3 Polymer Technology
3 Polymer Technology
3 Polymer Technology
TECHNOLOGY
Contents
Polymer Technology-
What are Polymers?
Classification of Polymers,
Mechanism of Polymerization.
Some major Polymers (Plastics) and their applications
Natural rubber-
Processing of Natural rubber,
vulcanization,
Properties and applications
Identification of Plastics by simple methods
Environment Friendly Polymers
POLYMER
Polymer is a Greek word- “Poly” means “many” and “Meros”
means “Parts”.
When large number of a single repeating unit combines and
form macromolecule, the resultant high molecular weight
compound is called Polymer
The single repeating unit which is combining together to
form macromolecule of higher molecular weight is called as
Monomer.
POLYMERIZATION
The process of linking the repeating units (monomers) to
form high molecular weight compound (polymer) is called
Polymerization
Degree of Polymerization: The number of repeating units in
chain formed in a polymer is known as the Degree of
Polymerization.
CHARACTERISTICS OF POLYMERS
Polymeric molecules are very big molecules. Their average
molecular weights may approach 105 or more.
Polymers are semi crystalline materials. It means they have
both amorphous and crystalline regions.
The intermolecular forces in polymers can be Vander Waals
Forces, Dipole- Dipole attractions or Hydrogen Bonding.
Polymers are combustible materials.
Generally, Polymers are thermal and electrical insulators.
The chemical, electrical, optical, mechanical and thermal
properties of polymers depend on size and shape of polymers
and their intermolecular forces.
ADVANTAGES OF POLYMERS
Low densities and cost of transportation is low.
Excellent resistance to corrosion.
Thermal and electrical insulators.
Rubber- inherently flexible polymer, have excellent elasticity
and damping qualities.
Ability to take the variety of colors, shades, etc. which do not
fade easily.
Easily mouldable even into complex shapes with reproducible
dimension with minimum of fabrication and finishing cost.
DISADVANTAGES OF POLYMERS
Lower strength and stiffness, easily get deformed under load.
Combustible (except metals and ceramics).
Temperature limitations in service, low heat resistance and
embrittlement occurs at low temperature.
Time- dependent properties, they show creep.
CLASSIFICATION OF POLYMERS
ON THE BASIS OF OCCURRENCE
NATURAL POLYMERS
These are obtained from natural sources (plants and animals).
Example: starch, cellulose, rubber, protein, silk
SYNTHETIC POLYMERS
These are synthesized by men. Most of them are long chain organic molecules containing
thousands of monomer units.
Example: Polythene, nylon, PVC, etc.
ON THE BASIS OF THEIR STRUCTURE
LINEAR POLYMERS
Each monomeric unit is linked with two other monomeric units on either side, forming a
continuous straight chain. The monomeric units are added on to each other forming a
long chain.
Example: High density polythene (HDPE)
BRANCHED POLYMERS
Most of the monomeric units are linked with two other on either side. Some monomeric
units are linked with a third monomeric unit.
Example: Low density polythene (LDPE)
CROSS LINKED POLYMERS
When a bi-functional monomer is mixed in small amount with tri- functional
monomers, a three dimension network polymer is formed
ON THE BASIS OF TACTICITY
The orientation of monomeric units in a polymer molecule can take place in an orderly or disorderly
manner with respect to the main chain. The difference in configuration is known as Tacticity.
ISOTACTIC POLYMER
All functional groups are present on the same side of the chain.
SYNDIOTACTIC POLYMER
Functional group is present in alternating fashion around the main chain.
Example: Gutta Percha
ATACTIC POLYMERS
Functional groups are arranged randomly.
Example: Polypropylene
ON THE BASIS OF REPEATED UNITS
HOMOPOLYMERS
Entire polymer chain is made up of one single repeat unit.
CO-POLYMERS
Have more than one type of repeating unit in the polymer backbone.
