers (or pre-polymers) which occur either in
solid or liquid form. They may be used as adhesives, varnishes or molding materials
for plastics.
Examples: Phenol-Formaldehyde resin (Novalac),
Urea-Formaldehyde resin, Epoxy resins, etc.

Mechanical behaviour (stress-strain property) of 3 types of polymers

rigid/plastics

fiber( high strength)

flexible plasti

stress in psi

elastomer

———

a
 Classification on the basis of Tacticity:

A vinyl polymer, i.e., -[CH,-CH(R)]- is characterised by presence of an asymmetric

carbon atom in each of repeat units of the chain molecule, and a type of stereo
chemical difference that may arise in segments of the chain is d/l isomerism.
Isotactic :(same order) Here all R groups lie above (or below) the plane of the main
chain. Because of high order of regularity in these structures fostering close packing of
molecular chains, they are highly crystalline.
R R R R R R
| | | | | |

thee
-

x=
Example: Polypropylene

Syndiotactic: (Contrasting order) R is arranged alternatively, one above and one below
the plane of the main chain

Eg: Polystyrene

R { i Ri
Atactic: (without order) Completely random placement of R groups
R R R
Eg: PVC teats sce ala
nature.
 Explain Polymers and their Classification

> Side aroups of the > Side g roups of polymer

monomers tie on the are arranged in an
same side of the chain alternate m

oe 6
veveves eet Poymer
— ae
poles
;
> Side groups are arrange
in an irreguiar or random
manner around the main
chain

4 eSeyes-
 Classification on the basis of arrangement of molecules:

When cooled from molten state, polymers exhibit different tendencies to crystallize, at
different rates depending on many factors, such as prevailing physical conditions,
chemical nature of the polymers, their molecular symmetry, structural regularity
/irregularity,(stereo regularity, chain branching, copolymerisation, geometrical
isomerism, etc.).

Bulky pendent groups or short chain branches of different lengths hinder molecular
packing and inhibit crystallization.

The nature of crystalline state of polymers is not simple.

Amorphous state Crystalline state Semi-crystalline state

ek dei saeibagh das Syndiotactic polystyrene polyethylene (PE)
Atactic polystyrene Sutletavia hthalate (PET
Polycarbonate
y Nyon
Polyketones ponyeenene fereeraare (PTFE)
polytetrafluoroethylene iEev
Polyisoprene Kavlar and Namav isotactic nolvnronviene (PP).
Amorphous state is characterized by a completely random arrangement of molecules
(chains). Polymers such as natural or synthetic rubbers, glassy polymers (like as poly
styrene, acrylate, methacrylate polymers) have a long repeating unit or with a low
degree of symmetry (bulky side chain) and form amorphous structures.
These polymers are soft and flexible, low density and strength, higher flexibility.
Amorphous polymers, free from fillers or other impurities are transparent. Normally,
thermoplastic polymers can exist in amorphous state. They possess wide range of
softening point.

Crystalline state is characterized by an orderly arrangement of polymer chains. High

degree of crystallinity imparts a denser packing of molecules, thereby increasing the
intermolecular forces of attraction. This accounts for higher and sharper softening point,
greater rigidity and greater density, as compared to amorphous polymers. They are
generally hard and brittle. Polymers showing a high extent of crystallinity (>60%) are
commonly known as crystalline polymers. They are more resistant to solvents and
chemicals compared to their amorphous counterparts.
Semi-crystalline polymers consist of crystallites embedded in an amorphous matrix.
Here, crystalline zones have orderly arranged molecules/chain segments while
amorphous zones have a lack of regular arrangement of chains.

In such polymers, the crystallites provide hardness, rigidity and heat resistance, whereas
the amorphous matrix areas provide flexibility. In actual practice, many polymers belong
to this category. Crystallization tendency can be decreased by copolymerisation, because
it lowers the structural symmetry.

The importance of amorphous phase in semi-crystalline polymers:

(i) It provides flexible matrix for displacement of crystallites which is important for good
mechanical properties
(ii) It provides a medium for stress transfer and energy dissipation
(iii) It provides the regions which can accept the dye and also moisture absorption
(iv) fillers and additives are accepted by amorphous phase
 Classification of polymers based on nature of monomers:
Homo-polymers:
A polymer whose chain/molecules are composed of same kind of repeating units is
called as homopolymer.
Ex: -M-M-M-M-M- where M stands for identical monomer.
Eg: PE, PVC, PMMA, Teflon, etc.
Copolymers:
A polymer whose chain/molecules are composed of more than one kind of repeating
chemical units is commonly called a copolymer.
Ex: -M1-M1-M2-M2-M1-M2-M2-
Styrene-Acrylonitrile copolymer (SAN), Styrene-Butadiene copolymer (SBR), Styrene-
Acrylonitrile (Buna-N), P(VC-VAc)
The ultimate aim of preparing a copolymer is to obtain the desired properties in it.
Their properties are different from those of either homopolymer or random
copolymer.
A polyester, -PA-EG-MA-EG- where PA :Phthalic Acid, MA: Maleic Acid and EG: Ethylene
 Types of copolymers:
(i) Random Copolymer: It is a type of copolymer wherein two monomers appear in its
structure in a random sequence as
-M1-M2 —M2-M2-M1 —M2 —M1-M1 -—M2 — Eg: (Styrene, butadiene)
(ii) Regular Copolymer/Alternating Copolymer: In this type, monomer units appear
alternatively.
-M1—M2-—M1 -M2-M1-M2-M1-M2- Eg: (Vinyl chloride, vinyl acetate)
(iii) Block Copolymers: They are linear copolymers in which the like monomeric units occur
in relatively long sequences as blocks. The sequences follow one another along the main
chain
-M1 —M1 —M1 —M1 —M2 —M2-M2-M2-M1 —M1 —M1 -M1 -
Eg: (Acrylic acid, methylmethacrylate)
(iv) Graft Copolymers: are branched structures in which the monomer segments on the branches
and the backbone differ. In the following example, the
—M,— M,—— My My ——
main chain is made up of MI segment while the branched
structure has M2 segments. 7 t
Eg: (Vinylchloride, styrene) |
M2 M2

Me Ma
 Mechanism of Addition Polymerization (Chain-growth polymerization)

It is characterized by a self-addition of the monomer molecules, to each other very

rapidly, through a chain reaction without by product formation

(i) free radical (ii) ionic (cationic or anionic) or (iii) co-ordination mechanism
Free radical chain polymerization:
1. Initiation: The initiation of the chain growth is brought about by free radical
produced by the decomposition of compounds called initiators. Initiators are
thermally unstable and readily decompose into products called free radicals
UV light or heat
Re RR
(homolytic cleavage)

Organic peroxides, hydro peroxides, per acids, low molecular weight compounds
containing azo groups are useful as initiators
Initiators:
Organic peroxides, hydro peroxides, per acids, low molecular weight compounds
containing azo groups are useful as initiators

