MODULE -4

Polymers and green fuels

POLYMERS
INTRODUCTION
The word polymer is derived from two Greek words: Poly means many, meros means
units. Polymers have become the integral part of our day-to-day life; it may be tooth brush, a
wrapper on an ice cream candy, an artificial heart valve, contact lens etc. To put in one sentence
– it is a plastic age. Polymers are extremely large molecules that are essential to our daily life.
They are a main constituent of our food. Ex: starch, protein, etc. our clothes polyester, nylons,
etc., and our body made up of nucleic acids, proteins.
Polymers are natural and synthetic compounds with very high molecular weights
(ranging from 10000 to 100000). Polymers possess wide range of properties due to their long
ranging properties they can be used to manufacture of wide variety of articles. Most of them
are economical and are very useful. Examples of high polymers are cellulose, starch, glycogen,
proteins and etc;

Important commercial polymers are:

(i) Resins: These are the base materials used in the manufacturing of plastics by
mixing with fillers, plasticizers, lubricants, coloring agents and stabilizers.
(ii) Plastics: The materials which soften at certain temperature and harden at
characteristic temperature are known as plastics.
(iii) Elastomers: These consist of zigzag or helical chain of molecules, undergo
elastic changes when subjected to external source, but regain their original
shape when the force is withdrawn.
(iv) Fibers: Fibers are long thin thread like polymer chain, which do not stretch or
undergo deformation like elastomers. The molecular chains are arranged in
parallel, spiral, helical pattern.

Basic definitions:
Polymer: A polymer is a large molecule formed by the repeated covalent linkage of small
units called monomers. Ex: Starch, Polyvinyl chloride, Polyethylene, Nylon 6, 6 and etc.
Monomer: Monomer is defined as a simple molecule or single unit representing in a polymer
with two or more binding sites either unsaturation or having two or more than two functional
groups through which it forms covalent linkages with other monomeric units to form the
macromolecule.
Polymerization: Polymerization is the process of formation of a polymer by the repeated
covalent linkage of monomeric units.

Classification of polymers: Polymers are classified into two types as follows;

i) Natural Polymers.
ii) Synthetic (artificial) polymers.
i) Natural polymers: These are the polymers obtained naturally by plants and animals.
Ex: Silk, wool, natural rubber, protein, starch, cellulose, etc.
ii) Synthetic polymers: These are artificially prepared polymers also known as manmade
polymers.
Ex: PVC, Nylon 6.6, Polythene, Phenol, Formaldehyde, Resin etc.
Synthetic polymers possess wide ranging properties. They may be elastic or rigid, soft
or hard, transparent or opaque. Some possess the strength of steel, but are very light and
chemically inert. These properties have made them indispensable materials in engineering and
technology. The progress in the field of electronics and electrical engineering is closely
associated with that of synthetic high polymers.
Homo polymers: If all the monomeric units are same in a polymer called homo polymer Ex:
Poly ethylene.
Hetero polymer: If the monomeric units are different in a polymer chain called hetero polymer
Ex: Nylon 6, 6.
 Figure 1.2.1: Structure of polymers

Types of polymerizations: Polymerization occurs basically by two different modes. They

are addition polymerization (chain polymerization) and condensation polymerization (step
growth).
i. Addition polymerization:- Addition polymerization is brought about by linking
together simple unsaturated molecules such as alkenes or substituted alkenes without
the elimination of any by products.
Eg: Ethylene to polyethylene nCH2 = CH2 → [-- CH2 -- CH2 --]n

Addition polymerization is initiated using small number of substances called initiators.