ON THE BASIS OF MODE OF SYNTHESIS
ADDITION POLYMERS
Formed by direct addition of repeated monomeric units, without the elimination of any
product molecule.
CONDENSATION POLYMER
Formed by condensation of two or more than two monomers, with the elimination of
simple molecules like water, ammonia, hydrogen chloride, etc.
ON THE BASIS OF ITS BEHAVIOUR WHEN HEATED TO PROCESSING TEMPERATURES OR ON
THE BASIS OF MOLECULAR FORCES
THERMOPLASTIC POLYMERS
Can be easily softened repeatedly when heated and hardened on cooling with little change in properties.
Their hardness is a temporary property, subject to change with rise or fall of temperature. Thus, can be
processed again and again.
They have low melting points and can be repeatedly moulded and remoulded to the desired shapes.
They have either linear or branched structures.
Polymeric chains are held together by weak Vander Waals forces or Dipole- Dipole interactions or Hydrogen
Bonding.
There are no Cross- links.
EXAMPLE: Polythene, PVC, Nylon, Teflon
These materials are fabricated normally by the simultaneous application of heat and pressure.
THERMOSETTING POLYMERS
They undergo permanent change on heating.
When heated they get highly cross linked to form hard infusible and insoluble products.
They are permanently rigid due to the presence of cross links.
During moulding, they acquire 3- D cross linked structures, with permanently strong covalent bonds.
They cannot be reprocessed.
They are more chemically inert.
Their molecular weight is very high.
Example: Polyester, bakelite, melamine.
S. NO. THERMOPLASTICS THERMOSETS
1 Formed by addition or condensation Formed by condensation polymerization
polymerization
2 Linear or branched structures. 3-D, cross linked network structure
4 Low molecular weight thermoplastics are They are generally insoluble in any solvent.
soluble in their suitable solvents.
5 They can be re-moulded , re-shaped and re- They can’t be re-moulded and hence cannot be re-
used. used.
6 They can be reclaimed from waste i.e. they They cannot be reclaimed from waste, they cannot be
can be recycled. recycled.
7 During moulding of thermoplastics, there is They undergo chemical changes such as further
no change in their chemical composition. polymerization and cross linking during moulding
process.
8 Adjacent polymer chains are held together by Adjacent polymer chains are held together by strong
either vander waals forces, or by dipole- covalent bonds called cross links.
dipole interactions or by Hydrogen bonding.
9 They are tough materials. They are brittle materials.
Features:
No need of catalyst.
Highly exothermic
Once the reaction begins with initiator, it proceeds very fastly.
C=C in the monomer is utilized for polymerization.
The polymer molecular formula is an exact multiple of monomer
formula.
No by-product is obtained.
Mechanism: Initiation – Propagation –Termination.
Polymer molecule ends are not reactive or are dead.
CONDENSATION OR STEP POLYMERIZATION
It takes place by the condensation of two different
bifunctional or poly functional monomers having
functional group which have affinity for each other.
Example: -COOH and NH2 carrying monomers
undergo condensation polymerization.
It always accompanies with the elimination of small
molecules like H2O, HCl, etc.
FEATURES:
Catalyst may or may not be required.
Reaction is endothermic.
Reaction between functional groups take place slowly.
Functional groups like –COOH, -OH, -COOR, -NH2
are on the monomer molecules.
Molecular formula of polymer is not exact multiple of
monomer formula.
Usually a simple by-product is formed along with
polymer, therefore by-product separation is required.
Polymer molecule ends are reactive or live and if more
monomer is added, the polymerization can continue.
Low Density Polyethylene (LDPE)
Purified ethylene is first liquefied under
high pressure (1000-3000 atm) with the
help of primary and hyper compressors
It is then fed to the tubular reactor along
with catalyst (Hydrogen peroxide).
In this reactor, ethylene is polymerized into
polyethylene, a waxy solid, which comes
out from the perforation in the bottom of
the vessel.
Polymerization reaction is highly
exothermic, sometimes lead to explosion.
