POLYESTERS

 They are prepared by a polycondensation reaction between a

dicarboxylic acid and a diol. If both R’ and R are aliphatic,

the resultant polyester will be a fully aliphatic polyester.

 For a long time aliphatic polyesters were not of much

industrial importance, mainly because of their low melting

points.

 For instance, the polyester with a degree of polymerization

comparable to that of commercial polyethylene melts

somewhere in the range of 50 — 80°C. Whereas, the melting

point of polyethylene is around 120°C.

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 This problem of a low melting point was overcome

by introducing aromatic rings into the polyester

chain.

3
 The remarkable rise in the melting point of polyesters

produced by the incorporation of the aromatic ring is due to

the stiffening of the polymer backbone.

 Thus, a polyester such as polyethylene terephthalate (PETP)

has a high melting point because of the presence of the

aromatic ring and is commercially one of the most popular

polymers marketed under the trade name of Terylene or

Terene.

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POLYETHYLENE
TEREPHTHALATE
(PETP)
 The starting materials for PETP are ethylene

glycol and terephthalic acid.

 In commercial practice, however, dimethyl

terephthalate (DMT) is taken in place of

terephthalic acid. DMT is melt condensed with

ethylene glycol to give PETP.

 The first stage of the reaction (condensation) is

carried out at a temperature of 129 ⁰C with a low

vacuum, when methanol is recovered.

 The second stage (trans-esteriflcation) is carried out at

high temperatures around 200—250°C, under a very

high vacuum, so that the ethylene glycol can be

effectively removed.

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 APPLICATIONS OF PETP
 Polyethylene terephthalate melts at round 265°C and is

resistant to heat and moisture.

 This polyester is virtually unattacked by many chemicals.

 It is extensively used to make textile fibres.

 Garments made from its fibres resist the formation of wrinkles.

 PET is also made into films, which are used in the manufacture

of magnetic recording tapes, aluminised sheets for certain

special applications and so on.

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 What is a Resin ???
● Resins are low molecular
weight and low viscous
polymers with sufficient
number of active
functionality, which can
help in the formation of
three – dimensional
network structure in their
finish stage.
PHENOL
FORMALDEHYDE
RESIN (PF RESIN)
 Phenol-formaldehyde (PF) resins are formed by the

polycondensation between phenol and formaldehyde.

 The polycondensation reaction can be catalysed either

by acids or bases.

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If excess of formaldehyde is taken and the reaction allowed to
continue to almost all the available ortho- and para-positions
of the phenol molecules, a cross linked three-dimensional
polymer will ultimately result:
 In actual practice, however, the reaction is

carried out to a relatively low stage of

polymerisation, leading only to linear molecules.

 This is done in two ways.

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 In the first method, phenol is reacted with 75% of the
stoichiometric quantity of formaldehyde using an acid -
catalyst. In this case, owing to an insufficient quantity of the
formaldehyde only linear molecules are formed:

 The resin formed can be stored for any length of time without
hardening and further cross-linking, whenever necessary, can
be effected by adding excess of formaldehyde and then
heating. These types of PF resins are called ‘Novlak’ resins or
‘Bakelite’ resins.
 In the second method, equimolar quantities of phenol and formaldehyde are

reacted under alkaline conditions and the reaction rate and the extent of

conversion are carefully controlled so that the reaction is carried out only up

to linear stage.

 The resin formed, however, contains the entire quantity of methylol groups

at the ortho- and para-positions and, hence, on storage, slow reaction will

continue leading to the hardening of the resin.

 This type of resin, which is called ‘resol’, has, therefore, a limited ‘shelf life’.

Resols can be converted into the final cured product merely by heating.

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 Uses of PF Resin
 The Bakelite resins are usually compounded with

fillers such as asbestos powder or sawdust and

used for molding electrical items, telephone-

instruments and so on.

 The resols are used for making laminates.

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UREA -
FORMALDEHYDE
(UF) RESIN
 Urea, too, can condense with formaldehyde to form what

are known as urea-formaldehyde (UF) resins.

 Actually, the reaction proceeds in a manner similar to the

formation of the phenol-formaldehyde (PF) resin.

 Here also, mono and dimethylol derivatives are formed,

which further condense with urea to give the final resin

structure.

