Polymers

Syllabus
UNIT-I
Introductory Concepts and Fundamentals:
Definitions and concepts of plastics and polymers, comer, co-
monomer, mesomer, co-polymer , functionality, visco-elasticity,
Classification of polymers, methods of determining
molecular weights of polymers: Methods based on colligative
properties, Sedimentation velocity method, Sedimentation
equilibrium method, Gel-chromatography method, Light
scattering analysis method, End-group analysis method;
Natural polymers: brief study of rubber, shellac, rosin,
cellulose, proteins, Lignin.
 Contd.,
UNIT-II
Chemistry of Polymerization:
Elementary concepts of addition polymerization, condensation
polymerizationand co-polymerization, glass transition temperature
of polymers, methods of determining glass transition temperature,
degradation of polymers due to mechanical, hydrolytic, thermal
and backbone effects, Relation of the mechanical, thermal,
electrical, physical and chemical properties with the structure of the
polymer.
UNIT-III
Methods of Polymerization:
Mass, solution, emulsion and suspension, role of the initiators,
catalysts, inhibitors, solvents, fillers, reinforcing agents, stabilizers,
plasticizers, lubricants, blowing agents, coupling agents, flame
retardants, photo-degradants and bio-degradable on polymerization
UNIT-IV
Processing Equipment:
Mixing, compounding, extrusion, calendaring, laminating,
molding, compression, transfer, injection and blow molding.
 Contd.,
UNIT- V
Manufacturing Processes of Addition Products:
Polyethylene ( LDPE and HDPE), polypropylene, PVC and its copolymers,
Polystyrene and its copolymers and PTFE (polytetraflouroethylene)
Manufacturing Processes of Condensation Products:
Polyesters: PMMA, PET, PF, UF and MF resins, epoxy resins.

Text Books:
1. R. Sinha, Outlines of Polymer Technology: Manufacture of
Polymers,2004, Prentice Hall India Pvt. Ltd. (UNIT – I, II, III and V).
2. R. Sinha, Outlines of Polymer Technology: Processing Polymers,2004,
Prentice Hall India Pvt. Ltd. (UNIT – IV).

Reference Books:
1. Billymeyer, F.W.Jr., Textbook of Polymer Science, 3rd edition, 2006, John
Wiley & Sons
2. Anil Kumar. Gupta, R.K. Fundamentals of PolymerEngineering,2ndEd,
2003, Marcel Dekker.
 Course Outcomes
By the end of the course, the student will be able to
1. Classify polymers and determine molecular weight
of a polymer.
2. Identify the kinetics of polymerization and
importance of their properties.
3. Summarize the methods of polymerization.
4. Understand the principles and working of
processing equipment.
5. Select the manufacturing process for a polymer
compound.
 Polymer
• A polymer is a greek word (“poly” - "many“, “mer”-"part") is a large
molecule composed of many repeated subunits.
• The repeating molecules (monomers) are attached either in an end to end
fashion or branched by covalent bonds.
• Polymer chains are huge and typically consist of between 20,000 and
40,000 individual monomers
• This chain length is what gives the polymer most of its desirable
characteristics
• Individual chains interact to form a stronger overall substance through
entanglements and cross-links
• This chain length is what gives the polymer most of its desirable
characteristics
• A polymer can be either natural or synthetic
Plastics:
• It is derived from greek word “plastikos” – fit for moulding
• Plastics can be defined as the organic or inorganic substances either natural or
synthetic that can be moulded
• All plastics are polymers but not all polymers are plastics
Comer:
It is a monomer which does not react with others of its own species to form a polymer
Ex: Maleic anhydride

Comonomer:
It is a monomer which reacts with others of its own species to form a polymer
Ex: Styrene

