MACROMOLECULAR (POLYMER)

CHEMISTRY
 BASIC DEFINITIONS
• The word ‘‘polymer’’ is derived from the Greek words poly and meros, meaning many
and parts, respectively.

• Polymer: A substance composed of molecules that have long sequences of one or more
species of atoms or groups of atoms linked to each other by covalent bonds.
Peroxide
n H2C=CH2
120-200 °C
Ethylene Polyethylene

• Before 1920, the polymer was considered as physically-associated aggregates.

• In 1920, Hermann Staudinger said that polymers are composed of very large molecules
containing long sequences of simple units linked together by covalent bonds.
• In 1920, Staudinger introduced the word 'macromolecule' to describe polymers. He got
Noble Prize in 1953.

• Sometimes, polymer and macromolecule are used interchangeably.

• Macromolecules are materials with large sizes and high molecular

weights. While polymers also have large sizes and high molecular
weights but consist of repeating molecules in their chemical
structures.

• Polymer is formed by macromolecules.

Lignin (Macromolecule not polymer)
• All polymers are macromolecules, but all macromolecules are not
polymers.

• Polymers = Macromolecules, but Macromolecules ≠ Polymers

 Monomer, polymerization, degree of polymerization

• The repeating unit by which a polymer/macromolecule is formed is called Monomer.

• The process through which monomers linked together and formed a polymer is known
as polymerization.

• The number of repeating units in a polymer is known as ``degree of polymerization``.

• The most basic requirement for polymerization is that each molecule of monomer must
be capable of being linked to two (or more) other molecules of monomer by chemical
reaction, i.e. monomers must have a functionality of two (or higher).
 MONOMER FUNCTIONALITY AND POLYMER SKELETAL STRUCTURE
Linear polymerization

The functionality of a monomer is defined as the number of chain Branching polymerization

links it can give rise to. It is not necessarily equal to the number of
functional groups present in the monomer.

Polymers formed by chain polymerizations of olefinic monomers

contain a single C=C double bond; these monomers have a
functionality of two because each C=C gives rise to two chain links.

n H2C=CH2

Ethylene Polyethylene

If a monomer has a functionality greater than two, then this will lead to
the formation of branches and possibly the formation of a network
polymer, depending on the particular polymerization.

Difunctional Trifunctional Tetrafunctional Link formed by

Monomer monomer monomer polymerization
 POLYMER NOMENCLATURE
 IUPAC rules for determining polymer nomenclature are: (1) structure-based and (2) source-based names.
Monomer: CH3CH2CH2CH=CH2 Polymer: Structure-based name: Poly(1-propylethane-1,2-diyl)
(When the polymer structure is proven)
IUPAC name: Pent-1-ene
Source-based name: Poly(pent-1-ene)
(when the monomer can be identified)

Besides (a) derived from the place of origin of the material, such as Hevea brasilliensis—literally ‘‘rubber from Brazil’’—for
natural rubber.

(b) Nylons : according to the number of carbons in reactants. Nylon-6,6 is a product of 1,6hexamethylenediamine (6
carbons) and adipic acid (6 carbons).

(c) From their discoverer, Bakelite is discovered by Leo Baekeland in 1909.

(Bakelite)
CLASSIFICATION OF POLYMERS

(a) Based on the origin or source

(b) Based on the skeletal structure

(c) Based on molecular forces/structure (properties)…

 CLASSIFICATION OF POLYMERS: Based on the source or origin from which they are derived.

Polymers

Natural Semisynthetic Synthetic

These polymers are found in Prepared by chemical modification of Directly synthesized from
plants and animals. Examples are the natural polymers e.g., cellulose monomers by chemical
proteins, cellulose, starch, some derivatives such as cellulose acetate reaction. These Man-made
resins and rubber. (rayon) and cellulose nitrate. polymers are extensively
used in daily life as well as in
Industry.

