Chapter 20

POLYMERS
(revision)

Dr War War
Associate Professor
Engineering Chemistry Department
Yangon Technological University
Polymerization
• Polymers are macromolecules of high molecular weight which are
formed by linkage between large numbers of small molecules called
monomers.
Molar masses of polymers
(i) Number average molar mass Mn
(ii) Weight average molar mass Mw

(i) Number average molar mass Mn

N1M1 + N2M2 + …….. + NiMi NiMi
Mn = =
N1 + N2 + ………… + Ni Ni

N1 = molecules have molar mass M1 N2 = molecules have molar mass M2

Mn is the ratio of the total mass (w) of all the molecules of polymer
divided by the total number of molecules present.
(ii) Weight average molar mass Mw

w1M1 + w2M2 + …….. + wiMi wiMi

Mw = =
w1 + w2 + ………… + wi wi
w1 = the mass of polymers with molar mass M1
w
Numbers of moles n= , w =nM
M
n1M21 + n2M22 + …….. + niM2i niM2i
Mw = =
n1M1 + n2M2 + ………… + niMi niMi

Mw Distribution ratio
Mw Mn , 1
Mn

Mw
= 1, the polymer is homogeneous & contains polymers of same chain length
Mn

> 1 The degree of heterogeneity of the polymer

Degree of polymerization(DP)
The no. of repeating units present in a polymer molecule.

n[ CH2= CH2] [CH2 - CH2 ]n

n = a whole number , the degree of polymerization

Molar mass of = degree of x molar mass

addition polymer polymerization of monomer

Mn = DP x molar mass of monomer

Polymer do not have the same DP and show variation in molar mass.
# only average DP and average molar mass (Mn) #
2.
Mechanism of free radical addition polymerization
Three major steps
1. Initiation
2. Propagation
3. Termination
Initiation

Step 1. R - R 2R° endothermic reaction

R= peroxides, azocompounds or peracids

Step 2. R° + CH2 = CH2 R - CH2 - ºCH2

free
radicals ethylene monomer free radicals
exothermic reaction

Energy of endothermic < energy of exothremic

 Propagation

R-CH2- CH2° + CH2 = CH2 R- CH2 - CH2- CH2- CH2°

monomer free Dimmer free radical
radical

R- CH2 - ( CH2 )n - CH2 - CH2°

polymer free radical

Chain extension

Energy of exothermic reaction

Termination

By coupling of one polymer free radical with another polymer free

radical or initiator free radical to form stable dead polymer.

R-(CH2 ) n1 - CH2 - CH2° + R-(CH2 ) n2 - CH2 - CH2°

R-(CH2 ) n1 - CH2 - CH2 - CH2 - CH2 (CH2 ) n2 - R
Dead heavy polymer Energy of exothermic reaction
By disproporation of two polymer free radicals, a H atom attached to
one of the free radicals is shifted to other intermediate polymer;
two dead polymers, one unsaturated and other saturated are formed.

R-(CH2 ) n1 - CH2 - CH2° + R-(CH2 ) n2 - CH2 - CH2°

CH - CH°2
H

R-(CH2 ) n2 - CH = CH2
R-(CH2 ) n1 - CH2 - CH3
Saturated polymer Unsaturated polymer
Polyamide

HOOC-(CH2)4-COOH + H2N - (CH2)6- N H2 OC-(CH2)4-CO- HN - (CH2)6-NH-

Nylon 66
Adipic acid Hexamethylene Amide linkage
diamine

Uses:

Tooth brushes, ropes, carpets, clothing

e.g condensation polymerization
polyester
O O O“ O“
“ “
HO –C- -C –OH + HO- -OH HO –C- - C –O- -OH

Ester linkage
Dicarboxylic acid Diol Polyester (PET)

Uses:

Fibers, clothing soft-drink bottles, magnetic tape, plastic products

 Q. 1. What is functionality of a monomer?
Ans. It is the number of bonding sites of monomer

Q. 7. Differentiate between addition and condensation polymerization.

Ans. Addition polymerization is a reaction that gives a polymer, which is an exact multiple of the original
monomers.
Condensation polymerization takes place through different functional groups of monomers with elimination of
small molecules like H2O etc.

Q. 8. What is copolymerization?
Ans. Copolymerization is the point polymerization of two or more monomers, e.g., butadiene and
styrene to yield GR-S rubber.
1.(a) Define the terms
Degree of polymerization. (ii) Co-polymerization

1. (a) Explain tke terms with example

(i) addition polymerization
(ii) co-polymerization
(iii) condensation polymerization
Strength of polymer
Plastic deformation
Physical state
Solubility and chemical resistance

Shapes and forms – mechanical properties

Effect of heat
 Cross linked polymer Giant, three dimensional structure, strong &tough

Strength depends the chain length;

Straight chain polymer Low MW: soft & gummy but brittle,
Higher chain length: tougher & more resistant.