Therefore proper cooling is done with the
help of cooling towers.
After polymerization, mixture is transferred
to separator in which un-reacted ethylene
is removed and recycled.
After drying, Polyethylene pellets are stored.
Properties
Rigid, waxy, white, translucent material at room temperature
Show chemical resistance to strong acids, bases and salts
Good insulator of electricity
Due to highly symmetrical chain structure, it crystallizes
very easily
Has branched structure, flexible and tough
No strong intermolecular forces
Backbone is flexible
Applications
For making high frequency insulator parts
Bottle caps, flexible bottles
Moulded toys, sheets for packing materials, chemical plants
Tubes, pipes, coated wires and cables
Kitchen and domestic appliances
High Density Polyethylene HDPE
Ethylene (dissolved in a liquid hydrocarbon such as
cyclohexane) is polymerised in the presence of catalyst at
1.4- 3.5 Mpa pressure and at about 130-160 degree C.
After reaction, the mixture is passed to a gas liquid
separator where ethylene is flashed off, catalyst is then
removed from the liquid product.
Polymer is separated from the solvent by either flashing off
the solvent or by precipitating the polymer by cooling.
Properties
The HDPE molecules are linear. Hence it has high density
(0.95- 0.97 gm/ cubic cm).
Softening temperature is higher as compared to LDPE.
Has excellent insulation properties.
Free from odour and toxicity
It is more stiff and possesses greater tensile strength as
compared to LDPE.
Applications
HDPE film is used as wrapping material material instead of
paper for food products.
Because of better oxidation and UV- resistance, HDPE is
used for the manufacture of crates, food tubs, industrial
containers and overhead tanks.
It can also be used for domestic water and gas piping.
Bottle for milk, household chemicals and drug packagimg
are also made from it.
PVC is a thermoplastic polymer.
It is vinyl polymer constructed of repeating vinyl
groups having one of their hydrogen replaced
with a chloride group.
PVC is made by addition Polymerization.
Rigid or Unplasticized PVC
Vinyl chloride is mixed with water in equal parts,
small amount of catalyst and an emulsifier.
The mixture is vigorously stirred and then sent to
autoclave at 40 – 45 degree C.
The polymerization is completed in 60-70 hours.
The polymer is coagulated by acid and drier.
The desired properties in PVC can be achieved by
using plasticizers, stabilizers, lubricants and
fillers.
Properties
PVC is colourless, odourless and non- inflammable.
Presence of chlorine atoms on the alternate carbon atoms of PVC causes
an increase in the interchange attraction.
This increases the hardness and stiffness of polymer. Its softening point is
also high (148 degree C)
The Cl-Cl dipole makes PVC a polymeric polar molecule, but because of
the immobility of the dipole at room temperature power factor of PVC is
comparatively low.
It has superior chemical resistance but is soluble in ethyl chloride and
tetrahydrofuran.
It has excellent oil resistance and resistance to weathering.
Applications
Used for making bottles like bislery mineral water, cosmetics and
detergents.
Used for making pipe for drainage and guttering.
Shows chemical resistance therefore used in acid recovery plants for
handling hydrocarbons, many of which adversely affect the polyolefins.
Plasticized PVC
Preparation
Plasticised PVC is generally obtained by adding plasticizers such as-
dioctyl pthalate, dibutyl pthalate, etc.
Properties
Good insulator
It has completely replaced rubber insulated wire for domestic flex.
Applications
Used for making leather cloth which is used in car applications in
upholstery and trim, kitchen upholstery, bathroom curtaining bags, etc.
It is used for making plastic rain wear, baby pants, all PVC shoes for
beach wear and garden hose
Preparation
Teflon is a fluorocarbon as it is a high molecular weight
compound consisting wholly of carbon and flouroethylene.
Poly tetra fluoro ethylene is obtained by polymerization of
water-emulsion of tetra floro ethylene, under pressure in
presence of benzoyl peroxide as catalyst.