Protein cellulose acetate

Starch
 Classification based on SKELETAL STRUCTURE

Polymers

Linear Branched Cyclic Network or crosslinked

From the definition, one can say that polymer has only a linear structure but it is not true. It has four different
structures: (1) Linear, (2) Branched, (3) Cyclic, and (4) Network (crosslinked)

(1) Polyethylene (2) Polyethylenimine (3) Cyclodextrin (4) Bakelite

 CLASSIFICATION OF POLYMERS (based on molecular forces/structure)

Polymers

Thermoplastics Elastomers Thermosets

Crystalline Amorphous

Thermoplastics: Often called Plastics. linear or branched polymers which become liquid upon the application
of heat, can be moulded (and remoulded) into any shape. They have both the melting temperature (Tm) and
glass transition temperature (Tg) e.g, Polyethylene, polypropylene, nylon, polystyrene, etc.

Elastomers are crosslinked rubbery polymers that can be stretched easily to high extensions and rapidly
recover their original dimensions when the applied stress is released. Crosslinking density is less. They degrade
rather than become fluid upon the application of heat. e.g., butyl rubber (polyisobutylene), polysiloxanes
(silicone rubber), polyurethane (spandex) etc.

Thermosets normally are rigid materials and are network polymers in which chain motion is greatly restricted by
a high degree of crosslinking. They degrade rather than become fluid upon the application of heat e.g.,
Vulcanized rubber, Bakelite, Epoxy resin etc. Generally insoluble.
 INTRODUCTION TO STEREOCHEMISTRY Of POLYMERIZATION

Not only the skeletal structure and the chemical composition of the repeating units, but also
the molecular microstructure strongly influences the properties of a polymer.

Variations in the geometric and configurational arrangements of the atoms in the repeat
unit, and the distribution of these different spatial arrangements for the repeat units along
the chain, are of particular importance.

Natta used the term ‘‘tacticity’’ to describe the different possible structures of a polymer.

Tacticity is the arrangement of the pendant groups in space; i.e., isotactic, syndiotactic,
atactic.

A pendant group or side group is a group of atoms attached to a backbone chain of a long
molecule, usually a polymer.
 TACTICITY OF POLYMERS
Chiral is the term used to describe objects which are non-superimposable on their mirror image (e.g. human hands and feet).
The simplest chiral molecules have an sp3-hybridized carbon atom to which four different groups are attached, which makes the
carbon atom asymmetric. e.g., CH2=CXY, where X and Y are two different substituent groups, there are two distinct
configurational arrangements of the repeat unit

Tacticity is the relative stereochemistry of adjacent chiral centers within a

macromolecule.

The existence of two isomeric forms of the repeating unit, and in particular their distribution along the polymer chain, are of
great significance.
In isotactic polymers, all the repeat units have the same configuration.
Isotactic
In syndiotactic polymers, the configuration alternates from one repeat
unit to the next.
Syndiotactic
In atactic polymers, the repeat units have an irregular or random
placement of the two configurations.
The commercial polypropylene is essentially isotactic. Due to its regular
structure crystallinity is ~ 65 % and has good mechanical properties. Atactic
In contrast, atactic polypropylene is unable to crystallize because of its irregular
structure and is a soft, wax-like amorphous material which has no useful
mechanical properties.
HOMOPOLYMER

Formally, homopolymers are polymers made of with one species of monomer. But repeat unit which may contain
one or more species of monomer unit. The monomer unit is referred as structural unit.

Polyethylene
COPOLYMER
Polymers those contain two or more different types of repeat unit or

Polymer formed by two different monomers.

