IGH POLYMER

DEFINITION:

The word polymer is derived from the two greek words

poly ~

many

e.g.

mer

H H H H H H

I I I I I I

·c-c-c-c-c-c·

I I I I I I

H H H H H H

and

mers

~

parts or units

mer mer

HHHHHH H H H H H H

I I I I I I I I I I I I

·c-c-c-c-c-c· ·c-c-c-c-c-c-

I I I I I I I I I I I I

H CI H CI H CI H CH3 H CH3 H CH3

Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)

Polymers are macro molecules formed by linking smaller molecules repeatedly, called monomers.

Examples:

Polyethylene is formed by linking a large number of ethylene molecules

Polymerisatioo

Ethylene

H H

l~-cl

L I I Tn

H H

polyethylene

polystyrene is formed by linking styrene molecules

~ H

n [ C = C / ] Polymerisatiop

I -, H

o

styrene

H H

lc-cl

L I I Tn

o H

polystyrene

Classification of Polymers

Polymers can be classified in several ways, based on ~origin

~structure

~methods of formation ~response to heat ~properties (or applications)

The number of repeating units (n) in the chain is known as the degree of polymerization.

e.g. ,

D.P.

Polymers with high degree of polymerization are called high polymers and these have very high molecular weiqht (104 to 106).

Polymers with low degree of polymerization are called oligomers.

Based on the origin

polymers can be classified as ~Natural polymers ~synthetic polymers

Natural polymers are those which are obtained naturally e.g., Cellulose, Silk, Starch, RNA, DNA, Proteins etc.,

Synthetic polymers are those which are made by man e.g., polyethylene, polystyrene, PVC, polyester, etc.,

semi-synthetic polymers which are chemically modified natural polymers

e.g., cellulose acetate, cellulose nitrate, halogenated rubbers etc.,

Based on the molecular structure

polymers can be classified as

~Linear

~Branched

~Cross-linked

In linear polymers,

the monomeric units combine linearly with each other

secondary bonding

Branch polymers

Cross linked polymers

Based on the method of formation

~Addition polymers ~Condensation polymers

Addition polymers are formed by self-addition of monomers The molecular mass of a polymer is an integral multiple of the molecular mass of a monomer

:ondensation polymers are formed by condensation reactloi i.e., reaction between two or more monomer molecules with the elimination of simple molecules like water, ammonia, HCI etc.,

Based on the response to heat

~Thermo softening ~Thermosetting

thermosoftening or thermoplastics

soften on heating and can be converted into any shape and can retain its shape on cooling

thermosetting polymers

under go chemical change on heating and convert themselves into an infusible mass

Based on the properties or applications

DPlastics

o Elastomers DFibers DResins

Plastics

The polymers, which are soft enough at some temperature

to be moulded into a desired shape and hardened on cooling so that they can retain that shape.

e.g., polystyrene, polyvinylchloride, polymethylmethacrylate etc.,

Elastomers

The polymers in which the structural units are either zig zag or in helical chains.

They undergo elastic changes when subjected to an external force but readily regain their original shape when the force is withdrawn

e.g., natural rubber, synthetic rubbers, silicone rubbers etc.,

Fibers

In these polymers, the molecular chains are arranged parallel to each other in a spiral or helical pattern and

the molecular length is at least 100 times its diameter

e.g., nylons, terylene, etc.,

Resins

These polymers have a glossy appearance

These constitutes the major essential part of the plastics These suffers the polymerization reactions and impart different properties to plastics

e.g., polysulphide sealants, epoxy adhesives, etc.,

Functionality

the number of reactive sites or bonding sites

Some mono functional hydrocarbons H

H-t-OH Methyl alcohol II

H

Alcohols R -OH

Ethers

R~O~· R'

H H

:~ ~

H~C~O~C~H

~ ~

H H

H OH ~ / H-·C-·'C

~- . ~

-~ ~

H .

Dimethyl Ether

Acids

O.H !

R-C .'t

o

Acetic acid

Aldehydes

Aromatic hydrocarbons

R \

C·==O',

..

/.

H

H '\

C==·O Formaldehyde I

H

R

.

