Polymers

- According to (Chang 2008), a polymers is a molecular compound distinguished by a very

high molar mass, ranging into thousand and millions of grams, and it is made up of many
repeating units. The physical properties of these so-called macromolecules vary greatly
from those of small ordinary molecules and special techniques are required to study them
- Polymers are not like an ordinary compound. They involve complex chemical reactions to
form.
- The words polymer comes from the Greek prefix poly- “Many” and mers- “Parts”, thus
many parts.
- Example plastic like plastic use as packaging material because it consist of repeating units of
a monomer. Include plastic bottle and trays.
MONOMER, MER AND POLYMER
- The process on which the formation of polymers undergoes is called polymerization, which
involves the chemical combinations of many small chemical units known as monomers
“single parts” (Winslow, 1979), a mer “repeating units” and a polymer “the
macromolecule”.
- Polymers is form by a process known polymerization and a combination of a monomers.
Characteristics of Polymers
- Every polymer has very distinct characteristics, but most polymers have the following
attributes.
- . First, polymers can be very resistant to chemicals. Many chemicals we are using today
such as muriatic acid, chlorine and many more are so strong that it even damages our skin.
- Second, polymers can be both thermal and electrical insulators.
- Third, polymers are very light in weight with significant degrees of strength.
- Fourth, polymers can be processed in various ways.
- Fifth, polymers are materials with a seemingly limitless range of characteristics and colors,
because polymers can mimic cotton, silk, wool fibers, porcelain, marble, aluminum and zinc.
- Lastly, Polymers can be used to make items.
Polymers Based on Origin: Natural, Semi-synthetic and Synthetic Polymers
- There are three types of polymers based on origin: natural, semi-synthetic and synthetic
polymers.
- Synthetic polymers are derived from petroleum oil, and made by scientists and engineers.
- Examples of synthetic polymers include nylon, polyethylene, polyester, Teflon, and epoxy.
- Semi-synthetic polymers are mostly derived from naturally occurring polymers by chemical
modifications. For example, cellulose is a naturally occurring polymer.
- Cellulose on acetylation with acetic anhydride in the presence of sulphuric acid forms
cellulose diacetate polymers. It is used in making thread and materials like films, glasses etc.
- Vulcanized rubber is also an example of semisynthetic polymers used in making tires etc.;
gun cotton which is cellulose nitrate used in making explosive (Gouda, 2018)
Polymers Based Type of Monomer involved in the Structure: Homopolymer and copolymer
Polymers Based on Structure: Linear, Branched, Cross-Link and Network.
- There are two types of Monomer involved in the Structure of Polymers. First,
homopolymer- same monomer is repeated throughout the chain of polymer; and
copolymer- this is also known as heteropolymer as they are composed of two or more
different kinds of monomers.
Homopolymers
- Homopolymers can be classified as linear, branched, cross linked and network
homopolymers.
Linear polymers
- Branched polymers have short or long branches bonded on parent polymeric or it occurs
when groups of units branch off from the long polymer chain. These branches are known as
side chains and can also be very long groups of repeating structures.
High-density polyethylenes (HDPEs)
- HDPEs are mostly linear molecules that pack closely together and can assume fairly ordered
crystalline structure. It’s rigid and has good tensile strength.
Low- density polyethylenes (LDPEs)
- LDPEs have plenty of side chains branching off polymer molecules. It’s waxy, bendable
plastics that are lower melting than HDPE (Smith, 2005)
Cross linked and Network polymers
- They form long chains, either branched or linear, that can form covalent bonds between
the polymer molecules. As a result, it produces a stronger and more stable material,
because cross-linked polymers form covalent bonds that are much stronger than the
intermolecular forces that attract other polymer chains.
* Vulcanization
- Vulcanization is a process where the rubber is heated so the sulfur molecules in the rubber
polymer chains form covalent bonds with each other.
Copolymers
- According to Raymond Chang and Goldsby (2016), copolymers are also known as
heteropolymer as they are composed of two or more different kinds of monomers. It has
two major types, namely, polyamides and polyesters.
- Polyamides are the condensation of carboxylic acid and amine monomers while polyesters
are the condensation of carboxyclic acid and alcohol monomers.
- . Example of polyamide is Nylon-66 produced by mixing equimolar amounts of a six-C
diamine (1,6- diaminohexane) and a six-C diacid (1,6- hexanedioic acid).
- Example of polyester is Dacron, a popular polyester fiber, woven from 1,4
benzenedicarboxylic acid and 1,2 ethanediol.
- example is mylar films, used for recording tape and food packaging.
Copolymer can be further classified as alternating copolymer, block copolymer, graft copolymer
and random copolymers, gradient, periodic and aperiodic.
*Random Copolymer -the monomers are arranged in any order such as AABAAABBBBAB.
*Block Copolymers - two blocks of homopolymers are joined together. It can be
represented as AAAAAAABBBBBBB.
 *Alternating Copolymer - the two monomers are arranged in an alternative way and can be
represented as ABABABABAB.
*Graft Copolymer -The composition of the main chain is a preformed macromolecule and is
compositionally or configurationally different from the side chains or branches w/ repeat
units.
Kevlar (Another type of polymer)
- Kevlar is an extended application of Nylon and other polymers have stimulated a strong
demand for new “super” fibers with the heat resistance of asbestos, the stiffness of glass,
and strength much greater than steel.
- The average molecular mass of each polymer chain is 10⁵ amu.
- Kevlar ropes can replace steel ropes and cables (offshore oil drilling). In seawater, kevlar has
20 times the strength of steel.
- Kevlar is also used in manufacturing bulletproof vests and high-performance sports gear.
Classification of Polymers based on Molecular Forces: Thermoplastic and Thermosets,
Elastomers, Fiber-Forming Polymers
*Thermoplastics and Thermosets
Thermoplastics
- polymers become soft on the application of heat and thus can be molded in the desired
shape.
Thermosets
- polymers have individual chain bonded covalently during polymerization by application of
heat or chemical treatment. The shape cannot be changed and resist subsequent
mechanical deformation or heat softening or solvent attack.
*Glass transition temperature (Tg)