CH, CH CH CHy

IR —> me} + N=N + fam

CN N

©1406) — Opin . LO)

oO oO

9 =o)
Onutr —- ©-:

fo =
Benzoyl peroxide 2,2'-azo-bis-isobutyrylnitrile (AIBN)
The free radical attacks the double bond in the monomer molecule, resulting in the
formation of another free radical

X X

This process of electron pair coming down from its pi energy level to the sigma level is
associated with an energy release of 20 kcal as pi electrons are at higher energy level
than the sigma electrons. Hence the free radical attack on the monomer initiating
polymerization is an exothermic process, whereas free radical formation by initiator
decomposition is an endothermic process
2. Propagation:

ao"
R—CH,—CH = H3C-—CH, ———» R—CH,—CH—CH,—CH’
i Tac oe i ‘ 2—GH
xX xX

R Cech ol —cHf CH — oH
x a x
3. Termination:

This is the final step in polymerization, wherein growth of polymer chain stops

Since the decomposition of the initiator produces many free radicals at a time, each one

of them can initiate and propagate the chain growth simultaneously and hence, at any

given time, there may be quite a few growing chains present in the system.
 (i) Coupling:

The two growing chains unite by the coupling of lone electron present in each chain to
form a bond. This leads to formation of polymer chain of high molecular weight

eae tt + ponesaan

Rohe pHf Cryo cH parr foy—e GH-CHR

x x? x x x "x
(ii) Disproportionation:

One -H atom from one chain is abstracted by the other growing chain to get a
stable dead polymer

a i a , na op oie
Xx x x X xX xX

eee oe + pricH oH —arf ocr

K- S ie
dead polymers
 (iii) Chain transfer:

It is a method of chain termination which takes place by the transfer reaction. Here the
growing polymer chain abstracts H atom or some other atom from the initiator /
monomer / polymer / solvent / impurity, forming a dead polymer. Simultaneous
formation of a new free radical also takes place

R—CHe-GHt Chet cH—GH A ee R—CH,-CHL-CH,—CHL-CH,—CH, + R’e

X x * x . yon

The newly formed free radical may now initiate the polymer chain growth a fresh

So, termination and initiation takes place simultaneously in this case

Inhibitors:
Inhibitors are substances capable of inhibiting the chain growth by combining with active
free radicals forming stable products or inactive free radical. They act as free radical
scavengers, when used in small quantity

Eg: Hydroquinone, nitrobenzene, dinitrobenzene, benzothiazine, atmospheric oxygen,

diphenyl picryl hydrazide

OP
NO, N
A

SO
|

ies eee
NO
Some of the inhibitors such as diphenyl picryl hydrazide (DPPH) exist in the form of
stable free radicals which can easily stop the chain growth by direct coupling

ON O.N
i.

OQ OG
N—N NO. + P —___,_ N—N NO,

Atmospheric oxygen is a good inhibitor. The inhibiting action of oxygen is due to its
biradical nature.
Bde Gee ices This is why free radical polymerization is
Beigel a. be eee te generally carried out under nitrogen/
inert atmosphere

A major use of inhibitors is in the preservation of monomers during their production,

transportation and storage
Inhibitors are also used in the industry for the purpose of arresting the polymerization
to control the molecular weight
Wh nw. eee oe ee Le A od ee ee ae ake 2 Af ww Ad. we et
 lonic Polymerization

Two types: (A) cationic polymerization (B) anionic polymerization

Cationic polymerization:
Polymerization in which the initiation is done by a proton and the propagation carried

out by a carbonium ion is called cationic polymerization

Protonic acids such as H,SO,, HCIO, (H*) or Lewis acids such as BF3, AICI3, SnCl, ,TICl,
which are strong electron acceptors, initiate polymerization of monomers carrying

electron releasing substituents

All Lewis acids or Friedel-Crafts catalysts become effective in presence of a co-catalyst,

which complexes with the catalyst and acts as a proton donor. The co-catalyst may be

water, alcohol, organic acid, alkyl halide or even a hydrocarbon

Mechanism :

(a) Chain initiation:

BF, (Lewis acid), in presence of small quantity of water (co-catalyst) forms a hydrate
complex, which exist as ion pair as:

BF3+H20 ———» ___[F3B- OH] -------- H

Where H*’ is initiating cationic species and
[F,;B-OH] is counter ion

[F3B - OH] —-------H" + 4,c=CH ——> ee as [F3B - OH]

X
X
 (b) Chain propagation:

H,;C—CH’" [F,B-OH]! +n a ee joe [FB- OH)

X X

(c) Chain termination:

(i) Donation of a proton to the counter-ion:

as .
H3C erie (B00, Ho-He—ToH—cHlchi=oH + (F,B-OHTH"
i yom |

The formation of [F;B-OH]H* is called ion-pair precipitation

(ii) Formation of a covalent bond between carbocation and counter ion, OH”

HO
!

saa | cH — cH —cH,-ch [F38

- OH} —————_» re | CHC cH, + BF
x er | x xt |

Eg: Monomers containing electron releasing substituents, such as isobutylenes,

styrene, methyl styrene, vinyl ethers
 Anionic polymerization

monomers having electron-withdrawing substituents

Catalysts: Amines, alkoxides, hydroxides, alkyls and aryls of alkali (sodium) metals and
different Grignard reagents

Mechanism:

(a) Chain initiation:

NaNH, ———> Na 4 NH)

RLi weee | Ra

Na NH, H,C=CH —————————_ H2N—CH2-CH Na’

 b) Chain Propagation:

ee ee Na’ : n ae > H,N—CH, Hof cH cH ClCH Na’

n-1
X xX X

The difference between cationic and anionic process is that, in the former

case, the movement of the electron pair is in a direction opposite to that

of the chain growth, where as in the latter case, it is in the same direction.
(c) Chain termination:
- Not spontaneous unless some impurities are present or some strongly ionic substances

are added deliberately, no termination occurs

The chain ends remain potentially active

If a fresh quantity of monomer is added, the polymerization continues until all the

monomer added is consumed. Thus polymer is a living entity - living Polymers. They are

alive and keep on growing, as long as we supply afresh quantity of the monomer

It is essential that anionic polymerization is done in absence of all reactive impurities

The presence of small impurities like water, oxygen, carbon dioxide, even in traces will

cause termination by proton transfer

 Thus, living polymer formed in pure and uncontaminated systems, can be

terminated after complete conversion of monomers as and when desired by the

addition of proton transferring agent.

Usually block copolymers are prepared by this technique.

GH + NH, ee Pos oo Hache He—L-cHy— Ht CHa ot 6 aes

Ha-cHe—f : cH — oH city
e n-1
x oe (impurity) x * s

Eg: Butadiene, isoprene, styrene, acrylonitrile, methacrylonitrile, methylmethacrylate,

etc. — contain electron withdrawing groups
 Co-ordination Polymerization

Polymerization reactions of olefins and dienes which are catalysed by organometallic

compounds
R-CH,-T where T represents transition metals such as Ti, Mo, Cr, V, Ni, or Rh.

