POLYMERS:

Classification and Properties

Submitted by:
GROUP 3
Bucsit, Jan Patrick
Dasalla, Dorothy Joy
De Guzman, Alexis Kimberly
Gabriel, Chander Llanfair
Gumangan, Webster
Pascua, Sebastian

08, July 2023

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MONOMER
● Repeating molecular units
● Connected into polymers by covalent bonds.

The word monomer comes from mono- (one) and -mer (part). Monomers are small
molecules that may be joined together in a repeating fashion to form more complex
molecules called polymers. Monomers form polymers by forming chemical bonds or binding
supramolecular through a process called polymerization.

A monomer is a type of molecule that has the ability to bond with other molecules in
a long chain chemically; a polymer is a chain of an unspecified number of monomers.
Essentially, monomers are the building blocks of polymers, which are more complex types of
molecules.

POLYMER
● A large molecule (macromolecule) is built up by repetitive bonding (covalent) of
smaller molecules (monomers)
● Generally, it does not have a well-defined structure or molecular weight.
● Need to use statistical properties to describe.

The word polymer comes from poly- (many) and -mer (part). A polymer may be a
natural or synthetic macromolecule comprised of repeating units of a smaller molecule
(monomers). While many people use the term 'polymer' and 'plastic' interchangeably,
polymers are a much larger class of molecules that includes plastics, plus many other
materials, such as cellulose, amber, and natural rubber.

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 Polymers make up many of the materials in living organisms and are the basis of
many minerals and man-made materials. They have a wide range of applications and are
essential in various industries, such as plastics, textiles, adhesives, and packaging. The
structure and properties of polymers can vary significantly based on the choice of monomers
and the polymerization process employed.

Sometimes polymers are made from bound groups of monomer subunits (up to a few
dozen monomers) called oligomers. To qualify as an oligomer, the properties of the molecule
need to change significantly if one or a few subunits are added or removed. Examples of
oligomers include collagen and liquid paraffin.

POLYMERIZATION
any process in which relatively small molecules, called monomers, combine
chemically to produce a very large chainlike or network molecule, called a polymer. The
monomer molecules may be all alike, or they may represent two, three, or more different
compounds. Usually, at least 100 monomer molecules must be combined to make a product
that has certain unique physical properties—such as elasticity, high tensile strength, or the
ability to form fibers—that differentiate polymers from substances composed of smaller and
simpler molecules; often, many thousands of monomer units are incorporated in a single
molecule of a polymer.
The formation of stable covalent chemical bonds between the monomers sets
polymerization apart from other processes, such as crystallization, in which large numbers of
molecules aggregate under the influence of weak intermolecular forces. Two classes of
polymerization usually are distinguished.
In condensation polymerization, each step of the process is accompanied by the
formation of a molecule of some simple compound, often water.
In addition polymerization, monomers react to form a polymer without the formation
of by-products. Addition polymerizations usually are carried out in the presence of catalysts,
which in certain cases, exert control over structural details that have important effects on the
properties of the polymer.

TYPES OF POLYMERIZATION REACTION

ADDITION POLYMERIZATION
The monomer molecules bond to each other without the loss of any other atoms.
Addition polymers from alkene monomers or substituted alkene monomers are the biggest
groups of polymers in this class. Ring opening polymerization can occur without the loss of
any small molecules. Addition or chain-growth polymerization involves the rearrangement of

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bonds within the monomer in such a way that the monomers link up directly with each other

CONDENSATION POLYMERIZATION
-Two different monomers combine with the loss of a small molecule, usually water.
Most polyesters and polyamides (nylon) are in this class of polymers. It is a form of a step-
growth polymerization where smaller molecules or monomers react with each other to
form larger structural units (usually polymers) while releasing by-products such as water
or methanol molecule. The by-products are normally referred to as condensate.

CLASSIFICATION OF POLYMERS

Based on Origin:
1. Natural Polymers
-Polymers that are obtained from animals and plants are known as natural polymers.
A few examples of natural polymers are:
a) Polysaccharides: Cellulose and starch are very common examples of
polysaccharides. They are the polymers of glucose. The monomer of polysaccharides
is a monosaccharide.
b) Proteins: These are the polymers of α-amino acids. They are building blocks of
animal cells. They constitute an indispensable part of our food. Wool, natural silk,
etc., are proteins.
c) Nucleic acids: These are the polymers of various nucleotides. RNA and DNA are
common examples.
d) Natural rubber: The substance obtained from latex is a polymer of isoprene.
2. Synthetic Polymers
The polymer prepared in the laboratory is referred to as synthetic polymers or man-
made polymers. Examples are; PVC, polyethylene, polystyrene, synthetic rubber,
nylon-6,nylon-66. Etc

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Based on Chemical Structure:
1. Homopolymer
- is a polymer made from many copies of a single repeating unit.