Properties
Due to presence of highly electronegative fluorine atoms and
the regular configuration of the PTFE molecule results in very
strong attractive forces between the different chains. These
strong attractive forces are responsible for-
High density
Chemical inertness over a wide range of temperature.
Excellent electrical insulation properties.
Non- adhesive characteristics.
Very low coefficient of friction
Excellent toughness and heat resistance.
Applications
Wire and cable insulation
Laminates for printed circuitry
Coatings of frying pan
Non- lubricating bearings
Variety of seals, gaskets, packing valve and pump parts and
stop-cocks for burettes
Insulators for motors, generators, coil transformers and
capacitors.
It is formed from phenol and formaldehyde.
It is a thermosetting resin.
Properties
Phenolic resins are hard, rigid and strong materials
They have excellent heat and moisture resistance
They have good chemical resistance
They possess excellent electrical insulating character
Low molecular weight grade have excellent bonding
strength and adhesive properties
Applications
For making electric insulator parts like switches,
plugs, switch-boards, heater-handles, etc.
For making moulded articles like telephone parts,
cabinets for radio and television
For impregnating fabrics, wood and paper
As adhesives for grinding wheels
In paints and varnishes
The production of ion exchange resins
For making bearings, used in propeller shafts for
paper industry and rolling mills.
It is an opaque chemically thermoset resin
obtained by heating urea and formaldehyde in
the presence of ammonia or pyridine.
Properties
It gives clear, white products of good tensile
strength.
They have good electrical insulation
They have good chemical resistance
Good abrasion resistance
Good solvent, grease and moisture resistance
Applications
For bonding grinding wheels
Binder of glass fibres, rock wool, etc. which are
used for filtration and insulation purposes
Binder for foundry cores
Cation exchanger
Bonding plywood
Electrical insulation
Decorative articles like plates, drinking
glasses, dishes, etc.
Nylon is a generic designation for family of synthetic
polymers, more specified aliphatic or semi-aromatic
polyamides.
Synthetic fibre forming polyamides are termed as Nylons
The important polymers of this category are- Nylon-6,
Nylon-6,6, etc.
Properties
The structure of Nylons are linear that permits side-by-side
alignment.
Due to hydrogen bonds they have high crytallinity which
imparts- high strength, high melting point, elasticity and
toughness.
They are also sterilizable.
They have good hydrocarbon resistance.
They have good moisture resistance.
Applications
It is primarily used for fibres which find use in making
socks, carpets, etc.
It is also used in mechanical engineering for well-known
applications like gears, bearing, bushes, cams, etc.
It is also used for jacketing electrical ware to provide a
tough, abrasion resistant outer cover to protect the primary
electrical insulation.
It is a saturated polyester formed by
condensation of ethylene glycol and
terephthalic acid.
Properties
It is a good fibre forming material and is
converted into commercial fibres.
Such fibres have high stretch resistance (due
to high stiffness of polymer chains)
High crease and wrinkle resistance
High resistant to mineral and organic acids.
Applications
It is used for blending with wool to provide
better crease and wrinkle resistance.
They are used as glass reinforcing material in
safety helmets, aircrafts battery boxes, etc.
It is used in magnetic recording tape.
It is used in wide necked jars for coffee.
The organic polymers which possess elasticity are known as elastomers or rubber.
It has ability to undergo large deformation on applying stress and recover the original form after removing
the stress.
Types
1. Natural Rubber
2. Synthetic Rubber
Properties
Utilization over a temperature range from -80 to 300 degree C
Electrically insulatating
Withstands extremes of weather and outdoor environments indefinitely
Withstands exposure to fuels, oils and chemicals
Ability to be rendered flame-retardant and self-extinguishing
Maintains tensions and compression forces indefinitely
Conformable, adaptable, and accomodating of movement, shock, thermal changes, tolerances and
roughness
Absorbs vibration and noise and acts as an insulator
Possesses low thermal conductivity and can be used to reduce heat transfer
Friction properties similar to human skin and comfortable to grip
Applications
It is used in manufacturing motor tyres
In preparing shoe soles, gasket, cable insulation, conveyor belts, industrial hoses, gloves, etc.