Ziegler-Natta catalysts:
comprise of two components, catalyst and co-catalyst
Catalyst - halides of Ti, Mo, Cr, V, Ni, Rh having variable valance
Co-catalysts are organometallic compounds such as tri ethyl aluminium or di ethyl!
aluminium chloride (aryl or alkyl | - 1V group metals)
Imp Ex: Triethyl aluminium + TiCl,
Diethyl aluminium chloride + VCl,
Butyl lithium + TiCl,
Butyl magnesium iodide + TiCI,
AIR; acts as electron acceptor and TiCl, acts as the electron donor
Heterogeneous in nature
 Natta's bimetallic mechanism:

The structure of active centre can be considered as

R
R
N\
ZAI TK Cl oor AIR CI : Tic, *
4
Cl
R cl

The active centres are formed at the surface of the solid phase of the catalyst complex
and the monomer is complexed with the metal ion of the active centre before its
insertion into the growing chain takes place. Thus the polymer chain growth
propagates from the active centres

When the catalyst and co-catalyst components are mixed, there occurs a
chemisorption of the tri alkyl aluminium (electropositive) on the TiCl, solid surface,
resulting in formation of an electron deficient bridge complex which acts as active
centre. The monomer is then attracted towards Ti-C bond in the active centre, when it
forms a pi complex with the Ti -ion
R cl RL cl
is. / hzCaw=CH-CH , ——————» Al 1i,
e. mn Ti
“™\ +
Ra cl
R . cl: Cl ‘co
H2C—=CH-CH,

7V complex
the bond between
CH, R and Ti opens up
forming an electron
|
dificient Ti and carbanion
_ CH st ; CH;
fo
> R R *
. Gre
7 da =

R
| | —— ie.eo CH,
| ' Zo Ti attractspi electron pair to form sigma bond
a
Al Ti while the counter ion attracts electron Cl. “Ti,
fom ‘ “Cl dificient centre of the monomer
R \ . ©
fo
>
cl

mco..omer inserted in to
transition state giving
fing structure
The transition state now gives rise to the chain growth at the metal-carbon bond,
regenerating the active centre
R—CH —CH;,

CH>
Rv CH;
1. CH —CH;
H.C—CH

HC3 ~ oa cl ; ‘CH 3 H.C oh Ci

Al if. —e 7 7 and soon
H,C cl cl wf ,
3 H;C cl cl

The monomer inclusion is repeated in this manner and the orientation of the
substituent group of the monomer is always taken from the metal-ion end, resulting
in a stereo regular polymer
Factors such as type of catalyst system, catalyst crystal structure, molar ratios of the
catalyst components, temperature and solvent influence the type of stereoregular
structure of the polymer formed
 Cossee's monometallic mechanism:

Aluminium is chemisorbed on the solid TiCl;, leading to form five-coordinated titanium

ion, carrying a vacant d-orbital. The monomer is attracted towards the vacant d orbital to
form a Pi-complex. This gives rise to the growth of the polymer chain by monomeric
insertion at the Ti-Et bond in a particular spatial arrangement, leading to formation of
stereoregular structure

e cl R s “CH —CH,
Ti.—Q H,C=CH-CH : Bes : cl |
cr/\ seiaeeeeeeoe Ti 7 __HC i Ti x CH,
ci Cl cr /\ CH, cr/\
cl Cl ci Cl

R—CH-CHs
CH, oO CH —CH,

soon ae 5 Al tn |.
TZ Ct bn

ci Cl ci Cl
(i) Initiation:

Mt —R + H2C—CH Mt CH GHER

active centre
X Xx

(ii) Propagation:

Mt —CHy-CH-R +9 sD Mt —ore gif ounie-fR

x X x en
(iii) (a) Termination by an active hydrogen atom

Mt —cr-chf oli cHL-R +R R'—CHy-CHECH,-CHER + Mt-H

x xo x Kon
(b) Termination by transfer with monomer

at —or,-cuf-cly-cHER + H,C=CH ————__» H0=0-f-cly-cHER + Mt —CH)—CH,

] it. l
x 4 Xx x Xx

(c) Termination by spontaneous internal transfer

Mt —chy-cHf-cH,-cHER +» c=c-} cnc R+ Mt—H

x Kon x xn
where Mt denotes transition metals like Ti, Mo, Cr, V, Ni, and Rh
 The concept of average molecular weight
The given polymer material is mostly a mixture of molecules of nearly identical chemical
structures but varying in chain length or molecular weight. The molecules produced in
polymerization reactions have lengths that are distributed in accordance with a probability
function which is governed by the mechanism of reaction and conditions of
polymerization
Polymers are polydisperse and heterogeneous with respect to molecular mass. Therefore,
a concept of average molecular weight is important and relevant in case of polymers

Number average molecular weight

It is defined as the total mass of all the molecules in a polymer sample divided by the
total number of molecules present in it
Assume that there are n number of molecules in a polymer sample and mi of them have
molecular weight Mi: nz have molecular weight M2 and so on till we get ni having molecular
weight Mi.

Now, we have total number of molecules (n) given by: n = ni+n2+ n3+ng- ......... +ni. = > 0;

The number of molecules in fraction 1 = n;. Its number fraction =

So, the molecular weight contribution by fraction 1 = n,M,

ya,
\¥ the molecular weight contributions by other fractions are:

n,M, n;M, n.M.

¥ a," Ya, 5 Seavdeuvscsessoreevesevess Yn,
 Number average molecular weight of the whole polymer (Mz) will then be given by:

Ta ya ys Fa
ny , BoM. , 23M; | Se Otiat , 2M _ >» aM, = Tk

Evaluation of Mais useful in understanding the polymerization mechanism and kinetics. It

plays prime importance in determining the solution properties known as colligative properties.
It is determined by osmometric method. Polymer molecules of lower molecular weight
contribute equally and enjoy equal status with those of higher molecular weight in
determining these properties.
 Weight average molecular weight

a ¥a,M;
pe Sia,M,

Derivation:

The total weight of polymer = >yin\M,

The weight fraction of fraction 1 = n,M,

———
S'n,M,

n,M,
Then, its molecular weight contribution = —— x M
yaM,
 |. molecular weight contribution by the other fractions are as follows:

n)M; 03M; n,M?

Tale Sok en rae
— — —

The weight average molecular weight of the whole polymer (all fractions) will then be given by:

2 2 , 2
+ + Poca ewenteueeees +i =. &*— = M,
> 0,M;, Sn,M; Ya,M; Yi a,M; S'n,M;,
 M. is important in relation to bulk properties of polymers that reflect their load
bearing capacity
Softening, hot deformation, tensile and compressive strength, modulus and elongation,
toughness and impact resistance are much dependent on 4, values, in addition to
their chemical nature.
It is determined by light scattering method.

