:Polymers:

Definition: Thus compounds formed by large no of small molecules (monomer)

linked together are known as polymer. They are molecules with high mol. weights
(104 -106).Hence they are also known as macromolecules. E.g,

n C2H4 = (C2H4)n

Ethylene Poly ethylene

Monomers: The single repeating unit combining together to form a

macromolecule (polymer) is called a monomer.

Polymerization: The process of formation of polymers by linking of monomers is

called polymerization.
Degree of polymerization: The total number of single monomer units combining
together to form a polymer is called degree of polymerization. The polymers with
high degree of polymerization are called high polymers and those having
comparatively low degree of polymerization are called oligo-polymers.

Example: Calculate the degree of polymerization of Polypropylene

Mol.wt of polymer is 21420
Soln.
Degree of polymerization(n) = No. Avg. Mol. wt of polymer/ Mol.wt of CH 3 ⁻
CH=CH2
= 21420/42
= 510
Classification of polymers: Polymers are classified in several ways:
1. On the basis of origin:
i. Natural: (Starch, Cellulose, Silk etc.)
ii. Synthetic: (polythene, Nylon etc.)
2. On the basis of nature:
i. Organic: polymer backbone chain is made up of carbon atoms
ii. Inorganic: No carbon atoms in backbone chain e.g., Silicone rubbers.
iii. Hetero organic: Compound of silicon and germanium containing
carbon-carbon chain.
3. On the basis of mechanism of polymerization:
i. Ionic (Cationic & Anionic) polymers
ii. Coordination polymers
iii. Addition polymers (chain growth)
iv. Condensation polymers (step growth)
4. On the basis of physical state:
i. Amorphous : (Rubber)
ii. Semi crystalline: (Nylon, Polyesters)
iii. Crystalline: (Kevlar, Poly ethylene)
5. On the basis of number of monomers:
i. Homo-polymer: They contain same monomers. E.g., PVC, PE.
ii. Co-polymer: They contain different monomers. E.g., Buna S ,
Nitrile rubber etc.
6. On the basis of thermal behavior:
i. Thermoplastics: Ex. PVC, PE, Poly styrene etc.
ii. Thermosetting plastics: Ex., Bakelite, Polyester, Resin etc.
7. On the basis of molecular forces:
i. Elastomers ii. Fibres iii. Thermoplastic iv. Thermosetting polymers
8. On the basis of structure (shape):
i. Linear: M-M-M-M-M-M (homo polymer ),
m1 m2 m1 m2 m1 m2 m1 m2 (co-polymer)
ii. Branched:
M-M-M-M-M-M m1-m2-m1-m1-m1-m1
‫׀‬ ‫׀‬
M m2
‫׀‬ ‫׀‬
M m1
iii. Cross linked: M-M-M-M-M
‫׀‬ ‫׀‬
M M
‫׀‬ ‫׀‬
M-M-M-M-M
iv. Graft polymer: They have branched structure in which monomer are
backbone and branches differ.
m1- m1-m1-m1-m1
‫׀‬ ‫׀‬
m2 m2
‫׀‬ ‫׀‬
m2 m2
 v. Block polymer: A block of repeating units of one kind of monomer
is followed by block of another kind of monomer.
m1-m1-m1-m1-m1-m2-m2-m2-m2-m2
vi. Alternate: units are alternatively arranged.
m1-m2-m1-m2-m1-m2-m1
vii. Random: They have no regular arrangement: m1- m2-m1-m1- m2-
m1-m2-m1-m1
9. On the basis of Tacticity: In this orientation of side groups around the main
backbone chain in three dimensional structure of polymers may be different.
They may be orderly or disorderly arranged with respect to main backbone
chain. The difference in configuration affects their physical properties.
i. Isotactic: Side groups (functional groups) are on the same side of
main chain.
ii. Syndiotactic: Side groups (functional groups) occupy alternating
position.
iii. Atactic: Side groups (functional groups) are arranged in random manner.

