Chapter 6

POLYMER CHEMISTRY
Lecture/Lession Plan -3

POLYMER CHEMISTRY

A)Polythene(polyethelene): The monomer of polythene is ethylene. Polythene is prepared by

the addition polymerization of monomer ethylene in presence of heat catalyst produce either linear
or branch or semi branch polymer. Depending up on the density ethylene polymer is divided into -
1) Low density polythene (LDPE)
2) High density polythene (HDPE)
3) Linear low density polythene (LLDPE)
4) Ultrahigh molecular weight polythene (UHMWPE)

6.0.1 Low density polythene (LDPE)

Low density polythene is prepared by a number of methods. The common method for the prepa-
ration of LDPE is polymerization of ethylene monomer at high pressure (1000 - 4000 atm) and
temperature (2500 C) in presence of oxygen peroxide hydro peroxide( free radical generator). In this
process huge branched chains are formed through out every long back bone chain. The presence
of branches repel each other and the long chains are not well fitted to each other having some gap
produce low density (0.91 to 0.925 gm/cc) polymer.

Low density polyethylene

Characteristics of low density polythene:

a) Low density polyethylene have density is low (0.91 to 0.925 gm/cc).

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12 CHAPTER 6. POLYMER CHEMISTRY LECTURE/LESSION PLAN -3

b) It is branched chain addition polymer.

c) Semi crystalline polymer having crystallinity 45-50 percent.
d) Chemically inert, nonpolar and having dielectric property zero.
e) Tough but flexible.
f) Melting point 105 − 1100 C.
Uses of low density polythene:
a) As LDPE is a good insulator they normally used for the preparation of electrical wires and cables.
b) Pouch pack, squeeze bottles, delivery pipes are prepared from LDPE.
c) Toys, refill for ball pen and ball pen also prepared from LDPE.

6.0.2 High density Polythene(HDPE)

The common method for the preparation of HDPE is by the polymerization of ethylene monomer
at high pressure (30 - 35 atm) and temperature (70 − 2000 C) in presence of metal oxide catalyst like
CrO3 on silica alumina.
High density polythene can be prepared by the polymerization of ethylene monomer at low pressure
(5 - 7 atm) and temperature (60 − 700 C) in presence of Zieglar Natta catalyst like triethyl aluminum
and titanium tetrachloride. In this process of polymerization as there is absence of branch through
out the long chain back bone, the chains are well fitted to each other which makes the polymer a
high density (0.95 to 0.97 gm/cc) polymer.

High density polyethylene

Characteristics of high density polythene:

a) High density polyethylene have high density (0.95 to 0.97 gm/cc).
b) It is less branched.
c) Highly crystalline polymer having crystallinity 80-90 percent.
d) Chemically inert, nonpolar and having dielectric property zero.
e) Highly tough but flexible.
f) Melting point 130 − 1350 C.
Uses of high density polythene:
a) As HDPE is a good insulator they normally used for the preparation of high performance elec-
trical cables.
b) Bucket, cup, toys are prepared from LDPE.
c) Due to inertness it is used for the storage of H2 SO4 , pipes for LPG gas and water reserver also.
 13

6.0.3 Linear low density Polythene (LLDPE)

LLDPE can be prepared by the polymerization of ethylene monomer at 2500 C temperature and
low pressure with alpha olefin (butadiene hexene or octene) in presence of Philips or Zieglar Natta
catalyst like triethyl aluminum and titanium tetrachloride. The polymerization between ethylene
and butane or hexene occur in gaseous phase and octene in solution phase. In this process the short
branched chains are formed through out every long back bone chain. Due to presence of very short
branches, density of the polymer lies in between LDPE and LLDPE (0.92 gm/cc) polymer.

Linear low density polyethylene

Characteristics of linear low density density polythene:

a) Linear low density polyethylene have density in between low and high density polythene (0.92 to
0.925 gm/cc).
b) It is linear chain addition polymer with short branch.
c) Moderate crystalline polymer having crystallinity 70-75 percent.
d) Chemically inert, nonpolar and having dielectric property zero.
e) Moderately tough but flexibility more than LDPE.
f) Melting point 120 − 1250 C.
Uses of low density polythene:
a) As HDPE is a good insulator they normally used for the preparation of covering electrical wires
and cables.
b) Bag, polyethylene sheet, toys are prepared from LDPE.
c) Pouch bag pipes, bucket mug and flexible tube are prepared from LLDPE.