Poly(hexamethylene adipamide)
 MOLAR MASS AND DEGREE OF POLYMERIZATION

The molar mass (M) of a polymer which is simply the mass of 1 mol of the polymer and usually is quoted in units
of g/mol or kg/mol.
The molar mass (M) of a homopolymer is related to the degree of polymerization x, which is the number of
repeat units in the polymer chain and M0 molar mass of repeating unit M = xM0
MOLAR MASS AVERAGES 𝒄𝒐𝒑 𝒋
Mean repeat unit molar mass for copolymer (𝑴𝟎 ) = Ʃ𝑿𝒋 𝑴𝟎
The number-average molar mass (𝑴 ഥ 𝒏 ) is defined as the sum of the products of the molar mass of each fraction
multiplied by its mole fraction, ഥ 𝒏 = Ʃ𝑿𝒊 𝑴𝒊
𝑴

where Xi is the mole fraction of molecules of molar mass Mi and is given by the ratio of Ni to the total number of
molecules. Ʃ𝑵𝒊 𝑴𝒊
ഥ
𝑴𝒏 =
Ʃ𝑵𝒊
The weight fraction Wi is defined as the mass of molecules of molar mass Mi divided by the total mass of all the
molecules present, 𝑵𝒊 𝑴𝒊
𝑾𝒊 =
Ʃ𝑵𝒊 𝑴𝒊

The weight-average molar mass (𝑴 ഥ 𝒘 ) is defined as the sum of the products of the molar mass of each fraction
multiplied by its weight fraction, Ʃ𝑵𝒊 𝑴𝟐 𝒊
𝑴ഥ 𝒘 = Ʃ𝑾𝒊 𝑴𝒊 ഥ𝒘 =
𝑴
Ʃ𝑵𝒊 𝑴𝒊
 MOLAR MASS AND DEGREE OF POLYMERIZATION
ഥ 𝒘 /𝑴
The ratio (𝑴 ഥ 𝒏 ) must by definition be greater than unity for a polydisperse polymer and is known as the
polydispersity or heterogeneity index (PDI).

In 2009 IUPAC recommend to use uniform polymer (instead of monodisperse) and non-uniform polymer
(instead of polydisperse). They recommended that polydispersity should be replaced by a new term, dispersity
(Đ).

ഥ 𝒘 /𝑴
The molar mass dispersity (ĐM = 𝑴 ഥ 𝒏 ) . The degree-of-polymerization dispersity (ĐX = 𝒙
ഥ𝒘 /ഥ
𝒙𝒏 ) and for most
polymers Đ = ĐM= Đx.
Ʃ𝑵𝒊 𝑴𝟑 𝒊
The z-average molar mass 𝑴 ഥ𝒛 =
Ʃ𝑵𝒊 𝑴𝟐 𝒊
The number-average and weight-average degrees of polymerization are given by
ഥ𝒏
𝑴 ഥ𝒘
𝑴
ഥ𝒏 =
𝒙 ഥ𝒘 =
𝒙
𝑴𝟎 𝑴𝟎

A typical weight-fraction molar mass distribution curve

 Problem
A sample of polystyrene is found to have a number-average molar mass of 89,440 g mol-I. Calculate the
number-average degree of polymerization of this sample. Assuming that the sample has a molar mass
dispersity of 1.5, calculate its weight-average molar mass.

Polystyrene repeating unit – C8H8 (M.W. = 12*8 + 1*8 = 104) ഥ 𝒘 /𝑴

ĐM = 𝑴 ഥ𝒏
Ʃ𝑵𝒊 𝑴𝒊 ഥ𝒏
𝑴
ഥ𝒏 =
𝑴 = 89440 ഥ𝒏 =
𝒙 = 89440/104 = 860 1.5 = Mw /89440
Ʃ𝑵𝒊 𝑴𝟎
Mw = 1.5*89440 = 134160 g/mol
Calculate the mean repeat unit molar mass for a sample of poly[ethylene-stat-(vinyl acetate)] that
comprises 12.9 wt% vinyl acetate repeat units. Given that its number-average molar mass is 39,870 g mol-
I, calculate the number-average degree of polymerization of the copolymer.