For example Atactic poly propylene is gummy solid while isotactic version is
highly crystalline and tough.
 Difference between Thermoplastic & Thermosetting polymers

S Thermoplastics Thermosetting Plastics

N.
1. They are formed either by addition They are formed by condensation
or condensation polymerization polymerization.
2. They have either linear or They have three dimensional network
branched structure structure
3. Adjacent polymer chains are held Adjacent polymer chains are held
together by Vander wall together by strong covalent bonds (cross
bond/hydrogen bond or dipole links)
forces
4. They soften on heating and stiffen They do not soften on heating
on cooling
5. Low molecular weight They are almost insoluble in any solvent
thermoplastics are soluble in
suitable organic solvents
6. They can be remolded, reshaped They cannot be remolded hence can’t be
and re used reused
7. They can be reclaimed from wastes They can’t be reclaimed from wastes so,
so can be recycled can’t be recycled

8. There is no change in their They undergo chemical changes such as

chemical composition during further polymerization and cross linking
molding during molding process
9. They are usually soft, weak and They are usually hard, strong and more
less brittle brittle
10 Example: Example:
. PE,PP,PS,PVC,PMMA, PF,UF,MF,EPOXY etc.
PTFE, Nylon, Polyester etc.
:Biopolymerization and Bio-polymers:
A polymerization process for the production of bio polymers is called bio
polymerization. Biopolymers breakdown easily and are suitable for domestic
composting (manure making).
Types of bio polymerization:
1. Using microbes: Bio-plastics or biopolymers are made by using microbes.
These are polyesters that are produced by a range of microorganisms
cultivated under different nutrients and growth conditions.
Bio plastics are made from a compound called poly-hydroxy-alkanoate
(PHA). Bacteria accumulate PHA in the presence of excess carbon source.
Poly-3-hydroxy butyric acid (PHB) is the most common microbial PHA.
Carbon source
PHA → Bio-plastics
(Bacteria) PHB
Archae bacteria, gram positive bacterium and gram negative bacterium are
used for this purpose. Specific examples are Bacillus megaterium, Ralstonia
eutropha and Bacillus mycoids etc.
2. Using fermentation: Fermentation is the use of micro organisms to break
down organic substances usually in the absence of oxygen. Following types
of fermentations are carried out usually:
i. Bacterial polyester fermentation:

Sugar of harvested plants + Ralstonia Eutropha → Polyester

(Separated from bacterial cell)
ii. Lactic acid fermentation:

Bacteria H O
‫‖ ׀‬
Sugar → Lactic acid (CH3CH(OH)-COOH )→ product(lactide) CH3CH-O- CO-CH(CH3) O-CO → - [O-C-C-]n-
‫׀‬
2 molecules CH3
Poly lactic acid
Or Polylactide(PLA)
Advantages of bio-polymerization:
i. It is eco-friendly
ii. Product biopolymer is biodegradable
iii. It is derived from renewable source so possess good mechanical
properties.
Limitations:
i. They undergo thermal degradation.
ii. They are brittle.
iii. They do not possess reactive groups so they interact poorly with fibers
(additive).
iv. Processing of biopolymers is difficult.
Biodegradable polymers: Are those polymers which get decomposed by the
process of biodegradation.
Biodegradation: A process carried out by biological systems( fungi/bacteria)
wherein a polymer chain is broken by enzymatic action.
Env. Biodegradation Env
-------- (polymer) → __----------___ ( fragments of polymers) + Bacteria

Types of Biodegradable polymers:

i. Natural: Natural rubber, collagen, lignin, poly ( - γ- glutamic acid) etc
ii. Synthetic : Poly vinyl alcohol, poly anhydrides, poly(3-hydroxy
butyrate-CO—3-hydroxy valerate (PHBV).
Applications:
i. Poly ( β-hydroxy butyrate) or PHB: is used in manufacture of shampoo
bottles.
ii. β-hydroxy butyrate- β-hydroxy valerate or HB-HV : is used in matrices
for controlled release of drugs.
iii. Poly lactc acid Or PLA: is used in medical applications such as sutures,
drug delivery systems and wound clips etc. It is also used as coatings for
fertilizers and pesticides( Timed release coatings)
iv. For making Packaging materials for food packs/boxes/serving trays etc
v. Blown starch pallets are used for shipping fragile goods
vi. They are used for making wrapping films for vegetables and fruits.
Advantages of bio- degradable polymers:
i. Their waste processing is easy.
ii. They are environment friendly.
iii. They are available on sustainable basis.
Limitations:
i. Their recycling is not done.
ii. They are very expensive.
iii. They are not easily available.
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Preparation, properties and uses of polymers

PVC (PolyVinyl Chloride): It is commonly used polymer especially for

electrical insulation. It is prepared by polymerization of vinyl chloride in
presence of small amount of peroxides (hydrogen peroxide/ benzoyl
peroxide) in an autoclave under pressure at 40-45˚C.