Phenol

Some bi functional hydrocarbons

adipic acid (hexanedioic acid)

Terephthalic acid

ethylene glycol

1,6-hexanediamine

Stereo regular polymers (or) Tacticity of Polymers H H H H H H H H

I 1 I II I I I

-c-c-c-c-c-c=c-c-

~®~®~®~®

~ ~ ~ '~ ~ ~ y ~

-c-c-c-c-c-c-c-c-

~ ® ~ k k ® k ~

~ f f Y ~ ~ y y

-·c-c-c-·c-·c-· c-·c-c-·

~Qb~®~~~®

Isotactic On one side

Syndiotactic Alternating sides

Atactic Randomly placed

- Conversion from one stereoisomerism to another is not possible by simple rotation about single chain bond; bonds must be severed first, then reformed!

An isotactic 17{) iY111e r

.A syndiotactic polymer

(side groups on altemating sides of the backbone)

HR RHHR RHHR R.H.HR

~ '. ~

HR HR RH:HR RH RH.H R

Types of Polymerisation

Polymerisation occurs basically in two different modes.

• addition (chain growth) polymerization

• condensation (step growth) polymerization

• Addition

- monomers react through stages of initiation, propagation, and termination

- initiators such as free radicals, cations, anions opens the double bond of the monomer

- monomer becomes active and bonds with other such monomers

- rapid chain reaction propagates

- reaction is terminated by another free radical or

another polymer

• condensation

- two monomers react to establish a covalent bond

- a small molecule, such as water, HCI, methanol or CO2 is released.

- the reaction continues until one type of reactant is used up

DISTINGUISHING FEATURES OF ADDITION AND CONDENSATION POL YMERISATION

ADDITION

Monomers undergo self addition to each other without loss of by products

It follows chain mechanism Unsaturated vinyl compounds undergo addition polymeristion

Monomers are linked together through C - C covalent linkages

High polymers are formed fast

Linear polymers are produced with or without branching

e.g., polystryrene, plexiglass, PVC, etc.,

CONDENSATION

Monomers undergo intermolecular condensation with continuous elimination of by products such as H20, NH3, HCI, etc.,

It follows step mechanism

Monomers containing the functional groups (-OH, -COOH, -NH2' .... ) undergo

this polymerization

Covalent linkages are through their functional groups

The reaction is slow and the polymer molecular weight increases steadily throughout the reaction

Linear or cross linked polymers are produced

e.g., nylons, terylene, PF resins, etc.,

CoPolymers

• Random, Alternating, Blocked, and Grafted

• Synthetic rubbers are often copolymers.

e.g., automobile tires (SBR)

Styrene-Butadiene Rubber random polymer

Free Rad'icall Polymerizal~or1

Addition polymerization can be explained on the basis of free radical mechanism

It involves three stages

viz., (i) Initiation

(ii) Propagation (iii) termination

Initiation

I (Initiator)

Ll or *

-----> R

u.v.1ight (Free radical)

H H

I I

R* + C== C

I I

(Free radical) X H

Vinyl monomer

~ ~

----> R-C-C*

I I

H X

(new free radical)

Propagation

The new free radicals attack monomer molecules further in quick succession leading to chain propagation

l- I- l- I- ~ ~ ~ ~
I I I I
F - (- C* ( == ( F - (-( - ( -C*
I I I I I I I I
l- ) ) l- I- ) l- )
(Free radical) Vinyl monomer (new free radical) ~ ~ ~ ~

F - ( - ( - ( - C* of

I I I I

I- ) I- )

(new free radical)

at m th stage,

I- l-

I I

( =(

I I

) I-

Vinyl monomer

1-1 1-1 I- I- I- l-

I I I I

F - ( -( ---+- ( - C ---+--- ( - C* of

I I I I I I

1-) 1-) m-2 I- )

I- I- I- I- I- l-

I I I I I I

> F - ( - ( - ( - C - ( - C*

I I I I I I

I- ) I- ) I- )

(another new free radical)

I- l-

I I

( =(

I I

) I-

7

1-1 1-1 I- I- I- l-

I I I I

F - ( -( -----+- ( - C ---+--- ( - C*

I I I I I I

1-) 1-) m-Lh )

