EFT1263: CHEMISTRY IN APPLIED SCIENCE

L11: INTRODUCTION OF
ORGANIC CHEMISTRY AND
FUNDAMENTAL OF POLYMER
CHEMISTRY (II)
L11: PENGENALAN KIMIA ORGANIK
DAN ASAS KIMIA POLIMER (II)

Nor Shahida binti Shafiee @ Ismail

PhD (Organic Geochemistry)
Faculty Of Earth Science
Universiti Malaysia Kelantan (Jeli Campus)
shahidashafiee@umk.edu.my
L10 & 11 OUTLINE:
• Part I
• Alkanes, Alkenes, Alkynes, Alcohols, Ketones, Aldehydes, Carboxylic acids, Aromatic
compounds and Amines.
• Part II
• Definition, classification and naming of polymers.
• Processes of polymer synthesis: bulk, solution, suspension
• Thermosets: fenoplast, aminoplast, unsaturated polyesters, polyurethanes epoxy resins.
• Structures of polymers from diene monomers
 POLYMERS
• By definition, polymers are large molecules made by bonding
(chemically linking) a series of building blocks.
• The word polymer comes from the greek words for “many
parts.” Each of those parts is scientists call a monomer (which
in greek means “one part”).
• Many objects in daily use from packing, wrapping, and building
materials include half of all polymers synthesized. Other uses
include textiles, many electronic appliance casings, CD's,
automobile parts, and many others are made from polymers. A
quarter of the solid waste from homes is plastic materials

Exist in countless forms

Chemical structure

Physical properties

Mechanical behavior

Thermal characteristics
 Monomer and polymer

• "Mer" is used to indicate a building block.

• a monomer (single mer), a dimer (two mers), a
trimer (three mers), and a polymer (many
mers).
• The polymer grows as the result of successive
reactions of the monomers that lengthen the
polymer chain.
• Polymers are macromolecules built up by the
linking together of large numbers of much
smaller moleculs.
• The small molecules which combine with each
other to form polymer molecules are term
monomers

Polymerisation: the process of linking the repeating units

(monomers) is termed as polymerisation
 CLASSIFICATION OF POLYMERS Natural polymer

Based on origin of
Semi-synthetic
source

Synthetic polymer

Linear polymer

• Polymers cannot be classified under one Branched chain

Based on structure
category because of their complex structures, polymer

Cross-linked
different behaviours and vast applications.

Classification of polymers
polymer

• We can, therefore, classify polymers based on Thermoplastic

the following considerations. Based on

Thermosetting
molecular force

Elastomer

Addition polymer
Based on mode of
polymerization
Condensation
polymer

Organic polymer
Based on
backbone of the
chain
Inorganic polymer
Homo polymer and copolymer
• Heteropolymer or co-polymer: it consists of different
Polymer can be classified based on their composition @
type of monomer units.
repeating unit
• Homopolymer: in this type, a single type of monomer unit is • When two or more different monomers together to
present. polymerise their result is called copolymer

• Homopolymer are synthesized from a single type of • Types of copolymer

monomer • Statistical copolymer

• Homopolymer are consist of chain with identical bonding • Alternating copolymer

linkage to each monomer unit. • Block copolymer
• Graft copolymer

Homopolymers Copolymers
Definition Made up of the Made up of two
same monomer or more different
type of monomers
Example A-A-A-A-A A-B-A-B-A
Straight chain polymer and cross linked polymer

Polymer can be classified based on their structure.

• Linear polymers: the structure of polymers containing long and straight

chains fall into this category.
• Branced polymers: When linear chains of a polymer form branches,
then, such polymers are categorized as branched chain polymers.
• Crosslinked polymers: They are composed of bifunctional and
trifunctional monomers. They have a stronger covalent bond in
comparison to other linear polymers.
 Thermoplastic and thermosetting polymers
Polymer can be classified based on thermal behavior.
Strong cross-link
Strong link into bond
Thermoplastic polymers polymer chain Thermosetting polymers