6.0.4 Ultrahigh molecular weight polythene (UHMWPE)

Ultra high molecular Weight polyethylene is prepared from ethylene monomer by using of compres-
sion moulding followed by ram extrusion gel spinning and by Kneading. Ultimately annealing of the
polymer is done by heating the material at 1350 C temperature and cooling down at 50 C temperature
per hour up to 650 C. Then the material is covered by heat insulating blanket for a day to bring
down the temperature to room temperature.
14 CHAPTER 6. POLYMER CHEMISTRY LECTURE/LESSION PLAN -3

Ultra high molecular weight polyethylene

Characteristics of ultra high molecular weight polythene:
a) High density polyethylene have density is low (0.95 to 0.97 gm/cc).
b) Long back bone linear chain addition polymer having molecular weight 2 to 5 million or more.
c) Highly crystalline polymer having crystallinity 80-90 percent.
d) Chemically inert, nonpolar and having dielectric property zero.
e) Highly tough, enormous tensile strength due to long back bone chain.
f) Highly resistance to abrasion and ultra violet radiation.
f) Melting point 135 − 1450 C.
Uses of ultra high molecular weight polythene:
a) As ultra high molecular weight poly ethylene have enormous tensile strength due to long back
bone chain they are normally used for the heavy duty gloves, armor for vehicle, preparation of high
performance electrical cables.
b) String for high performance bow.
c) As rope for climbing, suspension rope in parachutes.

6.0.5 Polyvinyl chloride(PVC)

Depending upon the characteristic polyvinyl chloride are two types-
1) Rigid polyvinyl chloride
2) Plasticised/flexible polyvinyl chloride
1) Rigid polyvinyl chloride: Rigid polyvinyl chloride is a homopolymer which is prepared from
gaseous vinyl chloride (monomer) in water emulsion at a temperature 30 − 450 C, and a pressure 1-5
atm. in presence of benzoyl peroxide or cumene hydro peroxide catalyst.
2) Plasticised/flexible polyvinyl chloride: Plasticised/flexible polyvinyl chloride is prepared
by exactly same process as described above and additionally some plsticizer molecule like dioctyl
phthalate, dibutyl phthalate etc. are being added.
Characteristics of Polyvinyl chloride:
a) Polyvinyl chloride is colour less, odour less, fire retardant polymer.
b) It is an addition polymer .
c) Low crystalline polymer having crystallinity 30-50 percent.
d) Chemically inert, nonpolar, moisture resistance and highly resistance to any acid base.
e) Highly tough but flexible.
f) Melting point 200 − 2050 C.
Uses of Polyvinyl chloride:
a) As PVC is a good insulator they normally used for the preparation of insulating materials in
electrical wire.
6.1. THERMOSETTING PLASTIC 15

b) Bucket, sheet for flooring, plate are prepared from PP.

c) PP is used for preparation of bathroom door, storage tank for fruit juice, oil etc.

6.1 Thermosetting plastic

The polymers which have strongest inter molecular forces like Van der Walls forces dipole-dipole
interaction among the polymeric backbone chain and hydrogen bonding than elastomers thermoplas-
tic and fiber resulting comparatively strongest mechanical properties like tensile strength modulus
of ruptured modulus of elasticity elongation at break flexural strength impact indentation strength
abrasion test tearing strength etc. due to presence of three dimensional cross linking among the
polymeric chains. The main property of thermosetting plastics is these are hard at room tempera-
ture due to presence of three dimensional network cross linking on application of heat the polymer
become more hard as farther cross linking takes place and ultimately gets burnt but never melt.
Depending on this characteristic of thermosetting plastics cannot moulded again are not reversible
and recyclable. Examples: Bakelite(PF resin), Melamin formaldehyde resin(MF) Urea formaldehyde
resin(UF)
Different thermosetting polymer:

6.1.1 Phenol-formaldehyde resin

Phenol formaldehyde is an important polymer in making different composite materials as well ply-
wood. It is a brown black color viscous liquid prepared from phenol and formaldehyde at a temper-
ature 140 − 1450 C in presence of catalyst called resol. At high temperature poly condensation takes
place and it becomes three dimensional cross linked, brittle and hard mass solid called BAKELITE.
Bakelite is formed through methylol(-CH2 OH formation which ultimately converted to methylene(-
CH2 −) by removal of water molecule. Generally,phenol-formaldehyde polymer are two types-
1) Novoloc
2) Resol

6.1.2 Novoloc

When phenol and formadehyde ratio greater than one (normally, phenol : formaldehyde =1: 1.5-
1.8) in presence of acid catalyst (normally oxalic or acetic acid) only linear long chain polymer is
formed having methylene linkage and some ether is also formed. This polymer is mainly used for
the preparation of laminates. Novoloc also can be converted to bakelite by the addition of Hexam-
ethylene tetramine (commercially called Hexa which on hydrolysis produce formaldehyde) heated at
140 − 1450 C, poly condensation take place and it becomes three dimensional cross ling, brittle and
hard mass solid.
16 CHAPTER 6. POLYMER CHEMISTRY LECTURE/LESSION PLAN -3

Phenol-formaldehyde(NOVOLOK) polymer

6.1.3 Resol

When phenol and formadehyde ratio is less than one (normally, phenol : formaldehyde = 1: 1.5-1.8)
in presence of alkali catalyst (normally NaOH) linear long chain as well as some cross linked polymer
among the polymeric methylene linkage also formed.

Phenol-formaldehyde(resol) polymer

Resol is mainly used for the preparation of marine grade plywood composite board etc.
When resol is heated at a temperature 140 − 1450 C poly condensation take place and it becomes
three dimensional cross linked, brittle hard mass solid polymer called BAKELITE. Bakelite is
formed through methylol (-CH2 OH formation which is ultimately converted to methylene (-CH2 −)
by removal of water molecule.
6.2. PLASTICIZER 17

Phenol-formaldehyde(bakelite) polymer

Properties of bakelite:
a) It is high thermal and electrical resistance. b) It is hard rigid and scratch proof. c) It is resistant
to many inorganic and base.
Use of bakelite:
a) Novoloc is used for the preparation of laminates.
b) Resol is used for preparation of comb, P.O. Box, marine grade, shutter grade, Boilling water proff
ply board, block board, flush door etc..
c) Resol is used for preparation of electrical board, switch etc.

6.2 Plasticizer

There are certain plastics which are not soft sufficiently on heating; and during the plastic properties
(soft,flexibility, less brittleness etc.) are lost. To improve these plastic properties, some organic
compounds are added to these plastic material which make the plastic materials soften. These
external organic compounds are called plasticizer. For example: PVC is extremely hard and brittle
but it can be converted to highly flexible PVC by addition of small amount dioctyl phthalate or
n-butyl phthalate. Other examples of plasticizer are Dibutyl phthalate, cresyl phthalate, Dialkyl
phthalate etc.
Difference between thermoplastic and thermosetting plastic polymer
18 CHAPTER 6. POLYMER CHEMISTRY
Thermoplastic
A) Maximum thermoplastic polymer are
formed by addition polymerization in
few cases condensation polymerization.
B) The molecular forces are
normally weak.
C) Polymer backbone chains are
connected together by Van der Wall’s
or dipole-dipole attraction or H-bonding.
D) These polymers are normally
soft and flexible.
E) These polymers are normally
linear or branch
F) On application of heat these
polymers become soft and again
become hard on cooling.
G) On continuous heating these
polymer get melt.
H) These polymers are recyclable.
I) These polymers soluble in
many organic solvent.
J) Example of these hese polymers
are PF resin(Bakelite), MF resin,
UF resin Epoxy rein, Polyester resin etc.
LECTURE/LESSION PLAN -3
Thermosetting plastic
A) Thermosetting plastic polymer
are formed by only
condensation polymerization.
B) The molecular forces are
tremendously strong.
C) Polymer backbone chains are
connected together by
strong covalent bond.
D) These polymers are normally
hard and brittle.
E) These polymers are normally
cross linked polymer
F) On application of heat the these
polymers become more hard
due to farther cross linking.
G) On continuous heating these
polymers get burnt.
H) These polymers are not recyclable.
I) These polymers insoluble
in organic solvent.
J) Example of these hese
polymers are PVC,PE,
PP