Generally, for synthetic polymers, yy. s greater than M.,- If they were to be equal, the
polymer may be considered as pertectly homogeneous (each has same molecular
weight), but this does not happen in polymers. Since heavier molecules contribute more
towards yy, than light ones

Degree of polydispersity _ ; ;
is indicative of the extent (degree) of polydispersity
Mw and is a useful measure of the breadth of the
M molecular weight distribution curve.
Problems 1. Consider three hypothetical mono dispersed systems with M = 10,000. M =
100,000, M = 1,000,000, respectively. Calculate the Ms and Mw for each, after adding each
other in equal percentage. If 20% of another monodisperse system with molecular mass of
1,50,000, is mixed with the above polymer, what would be the new Maz and Mw values?

= nM 10K x 4+100K x24+1000K x4

Solution: Ma:= .4s= SS = ? (imterms of K)
Da

2 A
_ _ aM; 2
- 10.000 2
a 1 Ten 2
251 =a
”
Sa,M, 10,000 x = +100,000 x= +1,000,000 x

1SOK x 2 + Kx
(Ma )20+80 = —— = ? (in terms
of K)

_ 150,000? x4. + (277 x 4

150.000 Xz + (2?) x 3
Problem 6: Equal masses of two mono-disperse systems with molecular masses 10,000 and
1,00,000 are mixed to get a poly-dispersed system. Calculate its Mz. Mw and polydispersity
index (PI). (4 marks)

Solution: Let mi = m2 = 2,.00.000 (say).

.
Then, number of moles n; = mee = 200.000 ne
molarmassof M, 10.000
mass m, _ 2.00,000
Also, number of moles n2 = =2
molar mass of M, = 1,00.000
n,M,+n,M, _[20x10,000]+[2 x 1.00.000]
Mz = =18.182 gmol™
n,+n), 20+2

Sex BMI+ M3 _ [20% (10.000)"}+12x (,00.000)"] _ 5 099

12s 2 2 >
» mol”
2 > 2

n,M, + n,M, 20 x 10,000] 7 [2 x 1,00.000]

PI=
Me _
ma
55,
——— = 3.02
Mz 18.182
 Lecture-5

CY 110:POLYMER SCIENCE

Polymerization Techniques
 Polymerization Techniques
1. Bulk or Mass polymerization 2. Solution polymerization
3. Suspension polymerization 4.Emulsion polymerization

Bulk Polymerization

Monomer - liquid state, initiator and the chain transfer agent (used to control the
molecular weight) are dissolved in the monomer
The homogeneous reaction mass is heated or exposed to radiation sources for initiating
the polymerization and it is kept under agitation in nitrogen atmosphere for proper
mass and heat transfer
As the polymerization proceeds, the viscosity of the medium increases. Desired
temperature is maintained by heating or cooling
When the reaction completes, the molten mass is extruded into rods/sheets/solid
polymer
Advantages:
It is a simple method, requires simple reactor
The conversion is high. The purity of the product is high (since except initiator and chain transferring
agent, no other additives is used)
The product needs neither isolation nor purification
The product has high optical clarity

Disadvantages:
Agitation of the reaction mixture is difficult, as the mass becomes more and more viscous. This leads to
the products with very broad molecular weight distribution
As the medium gets viscous, the diffusibility of growing polymer chain becomes restricted. The
probability of chain collision becomes less, termination become difficult. Active free radicals sites
accumulate and rate of polymerization increases enormously causing auto-acceleration (gel formation),
uncontrolled exothermic reaction which can lead to explosion
Due to very low thermal conductivity of polymers and exothermic nature of polymerization reaction,
there is a danger of reactants overheating which leads to explosion
Very poor heat and mass transfer is the major demerit of this method
Careful control of temperature is required in this method. This technique is suitable for less exothermic
polymerization reactions

Meh. ewe ein Af RARAAR ote eee weld ebend eeble we fe ee wn te abn ~ sb At
 Solution Polymerization
The monomer is dissolved in a suitable inert solvent along with chain transfer agent. The free radical
initiator is also dissolved in the solvent medium
lonic or coordination catalyst either be dissolved or suspended
The homogeneous solution is kept under constant agitation and heated to a temperature of
polymerization to initiate the reaction. After completion of the reaction, the polymer is isolated either by
evaporation of the solvent or by precipitation by adding a non-solvent and subsequent filtration
Advantages:
* The solution can be directly used in adhesive / coating compositions
¢ The presence of inert solvent medium helps to control increase in viscosity and promote a proper heat
transfer and mass transfer
Disadvantages:
* Inert solvent may allow growing polymer chain transfer to the solvent and hence it is difficult to achieve
very high molecular weight products
* The polymer formed will have to be isolated from the solution either by evaporation of the solvent or
by precipitation in a non-solvent. Removal of their final traces is difficult. Purity of polymer is less

Industrial production of PAN by free radical polymerisation and that of poly(isobutylene) by cationic
polymerization, block copolymerization are made by this technique
 Suspension Polymerization
This is a case of heterogeneous polymerization and is designed to combine the advantages of both bulk and
solution polymerization

The water insoluble monomer is suspended in water in the form of fine droplets by continuous agitation

These droplets are prevented from coalescence by using suitable water soluble protective colloids and

surface active agents

The size of the monomer droplets formed depends on the monomer-to-water ratio, the type and

concentration of stabilizers and speed of agitation

Generally, monomer soluble initiators such as organic peroxides or azo compounds are utilized

Low concentration of suitable water-soluble polymers such as carboxymethyl cellulose or methyl cellulose,

polyvinyl alcohol, gelatine, etc., are used to raise the medium viscosity and to stabilize the suspension

Sometimes, a small amount of finely divided clay particles such as kavolin or china clay is added to interfere

with the agglomeration of droplets

The reaction mass is heated to polymerisation temperature. At the end, polymer appears in the form of
tiny spherical beads or pearls in the reactor. Hence this process is called bead or pearl polymerization

The polymers are filtered, washed thoroughly with water to remove the water soluble stabilizers and
finally dried
Here continuous aqueous phase separating monomer droplets acts as efficient heat transfer medium.