Mesomer:
It is an identifiable unit in the polymer structure, meso is a greek derived word – middle
Molecular formula for mesomer and monomer is same in addition process
 Copolymers
• Most polymer chains are made up of one type of monomer (for example, red
beads)
• However, some polymers are made up of different types of monomers (for
example, blue and red beads) - these are called copolymers
• Classification was made based on the polymer chain
• There are four main types of copolymers
– Alternating
– Random
– Block and
– Graft
• In alternating copolymer the mesomers are arranged in alternate manner
• Random copolymer has different mesomers in random sequence
• Block copolymers have different mesomers arranged like blocks
• In graft copolymer, one species of mesomer is attached to chain of another
species in such a way that one type of mesomer is attached to the chain of
another type
 Copolymers
• The different monomers can be arranged either in
an alternating or random fashion
 Alternating
...-red-blue-red-blue-red-blue-red-blue-red-…
Random
…-blue-red-red-blue-red-blue-blue-red-blue-…
Block
…-R-R-R-R-R-R-B-B-B-B-B-B-R-R-R-R-R-R-…
Graft
…-R-R-R-R-R-R-R-R-R-R-R-R-R-R-R-R-R-…
|
B-B-B-B-B-B-B-B-B-…
Important
constitutions for
synthetic
polymers

1
2
 Types of polymers
• There are two main types of polymers
– Natural
– (cotton, silk, wood, leather…)

– Synthetic
– (plastics, nylon, latex…)
Functionality:
•It is the ability to form primary valence bond or can also be said as a
combining capacity of a molecule for a particular reaction or the
number of positions available in a molecule for the particular
reaction
•A molecule is termed as bi-, tri-, poly functional
Ex: Hydroxyl acid – mono-functional
Ethylene glycol – bi-functional
Glycerol – tri-functional
Viscoelasticity:
•It is the property of a material that exhibits both viscous and elastic
characteristics when undergoing deformation
• Time and temperature dependent
•Polymers exhibit all the properties of a elastic solid and a viscous
liquid
 Classification of polymers
• Solid Polymers are classified as crystalline and amorphous(High/low
molecular weight substances)
• Classification:
• Polymer reaction to stress and temperature
• Polymer mechanical strength and behaviour
• Production methods
• Molecular arrangement of polymers
• Type of mesomer involved in the polymer
• Morphology of polymer
• Reaction to stress and temperature
• Thermoplastic/Thermoplasts: Polymer shape can be repeatedly
changed by heating/pressure
• Thermosets: These polymers if once heated or pressurized into a
particular form cannot be formed again
• Rubbers: These polymers when subjected to heat, pressure first
behave like thermoplastics and subsequently become highly elastic
• Vulcanisation or curing enables the polymer to arrest elasticity
 Contd…
• Mechanical strength and behaviour
• Elastomers: They have low initial moduli of elasticity(10-100psi)
• It can sometimes be as high as
1000%(extensibility) Elasticity is directly
proportional to temperature At brittle point,
material becomes brittle
• Plastomers/Plastics: They have high initial moduli of elasticity than
elastomers(100-1000psi)
• When plastomers are deformed some part of it undergoes permanent
deformation while the other can be regained
• Extensibility range: 100-200%
• Extensibilty, µ, elastic moduli = f(T)
• Fibers:
• They have high initial moduli of elasticity(1000-10000psi) , low
extensibility(10-20%)
• When subjected to deformation , it is permanent(majority), rest is
reversible(partly instantaneous/delayed)
 Contd…
• Production methods of polymers:
• Addition/chain reaction polymers – Addition polymerization
• Simple low molecular weight molecule with double bond breaks and
joins with other similar molecules to give the polymer
• Monomers react to form a polymer without net loss of atoms

n monomers one polymer molecule

Example of addition polymers
Free-Radical Addition Polymerization of
Ethylene
H2C CH2

200 °C O2
2000 atm peroxides

CH2 CH2 CH2 CH2 CH2 CH2 CH2

polyethylene
Free-Radical Polymerization of Propene

H2C CHCH3

CH CH CH CH CH CH CH
CH3 CH3 CH3 CH3 CH3 CH3 CH3

polypropylene
 ..
RO..• Mechanism
H2C CHCH3
 ..
RO:
Mechanism
H2C CHCH3
•
 ..
RO: Mechanism
H2C CHCH3
•

H2C CHCH3
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3
•
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3
•

H2C CHCH3
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3
•
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3
•

H2C CHCH3
 Likewise...

