POLYMERS

The term "polymer" comes from the Greek words "poly" meaning many and "mer" meaning
parts. Polymers are large molecules consisting of multiple repeating units linked by covalent
bonds.
The monomer is the basic building unit that repeats itself to form a polymer.
Example: Ethylene.
Polymerization: It is a process by which simple low molecular weight compounds combine
to form a complex high molecular weight compound called polymers.
Condition:
This requires that each molecule of the compound should have the capability to react with at
least two other molecules. i.e., it should have at least two reactive sites.
The degree of polymerization is defined as the number of repeating monomeric units in a
polymer.
Degree of polymerization
(i) –(CH2-CH2-)1000 : 1000
(ii) 10 –(CH2-CH2-CH2-)50000 : 50000
M w of polymer
Degree of Polymerization ( DP )=
M w of repeating unit
If Dp = 1 then it is monomer; Dp=2 dimer; Dp = 3 trimer; Dp = 4 tetramer, Dn=n;
Oligo polymers
Polymers with a low degree of polymerization are known as oligo polymers and their
molecular weight ranges from 500 - 5000.
High Polymers
Polymers with a high degree of polymerization are known as high polymers and their
molecular weight ranges from 10,000 - 2,00,000.
FUNCTIONALITY
Functionality is the number of reactive sites or the number of binding sites. So, a monomer
should at least be bifunctional to undergo polymerization.
Significance: Depending on the functionality of the monomer used, linear, branched, or
three-dimensional cross-linked polymers are obtained.
Classification of polymer
(A) Classification Based on Source: Natural, Synthetic
Natural polymers: Synthesized in nature (OR) Isolated from natural materials
 Example: Cotton, Silk, Wool
Synthetic polymer: Man-made (OR) Synthesized from low molecular weight compounds
Example: Nylon, Terylene etc
(B) Classification Based on Physical State: Amorphous, Crystalline
Amorphous polymer: A polymer with a less ordered arrangement of chains and weak
intermolecular forces. Example: Vinyl polymers
Crystalline polymer: A polymer with an ordered structure that has been allowed to
disentangle and form crystals. The intermolecular forces are high. So
greater strength and higher density. Example: Cellulose
(C) Classification on the basis of Structure
On this basis, polymers have been broadly classified into three types:
1. Linear Polymers: Polymers comprising long and straight chains are called linear or
straight-chain polymers. e.g., High-density polyethylene (HDPE)

2. Branched-chain Polymers: Polymers comprising linear chains with branches are called
as branched-chain polymers. e.g., Low-density polyethylene (LDPE).

3. Cross-linked Polymers: Polymers in which various individual chains are connected

together by covalent bonds (cross links) are called cross-linked polymers. These polymers are
formed from bi-functional and tri-functional monomers and the additional functionality
produces the cross links. e.g., Bakelite and Melamine
(D). Classification on the basis of the nature of Monomers
On this basis, polymers have been broadly classified into two types:
1. Homo-polymers: Polymers which are comprised of only one type of monomer are called
homo-polymers. e.g., Polyethene, PVC, Nylon-6, etc.
This can be represented as: -A-A-A-A-A-A-A-A-A-A-A-A-A-A-, or -(A-)n
2. Co-polymers: Polymers which are comprised of more than one (generally two) type of
monomers are called as homo-polymers. e.g., Nylon-6'6, Terylene, SBR, etc.
Co-polymers have further been classified into four types on the basis of the relative
arrangement of the monomer units with respect to each other. These are:
i). Alternate Co-polymers: Polymers comprising of alternating A and B units. The order is
regularly followed throughout the chain.
This can be represented as: -A-B-A-B-A-B-A-B-A-B-A-B-A-B-, or -(A-B)n
ii). Block Co-polymers: Polymers comprising of regular alternating blocks of A and B units.
The order is regularly followed throughout the chain.
This can be represented as: -A-A-A-A-A-B-B-B-B-B-A-A-A-A-A-B-B-B-B-B
iii). Graft Co-polymers: Polymers in which the main chain is comprised of one type of
monomer and the other monomer forms the branches. Therefore, for a graft co-polymer, the
polymer must be branched.
This can be represented as B-B-B-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-B-B-B
iv). Random Co-polymers: Polymers in which no regular order of arrangement is followed
by the monomer units.
This can be represented as: -A-A-A-A-A-B-B-A-B-B-B-B-B-B-B-A-A-A-
The most common type of co-polymers are alternate co-polymers.
(E). Classification on the basis of Inter-molecular Forces
On this basis, polymers have been broadly classified into four types:
1. Elastomers
Polymers in which intermolecular (inter-chain) forces are very weak (van der Waals forces)
are called elastomers. These are rubber-like solids weak interaction forces are present.
e.g., Rubber.
2. Fibres
Polymers in which intermolecular (inter-chain) forces are very strong (Hydrogen bond or
dipole-dipole interaction) are called Fibres. These are strong, and tough, with high tensile
strength. e.g., Nylons, Terrylene, etc.
3. Thermo-plastics
Polymers in which intermolecular (inter-chain) forces are intermediate are called as
thermoplastics. These polymers on heating become soft and on cooling again become hard
and retain their original shape. In this case, the intermolecular forces, on heating, get weaken
and
the polymer becomes soft and vice-versa. It is purely a physical change and physical changes
are generally reversible. Therefore, these polymers are recyclable, i.e., they can be molded
and re-molded again and again. e.g., Polyethene, Polyvinyl chloride, Polystyrene, etc.
4. Thermo-settings
Polymers in which there is extensive cross-linking, are called as thermo-settings. These
polymers on heating become soft and on cooling again become hard but do not retain their
original shape. In this case, the cross-links get broken and rearranged on heating. It is purely
a
chemical change and chemical changes are generally irreversible. Therefore, these polymers
are not recyclable, i.e., once molded, they cannot be molded again. These polymers greatly
improve the material’s mechanical properties. e.g., Bakelite, Epoxy resins, etc.