-The glass–liquid transition, or glass transition, is the gradual and reversible transition in
amorphous materials (or in amorphous regions within semicrystalline materials) from a
hard and relatively brittle "glassy" state into a viscous or rubbery state as the temperature
is increased.[1] An amorphous solid that exhibits a glass transition is called a glass. The
reverse transition, achieved by supercooling a viscous liquid into the glass state, is called
vitrification.
-A material characterizes the range of temperatures over which this glass transition occurs.
-It is always lower than the melting temperature, Tm, of the crystalline state of the
material, if one exists.
-Despite the change in the physical properties of a material through its glass transition, the
transition is not considered a phase transition.
Above this temperature – polymer is rubbery and tough
*Materials with low Tg - if we want automobile tires to be tough and elastic
*Plasticizers- can make them more flexible and less brittle by lowering the Tg
Below temperature - polymer is like glass - hard, stiff and brittle
*Materials w/ Tg values above room temperature - if we want plastic substitutes for glass to be
glassy.
ELASTOMERS
- Elastomers (or rubbers) are polymers with considerable extensions which are reversible,
examples are natural and synthetic rubbers.
- Synthetic rubbers are now used much more extensively and they are based on other
polymers and produced from the distillation of oil.
- Many components do not require great strength but they do require softness, flexibility
and reversible elongation.
Fiber-Forming Polymers
- The fiber forming polymers are linear macromolecules that are usually suitable for making
man-made fibers
- The term “synthetic fiber” will be used to denote all manmade fibers manufactured from
non-cellulosic raw materials.
- Examples are hydrophobic polymer fibers like nylon and polyester often blended with
cotton, viscose or wool.
Polymer Recycling
- According to Smith (2005), in recycling plastic in the United States, they follow the “Big
Six” Recycling code (1-6). The lower the number, the easier to recycle.
POLYMERIZATION
- a chemical reaction in which two or more molecules combine to form larger molecules
that contain repeating structural units. It is usually formed with the same type of
repeating molecules (homopolymers) or form with two or more different molecules
(copolymer)
TYPES OF POLYMERIZATION
- There are two general types of polymerization reactions: addition polymerization and
condensation polymerization. In addition polymerization, the monomers add to one
another in such a way that the polymer contains all the atoms of the starting monomers.
Ethylene molecules are joined together in long chains (Chanda, 2017).
Chain-Reaction (Addition) Polymerization
- The bond lines extending at the ends in the formula of the product indicate that the
structure extends for many units in each direction.
- During the polymeriation of ethene, thousands of ethene molecules join together to make
poly(ethene) - commonly called polythene. The reaction is done at high pressures in the
presence of a trace of oxygen as an initiator.
Step 1: Chain Initiation
- The oxygen reacts with some of the ethene to give an organic peroxide.
- Organic peroxides are very reactive molecules containing oxygen-oxygen single bonds
which are quite weak and which break easily to give free radicals.
Step 2: Chain Propagation
- In an ethene molecule, CH2=CH2, the two pairs of electrons which make up the double
bond aren't the same.
- One pair is held securely on the line between the two carbon nuclei in a bond called a
sigma bond.
- The other pair is more loosely held in an orbital above and below the plane of the
molecule known as a ππ bond.
Step 3: Chain Termination
- That immediately stops the growth of two chains and produces one of the final molecules
in the poly(ethene)
- It is important to realize that the poly(ethene) is going to be a mixture of molecules of
different sizes, made in this sort of random way.
- Because chain termination is a random process, poly(ethene) will be made up of chains of
different lengths.
Step-Reaction (Condensation) Polymerization
- A large number of important and useful polymeric materials are not formed by chain-
growth processes involving reactive species such as radicals, but proceed instead by
conventional functional group transformations of polyfunctional reactants.
- These polymerizations often (but not always) occur with loss of a small byproduct, such as
water, and generally (but not always) combine two different components in an alternating
structure.
-