2. Copolymer
-usually into long chains, of molecules of two or more simple compounds (the
monomers forming the polymer).

Based on Polymeric Structure

1. Linear Polymers
-Linear polymers are polymers in which monomeric units are linked together to form
long straight chains. The chains are very well ordered in relation to one another, and
The structure is densely packed. As a result, linear polymers have high densities,
melting points, and tensile strengths. Polyethylene, nylon, and polyester are a few
examples.

2. Branched-chain Polymers
-Branch chain polymers have a branched-chain of monomeric units. These polymers
do not pack well due to the presence of branches. As a result, when compared to a
linear polymer, branched-chain polymers have lower melting points, densities, and
tensile strength. Both addition and condensation can form branch chain polymers.
Examples are amylopectin, glycogen, low-density polyethene and all vulcanised

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 rubbers.

3. Cross-Linked Polymers
-In these polymers, the initially formed linear polymeric chains are joined together to
form a three-dimensional network structure. These polymers are hard, rigid, and
brittle. Cross-linked polymers are always condensation polymers. Resins are an
example of cross-linked polymers.

Based on the Arrangement of monomers

1. Block Polymer
-comprised of two or more chemically different chains joined together by covalent
bonds, a polymer comprising molecules in which there is a linear arrangement of
blocks

2. Graft Polymer
-of two or more different chemical chains in which a chain (named backbone) has
multiple branches formed from macromolecular chains with a chemical composition

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 different from that of the backbone.

Based on Tacticity

1. Isotactic
-Polymers with isotactic tacticity have pendant groups highly ordered around the
hydrocarbon backbone chain. The pendant groups are all located on one side of the
hydrocarbon backbone chain. This usually causes isotactic polymers to arrange
themselves in higher ordered structures with a high level or linear order, such as semi-
crystalline or helical configurations.
2. Syndiotactic
-Polymers with syndiotactic tacticity have pendant groups in ordered, alternating
patterns around the hydrocarbon backbone chain. The pendant groups can be located
on any side of the hydrocarbon backbone chain, but they present regular patterns. The
regular structural configuration of syndiotactic polymers can result in crystal
structures.
3. Atactic
-Polymers with atactic tacticity have pendant groups in disordered, random patterns
around the hydrocarbon backbone chain. The resulting macroscopic structures usually
lack translational symmetry and are amorphous.

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Based on Thermal Behavior
1. Thermoplastic
-The polymer that softens on heating and can be converted into any shape on cooling
is called thermoplastics. The process of heating, reshaping, and retaining the shape on
cooling can be repeated several times without affecting their properties much.
Examples are Polycarbonate, Polytetrafluoroethylene, etc.
2. Thermosetting
-The polymer that softens on heating and can be converted into any shape on cooling
is called thermoplastics. The process of heating, reshaping, and retaining the shape on
cooling can be repeated several times without affecting their properties much.
Examples are Polycarbonate, Polytetrafluoroethylene, etc.

Based on Molecular Forces

The mechanical properties of polymers, such as tensile strength, toughness, elasticity,
and so on, are determined by intermolecular forces in the macromolecules, such as Van der
Waal forces and hydrogen bonds. Polymers are classified into four types based on the
magnitude of their intermolecular forces.

1. Elastomers
-An elastomer is a plastic that stretches and then reverts to its original shape. It is an
amorphous polymer that is randomly oriented. The structure of elastomers has cross-
linking to prevent the chains from slipping over one another. The polymeric chains
have very weak Van der Waal forces. For example, vulcanized rubber.
2. Fibers
-Fibers are linear polymers with hydrogen bonds or dipole-dipole attraction holding
the individual chains of polymer together. The polymeric chains in the fibres are
highly ordered with respect to one another. Fibers have the highest tensile strength
and negligible elasticity due to strong intermolecular forces of attraction and highly
ordered geometry. They are crystalline in character and have a high melting point and
low solubility. Cellulose, nylon, wool, silk, etc., are some examples of fibers.

Based on Modes of synthesis

1. Addition polymers
– Addition polymers are formed by a reaction in which monomer units simply add to
one another. The monomers usually contain carbon–carbon double bonds. Addition
polymers include polystyrene, polyethylene, polyacrylates, and methacrylates.