• The polymers that undergo chemical changes and

• The polymers that soften on heating and which can be
converted into any shape on cooling are called
thermoplastics.(weak intermolecular polymer chain.
• No cross-link between chains.
• The process of heating, reshaping and retaining the
shape on cooling can repeated several times without
affecting their properties much. Soften when heated.
• Linear or branched polymer
cross-linking on heating and become permanently
hard, rigid and infusible on cooling are called
thermosetting polymers
• They do not soften on reheating instead they
undergo degradation
• Strong covalent bonds between polymer chains.
• Remain hard when heated.
Thermoplastic polymers
• Thermoplastic polymers are known as thermoplast.
• Solid material at room temperature
• Viscous liquids when heated
• When heated (and eventually liquefy) and harden when cooled
processes are totally reversible and may be repeated.
• On a molecular level, as the temperature is raised, secondary
bonding forces are diminished so that the relative movement of
adjacent chain is facilitated when stress is applied.
• Irreversible degradation results when the temperature of a molten
thermoplastic polymer is raised to the point at which molecular
vibration become violent enough to break the primary covalent
bonds.
• Eg. Polyethylene, polyvinylchloride, polypropylene, polystyrene and
nylon.
Thermosetting Polymers
• A thermoset is a type of plastic that undergoes a chemical
change during production that cannot be repeated or
reversed.
• Elevated temperature produce a chemical reaction that
hardens the material.
• If reheated, thermosets degrade and char rather than soften.
• High cross-linked by covalent bonds (polymer network)
• Thermosetting polymers initially begin as linear chains
• Heat and pressure initiates the cross-linking process
• Cross-linking results in permanent chemical bonding of the
individual polymer chains to one another
• Upon heating, unlike thermoplastics, thermosets remain solid
until temperature reaches the point where thermoset begins to
degrade.

• Eg. Phenolic resins, amino resins, polyester resins, silicone

John Wiley & Sons, Inc. M.O Groover. Fundamental of Modern
resins, epoxy resins, and polyurethanes etc. manufacturing
Thermoplastic vs Thermosetting
 Natural polymers and Synthetic polymer
Polymer can be classified based on their Source Origin.
Natural polymers.
• Polymer that found and occur naturally are
known as natural polymers (found in plants
and animals).
• Polypeptides in protein-silk, collagen,
keratin.
• Polysaccharides-cellulose, starch, glycogen.
• Nucleic acid, DNA and RNA

Synthetic polymers.
• These are man-made polymers.
• Plastic is the most common and widely used
synthetic polymer.
• Elastomers - solids with rubber-like qualities
• Rubber (carbon backbone often from
hydrocarbon monomers)
• silicones (backbone of alternating silicon and
oxygen atoms).
• Fibers
• Solid materials of intermediate characteristics
• Gels or viscous liquids
 Natural Polymers: Organic & inorganic
• Organic polymers play a crucial role in living things,
providing basic structural materials and participating in vital
life processes.
• For example, the solid parts of all plants are made up of
polymers.
• These include cellulose, lignin, and various resins. Cellulose
is a polysaccharide, a polymer that is composed of sugar
molecules.
• Lignin consists of a complicated three-dimensional network of
polymers.
• Wood resins are polymers of a simple hydrocarbon, isoprene.
• Another familiar isoprene polymer is rubber.
• Many inorganic polymers also are found in nature,
including diamond and graphite.
• Both are composed of carbon.
• In diamond, carbon atoms are linked in a three-
dimensional network that gives the material its
hardness.
• In graphite, used as a lubricant and in pencil “leads,” the
carbon atoms link in planes that can slide across one
another.

Cellulose polysilanes

DNA polyphosphazenes
Natural Polymers: Natural rubber

• Natural rubber is a natural polymer.

• Latex is a milk like liquid that flows
out after the bark of the rubber tree
is cut. Latex is a mixture of rubber
particles and water.
• Formula of rubber is (C5H8)n, where
n is about 10,000.
• The monomer of natural rubber is
isoprene, or 2-methyl-1-3,-
butadiene (IUPAC).
polymerisation
 Synthetic polymers
• Synthetic polymers are polymers made in industry
from chemical substances.
• Synthetic polymers can be synthesized or artificially
created by man in the lab. Through scientific Nylon is made by condensation polymerization from the monomers
research, scientist are able to copy the structures of dicarboxylic acid and diamine.
natural polymers to produce synthetic polymers.
They are commercially produced in large quantities
to satisfy man's needs
• Many of the raw materials for synthetic polymers are
obtained from petroleum, after the refining and
cracking processes.
• Synthetic polymers are usually referred to as
“plastics”.
• The most common types are nylon and polythene,
fibre etc..
• Synthetic polymers are produced in different types of
reactions.
https://www.youtube.com/watch?v=c7ihpZhCj6k&t=251s
 Polymer Nomenclature
Difficulties
 variations in chain length
 Mw/Mn (PDI)
 stereocenter patterns
 iso-, syndio, attactic, etc.
 d-l-d-l-d-l-d-l
 copolymer arrangement/pattern
 regular, random, block, etc. A-B-A-B-A-B
 structure irregularities
 branching, impurities
 imperfections
 head-to-tail, head-to-head, mmmm, etc.
Types/methods of nomenclature
• Source name (more common use) To be based on names of corresponding
monomer
eg. Polyethylene, Poly(vinyl chloride)
• IUPAC name based on Constitutional Repeating Unit (CRU), systematic name.
eg. Poly(methylene, Poly(oxyethylene)
• Functional group name, according to name of functional group in the polymer
backbone.
eg. Polyamide, Polyester
• Others;
• based on monomer name (polystyrene)
• Structure based (more systematic)
• emphasizes actual structure (polymethylene)
• used in both source and structure names
• Abbreviations and acronyms
• PMMA poly(methyl methacrylate)
• Trade names
• marketing and technological literature
Polymer Nomenclature: Source-based names
• Most polymer names used by polymer scientists are source-
based; i.e., they are based on the common name of the
reactant monomer, preceded by the prefix “poly.” Source based (homopolymers)