-(CH2-CH2)n-(CH2-CH(CH3COO)m-

M.W. =C2H4 = 28 g/mol , 87.1 g/28 g/mol =3.11 mol = 0.95 mol fraction
M.W. =C4H6O2 = 86 g /mol, 12.9 g /86 g/mol = 0.15 mol = 0.046 mol fraction

𝒄𝒐𝒑 𝒋
Mean repeat unit molar mass for copolymer (𝑴𝟎 ) = Ʃ𝑿𝒋 𝑴𝟎 = (0.95*28 + 0.046*86) = 30.55 g/mol
ഥ𝒏
𝑴
ഥ𝒏 =
𝒙 = 39870/30.55= 1305
𝑴𝟎
 calculate the degree of polymerization of a sample of polyethylene [ (CH2-CH2)n], which has a molecular weight
of 150,000 g/mol.
The molecular weight of a repeating unit, Mo= (12 x 2 + 1 x 4) g/ mol = 28 g/mol
DP = M/Mo
= 150,000 g/mol / 28 g/mol
= 5.35 x 103
The particular molecule contains 5.35 x 103 of repeat units.
TYPES OF POLYMERIZATION
CLASSIFICATION OF POLYMERIZATION REACTIONS
Previously, Carothers classified POLYMERIZATION REACTIONS, based upon comparison of the molecular
formula of a polymer, how they formed from monomer.

Condensation polymerizations: yield polymers with repeat units having fewer atoms than are present in the
monomers and involve the elimination of a small molecule (e.g. H2O, HCI).

Addition polymerizations: yield polymers with repeat units having identical molecular formulae to those of the
monomers from which they are formed.
n H2C=CH2

Ethylene Polyethylene
Later, it is divided into two ways:
(1) Step-growth polymerizations: Polymerizations in which the polymer chains grow step-wise by reactions
that can occur between any two molecular species (Condensation)

(2) Chain-growth polymerizations: Polymerizations in which a polymer chain grows only by reaction of
monomer with a reactive end-group on the growing chain, and usually require an initial reaction between the
monomer and an initiator to start the growth of the chain. (Addition)

The modern preference is (a) step polymerization and (b) chain polymerization.
Formation of Step Polymerization Chain Polymerization
Dimer

Trimer
Tetramer

Pentamer

Hexamer

Heptamer

Octamer

I= initiator, O= monomer and repeat unit, - =chemical link

Sl. Addition Polymerisation Condensation Polymerisation
No

1. Involves monomers contain unsaturated Involves monomers those are bifunctional or

group. trifunctional .
2. No elimination of small molecules like Elimination of small molecules like H2O, HCl, or
H2O, HCl, or CH3OH occurs. CH3OH occurs.
3. Polymers formed by this method have Polymers contains less number of atoms than the
identical number of atoms compared to the monomers reacted.
monomers reacted.
4. It can be described by the chain growth It can be described by the step-growth
polymerization. polymerization.
5. Formed products are called addition or Formed products are called addition or chain
chain polymers. polymers.
6. Example: Polyethylene from ethylene Example: Nylon 6, 6 from Adipic acid and
hexamethylene diamine
 Mechanism of addition reaction:
(a) Free-radical Polymerisation (b) Ionic Polymerisation (Cationic and Anionic), and (c) Co-ordination
Polymerization

(a) Free-radical Polymerisation

(b) Ionic Polymerisation (Cationic and Anionic)
(c) Co-ordination Polymerization
Buna-S
Examples of Addition Polymers
Synthesis, Properties and Uses
(Polypropylene, polystyrene,
PVC, Teflon)
 Addition Polymers: Synthesis of Polypropylene, polystyrene, PVC, Teflon

Ziegler-Natta Catalyst : [TiCl3 + Al(C2H5)2Cl] or [TiCl4 + Al(C2H5)3]

Polystyrene can be prepared by addition polymerization methods (free-radical or ionic)

60 °C

Properties: Polystyrene is a hard, brilliantly transparent, stiff resin. It is most widely used plastic. At
room temperature, the thermoplastic polymer is a solid but when heated above 100 °C it flows. It
becomes rigid again when it cools down. Polystyrene is insoluble in water. Polystyrene is non-
biodegradable. It is easily dissolved by many aromatic hydrocarbon solvents and chlorinated solvents.
It is widely used in the food-service industry as rigid trays, containers, disposable eating plates, bowls,
etc.