One of the important initiator is Ziegler–Natta catalyst {TiCl4 + Al (C2H5)3}. The

initiators impart regular structure to the polymer.

ii. Condensation polymerization:- Condensation polymerization is brought about by
linking together different monomer molecules accompanied by the elimination of small
molecules like H2O, NH3 and HCl. Thus the resulting material is a copolymer.
Eg: Condensation between a dicarboxylic acid [HOOC-X-COOH] and a dihydric
alcohol [HO-Y-OH] to give polyester with the elimination of water.
n[HOOC-X-COOH] + n[HO-Y-OH] → HO-[--OC-X-COO-Y-O]n-H + (2n-1)H2O
If a diamine is used instead of dihydric alcohol, the resulting polymer is a polyamide
like nylon. Nylon is made by the condensation of adipic acid [HOOC-(CH2)4-COOH]
with hexamethylenediamine [NH2-(CH2)6-NH2].

n H2N – (CH2)6 – NH2 + n HOOC – (CH2)4 – COOH →

H-[NH- (CH ) – NH – CO - (CH ) – CO]n-OH+ 2nH O

2 6 2 4 2

Nylon-6,6
In addition polymerization, the degree of polymerization (DP) ie., the length of the polymer
chain is determined by the time during which the chain grows. In condensation polymerization
the degree of polymerization is determined by the availability of the reactive groups at the end
of the chain.

Molecular weight of polymer: The average molecular weight of the polymer is the
product of average degree of polymerization and the molecular weight of repeating unit. It is
given by

̅ = 𝐷𝑃
𝑀 ̅̅̅̅ 𝑥𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑜𝑛𝑚𝑒𝑟

Average Molecular Weight is determined by the statistical methods i.e.

Number Average Molecular Weight:

Number average molecular weight is the mole fraction of molecules in a polymer sample. It is
a way of determining the molecular mass of a polymer. It gives the average of the molecular
masses of the individual macromolecules. In other words, it is the total weight of the sample
divided by the number of molecules in the sample. ̅ 𝑛 = ∑ 𝑛𝑖𝑀𝑖/ ∑ 𝑛𝑖
𝑀
Where, Mn is the number average molecular weight, Ni is the number of molecules of
molecular mass Mi, and Mi is the weight of a particular molecule of the sample.

Weight Average Molecular Weight:

Weight average molecular weight is the weight fraction of molecules in a polymer sample. It
is another way of determining the molecular mass of a polymer. It gives the average of the
molecular masses of the individual macromolecules in the polymer sample. We can find this
parameter using the following equation: ̅ 𝑤 = ∑ 𝑛𝑖𝑀𝑖 2 / ∑ 𝑛𝑖𝑀𝑖
𝑀
Where Mw is the weight average molecular weight, Ni is the number of molecules of molecular
mass Mi.

Polydispersity index: In order to have an idea about the homogeneity of a polymer, the term
polydispersity index is used. It is the ratio of mass average molecular mass to the number
average molecular mass. PDI=Mn/Mw.
For natural polymers, PDI is usually equal to one which means that they are monodisperse.
Such polymers are more homogeneous.
Synthetic polymers on the contrary generally have PDI > 1 which means that they are less
homogeneous.

NUMERICAL PROBLEMS
1. In a polymer sample, 20% of molecules have molecular mass 15000 g/mol, 35% of
molecules have molecular mass 25000 g/mol, remaining molecules have molecular
mass 20000 g/mol, calculate the number average and weight average molecular
masses of the polymer, and PDI.

Solution: Given from the problem; n1 = 20 and M1 = 15000 g/mol

n2 = 35 and M2 = 25000 g/mol
n3 = 45 and M3 = 20000 g/mol
The number average molecular mass of the polymer is given by,
Mn = N1xM1 + N2XM2 + N3M3
N1+N2+N3
(20x15000) + (35x25000) + (45x20000)
= --------------- ---------------- ------------
20 + 35 + 45

= 300000+ 875000+ 900000 / 100 = 2075000 / 100 = 20750 g/mol

The weight average molecular mass of the polymer is given by,

Mw = N1xM12 + N2XM22 + N3M32

N1xM1 + N2XM2 + N3M3
20x(15000)2 + 35x(25000)2 + 45x(20000)2
= --------------- ---------------- ----------------
20x15000 + 35x25000 + 45x20000
= 21385 g/mol
Polydispersity Index, PDI = Mw / Mn.
PDI = = 21385 / 20750 = 1.03
PDI >1, the given polymer is less homogeneous and polydisperse in nature.