H2C=CHCl polyvinyl chloride

H2C=CHC6H5 polystyrene

F2C=CF2 Teflon
 Condensation polymerization
Condensation polymerization: Here the polymer grows from monomers by
splitting off a small molecule such as water or carbon dioxide.
• Monomer does not retain its characteristic molecular formula in mesomer
• Monomer need not contain double bond

Example: Formation of amide links and loss of water, Nylon

Monomers

First unit of polymer + H2O

29
Classification of polymers:
• Based on molecular arrangement:
• Linear: Mesomer/monomer units are arranged linearly or joined together
end to end, they are soluble and fusible
•Bivalent molecules give linear polymers
• Ex: HDPE, Nylon
• Branched: Chains includes molecules which have valencies of more than
two
• They are more soluble and fusible
•Ex: LDPE
• Crosslinked: Insoluble and infusible
• Network: High crosslinking,3D structure
• Ex: Rubber, Phenol formaldehyde
 Contd…
• Based on type of mesomer involved:
• Homopolymer: composed of only one type of mesomer
•Ex: Polyethylene, Polyvinylchloride, etc
• Heteropolymer: Copolymer – As copolymer can have more than one
mesomer
• Based on morphology:
• Crystalline: The chains are very closely packed, these are more opaque
• Amorphous: Chains are loosely held, hence more transparent
 Methods of determining molecular weight of a polymer
• In general polymers are non homogeneous of varying molecular sizes, chain
lengths, hence average molecular weights are used
• Methods include:
•Method based on counting the number of molecules in a known mass –
Number average molecular weight,M n
•Method based on weights of various fractions of a polymer when
subjected to distillation – Weight average molecular weight,M w
• Method of obtaining Z-average molecular weight
• Viscosity measurement method
• Ebulliscopic or elevation of boiling point method, cryoscopic or
depression of freezing point method
• Vapour pressure method
• Osmotic pressure method
• Sedimentation velocity method
• Sedimentation equilibrium method
• Analysis of light scattering or spectrophotometer method
•Gel – chromatographic analysis method
• End group analysis method
 Number average molecular weight
•No. of moles in a sample of polymer = molecular species present in the
sample
Total no. of moles =  N i in the sample
• Total weight of sample = sum of weights of each molecular species
W   wi   N i M i
• Number average molecular weight,
 wi  N i M i
W 
 Ni  Ni

• The no. of moles present in sample is determined by end group analysis

method or osmotic pressure method
 Weight average molecular weight
 wi M i  N i M i 2
• It is defined as M w  
 wi  NiM i

 Mw   Mn
Mw
- poly dispersity index
Mn
• If poly dispersity index varies from 1.02 to 20, polymer is mono disperse

• Weight average molecular weight is determined by sedimentation equilibrium

method or by analysis of light scattering method
 Z- average molecular weight
• It is determined by sedimentation equilibrium method
 wi M i 2  N i M i 3
Mz  
 wi M i  N i M i 2
• For linear condensation polymers
(1 4 p  p 2 )
M n : M w : M z  1: (1 p) :
(1 p)
Where p is the extent of reaction
If p=0, 3 molecular weights approach one another in value

If p=1, M n : M w : M z  1: 2 : 3
 Viscosity average molecular weight
• It is determined from viscosity measurements
•They are used in equation where intrinsic velocity, molecular weight
relationship of sample follows the staudinger’s equation
• Based on the polymer-solvent system , a relation was developed
[ ]  kM a
From which constant a is obtained 1

a 1a   N i M i a1  a
M v  [wi M i ]  
  Ni M i 
• If a=1, viscosity average = weight average
 Cryoscopic and Ebullioscopic methods
• Substance is completely soluble in solvent
• Lowering of freezing point or elevation of boiling point is proportional to the
amount and nature of substance dissolved in it
• Equation for freezing point curve or boiling point line
T R
   ln a s
TxT  Ls 
Where as is the non-ideality factor or activity coefficient
T  (T fs  Ts )or(Tb  Tbs )
Where T f , Tfs , Tb, Tbs are the freezing and boiling points of solution and solvent
respectively, Tx can be either either freezing or boiling points of solvent, R –
gas constant, Ls is the molar heat of fusion or evaporation of solvent
• For very dilute solutions – Raoult’s law is valid
 wA  1000   Ts 2 M s 
T  KC  K   K  k f ork b KR  
w  M   100L 
 s  A   
k f is the freezing point depression constant, kb is the boiling point elevation
constant, C is the molality of solution
 Contd…
Disadvantages:
When used for low molecular weight compounds
•Vapor pressure depression is too small when compared to the
changes in temperatures
• These methods are valid only at the boiling point or freezing point of
the solvent
• Hence at room temperatures determining the molecular weight by this
method is not possible
 Vapor - pressure method
• Considering polymer solution as an ideal solution Raoult’s law can be applied