Uses
1. Medically it is used for sterilizing test tubes, diagnostic components.
2. In food service packaging as rigid trays, containers, disposable eating plates, bowls, etc.
3. As thermal insulation in refrigerators, freezers, etc.
4. Used in housing in all IT equipment such as Television, computer, etc.
Or using a persulphate
initiator through free-
radical polymerization.
 Examples of Condensation Polymers
Synthesis, Properties and Uses
(Nylon, PET, Polyurethane, and Synthetic
rubber )
 Nylon 6, 6 , Nylon 6 and Nylon 6, 10
Nylon 6,10:

Properties: Nylon 6/10 has good resistance to most solvents and to

dilute mineral acids. It also resists the environmental stress-cracking
action of salts such as zinc chloride.

Uses: are used in a wide range of applications including zip fasteners,

electrical insulators, precision parts, and filaments for brushes.
Nylon 6:

The first number in the name is the number of carbon atoms in Uses of Nylon
the diamine monomer and the second number is the number of •It is used for making strings of musical instruments and as a thread in bristles for
carbon atoms in the diacid (or diacid halide) monomer. toothbrushes.
•It is used in the synthesis of artificial fibres.
Nylon 6 fibres are tough, possessing high tensile strength, elasticity and lustre. •It is also used to make fishnet.
They are highly resistant to chemicals such as acids and alkalis. The fibres can
•In the industries, nylons are used for making Conveyor and seat belts, parachutes,
absorb up to 2.4% of water, although this lowers tensile strength. The glass
transition temperature of Nylon 6 is 47 °C. airbags, nets and ropes, tarpaulins, thread, and tents
 Terelene / Dacron / Polyethylene terephthalate (PET)
Polyethylene terephthalate (PET) is a condensation polymer of ethylene glycol and terephthalic acid. It is performed at 80-
300 °C using an acid catalyst.

Properties:
•Crystal clear polymer – It is a crystal clear polymer with good purity and health. You must have seen the sparkling PET
bottles with brilliant glass-clear presentation attract us.
•Purity – The products of PET taste good and comply with international food contact regulations.
•Safe – The objects made from PET like bottles are tough and virtually unbreakable therefore can be easily used for storage
and transportation. This polymer has a high impact and tensile strength which makes it ideal for carbonated products.
•Good barrier – PET products have low permeability to oxygen, carbon dioxide and water, therefore, it maintains the integrity
of products with good shelf life.
•Recyclable – PET polymer is recyclable and can be reshaped in different shapes.
•Good resistance power – PET products have good resistance against different chemicals such as acids, bases, etc.

Uses:
1.For the manufacturing of shopping bags, water bottles, containers, bags, microwaves containers, carpets and packaging films.
Polyurethane (PU or PUR) is an organic polymer
prepared by addition reaction. Most polyurethanes do
not melt upon heating and can, therefore, be classified
as thermosetting polymers.

Diisocyanate and diol: These reactions usually require

the presence of a catalyst (tert. amine) or some
ultraviolet light in order to overcome the activation
energy barrier.
Government Rubber (GR).
Butyl rubber
Properties: flexible, resistant to acid, alkali, ozone,
98% 2% biocompatible, insulating material.
Low temp ( -105 to -85 °C)
Lewis acid (AlCl3), cationic Uses: Tubeless tyres, inner tubes, football bladder,
polymerization glove-box gloves.

Aramid (Aromatic amide) Properties: Extremely strong, lightweight, and

resistant to corrosion and heat.
-(2n-1) HCl
n Uses: Making body of aircraft, bulletproof vests,
Condensation car brakes, boat, and body armor.
PE, LDPE, HDPE

HDPE: Branched, less

intermolecular attractive
forces, less crystalline,
higher volume and low
density

HDPE: Linear, more

intermolecular attractive
forces, crystalline, less
volume and high density.
Conductive polymer
• In 1977, Shirakawa, MacDiarmid, and Heeger were able to increase the conductivity of trans polyacetylene
samples, after doping, to a conductivity of about 1000 S/m or 1 S/cm. They got Nobel Prize in 2000.