Viscosity build-up is negligible

Advantages:
* Due to ready availability, low cost, non-toxic nature, ease of storage, water is the most suited
suspension medium
¢ Isolation of product is easy. The process is economical and polymer has narrow molecular weight
distribution and proceeds to 100 % conversion
* Each tiny droplet behaves as a miniature bulk polymerization system resulting in efficient
conversion

Disadvantages: Water insoluble monomer, Difficult to control the particle size, purity may not be 100%

Expandable polystyrene beads, styrene-divinyl benzene co-polymer beads (used in ion-exchanger

resins), polyvinyl acetate beads are produced by this method using free radical initiators
 Emulsion Polymerization

The monomer is dispersed in the aqueous (water) phase, not as discrete droplets, but as a uniform
emulsion
The emulsion is stabilized by surface active agents-surfactants, protective colloids and certain buffers
Surfactants serve the purpose of lowering the surface tension at the monomer-water interface and
facilitate emulsification of the monomer in water

The surfactant can be anionic (alkali salt of fatty acid - soap) or cationic (alkyl amine hydrochloride) or non-
ionic (alkyl glycosides). Small volume of a selected buffer solution minimizes or eliminates variation of pH
of the system (due to hydrolysis or other reactions)

A low concentration of water soluble polymer (called protective colloids) is also added to control the
polymerization process and to get stable emulsion
Water soluble initiators such as per-sulphates, hydrogen peroxides, redox initiators are widely used. The
whole system is agitated in the absence of oxygen at the desired temperature

The polymer is obtained in the form of well-stabilized latex. It is then isolated by coagulation using
electrolyte or by dry freezing
 Theory of emulsion polymerization:
The monomer is dispersed in the aqueous phase as a uniform emulsion which is stabilized by adding
surfactants. It is normally a soap or detergent (aryl sulphonic acids)

Surfactant molecules have hydrophobic tail and hydrophilic head. At very low concentration, it gets
completely dissolved in water. At a little higher concentration, it gets dispersed. When the concentration
exceeds critical micelle concentration (CMC), the surfactant molecules form a number of micelles

A micelle is an aggregation of 50-100 molecules oriented with tails inwards and heads outward facing
aqueous phase. The interior of micelle is provided with hydrocarbon environment, wherein the monomer
molecules can easily be entrapped

When the monomer is added to the system and agitated, emulsification takes place due to favourable
environment. The resultant emulsion is a colloidal solution of micelles having solubilized monomer at their
interior dispersed in continuous water phase containing soluble surfactants

° e »
aeSOS 0-H sNe” ——_____-—-@ e : i «@
6 ‘ a NS \I/ a
t t t Se
nonpolar tail water soluble head nonpolar tail water soluble head jy lab eS
oe | .
Sodium Lauryl Sulfate Lazy chemist’s representation of
_—@® Surfactant Molecule
@ Initiator Molecule

Gg coy
\ Micelle —

©
\
-@
oo
H-O-O-H 20H:

SO, + Fe?* > Fe?* + SO,? ¥. SO," 86

In the presence of water soluble initiator, the free radicals are formed in aqueous phase and slowly diffuse
through the aqueous phase, penetrate into micelle and initiate polymerization in solubilized monomer at
the interior of micelle

The polymerization growth inside the micelle causes its swelling. As and when monomer inside the micelle
is consumed, further more monomer diffuses into the interior of micelle from the external monomer
droplet

The chain growth continues until another radical species enters and arrests the chain growth. Then the
polymer chains so formed agglomerate into fine particle and get surrounded by surfactant layer of the
micelle

At a particular stage, the micelle bursts and loses its identity. At the end, a milky white dispersion called
‘latex' is formed. The latex is finally coagulated by destabilizing the emulsion

This theory is only representative one wherein the monomer is completely insoluble in water and the
initiator is monomer insoluble
Advantages:

* Polymerization proceeds at the micelles, where the surface/volume ratio is very high, the rate of
polymerization is quite high

* The number of radicals in a micelle is very much limited and since there is continuous supply of
monomer to the growing polymer chain leads to high molecular weight polymer

¢ Milky white polymer dispersion in water (latex) can be used directly for the production of adhesives,
water soluble emulsion paints

¢ The polymer obtained by this technique requires additional clean up and purification steps. It is difficult
to remove entrapped coagulants, emulsifiers, etc. Coagulation of latex is another additional step
involved.

It is the most widely used industrial technique and monomers such as vinyl chloride, butadiene,
chloroprene, vinyl acetate, acrylate and methacrylates are polymerized conveniently
 Lecture 6

Glass Transition Temperature (T,)

 What Is Ty?

«When amorphous polymers are cooled below a certain

temperature, they become hard, stiff, brittle (glass-like) and
when heated above this temperature, they will be soft and
flexible (rubber-like). This transition temperature is called as
glass transition temperature (T,).

* Ty is an important parameter as it decides the workability and

use of a given polymer
 Flow Temperature (T,)

¢In rubber-like state, only segmental motion can take place in

polymers

¢On heating much above Tg, polymer chain eventually obtains

sufficient energy, molecular mobility comes into picture and polymer
behaves as a viscous liquid

¢ This temperature is called as “flow temperature (T,)° for the polymer

Variation of stiffness with temperature

7
PS
(MPa) ————_+»
Stiffness/Modulus
 Factors influencing T,
¢ Crystallinity
¢ Flexibility
¢ Intermolecular forces
¢ Nature of side groups
¢ Cross-linking
¢ Molecular weight
¢ Plasticizers
 Factors influencing I,
Crystallinity:

¢ Crystallinity refers to orderliness.

¢ In crystalline polymers, the chains are arranged in a regular pattern and are
held by strong cohesive forces

¢ In non-crystalline or amorphous polymers, segmental and chain mobilities are

easier when compared to crystalline polymers

* Stereo-regular polymers have higher crystallinity, hence display higher T,

Higher the crystallinity, higher the T,

 Factors influencing I,
Flexibility

¢ Flexibility refers to the degree of freedom with which the different

segments of the polymer can rotate along the chain backbone around the
covalent bond

¢ Single bonds are easier to rotate than double or triple bonds

¢ Presence of cyclic or aromatic groups on the polymer chain backbone

can make the free rotation difficult

Higher the flexibility, lower the T,

Factors influencing I,
Intermolecular forces

The nature of intermolecular forces operating between different segments

(chains) of polymer can influence T,

Ex.: In hydrocarbon polymer such as polyethylene, only van der Waals force
is holding the polymer chains together

If polymer chain contains polar functional groups, such as nylon 6, then they
are held strongly by dipole-dipole interaction as well as hydrogen bonding,
restricting their movement. This will lead to rise in T,
Factors influencing T,
Intermolecular forces

Yh

ZT
Polyethylene, T,: -125 °C Nylon 6, T,: +50 °C

Higher the strength of intermolecular forces, higher the T,

 Factors influencing I,
Nature of side groups:
lf the side groups present on the polymer backbone hinder the free
rotation about the carbon-carbon bond, then the chain mobility is
restricted, resulting in the increase of T,
Example:

CH3

Poly(a-methylstyrene) T, = 170 °C Polystyrene, T, = 100 °C

https://lectures.iris.nitk.ac.in/presentation/592b77fb339d5381
9a4eae51d2c3eb5617410285-
1609420069455/presentation/51b0e9b52bf85863c15532571c
2a2e3221593290-1609420129630/slide-11.png
 Factors influencing I,
pottery, Poly(methylacrylate) T, = +10 °C
HsC.0-NG

CH-CH, ano
HaC-H2C. 6 Ag Jn Poly(ethylacrylate) T, = -24 °C

A, at CH-CH 7 Poly(butylacryl
lacrylate)
ate) T, T, = -54 °C
H3c°*e""*0 SO
H.
Factors influencing I,

Cross-linking:

¢ Cross-linking of chains can decrease the flexibility

* As the extent of cross-linking increases, the T, increases

Factors influencing I,

Molecular weight:

* In general, T, increases with increase in molecular weight

¢ High molecular weight chains can coil, entangle to one another and also
they will have fewer chain ends resulting in lower free volume

Example:

Polystyrene, T, = 40 °C at M, = 3,000

Polystyrene, T, = 100 °C at M, = 300,000

 Factors influencing IT,
Plasticizers

¢ Plasticizers are low-molecular weight, non-volatile substances which are added to

the polymers to improve their flexibility and processibility.