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 2. Condensation polymers
– Condensation polymers are formed by the reaction of bi- or polyfunctional molecules,
with the elimination of some small molecule (such as water) as a by-product. Examples
include polyester, polyamide, polyurethane, and polysiloxane.

DIFFERENTIATING NATURAL AND SYNTHETIC POLYMERS

NATURAL POLYMERS
-Natural polymer is a material that is a result of the biological process. It is present in
the human body and also in other forms of life such as plants and animals. Proteins, amino
acids, peptides, RNA, and DNA, are all forms of natural polymers found in the biological
system. In plants and animal life. Also, we can find natural polymers in one or the other type.
Examples of natural polymers are wool, silk, honey, and others.
All four of the main classes of biological molecules (nucleic acids, proteins,
carbohydrates, lipids) include polymers. Most of the natural polymers encountered in
everyday life are proteins, such as keratin in wool and hair; cellulose from plants; and
collagen in skin.

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 • Collagen– Collagen is one of the natural polymers and is a protein. This collagen-
polymer is also a fibre that creates an elastic layer below the skin and thus helps in
keeping it supple and smooth.
• Latex- Latex is known to be a kind of rubber, and rubber is a natural polymer. This
latex occurs in both forms either synthetic or natural. The natural form of latex is
mainly collected from the rubber trees and it is also found in a variety of plants
including milkweed. It can also be prepared artificially by the process of building up
long chains of molecules of styrene.
• Cellulose– Cellulose is one of the most abundant organic compounds found on the
Earth and moreover the purest form of natural cellulose is cotton. The paper
manufactured from the woods of trees and also the supporting materials in leaves and
plants mainly comprise cellulose. Like this amylose, it is also a polymer which is
made from the monomers of glucose.
• Starch– Starch is the derivative of condensation polymerization and consists of
glucose monomers, which further split into water molecules when combined
chemically. Starch is a polymer of the monosaccharide glucose. The molecules of
starch consist of 2 kinds of glucose polymers namely amylopectin and amylose which
are the main components of starch in most plants.

SYNTHETIC POLYMERS
-Synthetic polymers are those materials that are a result of a process that takes place
in a laboratory. As the name suggests, synthetic is something that is not natural. So, we can
say that it is made in laboratories and factories by human beings. The persons who make this
material can be scientists or engineers. The most common examples of synthetic polymers are
PVC, acrylic, Teflon, and polythene.

Examples of synthetic polymers include:

• Bakelite, the first synthetic plastic
• Neoprene
• Nylon
• Rayon
• Teflon

The seven types of plastic include:

1. Polyethylene Terephthalate (PETE or PET)
2. High-Density Polyethylene (HDPE)
3. Polyvinyl Chloride (PVC)
4. Low-Density Polyethylene (LDPE)
5. Polypropylene (PP)
6. Polystyrene or Styrofoam (PS)
7. Miscellaneous plastics (includes: polycarbonate, polylactide, acrylic, acrylonitrile
butadiene, styrene, fiberglass, and nylon)

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STRUCTURE OF POLYMERS
Polymers consist of extended molecules that contain chains of carbon linked to each
other in a regular pattern. As they are held together to form concentrated covalent bonds.
Intermolecular forces between the long chains appear to be more colossal than simple
molecules.
Polymer molecules may combine up to millions of monomers (mers) forming a one-
dimensional structure (chain), two-dimensional structure (planar molecules) or three-
dimensional structure. For instance, organic polymers are compounds built from hydrocarbon
base monomer units. Aside from hydrogen and carbon being incorporated in polymer
molecules, oxygen, nitrogen, chorine, fluorine, silicon, phosphorous, and sulfur can as well be
part of the atoms linked in a long chain.
Polymers are divided into different structures such as branched polymer, copolymer,
graft copolymer and block copolymer.

PROPERTIES OF POLYMERS

PHYSICAL PROPERTIES
Polymers possess diverse physical properties that influence their performance and
applications.
Tensile strength determines a polymer's ability to elongate without breaking, thereby
impacting its overall strength and durability.
Polymers generally exhibit high melting and boiling points, which rise with stronger
intermolecular forces and longer chains. Hard polymers resist penetration, withstand wear and
tear, and find use in constructing devices.
Density categorizes polymers as high-density or low-density based on their mass
differences.
Heat capacity and conductivity determine a polymer's insulation capabilities, with
molecular stiffness dictating its heat conduction.
Thermal expansion measures a polymer's dimensional changes with temperature
variations. Crystallinity affects a polymer's brittleness, with less crystalline polymers being
more useful.