Polymerization
(Auto clave) Plasticizers ( DOP-Di octyl phthalate/dibutyl
40-45˚C Phthalate/ tricresyl phosphate)
n CH2 = C H --------------- → [-CH2 -C H-]n --------→ PVC (Plasticized)
‫׀‬ Benzoyl peroxide / ‫׀‬
Cl H2O2 Cl
PVC (rigid)

Vinyl chloride so needed is generally obtained by treating acetylene with

HCl in presence of metal chloride as catalyst.
60-80˚C
1-1.5 atm P
CH ≡ CH + H Cl -------→ CH2 ꞊ CH − Cl
Acetylene M Cl2 Cat. Vinyl Chloride
Properties:
1. Colorless, odorless, non inflammable and chemically inert (sp.gr 1.33).
2. Resistant to light, oxygen, inorganic acids and alkalis.
3. Soluble in hot chlorinated hydrocarbons.
4. Possesses high stiffness /rigidity as compared to polythene but is brittle.
Its softening temperature is 148˚C.

Uses:

1. Rigid PVC is used for making sheets for tank lining, refrigerator
components, tires, cycles, mudguards, bottles for edible oils, fruit
squashes, bislery, cosmetics and detergents etc.
2. Plasticized PVC is used for making rain coats, table cloths, electrical
insulation like covering of cables, chemical containers.
3. Thermal insulation foam (used in buildings, cinemas, aircrafts, conveyor
belts used in coal mines etc.
4. It is used for making bath room curtains, ladies hand bags, shoes and
garden hoses.

PVA (Poly Vinyl Acetate): It is prepared by heating vinyl acetate in

presence of benzoyl peroxide or acetyl chloride as catalyst.

Polymerization
Δ
n CH2 = C H --------------- → [-CH2 − C H-]n
‫׀‬ benzoyl peroxide / ‫׀‬
OCO CH3 Acetyl chloride OCO CH3
Vinyl Acetate PVA (Poly Vinyl Acetate)

Vinyl Acetate is obtained as follows:

HgSO4 cat.
CH ≡ CH + CH3 COOH ------- → CH2 ꞊ CH− OCOCH3
Δ Vinyl Acetate

Properties:
1. Colorless and transparent amorphous polymer.
2. Possesses low softening temperature (Tg = 28˚C only). Hence, the articles
are distorted even at low temperature under the influence of compressive
and tensile forces.
3. Low mol. weight polymers become gum like when masticated (like
chewing gums).
 4. Fairly soluble in organic solvents and acids.
5. Resistant to water, atmospheric oxygen and chemicals.

Uses:

1. It is used for making records, chewing gums.

2. Used in surgical dressings, paints, lacquers and enamels.
3. Coatings of card boards, textile finishing.
4. Bonding: Paper, leather and textiles etc.

Teflon (Poly Tetra Fluoro Ethylene/Fluon):

It is a brand name of a number of fluorinated polymers. It is prepared

polymerization of tetra fluoro ethylene under pressure in presence of benzoyl
peroxide as catalyst.

Polymerization
Pressure
n CF2=CF2 --------------- → [−CF2 − C F2−]n
Benzoyl peroxide PTFE (Teflon)
Properties: Due to highly electronegative fluorine atoms and twisted zigzag
structure, it has :
i. High density ( sp gr. 2.1-2.3), chemically inertness over wide temperature
range.
ii. Excellent electrical insulation properties & it is non adhesive.
iii. Very low coefficient of friction, excellent toughness & heat resistance. It
behaves like thermosetting polymer.
iv. Excellent optical properties.

