DKTE Textile and Engineering Institute, Ichalkaranji

Unit No. 5 – Polymers for Engineering Applications

 The term “Polymer” is derived from the two words which is ‘Polys’ & ‘Meros’. Poly means many
and meros means units.
 The polymer occur in the nature in the form of starch, silk, wood, cotton, cellulose and protiens.
 Since ancient time man started using these natural polymers.
 Another important natural polymer, rubber was known to man since hundreds of years. In eighteen
century it was used for the production of total wears, rain coats and tyres.
 In recent years many polymers were investigated by different reaction & used. There are different
types of polymers having variety of application in every field of science, technology, domestic &
industry.
 We will consider in this chapter details about polymers.

Important Terms in Polymer-

1) Definition-
Polymer is a large molecule weight formed by linking large number of small molecules known as
monomer.
2) Monomer-
A monomer having two or more functional groups which is repeating unit in the formation of
polymer.

Examples – a) Ethylene - CH2 = CH2

b) Ethylene Glycol – HO ─ (CH2)2 ─ OH
c) Vinyl Choride – CH2 ─ CH = Cl
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3) Degree of Polymerisation –

Degree of polymerisation is defined as the actual number of monomer units present in polymer chain.

M = Dp X Mw

Where,

M = Molecular weight of polymer

Dp = Degree of polymerisation

Mw = Molecular weight of monomer

Examples

Classification of Polymer

The polymers can be classified by variuos ways

1) Polymers includes large no of materials.

2) Polymers have different properties.
3) Polymers have different structure.
4) Polymers behave in different manner.

Classification Based on Occurrence of polymer-

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1) Natural Polymer –
 The Natural Polymers occurs in the nature.
 They are also called as biological polymers.
 Examples
i) Proteins & enzymes are natural polymers present in the body of man and animals.
ii) Rubbers, cotton, starch obtained from plants.
iii) Silk & wool obtained from animals.

2) Synthetic Polymers-
 These are manmade polymers. These Polymers are Sythesized from low molecular weight
substance. i.e. Monomer.
 They can be manufactured as per need & their molecular weight can be controlled.
Different reactions such as addition and condensation reaction can be used for their synthesis.

Example –
Polypropylene is obtained from propylene by simple addition reaction .

Types of Polymerization-

There are four types-

Addition or chain polymerisation

Co-polymerisation
Condensation
Free radical polymerisation
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Glass Transition Temperature (Tg):

• Glass transition temperatures: Glass transition temperature is important parameters relative to
applications of polymers.
Definition: The temperature at which the polymer undergo the transition from glassy to rubbery state.
The upper and lower temperature limits are important in glass transition temperatures for numerous
applications.
Below Tg: Polymers are hard and brittle like glass, due to lack of mobility
Above Tg: Polymers are soft and flexible like rubber due to some mobility
Above Tg: Physical and mechanical properties of polymer change

Factors influencing glass transition temperature:

Upon heating through the glass transition temperature, the amorphous solid polymers transforms from a
rigid mass to a rubbery state and the molecules which are virtually frozen in position below Tg.
1. The presence of bulky side groups
2. Polar side atoms or groups of atoms (e.g.-OH) which effect on glass transition temperature.
3. Increasing the molecular weight also tends to raise the glass transition temperature
4. A small amount of branching will tend to lower Tg; on the other hand a high density of branches
reduces chain mobility and elevates the glass transition temperature.
5. As crystallainity increases Tg also increases.
6. As cross linking increases Tg also increases
7. Effective Plasticizers – Addition of plasticizer decreases Tg of the polymer.
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Thermo plastics: The polymers which can be repeatedly made soft and hard by heating and
cooling are called thermoplastics.
Examples: Polythene, PVC, Polystyrene
Polycarbonate:
These are the polymers in which monomers are linked through carbonate group.
Synthesis: polycarbonate is formed by condensation reaction of bisphenol-A (dihydroxy compound)
with diphenyl carbonate at 200 oC under reduced pressure.
Diphenyl carbonate is obtained by the reaction between phenol and phosgene in an alkaline medium in
presence of tertiary amine catalyst.