In lining of tanks
In tubings for carrying corrosive gases and oils
In making tyres of fighter aircrafts
Used as adhesives in electronic industries
Processing of Natural Rubber from Latex
Types of Synthetic Rubber
Silicone rubber is an elastomer (rubber-like material) composed
of silicone—itself a polymer—containing silicon together
with carbon, hydrogen, and oxygen
Requirements: Soldering iron rod, plastic samples.
Theory:
Thermoplastic polymers:
•Can be easily softened repeatedly when heated and hardened on cooling with little change in properties.
•Their hardness is a temporary property, subject to change with rise or fall of temperature. Thus, can be
processed again and again.
•They have low melting points and can be repeatedly moulded and remoulded to the desired shapes.
•They have either linear or branched structures.
•Polymeric chains are held together by weak Vander Waals forces or Dipole- Dipole interactions or Hydrogen
Bonding.
•There are no Cross- links.
•Example: Polythene, PVC, Nylon, Teflon
Thermosetting polymers:
•They undergo permanent change on heating.
•When heated they get highly cross linked to form hard infusible and insoluble products.
•They are permanently rigid due to the presence of cross links.
•During moulding, they acquire 3- D cross linked structures, with permanently strong covalent bonds.
•They cannot be reprocessed.
•They are more chemically inert.
•Example: Polyester, bakelite, melamine.
Procedure:
•The hot soldering iron rod is penetrated in the given samples one by one.
•The effect of heat is noted down.
Objective: To perform floatation test on the given plastic samples.
Requirements: Beakers, distilled water, 46% Isopropyl alcohol, 10% NaCl, Saturated NaCl,
Vegetable Oil, plastic samples.
Theory: One substance floats on the surface a fluid when density of the substance is less than that
of the fluid whereas it sinks if its density is higher than that of the fluid.
Floatation Chart of Plastics:
Procedure:
•Take 5 different beakers and label them as Beaker 1, 2, 3, 4 and 5.
•Add distilled water, 46% isopropyl alcohol, 10 % NaCl, saturated NaCl and vegetable oil in
Beaker 1, 2, 3, 4, 5 respectively.
•Take the first plastic sample and first drop it in Beaker 1.
•Observe whether it floats or sinks.
•Then on the basis of floatation behavior, move ahead to the next beaker.
•Repeat the same process for other plastic samples and note the behavior in the observation
table.
Floatation Behaviour (Floats/ Sinks)
S. 46%
Plastic Material Distilled Vegetable Saturated
No. Isopropyl 10 % NaCl
Water Oil NaCl
alcohol
Phenol formaldehyde Chars Yellow bright Phenolic odour Chars with Difficult
resin sooty cracking sound
Urea formaldehyde Chars Light yellow Smell of urea Chars with Difficult
Resin blue edges cracking sound
Immersion method
The most common method for the determination of the density of solid plastics is the immersion
method, described in ASTM D 792 and ISO 1183-1. A test specimen is weighed in air and its mass is
being recorded. It is then immersed in a liquid and its apparent mass upon immersion is recorded.
The density (mass ratio x the density of the liquid) is then calculated. The immersion liquid can be
either distilled water or a liquid lighter than water such as ethanol, n- butyl alcohol, IPA etc.
Procedure:
•The plastic sample is cut into pieces of equal dimensions.
•Assemble the density determination kit on the weighing balance.
•Remove the weighing pan, pan support, breeze break ring and dust plate from the balance.
Plastic material Density (gm/cc)
•Place the density pan stand on the balance.