Uses: It used in
i. Wire and cable insulation.
ii. Lamination for printed circuits.
iii. Non lubricating bearings.
iv. Variety of seals, gaskets, packing valves, pump parts, stop cocks for
burettes, non- stick coatings of kitchen utensils.
v. Motors, generators, transformers as insulating material.
vi. Surgical lamps and photo voltaic cells (due to low ref. index).
Nylon 6 ( Perlon L): It is obtained from a monomer called Caprolactam.
Capro- lactam is obtained from cyclohexane as follows:

→
Oxidation Cyclohexanone

Properties: Nylon 6 is:

i. Very light in weight.
ii. Insoluble in common organic solvents.
iii. Flexible and retains original shape after use.
iv. Abrasion resistant and can be blended with wool to increase strength.
Uses: It is used for manufacture of
i. Tyre cord, fabrics and ropes.
ii. Bearings, gears and electrical mountings etc.
Nylon 6: 6:
It is prepared by condensation polymerization of Hexa methylene diamine and
Adipic acid as follows:

Polymerization
H2 N-(CH2)6 - NH2 + HOOC - (CH2)4 – COOH→ [-HN−(CH2)6 -NH- CO - (CH2)4 - CO-] n

Hexamethylene Adipic acid -H2O Nylon 6:6

Diamine

Properties: It is linear and its chain possesses H bonds. Therefore, it has high
crystallinity, which imparts high strength, high m. p. & elasticity to it. It is

i. very light in weight.

ii. insoluble in common organic solvents.
iii. flexible and retains original shape after use.
iv. abrasion resistant and can be blended with wool to increase strength.
Uses:

i. It is mainly used to make fibers, socks, under garments, dresses and

carpets etc.
ii. It is used to make bearings, gears and bushes etc.
iii. It is used for outer cover for primary electrical insulation as jackets of
electric wares.

Polyester (Terylene or Dacron or PET( Poly Ethelene Terepthalate): It is

prepared by heating ethylene glycol & Terepthalic acid at 425-475˚C as
follows:
Properties:

i. It readily crystallizes because of symmetrical structure and numerous

polar groups. Its Tg & Tm are 80˚C & 265˚C respectively.
ii. Possesses resistance to hydrocarbon solvents ,moisture and abrasion
iii. Fibers of terylene have outstanding crease resistance and temperature
resistance
iv. Blend of terylene fibers with wool possesses better crease and wrinkle
resistance. These mixed fibers do not shrink and not attacked by moths.

Uses: It is used in

i. magnetic recording tapes.

ii. packing frozen foods.
iii. bottles for cola drinks, fruit juice and sauces.
iv. wide necked jars for coffees.
v. Glass filled PET is used for coffee machines, car heaters and water
meters.
vi. blending with wool.
Phenol Formaldehyde: These resins have high mechanical strength. These are
synthesized by condensation polymerization. They are thermosetting in nature. Raw
materials used are Phenol/Resorcinol and formaldehyde / furfural.
Preparation:- PFs are prepared by reaction of phenol with formaldehyde in the presence of acidic or
basic catalyst. The process may be carried out as follows
A mixture of phenol and formaldehyde are allowed to react in the presence of a catalyst. The process
involves formation of methylene bridges in ortho, para or both ortho and para positions. This results
first in the formation of linear polymer (Called NOVALAC) and then in to cross-linked polymer
called phenol-formaldehyde resin or bakelite.
 Novolac behaves like thermoplastic which dissolves in few aromatic solvents.
Hence, it is generally converted into thermoset – Bakelite by heating at about
150˚C in presence of catalyst.Which is highly cross linked solid and insoluble
polymer.

When phenol and formaldehyde are in 1:1 ratio mono methylol phenol is formed.
When phenol and formaldehyde are in 1:2 ratio di methylol phenol is formed.
When phenol and formaldehyde are in 1:3 ratio tri methylol phenol is formed.

Properties:

• These resins are rigid, hard and water resistant.

• They are resistant to acids, salts and organic solvents.

• They are easily attacked by alkalis due to presence of free hydroxygroup.

• They possess electrical insulating properties due to low thermal

conductivity.

Uses:

• They are used to fabricate insulators, plugs and switches.

• They are used as cation exchanger resin in water softening.

• They are used as adhesives in paints and varnishes.

• They are used in propeller shafts for paper industry and mills.

• They are used in telephone parts.

• They are used for impregnating fabric , wood and paper.

• In handles for cooker and sauce pans.

• Used as a binder for grinding wheels

Urea Formaldehyde Resins: They are also called as amino resins/plasts. They are
formed by condensation of Urea and formaldehyde. First the Mono and di methylol
urea are obtained, they undergo further condensation to give linear and partially /
highly cross linked polymers called UF resins.
1:1 1:2

>N-CO-NH-CH2OH ← H2 N- CO-NH2 + HCHO → HO- H2 C- HN- CO-NH –CH2 OH

Mono methylol urea Urea Formaldehyde Di methylol urea

Polym. ↓ Δ Polym. ↓ Δ basic med.