• They found that oxidation with chlorine, bromine, or iodine vapor made polyacetylene film 109 times more
conductive than the non-treated film.

• This treatment with a halogen was called ‘‘doping’’ by analogy with the doping employed with semiconductors.
Other oxidizing doping agents have been used such as arsenic pentafluoride.

• Reducing agents such as metallic sodium have also been successfully used.

• This chemical doping transforms the polyacetylene from an insulator or semiconductor to a conductor.

• A critical structural feature of conductive polymers is the presence of conjugated double bonds. For
polyacetylene, every backbone carbon is connected by a stronger localized sigma bond. They are also
connected by a network of alternating less localized and weaker pi-bonds. While conjugation is present it is
localized enough to prevent ready delocalization of the pi-bond electrons.

• The dopants cause the introduction of sites of increased or deficiency of electrons. When a deficiency of
electrons, or holes, is created, electrons flow to fill this hole, with the newly created hole causing other
electrons to flow to fill the new hole, etc. allowing charge to migrate within and between the polyacetylene
chains.
• The objective of doping is to make electrons delocalize or to induce the delocalization of electrons in a
molecule.
Achieving this band-like structure in polymer makes it able to move the electron with it.
 Conducting Polymer

(Conduction due to (Blended polymers in which

extensive conjugation in Intrinsically conducting polymer Extrinsically conducting polymer blended materials are
the backbone in the responsible for conduction.)
polymer chain)

Conjugated Doped conducting Polymers Polymers

conducting polymers with with
polymers (n, p doped) conducting conducting
elements blends
(Polymers
(formed due to charge (Polymer (Nonconducting
contain
transfer agent (dopant) matrix and Polymer blended
alternative
with conjugated conducting with conducting
double bonds)
polymers fibers) polymer)
Conjugated conducting polymers
 Polyacetylene
Properties/Characteristics:
• Polyacetylene has been produced by several methods, many
utilizing the Zeigler–Natta polymerization systems.
• Both cis and trans isomers exist. The cis polyacetylene is
copper-colored with films having a conductivity of about 10-8
S/m. By comparison, the trans-polyacetylene is silver-colored
with films having a much greater conductivity on the order of
10-3 S/m.
• The cis isomer is converted into the thermodynamically more
stable trans isomer by heating (150 °C).
• Conductivity is greatly increased when the trans-
polyacetylene is doped (to about 102 -104 S/cm).

Trans -78 degree C cis, above 150 C trans

Cis
Uses: Doped polyacetylene is used
Na+(C10H7)-

Na+(C10H7)-
 Poly(3-hexylthiophene) (P3HT)

Oxidative coupling

Nitrogen gas, CHCl3

Properties/Characteristics:
• Poly(3-hexylthiophene) (P3HT) is a derivative of polythiophene.
• P3HT is popular because of its wide availability, low cost, well-known morphology, and easy processability.
• P3HT is a semicrystalline polymer and its backbone is made up of isolated rings and linear side chains. This structural
arrangement enables the freedom to sample conformational space.
• The glass transition temperature of P3HT is recorded as 12 °C and it has a high tensile modulus of 200 MPa to 1 GPa,
which varies in accordance with the synthesis method and the purity of the sample.

Uses:
It is used in the optoelectronic and electronic fields mainly in energy storage devices like solar cell.
Properties: Easy to synthesize,
low cost, and high environmental
stability.

Uses: Anticorrosion material, in

LED, smart window,
supercapacitor.
Doping of polyaniline using inorganic acid (HCl, H2SO4, and HNO3) and organic acid
(para-tolune sulfonic acid) improve the electrically conductive property.

Bipolaron