Presence of polar group: intermolecular

forces & strength increases.
Linear –chain molecules are always soluble ---------------------------thermoplastics

3D polymer molecules are insoluble in any solvent --------------------thermosetting

Qualities of polymer depends on structure of the polymers

Artificially creating crosslinking converts thermoplastics material into thermosetting.

Amorphous state : Random arrangement of molecules in the polymer
flexibility

Crystalline state: regular arrangements of molecules or chain in a polymer

intermolecular force of attraction increases:
higher softening point, greater rigidity, brittleness & strength

Elastic character: very long chain polymer :

free rotating groups irregularly coil
entangled snorts: stretched and again returned back to original state
 Polymer soluble polar solvent
(polar groups) (water, alcohols)
( -OH gps or -COOH)

Polymer Soluble non-polar solvent

(non-polar groups) (benzene, toluene, CCl4)
H/C polymer

The greater the degree of cross-linking, less is the solubility of the polymer in a solvent.
The internal arrangement of long –chain molecules --------- fibers, plastics , rubbers

Internal forces between molecules low,

Molecules become bulky, Rubbery character
Form random arrangement ,

Internal forces are high, Fibrous nature

orderly arrangement

Intermediate force -------------- plastic nature

Strength of polymer is controlled by the length of the polymer chains & its cross-linking.

On increasing strain continuously ultimately the polymer chains are

uncoiled and fully stretched called necking .

After this point the polymers reaches its break point and yields.
 Glass Transition Temperature , Tg
Viscous liquid Both segmental & molecular motion
Visco fluid state Flow temperature
Only mixture ( no sharp mpt)

Tf

Rubbery state
(soft, flexible) Segmental motion
(visco elastic state) not Molecular motion

Tg

Glassy state : Segmental motion No

amorphous polymer Molecular motion
(hard , brittle plastic) Rigid solid
(frozen state)
Behavior of polymer is controlled by the temperature.

Amorphous polymer do not have mpt have softening points

At very low temp: both crystalline & amorphous polymer ;;;;;;; glass
On heating , Tg is reached after soft.

Amorphous polymer becomes rubbery and then gummy and on further heating it
liquefies.

Crystalline polymer on heating above Tg shows thermoplastic behavior and finally

liquifies.
(i) Resin (iv) Waxes, oils, stearates & soaps

(ii) Fillers (v) Coloring materials

(iii) Plasticizers (vi) Other additives

 Processing of plastics

(i) Calendaring. (v) Injection moulding.

(ii) Die casting (vi) Blow moulding

(iii) Film casting (vii) Extrusion moulding

(iv) Compression moulding.

(viii)Thermoforming(or) Vacuum forming .
No. Processing of plastics Types of polymer
1 Calendaring.
thermoplastics

2 Die casting
thermoplastics
3 Film casting
thermoplastics
4 Compression moulding.
thermoplastics
& thermosetting
5 Injection moulding.
thermoplastics
6 Blow moulding
thermoplastics
7 Extrusion moulding
thermoplastics
8 Thermoforming(or) Vacuum forming .
Important Thermoplastic
1. Polyethylene (PE)
• Ethylene (colorless gas at rtp)
• Dehydration of ethanol at 160°C m H2SO4 (lab)
• gas polymerization. 1500 atm,200 °C (upper) & 120 °C (lower) (manufactured)
▪ Two types of Polyethylenes :
• (i) Low density polyethylene LDPE (ii) High density polyethylene HDPE

(i) Low density polyethylene LDPE by using high pressure methods (1050-2000 kgf/cm2 )
using free radical initiator

(ii) High density polyethylene HDPE by using low pressure methods (31 kgf/cm2 ) using ionic
catalysts
Property PE LDPE HDPE
Appearance rigid, waxy, white, low sp. gr. low higher softening point,
Properties translucent non-polar hardness greater rigidity but low
material impact strength and it is
opaque and relatively
brittle
Chemical good chemical Low swells & High does not swell or
resistance resistance but acids, dissolves in H/C dissolve in solvents
alkalis and salt solvents
solutions, good
insulating property but
it is susceptible to
organic solvents
Chemical structure highly symmetrical branched structure Linear polymer
structure so it and it is flexible and
crystalizes easily tough
Uses sheets, tubes ,toys , coated-wires &cables, bags bottles, caps, insulating
No. Polymer Monomer Properties
1 PE CH2=CH2 good chemical resistance but acids, alkalis and salt
ethene
solutions, good insulating property but it is
susceptible to organic solvents
highly symmetrical structure so it crystalizes easily
LDPE Low swells & dissolves in H/C solvents
branched structure and it is flexible and tough
HDPE High does not swell or dissolve in solvents
Linear polymer
No. Polymer Monomer Properties
2. PP [CH3CH = CH2] • isotactic, highly crystalline polymer.
propylene • strength, moisture proofing quality, hardness
• Lightest all polymer.