Applications:

 It is used in making bullet proof windows.

 It is used in making roof of cockpit in fighter jets.
 It is used in making break free lenses.
 They are used making headlamps and optical reflectors in automobiles.
 Used in production of compact disc and DVDs.
 They are used in making body case of smart phones, mp3 players and computers.

Polyether sulfones:
Polyethersulfone abbreviated as PES is an amorphous, transparent, and pale amber high-performance
thermoplastic consisting of repeating phenyl groups linked by thermally stable ether and sulfonic
(-SO2-) groups. Its structure, as shown in Fig. 1
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PES is the most temperature-resistant transparent commercially available thermoplastic. Generally,

PES possesses high mechanical property, thermal stabilities, and chemical resistances.
Preparation:
Sodium salt of bisphenol-A reacts with di-para-fluorophenylsulfone in a solvent like dimethylsulfoxide
(DMSO) at between 130 and 160 oC to form poly (ether sulfone).

Application of Polyethersulfone:
 It is used in high temperature electrical applications, bakery-oven windows, and medical components.
 Reinforced grades are used for radomes, structural aircraft and aerospace components, and corrosion
resisting applications in packaging and chemical-plant hardware.
 PES is also widely used in aviation, microelectronics, automobile, membrane separation, etc.
 In membrane separation fields, PES has been prepared to ultrafiltration, reverse osmosis, and
nanofiltration membranes.
 PES is also widely used as biomaterials due to its thermal stability, mechanical strength, and chemical
inertness.
 Applications like hemodialysis, wastewater recovery, food and beverage processing, and gas separation.
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Thermosetting plastics: These are cross linked or heavily branched polymers and they can be
moulded only once. They cannot be reused.
Examples: Bakelite, urea-formaldehyde resin

1) Phenol Formaldehyde-
The Phenol Formaldehyde polymer manufactured by poly condensation reaction between phenol and
formaldehyde. The poly condensation reaction may be catalyzed either by acids or bases.

Step I: Formation of ortho and para hydroxy benzyl alcohols from phenol and formaldehyde:

Step II: Formation of Novalac from ortho-hydroxybenzyl alcohol

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Step III: Formation of Bakelite from Novalac

Properties-
a) It is a phenolic resin.
b) It is rigid, hard & scratch resistant.
c) It is water resistant insoluble solids.
d) It has excellent electrical insulating character.

Uses-
a) It is used in electric insulator parts like switches plugs, switch board heater.
b) It is used in making moulded articles like telephone parts, cabinets for radio television.
c) It is used as adhesives for grinding wheels.
d) It is used in Hydrogen exhanger resin in water softening.
e) It is High temperature resistance and hence used in missile nose cones.

2) Urea Formaldehyde-

Urea and formaldehyde react with each other in acidic/neutral condition to give mono & dimethylol
urea which undergo further condensation reaction to give linear/ partially cross-linked/ fully
crosslinked polymer.
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Step I: Urea-Formaldehyde formed by condensation reaction between urea and formaldehyde in

acidic or alkaline medium. The first product formed during formation is monomethylol urea than
dimethylol urea.

Step II: Polymerization can takes place from dimethylol urea with formation of cross- linked polymer.

A fully cross-linked urea-formaldehyde resin can be represented as:

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Properties –
a) Urea formaldehyde resin are cross linked.
b) It is water soluble’
c) It has excellent colour & colour retention.
d) It is low in cost.

Uses-
a) It is used in textile finishing resins & sizing agent.
b) It is used in Paper industry, Plywood industry.
c) It is used in organic solvants.
d) It used in spray dried powders & moulding powders.

3) Epoxy Resin-
Epoxy resins are surface coating material & commonly used. Epoxy resins are polyethers & have great
recognition in industries. The name ‘epoxy’ derived from the starting material Epichlorohydrin &
epoxide group CH2─CH2 present in molecular structure. O

Preparation-

1) Epichlorohydrin

2) Diphenylol propane ( Bis- Phenol A)

Compound is synthesized in three steps.