Ps o w A M s
M n for component A is M n 
o Pws
Ps is pure solvent pressure

P  Ps   ,  is the total pressure acting on the solution

o

But polymer solution is not ideal, so after incorporating the non ideal
concept wAM s
Mn 
(1 as )ws

wA , ws are the weight fractions of component A and solvent

as is the non-ideality factor

Ps  a s Pso
 Osmotic Pressure Method

•Suitable for high

molecular weight materials
• Polymer solution gets
diluted by solvent

•High molecular weight substances have

osmotic pressure in the range to measure
with good accuracy
•Semi permeable membrane preparation
is easy when large polymer molecules are
used
• As it permits only solvent molecules
to pass through the membrane.
• As system is diluted, entropy increases until the change is being encountered
by rise in pressure head
• At this point, chemical potential in both the limbs will be the same
• Pressure difference indicated by levels of 2 limbs gives osmotic pressure π
• By choosing different dilutions, a plot of (π/C) vs C is drawn
• When C=0, M n is obtained, given by:
    RT 
LtC0   
 C   Mn 

Where C is the polymer concentration in w/v

Disadvantage:

• Suitability of the membrane for a particular system

•Osmotic pressure method is suitable for polymers with M n in the range of
50000-1000000
 Sedimentation Velocity Method
• Principle: Svedberg’s population
“ Particles suspended in a liquid distribute themselves according to their size or
mass when put in a centrifugal field”
• This particle distribution is given by mathematical relationship at which
particles segregate
• Larger/denser particles sediment faster than smaller ones
• In a given field, sedimentation rate varies directly with centrifugal force,
inversely with frictional resistance encountered by molecules
• Centrifugal force depends on molecular weight of the sample
• Frictional resistance depends on molecular volume, molecular shape
Assumption: Centrifugal force encountered by frictional resistance and
molecular diffusion is negligible dx
RT  S o 
MA    S o  dt2 
m(1  A  )
1  A   Do   x f
RT
Do 
f
Disadvantage: It is not suitable for unfractionated polymers
 Sedimentation Equilibrium Method
• Moderate centrifugal field is applied to a polymer solution and the change in
concentration is noted with respect to time
• Sedimentation and diffusion takes place at the same time
• Sedimentation rate caused by centrifugal force creates concentration gradient
of solute molecules
• Mass transfer occurs as molecules in high concentration layer diffuses to
molecules in the low concentration layer
• At equilibrium, rates of both the phenomenon are same
dx dc
C D
dt dx
Where C is the solute concentration, x – distance from centre of rotation
dc
Using Svedberg equation, M A (1  A  ) 2 xC  RT
dx
2RT ln  C2 C 
MA   1
(1   ) (x  x 2 )
2 2
A 2 1

Above equation holds good even for unfractionated polymers, M w, M z can be

obtained
Polymers of 5000 – 500000 molecular weights are applicable
 Analysis of light scattering method
• When a beam of light is passed through a non absorbing polymer solution,
intensity of scattered light depends on size, shape of polymer molecules
• Light lost due to scattering: I  I o e l

Where Io , I are the entering and leaving light intensities

 is the turbidity of the solution, l – length of the cell
Using Debye equation,  is related to osmotic pressure as follows:
HC  1  d   RT  BC
 
  RT  dC C M
HC 1 2B  s (0.5   )
B   RT 

  C
 M w RT  M s   A 
Where C is concentration H 32 n  dn 
3 2 2

 
n is refractive index of solution 34 N o  dc 
No is Avogadro number
λ is the wavelength of light
By plotting HC vs C, extrapolating to zero concentration, molecular weight was
obtained 
 Contd…
Advantages:
• Gives width of distribution curve
• As sample molecular weight increases, precision increases
• Used for polymer at low concentrations