For example, • Use name of actual monomer

• polystyrene is the most frequently used name for the polymer • Polymonomer, i.e. Polyethylene

derived from the monomer 1-phenylethene, which has the • Common names may be used for
monomer
common name styrene.
• Use ( ) when two words or substituents
Eg. Poly(vinyl chloride), poly(1,2-
difluoroethylene)
• Use ( ) in cycle as needed
Polymer Nomenclature: Source-based names
• To name a polymer, prefix poly to the name of the monomer from which the polymer is
derived
• if the name of the monomer is one word. No parens (), are necessary
• For more complex monomers or where the name of the monomer is two words, enclose
the name of the monomer in parens (), for example poly(vinyl chloride)
Common
vs IUPAC
name
 PROCESSES OF POLYMER SYNTHESIS:
• The process of converting a monomer or mixture
of monomers into polymer is known as
polymerisation. Addition polymerisation

• There are two main ways to conduct • Bulk polymerisation

polymerisation • Solution polymerisation
• Addition polymerisation (chain-growth • Suspension polymerisation
polymerisation) • Emulsion polymerisation
• repeating units and monomers are same
• It applies to monomers having double bond or ring Condensation polymerisation
structure.
• Melt polymerisation
• Condensation polymerisation (step-growth
• Solution polymerisation
polymers)
• repeating units and monomers are not equal, to be
split out small molecule.
• It applies to monomers with functional group ( -
COOH,-COOR, -COCI, -OH, -OH, -NH2, -CHO, -
NCO, epoxy.
Addition polymerisation • Addition polymer is a polymer formed by chain addition
reactions between monomers that contain a double bond.
• A carbon – carbon double bond is needed in the
monomer.
• A monomer is the small molecule that makes up the
polymer.The polymer is the only product Involves the
opening out of a double bond.
• The conditions of the reaction can alter the properties of
the polymer.
• Reaction proceeds by a free radical mechanism
• Oxygen often used as the initiator
• Addition polymerisation Conditions are high pressure and
an oxygen initiator (to provide the initial free radical).
• Eg.Monomer = ethene
• Polymer = poly(ethene)

https://www.youtube.com/watch?v=1ZUg6ZC3ltA
 Bulk polymerisation technique

• The simplest technique, and gives the highest-purity polymer.

• Carried out by adding a soluble initiator to pure monomer in liquid
state.
• The initiator should dissolve in the monomer.
• The reaction is initiated by heating or exposing to radiation.
• As the reaction proceeds the mixture becomes more viscous.
• The reaction is exothermic and a wide range of molecular masses are
produced.
• An increase in temperature will increase the polymerization rate and,
therefore, generate additional heat to dissipate.
• Heat removal becomes particularly difficult near the end of the
polymerization when viscosity is high.
• Because high viscosity limits the diffusion of long-chain radicals
required for termination. This means -radical concentration will
increase and, therefore, the rate of polymerization also will increase.
• Bulk polymerization is carried out in the absence of any solvent or
dispersant and is thus the simplest in terms of formulation.
Solution polymerisation technique

• a method of industrial polymerization.

• A monomer is dissolved in a non-reactive solvent that

contains a catalyst.

• Heat removal during polymerization can be facilitated by

conducting the polymerization in an organic solvent or
preferably water which has both cost and handling
advantages as well as high thermal conductivity

• The requirements for selection of the solvent are both the

initiator and monomer be soluble in it have acceptable
chain-transfer characteristics suitable melting and boiling
points for the conditions of the polymerization and any
subsequent solvent-removal step.