Step – I: Preparation of epichlorohydrin

It is prepared by heating propylene and chlorine at 400 oC when allylchloride is formed. Allylchloride is
treated with water and chlorine at 3000 C when Glycerol dichlorohydrin is formed which decomposes to
give Epichlorohydrin. The reactions are represented as
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Step-II – Synthesis of Bis Phenol A

It is synthesized by heating acetone & phenol at 50 0C in presence of NaOH.

Step-III- Synthesis of epoxy resin

Condensation between epichlorohydrin and bis phenol takes place at 60 0C in the presence of alkaline
catalyst.

Here n varies from 1-20. Molecular weight ranges from 350-8000.

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Properties-
a) Epoxy resin show chemical inertness
b) Epoxy resins show high resistance to water, acids, alkali, organic solvents and many chemicals.
c) Epoxy resins are flexible because of widely spaced reactive groups.
d) Epoxy resins are though and heat resistant due to Cross linking present in the structure.

e) Epoxy compounds are discovered in same solvant to form solutions.

Uses-
a) Epoxy resins are best coating material. They give flexibility, toughness and resistance to
chemicals to the surface like metal, wood, paper, leather.
b) Epoxy resins are surface and patching material for roads.
c) They are useful for the preparation of adhesive, foams, industrial flooring, glass fibre boards.
d) Epoxy resins are used as laminating & casting materials for electrical equipment & stabilizers for
PVC resins.

4) Conducting Polymers-
The polymers that can conduct electricity to certain extent are called conducting polymer.
The conductivity of these conducting polymer lies between semi-conductor like Si, Ge
(10-5 to 10-2 ohm 10-2) and good conductors like metals Fe, Cu ( > 105 ohm 10-2).
The insulators have very low conductivity (10-8 to 10-18 ohm cm-2).
The conductive polymers are polyacetylene, Polyphenylene, polypyrrole, polythiophene
etc.

Types of conducting polymer –

A. Intrinsic Conducting Polymer ( ICP)-
i. The polymers which are inherently conductors i.e. they conduct elecricity of their own are called
intrinsic conductor.
ii. If alternate double bond is present in the polymer chain the polymer conduct electricity of its
own. Out of two double bond one strong ‘sigma’ bond & other bond is weak ‘ Pi’.
iii. Overlapping of conjugated Pi bond e- over the entire back bond takes place.
iv. This results in formation of conduction band and valance band.
v. The exhibition of Pi e- present in Valance Band is done by supplying heat or exposing to light
polymer conduct electricity.
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Examples-
Conjugated trans polyacetylene

Polyphenelyene-

B. Extrinsic Conductor-

Some polymers are made conducting by addition of suitable substance to the polymer. The conducting

polymers prepared by doping is called extrinsic conductor.

a) P- Type Doping=
Oxidising agent take halogen are dopped to conjugated chains . It extracts a pair of pi e- from
the chain and convert it into positively charged are called polyron.
The polymer chain has lost pi e- to halogen molecule called oxidative doping.
Example-
Polyacetylene + I2
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b) N- Type doping-
A reducing agent like alkali metal added to conjugated polymer chain which donate pair of
electrons to polymer chains leads to form polyrons & bi-polyron.

The polymer chain accept electron from Na atom called reductive doping.
Example- Polyacetylene + Na

Properties-
a) Conducting polymers are Flexible.
b) Conducting polymers are light in weight.
c) Conducting polymers are easy fabricate as compared to other materials.
Uses-
a) They are used in fuel cells.
b) They are used in conductive paints.
c) They are used in electrochromic displays.
d) They are used in manufacture polymeric batteries.
Used in cathode & solid electrolyte in batteries for automobiles.