¢ Plasticizer molecules penetrate into the polymer matrix, occupying the space
between the polymer chains and weaken the cohesive forces between them

Hence, presence of plasticizer reduces T,,

Example for plasticizers: epoxidized soya oil, trioutylohosphate, di-n-octyl phthalate

etc.
 Lecture /

Effect of polymer structure on

properties
otructure-property relationship

¢ Tensile strength & impact resistance

¢ Plastic deformation

¢ Chemical resistivity

¢ Elasticity
Tensile strength & impact resistance
¢ Tensile strength refers to resistance to stretching

¢ Impact resistance is a measure of toughness — how well a sample will

withstand the sudden onset of stress

¢ These properties are important for any useful commercial polymers and are
dependent on the molecular weight (DP) of the polymer

¢ Each polymer has a threshold molecular weight value below which it does not
possess useful strength

¢ Polymers having high degree of crystallinity exhibit high tensile strength and
high impact resistance
Tensile strength & impact resistance

¢ High molecular weight also leads to higher melt viscosity

¢ Melt viscosity at a given temperature is a measure of rate at

which the chains can move relative to each other

¢ Very high melt viscosity of polymer makes polymer processing

difficult
Polymer property vs molecular weight
 Plastic deformation
¢ What are plastics?

Plastics are high polymers which can be molded by the

application of heat and pressure

¢ Thermoplastics become soft on heating and hard on cooling and this

process can be repeated for a number of times

¢ Thermosettings fuse on initial heating, but on further heating become

permanently set insoluble, infusible, hard, and rigid. They undergo
irreversible change on heating
 Plastic deformation
¢ Thermoplastics are linear, stereoregular polymers where chains
are held by secondary forces such as van der waals, hydrogen
bonding and dipolar interactions

¢ On heating such polymers, the chains acquire sufficient energy

and overcome these interchain attractive forces. Hence, they
attain molecular mobility and flow like viscous fluid
 Plastic deformation
¢ Thermosettings have three dimensional structure

¢ All the monomeric units are held together by strong primary covalent
bonds throughout the structure

¢ Primary covalent bonds are not easily broken by heat, upon strong
heating, charring occurs instead of deformation

¢ Hence, thermosettings do not undergo reversible plastic deformation

 Chemical resistivity
¢ The hydrocarbon polymers having no polar groups generally swell or
dissolve in hydrocarbon solvents like gasoline, benzene,
cyclohexane etc.

¢ The polymers containing polar groups are attacked by polar solvents

¢ Example: starch, polyvinyl alcohol, polyvinyl acetate are soluble in

polar solvents

“Like dissolves like”

 Chemical resistivity
¢ Polymers containing residual unsaturation undergo oxidative degradation
when exposed to air, ozone or light

For example: the natural and synthetic rubbers which contain residual
unsaturation are susceptible for oxidative degradation in service
conditions

¢ High crystallinity and higher degree of cross linking makes the polymer
more chemical resistance

«In high crystalline polymers, due to denser packing of chains, the

penetration of solvent or chemical substances becomes difficult
 Elasticity
¢ Elasticity refers to the ability to stretch and retract rapidly (resilience)

¢ The polymers which exhibit elastic behaviour are termed as elastomers

¢ In anormal unstretched state, the polymer chains are in a random arrangement

(coiled, entangled)

¢ When stretched, the coiled chains begin to disentangle and straighten out. This
results in a better orientation and improves crystallinity

¢ Improvement in the crystallinity results in an increased force of attraction

between the chains, thereby causing the stiffness

¢ Once the strain is released, the chains return to their original coiled and
entangled form
 Lecture 8
Natural rubber

Compounding of rubber

Vulcanization of rubber
Natural rubber

¢ Rubbers are elastomers, i.e., polymers having elastic properties

«Elastomers undergo very large elongation under stress, yet

regain original dimension fully on release of stress

¢ Elastomers, being hydrocarbons, have negligible inter-chain

cohesive forces
Origin of natural rubber 1 pA
cis-1,4-polyisoprene trans-1,4-polyisoprene

¢ The principal form of natural rubber is Hevea, which consists of 97% cCis-
1,4-polyisoprene

¢ It is obtained by tapping the bark of a tree Hevea brasiliensis that grows

wild in South America and is cultivated in other parts of the world

¢ Rubber is stored in the form of white fluid called ‘latex’ behind the bark of

this tree

¢ The other types Gutta percha and balata, have trans-1,4-polyisoprene

structure, are much harder, less soluble and more crystalline than Hevea
Deficiencies of natural rubber
¢ It is hard and brittle at low temperature, and soft and sticky at
high temperature, making it difficult to handle
¢ It has poor keeping qualities as it develops obnoxious odor on
storage
¢ It is soluble in many hydrocarbon solvents and carbon disulfide
¢ It has high water absorption property
¢ It is readily attacked by acids and alkalies
¢ It has low tensile strength
¢ It has poor abrasion resistance
¢ It is sensitive to oxidative degradation
Compounding of rubber
Rubber compounding or formulation refers to the addition of certain
chemicals to raw rubber in order to obtain the desired properties.
Following ingredients are added to raw rubber:
¢ Antidegradants
¢ Plasticizers
¢ Fillers
¢ Dyes
¢ Curing agents
¢ Activators and accelerators
Antidegradants
An antidegradant is a compounding ingredient added into a rubber compound to retard the deterioration
caused by oxidation, ozone, light or combination of these. Hence, they can be classified as antioxidants
and antiozonants

Antioxidants are added to protect the rubber against oxygen attack while antiozonants are added to protect
the rubber against ozone attack

Antioxidants help protect the rubber compound from high temperature while in use and while the compound
is being mixed. These ingredients can absorb free radicals that can break the polymers bonds and reduce
service life of the compound

Example for antioxidants are mercaptans, sulfides, dithiocarbamates, dithiophosphates, esters of

phosphorous acid

The most common antiozonant is wax which protects the rubber from ozone attack. Ozone attack can lead
to aging and cracks. Acommon example can be seen when purchasing new tires. The surface of a new tire
will have a wax feel or show a slight haze.
 Plasticizer
¢ Plasticizers — low-molecular weight substances that modify the properties of the
elastomer, increasing the flexibility of the macromolecules and mobility of
supramolecular structures, but at the same time reduce their strength and
hardness.
¢ Plasticizers can be products of oil or coal refining (fuel oil, bitumen, oils, resins,
waxes, etc.) herbal products (pine resin, rosin, vegetable oil, fatty acids) and
synthetic compounds (polyesters, oligoester acrylates or polydienes).
¢ Various oils are used to help incorporate all the dry ingredients used in the
rubber compounding. They also help to reduce the viscosity of the overall
compound to help with molding. Adding more oil can also lower the hardness of
the rubber.
Fillers
Fillers are added to enhance the strength, abrasion resistance and tensile strength of rubber
compound. Also, Fillers when added to a rubber formulation will either lower the compound
cost or improve vulcanizate properties