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 Elasticity correlates with weak intermolecular bonds, enabling greater stretchability.
Permeability refers to a polymer's particle passage tendency, with low-density polyethylene
employed for air-tight food packaging. Refractive index measures light bending in polymers,
finding application in spectroscopy.
Most polymers exhibit poor electrical conductivity, but conductive polymers featuring
carbon-carbon double bonds are utilized in modern semiconductor devices to enhance electrical
conduction.

CHEMICAL PROPERTIES
1. Bonding and reactivity
– The strong covalent bond and other weak forces such as hydrogen bonding between
the particles of polymers determine its property like reactivity. Generally, polymers
are resistant to chemicals due to their low reactivity.

2. Interaction between the reactive groups

– Intermolecular forces among the monomers is decided by their dipole. The carbonyl
group (amide group) present at the side chains of the monomers is responsible for the
formation of the hydrogen bond.

3. Adhesion of polymers on the surface, its interaction with coating, and the external
environment also affects their quality, like paints.

4. Biodegradability
– Polymers can degrade by the action of decomposers. Natural polymers like rubber
are biodegradable, while synthetic polymers are non-biodegradable.

OPTICAL PROPERTIES
Optical refractive index n and the high frequency permittivity are linked in
electromagnetic theory. Absorption of optical radiation occurs by rearrangements of electrons
within molecules (visible and ultraviolet) and excitation of bond vibrations (infrared).
Additionally, scattering phenomena play a major role in determining optical properties. Light
scattering is a display of optical diffraction processes, which takes place noticeably in
polymer materials due to their having microstructural features of dimensions comparable
with optical wavelengths (Hall 1981).

COPOLYMERIZATION
A variety of monomers react to undergo polymerization to form polymers known as
copolymers.

USES OF POLYMERS
-Polymers play a huge role in our day to day lives and their use is wide and varied owing to
their unique individual properties.

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Some specific examples of polymers and their common uses:
● Polyethylene, also known as polythene, is one of the most prominent plastic
polymers, it has several excellent physical properties such as high ductility, high
impact strength, and very great chemical resistance.used for manufacturing various
containers, dispensing bottles, tubes, plastic parts for computer components, and
various molded laboratory equipment.
● Polycarbonate (PC) is a long-chain compound, formed by functional groups linked
to carbonate groups. It is considered thermoplastic, since it can be molded when
heated. The main applications of this compound are in CDs, filter containers, bottles,
showcases, partitions, etc.
● Polyurethane (PU) this polymer is composed of a chain of organic units connected
by urethane links. This option is widely used in metal sheets, car upholstery, thermal
insulation in waterproof clothing, casing, coatings, films, belts and frames.
● Polystyrene (PS) a homopolymer formed by the polymerization of the styrene
monomer. It is also part of the thermoplastic polymers examples, which gives it
greater flexibility. It can be used in the manufacture of thermal insulation, air-
conditioner fan cover, and toys, as well as machine and automobile parts.
● Polyvinyl chloride (PVC) is one of the most produced synthetic polymers in the
world. It can be characterized as rigid or flexible. Its main applications are in
partitions, translucent roof tiles, pipes and connections for water, window blinds,
sewers and ventilation.
● Polypropylene (PP) belonging to the group of polyolefins, polypropylene, also called
polypropene, is a thermoplastic compound produced by polymerization by adding the
propylene monomer. It can be applied in containers for food, chemicals, fibers,
oriented films, hospital material, among others.
● Polyethylene terephthalate (PET) is a thermoplastic composed of the reaction
between ethylene glycol and terephthalic acid. In general, this polymer is applied in
the manufacture of wires, fabrics, beverage packaging, cleaning products, brooms,
food, soft drinks, and others.
● Rubber is an elastomer polymer that is primarily characterized by its ability to regain
its original shape after being deformed. There are many different kinds of rubber, but
they all fall into two broad types: natural rubber and synthetic rubber.
● Nylons are generally produced by reacting difunctional monomers containing equal
parts of amine and carboxylic acid so that amides are formed at both ends of each
monomer. Used for textiles, carpets, molded parts, zip ties, conveyor belts, hoses,
polymer-framed weapons, seat belts, parachutes, ropes, and industrial cords.
● Silicone, also known as polysiloxane, is a high-performance elastomer made of
polymerized siloxanes (chains made of alternating silicon and oxygen atoms).Silicone
rubber is widely used in industries such as aerospace, automotive, construction,
medical, electricity, food processing, etc.

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