-[HN- CO-NH –CH2 -HN- CO-NH –CH2 -] -N- CH2-N–CH2 –N-CH2-

Linear ‫׀‬ ‫׀‬ ‫׀‬
O=C O =C O =C
‫׀‬ ‫׀‬ ‫׀‬
-N- CH2-N–CH2 –N-CH2-
Cross linked UF resin

Properties:
i. They are clear, transparent and colorless.
ii. Possess good electrical insulation property.
iii. Possess good chemical resistance (except strong acids and alkalis).
iv. Good abrasion resistance and light stability.
v. Resistant to water, heat and flame.
vi. Possess good adhesive characteristics.

Uses: They are used:

i. as adhesive for plywood and furniture.

ii. for finishing of cotton textiles.
iii. for making buttons, cups, jugs, vacuum flasks, bottle caps and colored
toilet sheets.
iv. as cation exchanger resin in water softening
v. as electrical insulator.

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Natural Rubber: Rubber is obtained from latex, a milky emulsion collected from
rubber tree. There are about 500 species of rubber trees. The bark of tree is cut at
intermittent places and the latex is collected in a container.

The latex is milky white watery emulsion of Isoprene (30-40% Isoprene & water).
The latex is further processed to get natural rubber. Latex is diluted to contain 15-
20% rubber, it is filtered and then coagulated with acetic or formic acid per 200
kg of rubber. Potash alum is used as coagulant some times. After washing it is
converted into crepe or smoked rubber. The composition of crude rubber is nearly
90-95% rubber HC (C 5 H8),2-4% protein and 1-2% resin .During this process the
isoprene molecules get polymerized to form long coiled chain of poly isoprene as
follows:
 Being CIS form the polymer develops coiled structure and hence possesses
elasticity.

Coiled structure of natural rubber

Properties and drawbacks of Natural Rubber:

1. Its plasticity is greater than elasticity. It cannot sustain stress thus when
stretched to a great extent, it undergoes deformation permanently.
2. It has large water absorption tendency which makes it weak.
3. It has very low tensile strength (200kg/cm2 ).
4. It is water repellent.
5. It shows resistance to alkalis and weak acids.
6. Due to presence of large percentage of un saturation in its structure, it is easily
attacked by various reagents such as HNO3, Con.H2SO4, organic solvents, air,
O2, O3 etc. and as a result it gets gradually disintegrated.
7. It has high tackiness (property of developing stickiness), Therefore, It is
difficult to store it.
8. It has very low abrasion resistance and durability
Vulcanization of rubber: Since natural rubber has many drawbacks, therefore,
it is essential to improve its properties . It is done by heating the rubber with a
suitable substance (called vulcanizing agent). This process is called vulcanization.
The process consists of heating the raw rubber at 110-140˚C with sulphur. The
sulphur combines at double bonds of Isoprene and provides cross linking between
the chains,which brings about stiffness in the molecule. The amount of sulphur
added determines the extent of stiffness ex. Ordinary rubber for tyres may contain
3-5% sulphur but hard rubber for battery case may contain about 30 % sulphur.
 Advantages of Vulcanization
Sno. Property Raw Vulcanized rubber
rubber
1 Tensile stength 200 kg/cm2 2000 kg/cm2
2 Resilience( Regain Good Very good
original shape)
3 Useful temp. range 10-60˚ C -40 to 100˚C
4 Resistance to moisture, Poor Good
oxidation & abrasion
5 Resistance to Poor Good but limited
org.solvents
6 Tackiness ( stickiness) Good Slight
7 Elasticity Very high Low ( decreases with extent of
vulcanization i.e., depending on % S)
8 % elongation at break 1200 800
9 Moulding in desired Not easy Easy
shape
10 Durability Less Higher

11 Quality Inherent Can be controlled by vulcanization

 Synthetic rubber: These are artificially prepared rubber like product which can
be streched more of its original length and returns to original shape. It differs in
chemical composition and properties from those of the natural rubber because it is
produced artificially from other chemicals. Thus, synthetic rubbers are only rubber
like product which can also be vulcanized. Ex., silicone rubber, poly urethane,
Buna-S, Buna-N, SBR (Styrene butadiene rubber) etc.
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