Fillers can be classified into three categories, which are as following:

Diluents or extenders which are intended primarily to occupy space and are mainly used to
lower the formulation cost. This type of filler is also called non-reinforcing filler with particle
between 1,000 and 10,000 nm (1 to 10 um)

Functional or reinforcing fillers are those with particle size range from 10 to 100 nm (0.01 to 0.1

um) which when added to the rubber compound improve the modulus and properties like
tensile strength, tear resistance and abrasion resistance of the final vulcanizate.

In-between these two types are semi-reinforcing fillers with particle size range from 100 to
1000 nm (0.1 to 1um)
Fillers
Fillers can also be classified into black (carbon black) and non-black or white fillers.
These black or non-black fillers may come as diluents, reinforcing or semi-reinforcing
fillers depending on their particle sizes
Carbon black is a black fine powder, a product of thermal decomposition of gaseous
or liquid hydrocarbons. This gives the rubber compound physical strength and its
black color. They are of various particle sizes and surface activities. Variation in
particle size can bring changes in the rubber’s physical properties
The inorganic fillers include natural minerals (chalk, kaolin, bentonite, shungite, talc)
and synthetic reinforcing (colloidal silicic acid, magnesium oxide and zinc, calcium
silicate and aluminum fluoride, calcium fluoride) to obtain high strength, heat-
resistant, non-flammable character and corrosive resistant properties in rubber
compounds
White clays and Mineral fillers are typically less reinforcing than carbon black.
Blending of these fillers with carbon black helps reduce cost of the overall compound
 Dyes
Dyes used in colored rubbers are divided into inorganic and organic
The color intensity increases with decreasing particle size and their ability to be dispersed in
the rubber
The color of rubber affects resistance to aging under the influence of light
White, yellow and green colors of rubber are protective, and blue color accelerates the aging
process, and therefore rarely used. This is due to the rubber’s absorption or reflection of the
certain spectrum
Titanium dioxide ( a mixture of TiO, and BaSQ,), lithopone (a mixture of ZnS with BaSO,),
zinc oxide, zinc sulfide and titanium oxide are used as a white pigment
The intensity of the white color increases with increasing differences in refractive index
between the rubber and pigment, and also depends on the size and shape of the particles
and the other ingredients of the rubber compound
lron oxide Fe,O,, often in conjunction with lithopone and sulfurous antimony, selenium,
cadmium compounds, cinnabar mercury and sulfur, is used as red pigment
Chromium oxide gives blue-green color
Curing agents
Curing agents are chemicals which impart three dimensional network or crosslink structure
to the rubber molecular chains. In doing so, they react with active sites in the rubber to form
crosslinks between the chains.

Sulfur is the most common curative for rubber compounds. Rubber polymers are just
entangled hydrocarbon chains than won't hold shape.

Back in 1839, Goodyear discovered that rubber chains can be bonded together by heating
the rubber with sulfur, called vulcanization. Bonds of carbon — sulfur — carbon are formed in
this process.

Another common vulcanizing agent, peroxide creates direct bonds to the carbon chains
forming carbon — carbon bonds. These bonds take more energy to break, thus typically giving
higher service temperatures and low compression sets. Some polymers can only be cross-
linked with peroxides.
 Accelerators and activators
¢ Accelerator: Accelerators make the sulfur interlinking reaction occur faster and
more efficiently. In other words, accelerators are used in small amounts to
increase the rate of cure and the efficiency with which sulfur is utilized in
crosslinking. Accelerators also control the onset and extent of reaction between
sulfur and rubber. Ex.: thiourea, dithiocarbamate etc.

¢ Retarders are added to the rubber formulation in order to reduce the tendency of
a rubber compound to vulcanize prematurely (delay the onset of cure) by
increasing the scorch delay (prevulcanization).
 Activators

¢ Activators in rubber formulation are typically metal oxides and

hydroxides (such as oxides, and hydroxides of zinc, lead,
magnesium, calcium, cadmium, bismuth or combinations thereof),
especially in the presence of stearic, palmitic, oleic acids and their
zinc salts

¢ Activators can form rubber soluble complexes with the accelerators

and help them to react better with sulfur during vulcanization.
Vulcanization
¢ Vulcanization is a cross-linking process in which individual
molecules of rubber (polymer) are converted into a three
dimensional network of interconnected (polymer) chains
through chemical
> cross ae Sulfur).
X
_ Sulfur
“Heat

.! Rubber Vulcanized (Crosslinked) Rubber

_Sulfur_
Heat
Vulcanization
Rubber vulcanization is carried out by heating the raw rubber with
Sulfur and other agents at 120-150 °C for 1-4 hours

The degree of vulcanization introduced in vulcanized rubber depends

on the amount of sulfur used

Tire industry uses 3-5% sulfur

If the amount of sulfur is increased to 30%, a hard and rigid rubber called
ebonite is produced
 Lecture 9

Synthetic rubbers
Synthetic rubber

¢ Synthetic rubbers are man-made rubbers

¢ One of the greatest scientific discoveries in the history

¢ Buna-S, Neoprene (polychloroprene) were among the earliest

made synthetic rubbers
Advantages of synthetic rubbers
¢ Produced from petrochemical raw materials in abundant
amounts
¢ Economical
¢ In certain cases, they are superior to natural rubber
¢ They can be tailor-made for diverse applications
¢ Improved properties
Buna-S (SBR)

¢ Buna-S is a copolymer of styrene and butadiene, hence the

name Styrene-Butadiene-Rubber (SBR)

¢ Monomers required for its synthesis are styrene and 1,3-

butadiene 4 '

C C

on
synthesis of 1,3-butadiene and Styrene
Synthesis of Buna-S

* Emulsion polymerization method is used

* 3:1 (by parts) ratio of 1,3-butadiene to styrene is emulsified
in water by using soap or detergent
* peroxide initiators are used
* depending on the temperature utilized during the reaction
* SBR is named as cold or hot SBR
Properties of SBR

¢ SBR is widely used because of its availability and economical price

¢ SBR has high tensile and impact strength, resilience, and abrasion
resistance

¢ SBR is flexible at low temperatures and has decent heat resistance

¢ SBR is also water, organic acid, ketone, alcohol, and aldehyde

resistant
Uses of SBR

¢ In the manufacturing of scooter, motor cycle, car tires

¢ In the manufacturing of conveyor belts, footwears, hoses,

gaskets, and electrical insulation
Silicone rubber

¢ Silicone (polymethylsiloxane) is an inorganic polymer

¢ It has a chain of alternating silicon and oxygen atoms and each

silicon atom is bonded to two methyl! groups

efoto} din
n bu,
synthesis of silicone rubber
Vulcanization of silicone rubber
Properties of silicone rubber