Limitations:
•As measurements are noted using light scattering, impurities/dust
particles/coarse ones give errors
• Not good for low molecular weight materials
• Polymer/solvent colour affects the accuracy of the method
 Gel - Permeation Chromatography Method
• Also called as Size exclusion chromatography method
• Column is filled with gel or porous solid beads which have pore size smaller
than that of polymer molecules
• Materials used here includes gel, glass for polar molecules, highly cross-
linked polystyrene for non polar molecules
 Contd…

Process:
•Solvent stream flows through the column and dilute polymer solution is
introduced to it
•Molecules smaller than pore size of gel enters the beads, larger ones will pass
on(short retention time)(smaller ones – more retention time)
• Retention time is the amount of time between the injection of sample and its
elution from the column
• A chromatogram was drawn for retention time or volume vs amount of eluted
molecules
• Calibration plots were drawn using retention volumes relating molecular sizes
 End group analysis method
•The long chain nature of polymers limits the groups to end groups, so end
group analysis is made
• Here the no. of molecules in a given weight of sample was counted
• The process becomes more insensitive at high molecular weights, since
fraction of end groups becomes too small to measure
• This loss of precision occurs at molecular weights >25000(inability to purify
samples, reagents, lack of sensitivity in methods)
• It covers both addition and condensation polymers
• Condensation polymers – based on the analysis of functional groups
• Addition polymers – based on kinetics
 Natural Polymers
• Natural polymers – resinous materials obtained from plants
and animals
• Sealing wax – natural polymer – used as a plastic material
• Pottery – natural polymer
• Clay, glass – mineral origin – can be used as plastic material
• Resins of animal origin
• Shellac
• Proteins(glue, gelatin)
• Casein
• Resins of plant origin
• Rosin
• Rubber
• Proteins
• Lignin
• Cellulose
Rosin:
• Obtained from trees as exudates
• Sources
• Stumps of rosin yielding trees that are underground for nearly
10years
• Trees when trapped(Recent Source)
• Rosin is a by-product of paper industry
• Major contents of rosin – cyclic acids – Abeitic acid – major constituent
•Natural rosin – 60% organic matters(saturated, unsaturated fatty acids,
resins, esters, alcohols, high molecular weight hydrocarbons, waxes are
also present)
• 20 - 30% is used in sizing of paper
• Rosinate of lead, zinc, manganese used in paints for drying of oils
•Rosin in the form of salts are used in soaps and greases
Manufacturing process of Rosin:
• Pine tree tappings – 68% rosin, 20% turpentine and rest water
• By steam distillation, turpentine is removed as volatile compound,
rosin which remains in the still is collected as residue
• Old pine stumps – 20% rosin
•Wood – shredded, extracted using a low boiling solvent(recovered by
steam distillation – Turpentine(Rosin+solvent) undergoes distillation)
•Rosin, turpentine passes through a still – crude turpentine, rosin are
separated

• Decolourisation
• Passing through fuller’s earth
• Using synthetic magnesium silicate
• Mixed with furfural, naphtha and heated to 52℃ till complete miscibility
is observed. Upon cooling furfural layer contains the coloured matter,
naphtha layer contains rosin. As per the ratios of furfural and naphtha, rosin
colour varies from lighter yellow to darker coloured ones
Shellac:
• It is a natural resin, forest product
•Insects(Tachadia lacca/Laccifer lacca) – thrive by absorbing the sap of a
variety of soft wood trees through their stingers and exude a semi polymerized
product – gum like substance(like spider which exudes the web)
•Mother insect lays eggs, cover them and itself with exudation. When eggs
hatch young ones break through the shell and migrate to another tree to
repeat the process. The hard crust left on the tree branches acts like stick lac –
collected, crushed, purified by heating and filtering the molten lac to remove
the twigs, etc, which was then washed, dried, transported as shellac.
•Shellac has a complex chemical composition, which may vary slightly
depending on the host tree, species of the insect and environmental
conditions.
•It is a mixture of resin (70–80%), wax (6–7%) and colorant molecules (4–8%),
obtained by refining stick lac, which is the material collected directly from the
plant.
•Shellac is of 2 types
• Hard lac
• Soft lac
Rubber:
• Natural Rubbers – source – variety of tropical trees, shrubs and vines
•Milky latex from plants – emulsion of several poly hydrocarbons in an
aqueous medium
•Several naturally occurring proteins, esters of fatty acids are called lipids –
stabilizers for emulsion
• Latex on coagulation gives rubber
• Type of rubber varies from plant to plant and place to place