At some stage this chain propagation is terminated when the

free radicals combine either by coupling (combining) of the two radicals or by disproportionation

coupling

I- I- I- l-

I I I I

---+- ( - C -+--- ( - C* +

I I I I

I- )< m-Lh )<

F

,

I- I- I- l-

I I I I

C* - ( ---+- ( - C --+--F

I I I I

)< I- )< I-

m-l

I- I- I- I- I- I- I- l-

I I I I I I I I

F ---+-( -C -+---( -C-C-( ---+-( -C--+--F

I I I I I I I I

I- )< m-Lh )< )< I- )< I-

saturated highpolymer (dead polymer)

m-l

d isproportionation

l- I- l- I- l- I- l- I-
I I I I I I I I
F (-c ( -c* + C" -( (-c F

I I I I I I I I
I- )( m-Il- )( )( I- )( I- m-I
,
l- I- l- I- l- I- l-
I I I I I I I
F (-c (=c + 1--(-( (-c F

I I I I I I I I
I- )( m-Il- )( )( I- )( I- m-I unsaturated oligomer (dead polymer)

saturated oligomer (dead polymer)

TECHNIQUES OF POLYMERISATION

Addition polymerization is brought about using four different techniques

• Bulk or Mass polymerization

• Solution polymerization

• Suspension polymerization

• Emulsion polymerization

Bulk or Mass Polymerization

only the monomer and the initiator are involved

monomer is taken in the liquid state

the initiator should dissolve in the monomer

Initiation can be done either by heating or by exposing to radiation

the reaction is exothermic

As the reaction proceeds, the reaction mixture becomes

•

VISCOUS

the polymer molecules with wide range of molecular masses will be obtained

Advantages:

The method is simple

It needs simple equipments

The percentage of conversion is high

Product obtained is pure with high optical clarity

Disadvantages:

as the reaction proceeds stirring become difficult as the product becomes more and more viscous

Uncontrolled temperature rise may lead to

discoloration

thermal degradation

branching

cross linking

and some times explosion also

Solution Polymerization

the medium chosen is an inert solvent

the monomer, the initiator and a chain transfer agent should dissolve in an inert solvent

The solution is heated with constant agitation After the reaction is over,

the polymer formed may dissolve in the solvent along with the monomer or may be precipitated

Advantages:

Solvent will reduce the viscosity of the reactant mixture heat transfer will be better

Disadvantages:

the polymer will not be pure and has to be isolated by chemical techniques

high molecular mass polymers will not be obtained

Suspension Polymerization Water is used as a solvent

the monomer is suspended in water as droplets of colloidal size

Initiators used are soluble in monomer droplets

protective colloids are added to suppress the coagulation of the monomer molecules

The reaction mixture is heated or exposed to radiation with constant stirring.

Polymerisation takes place inside the droplet

the polymer formed being insoluble in water, produce spherical pearls or beads

Advantages:

Process is cheap since it uses water as a solvent instead of costly solvents

Viscosity increase is negligible

Agitation and thermal control are easy Product isolation is easy since the product is insoluble in water

Product formed is pure

Disadvantages:

the method can be used only for water insoluble monomers

it is difficult to control polymer size

Emulsion Polymerisation

This method is used for water insoluble monomers

Emulsion of water and the monomer is allowed to form

Emulsion is the colloidal dispersion of a liquid in another immiscible liquid

To maintain the system stable, a small amount of an emulsifier will be added

Soaps and detergents are examples for emulsifiers

Emulsifier contains

a hydrophilic (water loving) polar end group (head) and a hydrophobic (water hating) non polar end group (tail)

At very low concentration, the soap or detergent (emulsifier dissolves completely in water

at slightly higher concentrations, the emulsifier molecules form aggregates, called miscelles

The monomer molecules dissolve in the hydrocarbon centre of the miscelles

water soluble initiator will be added and the system is kept agitated at the required temperature.