¢ High thermal stability up to 250 °C

¢ Water repellent

¢ Exceptional weatherability (virtually no change in its physical

properties even upon prolonged exposure to wind, rain, UV
rays, ozone)

¢ High resistance to oils, solvents and chemicals

Uses of silicone rubber

¢ High temperature cable insulation and safety glass interlayers

¢ Water-proof surfaces and clothing

¢ Tires of fighter aircrafts

¢ Artificial heart valves, transfusion tubing and padding material in

plastic surgery
 Lecture 10

Conducting Polymers

Biodegradable Polymers
 Information Department, P.O. Box 50005, SE-104 05 Stockholm, Sweden
Phone: +46 8 673 95 00, Fax: +46 8 15 56 70, E-mail: info@ kva.se, Web site: www.kva.se

(Advanced Information)
The Nobel Prize in Chemistry, 2000: AlanJ. Heeger Alan G. MacDiarmid Hideki Shirakawa
Conductive polymers Prize share: 1/3 Prize share: 1/3 Prize share: 1/3

Prize motivation
The Royal Swedish Academy of Sciences has decided to award the Nobel Prize in Chemistry for 2000 to three
scientists who have revolutionised the development of electrically conductive polymers.

Professor Alan J. Heeger at the University of California at Santa Barbara, USA

Professor Alan G. MacDiarmid at the University of Pennsylvania, USA and
Professor Hideki Shirakawa at the University of Tsukuba, Japan

are rewarded “for the discovery and development of electrically conductive polymers ”’.

https://www.nobelprize.org/prizes/chemistry/2000/popular-information/
 What are conducting polymers’?
¢ Organic polymers with highly delocalized pi-electron systems,
having electrical conductance of the order of a conductor
@ Example: rw :
 synthesis of conducting polymers
An organic polymer can be converted into a conducting polymer if it has the following
characteristics:

¢ Linear structure

¢ Extensive conjugation in polymeric backbone

The conducting polymers are synthesized by doping, in which charged species are
introduced in organic polymers having pi-backbone. The important doping reactions
are:

¢ Oxidative doping (p-doping)

¢ Reductive doping (n-doping)

¢ Protonic acid doping (p-doping)

Oxidative doping (p-doping)

¢ In this process, the pi-backbone of a polymer is partially

oxidized with the help of an oxidizing agent

¢ This creates positively charged sites on polymer backbone,

which are current carriers for conduction

¢ The oxidizing agents used in p-doping are iodine vapor, iodine

in CCl,, HBF,, perchloric acid and benzoquinone
Mechanism of conduction (p-doping)
Mechanism of conduction (p-doping)
¢ The removal of an electron from the polymer pi-backbone using a suitable
oxidizing agent leads to the formation of a delocalized radical ion called
polaron

¢ A second oxidation of a chain containing polaron, followed by radical

recombination yields two charge carriers on each chain

¢ The positive charges present on the polymer chains are compensated by

the anions I, formed by the oxidizing agent during doping

¢ The delocalized positive charges on the polymer chain are mobile (not the
dopant anions)
Mechanism of conduction (p-doping)
¢ Thus, these delocalized positive charges on the polymer are
current carriers for conduction

¢ These charges must move along the chain and from chain to
chain for bulk conduction

¢ On doping polyacetylene using iodine in CCl,, for partial

oxidation, the conductivity increases from 10° S/cm to 10° to
10° S/cm
Mechanism of conduction (p-doping)
Mechanism of conduction (n-doping)

¢ In n-doping, the pi-backbone of a polymer is partially reduced by a

Suitable reducing agent

¢ This creates negatively charged sites on polymer backbone and

these are responsible for the conduction

¢ The most commonly used reducing agent for partial reduction of

polymer backbone is a solution of sodium naphthalide in
tetrahydrofuran (THF) co} Nat
The addition of an electron to the polymer backbone by
using a reducing agent generates a radical ion or a
polaron
A second reduction of chain containing polaron, followed
by the recombination of radicals yield two negatively
charged carriers on each chain
These charge sites on the polymer chains are
compensated by Na* ions
 Protonic acid doping
¢ The synthesis of conducting polyaniline is a typical example of protonic acid
doping technique

¢ Polyaniline is partially oxidized first, by using a suitable oxidizing agent, into a

base form of aniline

¢ This base form of aniline when treated with aqueous HCl (1 M), undergoes
protonation of imine nitrogen atom, creating current carrying positively charged
species in the polymer backbone

¢ These charges are compensated by the anions (CI) of the doping agent, giving
the corresponding salt

¢ Protonic acid doping of aniline enhances the conductivity by appx. 9-10 orders of
magnitude
 Protonic acid doping
"

| Partial oxidation
Ammonium peroxy disulfate [NH,S.O,]

Protonation
Aq. HCl (1M)
Biodegradable Polymers
¢ Biodegradable polymers are defined as “polymers that are degraded or
catabolized, eventually to carbon dioxide and water, by microorganisms
(bacteria, fungi etc.) under natural environment”
¢ Biodegradable polymers can be returned to the soil and enrich it by being
composied with microorganisms
¢ Usage of biodegradable polymers can lower the cost of labor used for the
removal of conventional plastics from the environment since they degrade
naturally
¢ Moreover, decomposition and degradation of the biodegradable polymers
stabilizes the environment and increases the longevity of the landfills by
decreasing the garbage volume
¢ They can also be reprocessed into useful oligomers by microbial,
enzymatic, and hydrolytic treatment for other applications
Classification
1. Natural biodegradable polymers: These are derived from natural raw materials and renewable
resources,

example: polysaccharides (from starch and cellulose, lignin), proteins (gelatin, casein, wool,
silk), and lipids (fats and oil),

2. Polymers of polyhydroxyalkanoates (PHA’s family): These are obtained from microbiologically

produced materials or genetically modified bacteria

example: poly(hydroxybutyrate), poly(hydroxyvalerate), polyhydroxyhexanoate

3. Synthetic biodegradable polymers: These are obtained by chemical polymerization of biomonomers

example: poly(lactic acid) (PLA), polycaprolactone, polybutylene succinate, polybutylene

succinate adipate, polybutylene adipate/terephthalate, and polymethylene
adipate/terephthalate.
structures of few biodegradable polymers
CH3 O
OH H :

my O OH O OH
O ae n
HO5 O | OH
HO
HO}
HO - -
HOS |3

A
O SN
Applications of biodegradable polymers
¢ Medical applications: sutures, orthopedic devices,
cardiovascular accessories
¢ Drug delivery system
¢ Packing materials
¢ In cutlery making
¢ In food packaging industry
¢ Agricultural film