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 The hydrogen atoms of the imide group in the linear

polymer can be further replaced with methylol groups if

excess of formaldehyde is used:

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 As in the case of PF resins, the final composition of the

polymer depends on the ratio of the urea to

formaldehyde.

 Thus, if the linear polymer is heated subsequently

with more formaldehyde, a three- dimensional

network of the polymer will be produced with the

following structure:
MELAMINE -
FORMALDEHYDE
(MF) RESIN
 Melamine and formaldehyde can also react to give methylol

derivatives of melamine, as shown :

 The polycondensation of methylol melamine

derivatives with larger quantities of melamine,

will give a linear polymer.

 This polymer, when reacted further with

additional quantities of formaldehyde, will give a

three-dimensional network as shown, which is

found to be insoluble in many solvents.

 Uses of UF & MF Resin
 Both uncross-linked UF and MF resins (also known as amino resins)

are water soluble and hence, find use as textile-finishing resins.

 In the plywood industry, they are used as adhesives

 The resols are used for making laminates.

 Melamine resin also finds use in the manufacture of decorative

laminates. Compared to the phenolic resins, the amino resins, in

general, are colourless, and clearer and, hence, objects of lighter shades

can be made out of them.

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EPOXY RESINS
 The epoxy polymers are basically polyethers.

 One type of epoxy polymer (or epoxy resins as they

are generally called) is prepared from epichlorohydrin

and bisphenol-A.

 The reaction is carried out with excess of

epichlorohydrin.
 The epoxy resins can be further cured with substances

such as amines, polysulfides and polyamides

 Epoxy resins are excellent structural adhesives. When

properly cured, epoxy resins can yield very tough

materials. They are used in industrial floorings, foams,

for electrical insulations, etc.

RUBBERS
 INTRODUCTION

• Rubber is a polymer which can stretch and

shrink.

• It can be produced from natural sources (e.g.

natural rubber) or can be synthesized on an
industrial scale.

• The term ‘rubber’ was coined by J. Priestley

after knowing the fact that it can erase the
pencil marks.

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 PROPERTIES OF RUBBER

• The have high molecular weight of the order of 105 to 106 g/mol.
• They are soft and very flexible at room temperature.
• They are amorphous in nature in normal scale.
• The polymers must have sites for crosslinking in their structure in their
structure, so that they can be transformed into dimensionally stable state.
• They have the ability to extend their length several times (as high as 1000-
1200 %) on application of external stress and spontaneously recovered on
release of that stress. This is the main reason to call them elastomers.
• The intra and intermolecular attractions are poor, and need to be
reinforced in order to achieve the desired level of properties, etc.

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TYPES OF RUBBERS

Rubbers or elastomers are mainly of three types –

(i) natural rubber,
(ii) semi-synthetic or modified natural rubbers and
(iii)synthetic rubbers.

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 NATURAL RUBBER

• The plant used to collect NR latex is scientifically known as ‘Hevea

brasiliensis’.
• Chemically, Natural Rubber is isoprene (also known as 2-methylbuta-
1,3-diene).

Fig. Structure of Natural Rubber

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 USES OF NR

• NR is largely used in tyre industries in many parts of

different tyres.

• It is the only polymer which is solely used in aero-tyres.

• Further it is used in conveyor belts, power transmission

belts, footwear industries, etc.

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 SYNTHETIC RUBBERS

• The shortage of NR in many countries has repeatedly been the

major spur for the development of synthetic rubbers.

• Eventually a large number of synthetic rubbers so far have been

developed to obtain versatility in properties to fulfil the service

requirement of different applications.

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 FEW OF SYNTHETIC RUBBERS
Synthetic Rubbers Composition Uses

Isoprene Rubber (IR) Isoprene IR partly replaces NR in tyre

application, used in surface
coatings
Butadiene Rubber (BR) Butadiene Tyre industries, shoe sole, conveyor
belts

Isobutene-Isoprene Rubber or Butyl Isobutene & Isoprene Inner tube of tyres where gas
Rubber (IIR) permeability and thermostability are
of importance

Acrylonitrile-Butadiene Rubber or Acrylonitrile & Hydrocarbon oil transporatation,

Nitrile Rubber (NBR) Butadiene hoses, tubes, footwear, etc.

Chloroprene Rubber (CR) or Chloroprene Mainly in adhesives, joints seals,

Neoprene Rubber etc.

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