The initiator molecules diffuse into the centre of miscelles through its polar head

Reaction takes place at the centre of the miscelles

The polymer is formed and the miscelles begins to swell The monomer consumed inside the miscelles is replenished by diffusion from aqueous phase

This continues till the size of the polymer is big enough to come out of the miscelles

Advantages:

Rate of polymerization is high

polymers with higher molar masses are formed

thermal control is easy

control over the polymer molar mass is possible no viscosity build up and hence agitation is easy

Disadvantages:

the polymer formed may contain impurities such as the emulsifiers and coagulants

It needs further purification by other chemical techniques

GLASS TRANSITION TEMPERATURE (Tg):

Amorphous polymers do not have sharp melting points

They possess softening point

At low temperature, polymers exist as glassy substances

Since the molecular chains can not move at all easily in this state, the solid tends to shatter, if it is hit

If the solid polymer is heated, eventually it softens and becomes flexible

This softness and flexibility is obtained at the glass transition temperature

So the glass transition tetnperature can be defined as the temperature below which an amorphous polymer is brittle, hard and glassy and above the temperature

it becomes flexible, soft and rubbery

Glassy state -------> rubber state

(Hard brittle plastic) (soft flexible)

In the glassy state of the polymer, there is neither molecular motion nor segmental motion

When all chain motions are not possible, the rigid solid results

On heating beyond Tg segmental motion becomes possible but molecular mobility is disallowed. Hence flexible

The glassy state and the glass transition

• In general for ordinary compounds of low molar mass:

• crystalline solid

melting

• liquid

• increase in volume at Tnf,

v

r, T

• slopes of Fe and BA: expansion coefficients of crystalline phase and liquid, respectively.

Non-crystallisable materials

Some materials CANNOT crystallize, e.g. ordinary glass

Why?

Molecular structure is too

irregular V

liquid

amorphous ore ,.._glassy phase F"_-

rubber

T ·Cooling of liquid via AB continues until Dg

·The area BD has elastomeric properties and is the rubbery

state

• D is called the glass-rubber transition, T, = glass transition

temperature

• DE has the same slo e as CF

m

amn -r.( :~

[~OO

lRo ationel movemenrs o f smal ~ gl'OUpj~

Crystalline vs. Amorphous Phase transitions for long-chain polymers.

liquid

i: (sharp)

d)

2 thermoplastic

~ ~ 11)

a 1---------4 Tg

.0,.) gla:ss

~

crystalline polymer

broadT

. .. In

liquid

gummy

rubbery

amorphous polymer

actors influencing the glass transition temperature Glass transition temperature of a polymer depends on

parameters such as

• chain geometry

• cha i n flexi bi I ity

• molecular aggregates

• hydrogen bond between polymer chains

• presence of plasticizers and

• presence of substrates in the polymer chains

A polymer having regular chain geometry show high glass transition temperature

crystalline polymers have higher Tg s than amorphous polymers HIGH-DENSITY POLYMERS

Linear polymers with chains that can pack closely together. These polymers are often quite rigid.

Branched-chain polymers that cannot pack together as closely. There is often a degree of cross-linking.

These polymers are often more flexible than highdensity polymers.

the bulky groups on chain, increases the Tg of the polymer

Polyethylene Tg = -110°C

Polypropylene

<; Tg =

R

•

•• •

Polystyrene Tg = 100°C

The presence of H-bonds between the polymer molecules increases the Tg

• e.g., the Tg of nylon 6,6 (Tg = 50 °C) is higher than PE (Tg = -110 0

H 0 H 0 H H
nylon 6,6 II II polyethylene
I I
C C C C -c-c-
-N- -N- - -N- -
I I I I I H H
H H H H 14 H + +
+ + Van de-r Waals bonds
Hydrogen bonds + +
+ +
H H
H 0 H 0
II II -c-c-
I I
C C C c H H
-N- -N- - -N- -
I I I I I
H H H H H With H-bonds vs vdW bonds, nylon is expected to have (and does) higher Tg.

The presence of a plasticizer reduces the Tg of a polymer

The plasticizers are usually dialkyl phthalate esters, such as dibutyl phthalate, a high boiling liquid.

o

II

C,

o-c H2C H2C H2C H3

"O-C H2C H2C H2C H3 C

II

o dibutyl phthalate

The plasticizer separates the individual polymer chains from one another. It acts as a lubricant which reduces the attractions between the polymer chains.