 SOME IMPORTANT POLYMER

(1) Polyamides
Polymers in which monomer units are linked together by amide bonds. For polyamide
formation, the monomers should be polycarboxylic acids and polyamines. Generally,
dicarboxylic acids and diamines are used. Polyamides belong to the fibers as per the
classification on the basis of intermolecular forces.
Some Commercially Important Polyamides
There are many synthetic polyamides known as nylons like, Nylon-6,6, Nylon-6, Nylon-6,10,
Nylon-11, etc.
(i) Nylon-6'6
Nylon-6'6 is a co-polymer and its monomer units are adipic acid (Hexan-1,6-dioic acid) and
hexamethylene diamine (Hexan-1,6-diamine). Both these monomers can in turn be obtained
from Buta-1,3-diene. The reaction for preparation of Nylon-6'6 can be shown as:
(ii) Nylon-6
Nylon-6 is a homopolymer and its monomer unit is capro-lactam, a seven-membered cyclic
amide with six carbon atoms. The monomer can be obtained from cyclohexane via a series of
reactions involving Beckmann Rearrangement. During the preparation of Nylon-6, the
monomer Capro-lactam first undergoes decyclization by hydrolysis, yielding an open chain
real monomer aminocaproic acid (6-Aminohexan-1-oic acid), which undergoes self-
polymerization-in-a-regular order (Head to the tail manner). The reaction for the preparation
of Nylon-6 can be shown as:

Properties of Nylons:
Nylon fibers are linear structures in which the molecular chains are arranged parallel to each
other and held together by hydrogen bonding. The strong intermolecular forces make the
structure of these fibers more crystalline and impart their high strength, elasticity, and high
melting point.
 Nylons are chemically stable and resistant to abrasion.
 The yarn is smooth, long-lasting, and can be spun into fabric.
 The fabric is tough, lustrous, moisture resistant, easy to dye, retains color, and can be
set by heat and steam.
Applications of Nylons:
Nylons are used for making sports gear, fishing lines, etc. They are used for making combs
and toothbrush bristles. As an engineering application, nylons are used for making gears,
bearings, etc. They are used for jacketing electrical equipment to provide insulation and
resistance to abrasion. Nylon-6 is mainly used for making cords for tyers. Nylon-6'6 fibers
are used for making fabric for clothing, socks, sportswear, carpets, etc.
(2) Polyesters
Polymers in which monomer units are linked together by ester bonds. For polyester
formation, the monomers should be polycarboxylic acids and polyols. Generally, dicarboxylic
acids and diols are used. Polyesters belong to the fibers as per the classification on the basis
of intermolecular forces.
Some Commercially Important Polyesters
There are many synthetic polyesters like Polyethylene Terephthalate (Terylene), Polyethylene
Phthalate (Glyptal), Polybutylene Terephthalate, polytrimethylene Terephthalate, etc.
(i) Polyethylene Terephthalate (PET)
Polyethylene terephthalate is a copolymer and its monomer units are terephthalic acid
(Benzene1,4-dicarboxylic acid) and ethylene glycol (Ethane-1,2-diol). It is commercially
known as Terylene. The reaction to the preparation of Terylene can be shown as:

Properties of Terylene:
 Terylene has high mechanical strength and dimension stability.
 It is a very strong fiber and will suffer very little loss in strength when wet.
 It is elastic in nature and possesses the property of high crease resistance.
 It is stable in the temperature range of -40 - 100oC.
 It shows creep and abrasion resistance and good insulating properties.
 It shows low water absorption and at room temperature, it is resistant to water, dilute
acids, salts, aliphatic and aromatic hydrocarbons, and alcohols.
Applications of Terylene: This material has various uses such as in the production of video
and audio tapes, in the textile industry for creating durable clothing, and in the manufacturing
of clear bottles for food and beverages. Additionally, the fiber can be blended with cotton and
wool to produce other fabrics like terycot and terry wool, respectively.
(ii) Polybutylene Terephthalate (PBT)
Polybutylene Terephthalate is a semi-crystalline, white, or off-white polyester similar in both
composition and properties to polyethylene terephthalate (PET). The reaction to the
preparation of Terylene can be shown as:
It has somewhat lower strength and stiffness than polyethylene terephthalate, PET, is a little
softer but has higher impact strength and very similar chemical resistance. As Polybutylene
Terephthalate (PBT) crystallizes more rapidly than PET, it tends to be preferred for industrial-
scale molding.
Applications of PBT: Applications of Polybutylene Terephthalate (PBT) include electrical
and automotive components (including “under-bonnet”) and power tool casings.
(3) Polyphenols: The term “polyphenol” should be used to define compounds
exclusively derived from the phenols or phenylpropanoid or the polyketide pathway,
featuring more than one phenolic unit and derivatives. For example, Bakelite, t-BHQ
(i) Bakelite
Phenol-formaldehyde resin, commercially known as Bakelite, is a co-polymer and its
monomer units are Phenol and Formaldehyde. These polymers are obtained by the
condensation reaction of phenol with formaldehyde in the presence of either an acid or a base
catalyst. The reaction for preparation of Bakelite can be shown as:
Properties of Bakelite:
 Bakelite is a rigid, hard, and scratch-resistant material.
 It displays good electrical insulation properties.
 It has thermal stability up to of 200oC.
 It is resistant to water and shows low flammability.
Applications of Bakelite: It is used for making electrical equipment parts such as switches,
plugs, switchboards, cooker handles, electric iron parts, telephone parts, combs, etc.
Due to its hardness, it is used for making golf balls and heads for typewriters. It is
also used as a hot-setting adhesive for plywood, etc.
(ii) Polymeric 2-tert-butylhydroquinone (T-BHQ):

Properties: Their stability at high temperatures, retaining their antioxidant capabilities during
and after baking and frying. This is a non-poisoning, odorless, and colorless antioxidant.
TBHQ is highly safe with no pollution to the products and environment.
Uses: The most widely used food antioxidants due to their low cost, high performance, and
wide availability. The anti-oxygenation and anti-aging functions.
(4) Polycarbonate:
(i) LEXAN: LEXAN is a brand of polycarbonate, thermoplastic polymers, currently
produced by SABIC. It was first produced in 1960 after General Electric created a branched
polycarbonate nearly 50 years after polycarbonates were first discovered in 1898 by German
scientist, Alfred Einhorn.
Properties: Lexan is a type of polycarbonate (PC). It is incredibly tough, and resistant to
impacts. It is also lightweight when compared to glass. It is used in a variety of applications
where materials need to be strong, and virtually unbreakable. It is an amorphous
thermoplastic material, with a continuous use temperature range of up to 265° F (129° C).
Uses:
It is moldable and comes with a high strength, making it the ideal industrial plastic for just
about anything including food containers, airplane components, automobile manufacturing,
construction, golf cart windshields, security windows and doors, window glazing, print
materials and so much more.
(ii) Bisphenol-A And Diphenyl Carbonate (bis-PDC)
Preparation of Polycarbonate by condensation polymerization between bisphenol-A and
diphenyl Carbonate. Polycarbonate can also be made by condensation polymerization of
bisphenol-A and diphenyl carbonate to eliminate the use of carbonyl chloride (Phosgene)
which is an extremely poisonous gas.
Properties of Polycarbonate:
1. Polycarbonate has high strength making it resistant to impact and fracture. The polymer
can maintain its toughness up to 140 ℃ and down to -20 ℃.
2. Polycarbonate is an extremely clear plastic that can transmit over 90% light as well as
glass.
3. Polycarbonate has a refractive index of 1.584 and offers excellent optical properties.
4. Polycarbonate exhibits good chemical resistance against diluted acids, aliphatic
hydrocarbons, and alcohols.
5. Polycarbonates are thermally stable up to 135 ℃ offering good heat resistance. Their heat
resistance can also be improved by adding flame retardants with impacting material
properties.
Applications of Polycarbonates
1. Polycarbonates are used in electrical appliances such as refrigerates, air conditioners,
coffee machines, food mixers, etc.
2. Polycarbonates are also used in bulletproof windows, shelters, and skylights acting as the
best alternative to glass.
3. Polycarbonate has great medical applications where it is used in surgical instruments, drug
delivery systems, hemodialysis membranes, blood filters, etc.
(5) Polyoxymethylene (POM)
Polyacetal or Polyoxymethylene has a semi-crystalline nature. It is a high-performance
thermoplastic polymer. Known for its exceptional mechanical properties and versatile
applications. The reaction for preparation as given below:

Polyoxymethylene resins demonstrate well-balanced properties ranging from mechanical to

physical and flammability performance. The key benefits of POM resins include:
 Excellent mechanical properties over a temperature range up to 140°C, down to -40°C
 High tensile strength, rigidity and toughness (short-term)
 Low tendency to creep (as compared to nylon) and fatigue (long-term). Not
susceptible to environmental stress cracking
 A high degree of crystallinity and excellent dimensional stability
 High gloss surfaces
 Excellent wear resistance
 Good resistance to organic solvents and chemicals (except phenols) at room
temperature
 Low smoke emission
 Low coefficient of friction
 Low moisture absorption
Applications:
The Food and Drug Administration has approved Delrin for use in the food industry. It is also
used extensively in paintball markers, where it is used to make bolts, pump handles, and
many other parts.