3. PVC CH2 = CHCl PVC is a colorless, odorless, non-flammable, chemically-inert powder.

Vinyl Chloride It contains 53-55% Cl2 and softens at around 80°C.
It is resistant to water, light, O2, inorganic acids and alkalies, oil, petrol etc.,
but soluble in hot chlorinated hydrocarbons

4. PTFE [CF2 = CF2] •Teflon is a linear polymer with high degree of crystallinity of ~ 95%
Teflon tetrafluoroethylene •Its flow temp: is high (327°C )
•It is insoluble in all solvent.
•It is chemically inert and not attacked by acids, alkalis, oxidizing and
reducing agents
•It is not wetted by oil or water.
•It has high resistance to impact and wear and tear.
•It is thermally stable and has a good electrical insulating property.
No. Polymer Monomer Properties

5. PU Di isocynate & polyol PUs are spongy transparent linear thermoplastics

It has low thermal conductivity.
Its greatest advantage lies in fact that it can be made where they are
needed without any complex machinery—two liquid ingredients can
be mixed and moulded.

6 Nylon 66 Adipic acid & Nylon is strong, tough, elastic and can be dyed easily.
Hexamethylene diamine Nylon possesses high abrasion resistance and is chemically
stable.
It possesses high temperature stability and also high melting
(160°C-264°C).
It is insoluble in common organic solvents but soluble in phenol,
formic acid
 Q. 5. What is the basic difference between nylon 6 and nylon 66?
Ans. Nylon 6 is an homopolymer whereas nylon 66 is a hexo polymer.
In nylon 6, the composition of the monomer is the same as that of the polymer, but nylon 66 is formed
from the composition of the monomers are different.

Q. 6. Differentiate between a homopolymer and copolymer?

Ans. A homopolymer consists of many identical monomer units whereas a copolymer consists of
monomers of different chemical structures

Q. 11. Why is the density of HDPE different from LDPE?

Ans. HDPE is completely a linear polymer and hence packing of the chains is efficient and hence its
density is high. But for LDPE, due to its branched structure, packing efficiency is low and hence density is
low.

Q. 12. Why thermosetting plastics cannot be reused?

Ans. In thermosetting plastics, the monomers are bound to each other by strong covalent bonds, which
cannot be broken on heating. Thus by heating it cannot be softened to reshape and reuse.
 What are the classification of polymers based on their thermal behavior with examples?

Based on the thermal behavior, polymers are classified into thermoplastic polymers (Ex, PE, Polycarbonate,
Polytetrafluoroethylene) and thermosetting polymers (Ex, phenol-formaldehyde, urea-formaldehyde).

Q. 14. Why is teflon highly chemical resistant?

Ans. In teflon the most electronegative element F contributes to the strong attractive force within the chains
and hence is non-reactive towards other chemicals.
Important Thermosetting
Resins
Important Thermosetting Resins
No. Polymer Monomers Properties
1 Phenolic resins (or ) phenol with • phenolic resins are rigid, hard, water resistant
Bakelite formaldehyde • resistant to non-oxidising acids, organic solvents but are
susceptible to alkalies.
• Solubilities and melting point of resin gradually change
with rise of molecular weight.
• possess electrical insulating properties

2. Epoxy resin 2, 2-(bis)-4-hydroxy • Adhesion to various materials

phenyl propane • Flexibility
[bis-phenol] • Chemical inertness
epichlorohydrin • Toughness
• Stability at high temperature
• Low shrinkage during cure
3 Polyester ethylene glycol • the structure of the polymer is symmetrical and a
Terylene or Dacron with terephthalic number of polar groups are present it forms fiber easily.
acid • The fiber has high tensile strength and resiliency and is
stable to hydrolysis.
• The fabric made from the fiber is crease resistant.
Limitations of natural rubber