The Tg of a polymer is influenced by its molecular weight With increase in molecular mass, the Tg increases

However, it is not significantly affected if molecular weight is around 20000

e.g., PE (low Mw)

-110°C

PE (high Mw)

- 90°C

The glass transition temperature helps in choosing the right processing temperature

It also gives the idea of thermal expansion heat capacity

electrical and mechanical properties

T

rubber

•

VISCOUS

Ii qui du ..... ,...--T;::.-;;;h1~ m

_....... tough

•

~ ___.t~IT 9

mobile I iqu id

partially crystalline solid

crystalline solid

Molecular weight

T m: melting over wide range of T depends upon history of sample,

a consequence of lamellar structure thicker the lamellae, higher the T m"

Tg: from rubbery to rigid as T lowers

,TRUCTURE - PROPERTY RELATIONSHIP OF POLYMERS

Macromolecules show a wide range of properties which are quite different from those of respective monomers

They may be

elastic or rigid

hard or soft transparent or opaque

have strength of steel but can have very light weight

soften on heating or

can set to a hard mass on cooling the melt

These properties may vary from one type of polymer to another and even among the same type

The fundamental parameters which influence the structure-property relationship are

molecular mass

polarity crystallinity

molecular cohesion

the nature of polymeric chains and

stereochemistry of the molecules

The properties like tensile strength, crystallinity, elasticity, resistance to chemicals, wear and tear depend mostly on the polymer structure

Tensile Strength

This can be discussed based on

the forces of attraction and slipping power

Based on forces of attraction:

Strength of the polymer is mainly determined by the magnitude and distribution of attraction forces between the polymer chains

These attractive forces are of two different types primary or covalent bond

secondary or intermolecular forces

In straight chain and branched chain polymers, the individual chains are held together by weak intermolecular force of attraction

strength increases with increase in chain length (in turn increase in molecular weight)

as the longer chains are entangled (anchored) better

In cross-linked polymers, monomeric units are held together only by means of covalent forces

Branched

Oross-Ll n ked

Increase in Strength

Examples:

Linear Polymers: Polyethylene, polyvinyl chloride (PVC), polystyrene, polymethyl methacrylate (plexiglass), nylon, fluorocarbons (teflon)

Branched Polymers: Many elastomers or polymeric rubbers

Cross-linked Polymers: Many elastomers or polymeric

rubbers are cross-linked (vulcanization process); most thermosetting polymers

Network Polymers: Epoxies, phenol-formaldehydes.

Based on slipping power.

It is defined as the movement of molecules one over the other

It depends on the shape of the molecule

E.g., polyethylene molecule is simple and uniform the movement of molecules one over other is easy

i.e., slipping power is high

Hence it has less strength.

in case of poly vinyl chloride (PVC), the bulky chlorine atoms are present along the chain length hence movement is restricted

i.e., slipping power is less

Hence PVC has higher strength than PE

CI CI CI CI
I I I I
.•..•...•.•...•...
CI CI CI CI
I I I I
<;
CI CI CI
I I I
..•..•..••.....•..
CI CI CI
I I I
•..•.•...•...•.•.. Plastic deformation

When a polymer is subjected to some stress in the form

of heat or pressure or both, permanent deformation in shape takes place, which is known as plastic deformation

Slippage is more in case of linear molecules than branched and cross-linked, because of the presence of only the weak

intermolecular forces

at high pressure and temperature, the weak Vander waal's forces between molecules become more and more weak

Hence linear molecules show greatest degree of plastic deformation, under pressure

Such type of materials are called thermoplastic materials

No slippage occurs in case of cross-linked molecules, because of only primary covalent bonds are present throughout the entire structure

i.e., plasticity does not increase with rise in temperature or pressure or both

Such type of polymers are known as thermosetting polymers

However, when considerable external force

or temperature exceeding the stability of material is applied, it will result in total destruction

Crystallinity

Polymers are part crystalline and part amorphous

An amorphous state is characterized by complete random arrangement of molecules

crystalline form by regular arrangement of molecules

crystalline

•

region

amorphou

•

region

• A linear polymer will have a high degree of crystallinity, and be stronger, denser and more rig id.

• The more "lumpy" and branched the polymer, the less dense and less crystalline.

• The more crosslinking the stiffer the polymer.

And, networked polymers are like heavily crosslinked ones.