Place Plant Name Rubber

South America Bully tree Balata
Malaya, Borneo and Sumatra Guttapercha tree Guttapercha
Mexico and California Guayule tree Guayule
Brazil Hevea tree Caoutchouc
Cultivated in Malaysia, Indonesia, Srilanka, Central Africa and INDIA

• Latex contains 35% rubber hydrocarbons, 55% water, 4.5 – 5% proteins, 4% of

other resinous materials
• After coagulation, latex contains 85-90% rubber hydrocarbons, 10% water
• On mastication of coagulated latex, crepe rubber is obtained
• Natural rubber is a linear high molecular weight polymer of isoprene
 CH 2C(CH 3 )  CH  CH 2 n 
n ranges from 100000 – 500000
• Hevea rubber has cis-configuration where as balata, guttapercha has
trans-configuration(more thermoplastic, less elastomeric)
• The process of treating rubber with sulphur and heating is called
vulcanisation
• Automobile industry uses rubber grade with 2 – 3% sulphur
Proteins:
• It is made up of a number of complex nitrogeneous organic substances
– common constituent with amino acid in them, held together by
peptide bonds(R-CH-NH2-COOH)
•Proteins are amphoteric in nature – have both acidic, basic side chains,
found in all living plant and animal origins
• Classified as
• Simple
• Conjugated/fibrous
• Non-fibrous
• Simple proteins – on hydrolysis gives amino acids
• Conjugated proteins – have amino acids and other substances
• Fibrous/fibrillar – silk, wool, animal horn, etc
• Globular/non-fibrous – albumins, globulins, etc
• Industrial animal proteins – glue, photographic gelatin, edible gelatin,
fish glue, casein,etc
• Collagen(animal bones / marrows) on hydrolysis gives glue /gelatin
(Collagen)C102H149O38 N31  H 2 O  C102H151O39 N31 (Glue or Gelatin)
• Gelatin in its impure form is called as glue
• Glue – used in paper industry, rubber processing, book binding, wood
work, textile industry
• Glue in its highly purified form is used in ice creams, jellies
• For coating photographic plates, gelatin of less purity is used
• Fish glue - a cheaper grade – used in photo engraving, cold liquid
adhesive, higher grade is used for clarification of beverages
• Casein – obtained from milk(Cow’s milk casein content – 3%)
• Casein – precipitated from skimmed milk by an acid
• Soyabeans, corn are also rich in proteins
Lignin:
• They are resinous binders for the cellular fibers of plant materials
• Wood contains 35-90% of lignin content
• It is a waste product from paper industry
•It contains aromatic rings to which hydroxyl and methyl groups are
attached
•They are complex polyether of various poly hydroxy, n-propyl
benzenes(mol.wt – 4000)
•Lignin – source of methanol(obtained by destructive distillation of
wood)
• Uses: Production of insecticides, disperants of pigments and dyes,
leather tanning, metal cleaning
Cellulose:
• It is a major constituent of any plant widely used organic chemical in
the world

Source %Cellulose
Wood(Soft and hard) 40 – 50
Cotton and linters 88 – 96
Jute 65 – 75
Straw 44 – 51
Bamboo 45 – 50
Flax or hemp 85 – 90

• Pure cellulose is a linear polymer, glucosidic in structure, n≥3000

• Molecular weight of cellulose is as high as 800000
• For commercial applications, molecular weight is under 100000
•Uses: Fuel, furniture, paper, chemicals, synthetic fibers, plastics,
explosives, lacquers, etc
 Uses of Polymers
• Polymers are incorporated into nearly every
aspect of daily life
– Entertainment
– Sports
– Clothes
– Toys
– Household products
– Automotive
 Polymers - Pros and Cons
• A polymer has many very advantageous
properties. Polymers are:
– Lightweight
– Strong and durable
– Cheap
– Easy to manufacture
• Unfortunately, polymers do not easily
biodegrade and end up producing large
amounts of waste