Synthesis of polyaniline (PANI):

PANI is one of the promising and electrically conductive polymers. The most widely used synthesis
method for preparing polyaniline is chemically oxidative polymerization technique using aniline monomer
in acidic medium. The various method can be used for the synthesis of polyaniline are following:

1. Chemically oxidative polymerization

2. Electrochemical polymerization
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3. Vapor-phase polymerization
4. Photochemically initiated polymerization

2.1 Chemically oxidative polymerization (COP)

For preparing monomers to polymer such as aniline to polyaniline, chemical oxidative polymerization plays
most prominent role. It is a cheap method for preparing large quantities of polymers with less time. In this
method, chemical oxidizing agent initiates the polymerization process. The monomer compounds exhibit
high electron donating properties. Ammonium persulfate (NH4)2S2O8 is a strong oxidizing agent which has
been used to prepare polyaniline (PANI) from aniline monomer because it is highly soluble in water. APS
helps in generating radical cation sites in monomer and initiating the polymerization process. The prepared
monomer solution is kept within aqueous acidic medium at a low temperature. This reaction is later
allowed on a constant stirring for 5–8 hours in order to obtain the polymer precipitate.
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Applications of polyaniline

 Polyanilines are easily dissolved in alcohol and ketone, so can improve the reactivity in the application
of supercapacitor, sensor and water pollutant free applications.
 Due to semiconducting nature, excellent optical, electrical properties and higher thermal stability
polyaniline has extensive application in the field of optoelectronic device (like light emitting diode
(LED), organic solar cell).
 Engineering is the current focus of medicine, and advancements in this field need for new intellectual
technologies.
 Devices prepared from polyaniline, used in neuroscience that compensate for nerve weakening
 Polyaniline based material has been used to treat organ problems.
 Moreover, PANI applications in delivery systems have drawn a lot of interest; as a consequence, novel
delivery structures.
 PANI has been successfully used as an anti-corrosion barrier with positive outcomes.
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Polyvinylcarbazole-PVK: It is also known as photoconducting polymer

Procedure: Required amount of N-vinylcarbazole (NVK) is placed in a round bottomed 3-neck flask.
Suitable quantity of benzoylperoxide is dissolved in 100 ml acetonitrile and added to the flask which is
heated at 70 oC for 04 hours. The polymer is precipitated by methyl alcohol, washed with water and
acetone and dried under vacuum.

Applications of Photoconductive polymer:

 The photoconductive polymers have been successfully applied in laser printers.

 It is used with printers that usually use liquid chemicals in printing process.

 There is some potential application in photovoltaic cells.

 They are photo thermoplastic imaging, holographic recording and optical switching devices.

Self-healing Polymer (Silicone rubber):

Self-healing polymers are synthetically developed polymers and it repairs damaged part without any
human involvement to recover the initial physical and mechanical properties, more particularly
mechanical properties. Silicone rubber is an elastomer (rubber-like material) composed of silicone,
which itself is a polymer, containing silicon together with carbon, hydrogen, and oxygen.

Silicone rubber is generally non-reactive, stable, and resistant to extreme environments and temperatures
from -55 °C to +300 °C
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Synthesis: The most common method for preparing silicone rubber involves reacting a chlorosilane with
water. This produces a hydroxyl intermediate, which condenses to form a polymer-type structure. The
basic reaction sequence is represented as:

This is the favoured route although other raw materials such as alkoxysilanes can be used. The precursor
Chlorosilanes are synthesised using the “Direct Process”, involving the reaction of elemental silicone with an
alkyl halide thus,

Si+RX⟶RnSiX4-n (where n=0 to 4)

Applications: Silicone rubber is highly inert and does not react with most chemicals. Due to its
inertness, it is used in many medical applications.

i) Automotive and Aerospace:

 A UV-responsive microcapsule-based system can be used for damage healing of spacecraft coatings.
 Similarly, high-strength alloy with self-healing properties generally used in the aerospace industry.
 A self-healing tire was developed by styrene-butadiene rubber matrix and reclaimed tire waste as the
sustainable filler in automobile industry.

ii) Other applications:

 Industrial Machinery & Equipment’s like in Textiles & Garment Finishing equipments
 Food & Beverages processing
 Medical Equipment’s
 Transformer & other electrical equipment’s
 Lighting Equipment’s.
 Pouch Packing Machine.
 Thermal Insulation.
 In Pharmaceuticals like Pharma Machines
 Packaging Industries
 Dairy & Automobile Engineering
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Biodegradable polymer:

 Bio-degradable polymers are those polymers that can be decomposed by bacteria or micro-organisms is
called Biodegradable polymers.
 Natural Polymers undergo degradation easily. The synthetic Polymer does not undergo degradation
easily. The life of polymer may ranges from few 100 years to million of years.
 Polymers can be degraded by thermal, mechanical process, ultrasonic waves, light energy radiation & oxidation.
 These processes give degradation products which are harmful to environment. Therefore these methods
cannot be used for degradation of polymers.
 Therefore there is need for biodegradable polymer material used as disposable plastic packaging
material.

Example-
i) Aliphatic polyesters are biodegradable. Products of degradation are quickly metabolized. It is used for
disposable plastic packaging material.

ii) Polyglycolic acid which is obtained by glycolic acid monomer. PGA is used in medical operation to
stitches the wound due to automatic degradation in body.
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Synthesis and properties of Poly lactic acid:

POLYLACTIC ACID:
Poly-lactic acid (PLA) is highly versatile, biodegradable, aliphatic polyester which can be prepared from
100 % renewable resources, like corn and sugar beets. Poly lactic acids (PLA) are promising alternative
for petroleum-based polymers because of its properties and currently it is widely used polymers like
PVC.

Synthesis:

Poly-lactic acid can be produced using different routes and to produce high molecular mass PLA.
i) First one is direct condensation polymerization, but it usually leads to low molecular weight polymers
which then can be converted to higher molecular weight polymers by addition of chain coupling agents.
High temperatures will be required during the polymerization reaction.

ii) Second method is azeotropic dehydrative condensation where organic solvents are introduced into
reaction mixture to remove water, producing higher molecular weight product.

iii) Third method is ring opening polymerization (ROP), where PLA is produced by formation of lactide
monomer first and by help of catalyst then converted into final product. Different catalysts were used for
the synthesis of PLA: protonic acids, metals, metal-oxides.
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Properties:
Polylactic acid has good physical properties and can be used to yield various plastic products, such as
fast-food lunch boxes, and fabrics for industrial use.
i) Good tensile strength and ductility make it suitable for different processing means, such as molding.
ii) High-molecular-weight PLA has been used to produce non-dismantling surgical structures and low-
molecular-weight PLA as a drug-packaging agent.
iii) Polymer polylactic acid possesses good characteristics with regard to transparency, and heat
resistance.
iv) Polylactic acid has sufficient thermal stability up to 200 oC

Application of Biodegradable polymers in the medical industry:

Biodegradable polymers are used in a variety of medical applications like implantable large devices,
medical delivery and tissue engineering.

i) Drug Delivery Systems:

Biodegradable polymers can be engineered to degrade at specific rates, providing sustained release of
therapeutic agents and eliminating the need for frequent dosing. Drugs can be selectively delivered to
specific cells or tissues, minimizing off-target effects.

ii) Tissue Engineering:

Tissue engineering aims to regenerate damaged or lost tissues by combining cells, scaffolds, and
bioactive molecules. Biodegradable polymers provide temporary scaffolds that promote cell adhesion
and tissue regeneration.
iii) Surgical Implants
Surgical implants, providing numerous benefits over traditional permanent implants. Biodegradable
polymers have made significant contributions to bone fixation devices, offering screws, plates, and
pins
iv) Wound Healing
Biodegradable polymer-based wound dressings useful to care wound as compared to traditional
method. These dressings providing moisture, protecting against infections, and promoting the natural
healing process.
v) Biodegradable polymer used against anti-tumor and as anti-inflammatory agent.
vi) Biodegradable polymers have been used in dental applications like generation of membrane, as void
filler and tooth extraction.
vii) Used in Intestinal applications.