• Natural rubber softens at high temperature and becomes brittle at

low temperature.
• It is attacked by acids, oxidising agents, non-polar solvents.
• it is oxidised by air.
• Also on excessive stretching it gets permanently deformed
 Vulcanization Rubber
• Is a process (heating natural rubber with S at 135°C and
(1-4 hours)
• To improve the properties of natural rubber
• ‘S’ atoms form bridges between poly neoprene chains (a
part of double bonded carbon atoms)
• Degree of vulcanization ∞ the amt of ‘S’ added
•S Tensile stregth, chemical resistance and wear
and tear resistance
• Tyre ---3-5% S , filler--- C are added
• 32% S----full saturation ---a rigid non flexible rubber (
ebonite)
 Synthetic rubber
No. Synthetic rubber Monomer Uses

1. GR-S or Buna 1,3 butadiene + styrene • manufacture of tyres,

S. general-purpose • soles and other components of shoes,
synthetic rubbers • for insulating wires and cables, as
adhesives and lining for vessels.
2. GRA or Buna-N butadiene and acrylonitrile • to manufacture parts for automobiles,
Abrasion-resistant aircraft.
rubber • used for making conveyer belts, adhesives
and oil resistant foams
3. GR-M or Neoprene chloroprene or a chlorinated • for making conveyer belts, adhesives,
Commercial Grade butadiene. gaskets, as linings for reaction vessels and
Neoprene Rubber • for making pipes to carry corrosive gases
and oils.
Reclaimed Rubber

• waste rubber articles by the process of reclamation

• waste rubber articles are cut and powdered in a cracker.
• The unwanted ferrous materials are separated by electromagnetic
separator and then changed to an autoclave and digested with
caustic soda solution at 200°C under pressure for 8-15 hours.
• The fibres get hydrolysed i.e., devulcanization takes place.
• Sulphur is removed as sodium sulfide.
• It is washed, dried and finally reinforced with carbon black etc.
Uses
• Reclaimed rubber is used for making tyres, tubes, belts, shoe soles,
floor mats etc.
Conducting Polymers

• π-electrons conducting polymer.

• Conducting element-filled polymer
• Inorganic polymer
• Doped-conducting polymer.
• Blended conducting polymer
• Q. 18. What changes take place with polymers near glass transition
temperature?
• Ans. Below the glass transition temperature, the polymer is brittle
and above it, they would deform but not break.

• Q. 15. Why is PVC soft and flexible but bakelite is hard and brittle?
• Ans. In PVC the molecular chains are bonded to each other by Van der
Waal's forces and hence these long chains are flexible and can slip or
twist on applying force but in the case of bakelite the thermosetting
polymer chains are crosslinked by covalent bonds, so, it is hard and
no deformation can take place on applying force. When the force
becomes too large the covalent bonds are broken and it becomes
brittle.
• Q. 16. Why is natural rubber compounded?
• Ans. Natural rubber possesses many undesirable properties and so to
improve its properties it is usually compounded with different
ingredients like plasticizers, antioxidants, filler, colorant etc.

• Q. 17. Why is natural rubber vulcanized?

• Ans. Raw rubber has high elasticity, thickness, poor chemical resistance,
poor strength, large water absorption capacity etc. Vulcanization i.e.,
adding some sulfur at 100°C-140°C causes saturation of the double
bonds by S and hence stiffening of the polymer takes place.
Vulcanization, thus, improves all the above properties.
• Q. 3. What is ageing of rubber?
• Ans. Ageing is the autooxidation of rubber with time due to the
presence of double bond and due to this rubber becomes hard.
• Q. 4. When is vulcanization done? Mention some of the uses of
vulcanized rubber.
• Ans. Vulcanization is done after shaping the article. Tke shaping is
done with raw rubber along with suphur and other ingredients like
accelerators, antioxidants, fillers etc.
• Uses. Vulcanized rubber is used in vehicle tyres, hose, conveyer belt,
electrical insulation.
• Q. 13. What is natural rubber and what is gutta-percha?
• Ans. Natural rubber is long-coiled chains of poly cis isoprene and gutta-percha is
toughform of poly trans isoprene.

• Q. 16. Why is natural rubber compounded?

• Ans. Natural rubber possesses many undesirable properties and so to improve its
properties it is usually compounded with different ingredients like plasticizers,
antioxidants, filler, colorant etc.

• Q. 17. Why is natural rubber vulcanized?

• Ans. Raw rubber has high elasticity, tackiness, poor chemical resistance, poor strength,
large water absorption capacity etc. Vulcanization i.e., adding some sulfur at 100°C-140°C
causes saturation of the double bonds by S and hence stiffening of the polymer takes
place. Vulcanization, thus, improves all the above properties.

• Q. 18. What changes take place with polymers near glass transition temperature?
• Ans. Below the glass transition temperature, the polymer is brittle and above it, they
would deform but not break.