• Polymers with a long repeating unit or

with low degree of symmetry do not crystallize easily

• Isotactic and syndiotactic polymers are stronger and stiffer due to their regular packing arrangement.

• Optical properties: crystalline -> scatter light (Bragg) amorphous -> transparent.

Most covalent molecules absorb light outside visible spectrum, e.g. PMMA (Iucite) is a high clarity tranparent materials.

Which polymer more likely to crystallize? Can it be decided? Linear and highly crosslink

Networked Phenol-Forma Idehyde (Bakelite)

H

\ c=o

/

H

. .

cis-rsoprene

H H

I II

-c-c=='c-'c- 11 I II

H (g) H H

• Networked and highly crosslinked structures are near impossible to reorient to favorable alignment.

• Not possible to decide which might crystallize. Both not likely to do so.

Polystyrene (PS) possess greater strength when compared to PE and PVC because of the presence of bulky phenyl group.

R

•

•• •

Which polymer more likely to crystallize? Can it be decided?

H H

H H

random

poly(styrene - ethylene) copolymer

HH HHHHHHHH HH

II I I I I I I I II I I I

-c~,c~·c-c-'c-c-c-c-c-c- c-c-

~ I I I I I I II I I

HO I H H H H H H HIO I H H

a Iternati ng Poly(styrene-Ethylene) Copolymer

• Alternating co-polymer more likely to crystallize than random ones, as they are always more easily crystallized as the chains can align more easily.

Which polymer more likely to crystallize? Can it be decided?

Linear syndiotactic polyvinyl chloride Linear isotactic polystyrene

HHHCJHH

I I I I I II

-C-C,_-C_IC'_-C-IC-

I I I I I I

HC)HHHCl

HH

HH

• For linear polymers, crystallization is more easily accomplished as chain alignment is not prevented.

• Crystallization is not favored for polymers that are composed of chemically complex mer structures, e.g. polyisoprene.

• Linear and syndiotactic polyvinyl chloride is more likely to crystallize.

• The phenyl side-group for PS is bulkier than the CI side-group for PVC.

• Generally, syndiotactic and isotactic isomers are equally likely to crystallize.

Chemical Resistance

Chemical resistance of the polymer depends upon the

•

chemical nature of monomers and their molecular arrangement

•

As a general rule of dissolution,

'like materials attract' and

'unlike materials repel'

Thus a polymer is more soluble in structurally similar solvent

e.g .,

polymers containing polar groups like - OH, - COOH etc., usually dissolve in polar solvents like water, ketone, alcohol etc

but these are chemically resistant to non-polar solvents

Similarly non-polar groups such as methyl, phenol dissolve only in non-polar solvents like benzene, toluene, etc.,

polymers of more aliphatic character are more soluble in aliphatic solvents, hence chemical resistance is less in aliphatic solvents and more in aromatic solvents

polymers with more aromatic groups dissolve more in aromatic solvents, hence chemical resistance is less in aromatic solvents and more in aliphatic solvents

Polymers containing ester groups (e.g., polyesters) undergo Hydrolysis with strong alkalis at high temperature

Implies less chemical resistance in alkalies

Polyamides like nylon containing -NHCO- group can undergo easily the hydrolysis by strong acid or alkali

Polymers containing residual unsaturation e.g., rubbers (natural and some synthetic) easily undergo degradative oxidation in air in presence of light or ozone

Because of the dissolution of polymers in suitable solvents, there occurs softening, swelling and loss of strength of polymer material

The tendency of swelling and solubility of polymers in a particular solvent decreases with increase in molecular weight

Linear polymers have lower resistivity than branched chain and cross linked polymers

Permeability of the solvents in the polymers also depends on crystallinity

crystalline polymers exhibits higher chemical resistance than less crystalline polymers because of denser packing

Elasticity

Elasticity of the polymer is mainly because of the uncoiling and recoiling of the molecular chains on the application of force

a polymer to show elasticity the individual chains should not break on prolonged stretching

Breaking takes place when the chains slip over the other and get separated

So the factors which allows the slippage of the molecules should be avoided to exhibit an elasticity

The slippage can be avoided by

• introducing cross-linking at suitable molecular positions

• introducing bulky side groups such as aromatic and cyclic groups on repeating units

• introducing non-polar groups on the chains