•Place one balance weight (small) on the density pan stand. PE LDPE = 0.925,
•Place the beaker stand so that it does not touch the density pan stand. HDPE= 0.925-
•Attach the thermometer clamp to the beaker and insert the thermometer into the 0.965
thermometer clamp. PP 0.89- 0.91
•Pour a liquid with a known density (such as distilled water) into the beaker and place the
PS 1.05- 1.06
beaker on the beaker stand.
•Place the density pan on the density pan stand. PVC 1.41
• Adjust the amount of the liquid so that the sample, when placed on the lower pan (in the Poly Amide Nylon-6= 1.13-
liquid), is about 10 mm below the surface of the liquid. 1.14
•When the value displayed on the balance is stable, press the RE-ZERO key to set the PET 1.4
displayed value to zero. Now the balance is ready for density measurement.
PBT 1.31
•Now the plastic sample of standard dimension is taken and is weighed on air. Note down
the reading in the weighing balance (W1). PC 1.2
•Now place that sample on immersion pan which is inside the water. Again note down the POM 1.41-1.42
reading (W2). PPO 1.06
•Remove the sample from water and do this procedure for different pieces of plastic sample PPS 1.34
of similar dimensions.
•Take the average reading.
Requirements: Digital Melting Point apparatus, silicon oil, capillary tube, plastic sample in powdered form or in the form of fine
flakes.
Theory: The physical properties of a compound, such as melting point and boiling point can provide useful information which
can help in the identification of a sample or to establish its purity. The temperature at which a solid melts and becomes a liquid is
the melting point. Since this requires that the intermolecular forces that hold the solid together have to be overcome, the
temperature at which melting occurs will depend on the structure of the molecule involved
The melting behaviour of a crystalline or semi-crystalline polymer is a structure-sensitive property. A sharp melting point is
observed only for low molecular mass substances, but in polymers, a melting temperature range is observed on heating, from
the first change of shape of the solid particles to the transformation into a highly viscous or visco-elastic liquid, with
accompanying disappearance of the crystalline phase. The melting range depends upon a number of parameters, such as
molecular mass, molecular mass distribution, percent crystallinity, and thermodynamic properties. It may also depend on the
previous thermal history of the specimens. The lower or upper limit of the melting range, or its average value, is sometimes
conventionally referred to as the "melting temperature".
The unit consists of a built in magnetic stirrer, glare free background illuminator and cylindrical silicon oil bath. The
silicon oil bath consists of a plain cylindrical container. It is furnished with a cover fitted with special type of oil
immersion heater, having three small holes for holding the capillaries, one big hole for thermometer and another big
hole for boiling point tube. A variable speed stirrer is fitted in it. The apparatus can be used for determination of
boiling points, Temperature effect on viscosity /flow points and molecular weights by Rast’s method with suitable
accessories.
Melting View : Magnifying display of melting operation with the help of adjustable magnifying glass, Melting point
reading hold on by activating the “HOLD” key & reading is protected from power failure till “RESET” is not activated.
Digital Melting Point apparatus- LT 115 (Microprocessor Based)
Procedure:
•Fill the oil bath with silicon oil.
•Switch on the apparatus. Red LED indicating Stop will glow.
•Press RESET switch. Allow for at least 15 min to warm up.
Plastic material Melting Point ( ̊C)
•Display will indicate the temperature in ̊C of silicon oil bath.
•Sample is filled in capillary tube, about 3 to 4 mm from bottom. PE LDPE= 110-150
•Insert the capillary filled sample through port on the top of silicon oil bath. HDPE = 120-130
•Press Start. Orange/yellow LED indicating Start will glow and Red LED will
PP 155-165
become off.
•Green LED indicating Run will also glow with time. PS --
•Watch the process by magnifier. PVC 147
•When the substance melts, press the HOLD switch to stop the operation. Then the
Poly Amide 210-220
melting temperature will be displayed. (It will be saved even during power failure).
•Heating will stop. Green LED will stop glowing. PET 265
•Record the melting point. PBT 220
PC 225
POM 165-175
PPO --
PPS 275-290