• Examples of suitable organic solvents include aliphatic and

aromatic hydrocarbons, esters, ethers, and alcohols.
A catalyst is substance i.e a element or a compound
that increases the rate of chemical reaction
Emulsion polymerisation technique
• This technique is used for the production of large number of
commercial plastic and elastomer.
• The system consist of water insoluble monomer, dispersion
medium and emulsifying agents or surfactant (soap & detergent)
and a water soluble initiator (potassium persulphate/H 2O2 etc)

• The monomer is dispersed in the aqueous phase not as discrete

droplets but as a uniform emulsion.
• The emulsion of monomer in water is stabilised by surfactant.
Where a surfactant has a hydrophilic and hydrophobic end in tits
structure.
• When it is put into a water, the surfactant molecules gather
togather into aggregates called micelles.
• The hydrocarbon tails (hydrophopic orient inward and head
(hydrophilic) orient outwards into water.
• The monomer molecules diffuse from monomer droplets to
water and from water to the hydrocarbon cebtre of micelles.
Condensation polymers • Monomer A + monomer B polymer + small molecule (normally
water).
• Common synthetic condensation polymers include polyesters (the
ester linkage) and polyamides (the amide linkage as in proteins).

Condensation polymerisation
involves monomers reacting
polyesters
together and releasing a small
molecule in the process.

• Involves 2 monomers that have different

functional groups.
• They also involve the elimination of water or
another small molecule.
• There are synthetic condensation (e.g Nylon.
Polyester etc) and natural condensation (e.g
cellulose, cotton, wool, silk etc.)
 THERMOSETS
• Thermosetting plastics are low-molecular-weight monomers • the major thermosetting plastics, in order of
and oligomers with multiple reactive functional groups, which decreasing market volume, are
can be poured, melted, or squeezed into the shape we want polyurethanes, phenol-formaldehyde,
and then solidified again by chemical reactions forming urea-formaldehyde, and polyesters.
multiple primary covalent bonds that cross-link them into three- • More specialized thermosets include
dimensional molecules of almost infinite molecular weight. melamine formaldehyde, furans, “vinyl
• These are irreversible chemical processes that cannot be esters,” allyls, epoxy resins, silicones, and
repeated. polyimides.

• They account for 15 percent of the plastics industry, they • While they may sometimes compete with
include a great variety of chemical reactions and conversion each other and with thermoplastics, for the
processes, and they go into a very broad range of final most part, each of them has unique
products. properties and fills unique markets and
applications
• Thus, there is a great difference between thermoplastics and
thermosets, both in terms of materials chemistry and
applications, and in terms of the mechanical processes used to
produce finished products.
Polyurethanes
• polyurethanes are the leading family of thermosetting
plastics.
• Of the 100 or so families of commercial plastics, they are
the most versatile, finding use in rigid plastics, flexible
plastics, elastomers, rigid foams, flexible foams, fibers,
coatings, and adhesives.
• They offer unique qualities in processability, strength,
abrasion resistance, energy absorption, adhesion,
recyclability, and resistance to oxygen, ozone, gasoline,
and motor oil.
• Thus, they find major use in appliances, autos, building,
furniture, industrial equipment, packaging, textiles, and
many other fields.
• Their versatility comes from the range of liquid
monomers and oligomers that can be mixed, poured,
polymerized, and cured in a minute or so at room
Polyurethanes products
temperature.
Thermoset Type: Epoxy resin (ER)
• Epoxy Resins Epoxy resins enjoy a
combination of fast, easy cure, high adhesion
to many surfaces, and heat and chemical
resistance, which leads to a U.S. market of
600 million lb/yr with a wide range of uses in
plastics, coatings, and adhesives.
• The name “epoxy resins” is applied loosely
both to epoxy monomers and prepolymers,
and also to the cured thermoset final products
Unsaturated polyesters.

• Unsaturated polyesters are the fourth largest family of

thermosetting plastics, with a U.S. Market volume of 2
billion lb/yr.
• They are often called thermosetting polyesters or alkyds.
• In commercial use for 60 yr and now fairly mature, they
are the largest class of reinforced plastics (table 3.16),
popularly used in building panels, chemical equipment,
boats, cars, buses, trains, and planes.
STRUCTURES OF POLYMERS FROM DIENE MONOMERS
END OF PART II