2. A polymer sample contains, 5 molecules having a molecular weight of 2000, 4

molecules having a molecular weight of 3000 and 3 molecules having a molecular
weight of 4000. Calculate the number average and weight average molecular
weight.
 Solution: Given from the problem; n1 = 5 and M1 = 2000
n2 = 4 and M2 = 3000
n3 = 3 and M3 = 4000
The number average molecular weight of the polymer is given by,

Mn = N1xM1 + N2XM2 + N3M3

N1+N2+N3
(5x2000) + (4x3000) + (3x4000)
= ------------ -------------- -------------
5 + 4 + 3

= 34000 = 2833.33 g/mol

12
The weight average molecular weight of the polymer is given by,

Mw = N1xM12 + N2XM22 + N3M32

N1xM1 + N2XM2 + N3M3

5x(2x103)2 + 4x(3x103)2 + 3x(4x103)2

= --------------- ------------- --------------
5x(2x103) + 4x(3x103) + 3x(4x103)

= 20x106 + 36x 106 + 48x106

10x103 + 12x103 + 12x103

= 104 x 106 = 3.058823 x 103 = 3058.823 g/mol

34 x 103

CONDUCTING POLYMERS
“An organic polymer with highly delocalized pi-electron system, having electrical
conductance of the order of a conductor is called a conducting polymer”. The concept of
conductivity of conjugated polymers is now extended from polyacetylene to the number of
conjugated polymers such as polypyrrole, polythiophene, polyphenylene and polyanilene.
Conducting polymers are found to be highly promising materials for various
applications with inherent advantages such as flexibility, ease fabrications, stability, ease of
processability and above all with the low-cost conducting polymers are considered to be better
than conventional conducting inorganic materials.
The conducting polymers are synthesized by doping, in which charged species are
introduced in organic polymers having pi-back bone. The important doping reactions are;
Oxidative doping (p-doping), Reductive doping (n-doping) and Protonic acid doping (p-
doping).
1. Oxidative doping (p-doping): In this process, pi-back bone of a polymer is partially
oxidized using a suitable oxidizing agent. This creates positively charged sites on polymer
back bone, which are current carriers for conduction. The oxidizing agents used for this
process are iodine vapour, I2 in CCl4, perchloric acid and benzoquinone. Eg: Synthesis of
conducting polyacetylene.
2. Reductive doping (n-doping): In n-doping, pi-back bone of a polymer is partially reduced
by a suitable reducing agent. This creates negatively charged sites on polymer back bone.
These sites are responsible for conduction. The most common reducing agent used for n-
doping is a solution of sodium naphthalide in tetra hydro furan. Eg: Synthesis of conducting
polyacetylene.
3. Protonic acid doping (p-doping): In this technique, current carrying charged species (-
ve/+ve) are created by the protonation of imine nitrogen. Eg: synthesis of polyaniline.

Synthesis of conducting polyacetylene:

When acetylene gas is bubbled through heptane/toluene solvent containing Ziegler-Natta
catalyst, Polyacetylene solid film is formed at the gas-liquid interface. Cis polymer forms at
low temperature (-78 °C). Isomerization to the more stable trans form takes place on rising the
temperature of the film. Conductivity of doped cis films is two or three times greater than the
trans analogues.

[The Ziegler-Natta catalysts usually contain many mixtures of halides belonging to

transition metals like titanium, vanadium, chromium, zirconium and organic derivatives
of non-transition metals especially that of alkyl aluminium compounds. Ex: A mixture of
titanium tetrachloride (TiCl4) and triethylaluminum (Al(C2H5)3)], A mixture of tetra
butoxy titanium (Ti(OBu)4) and triethylaluminum (Al(C2H5)3)].
Conduction mechanism of polyacetylene:
The conductivity of these polymers is believed to be a result of the creation of charge-transfer
complexes between the polymer and halogen. Charge transfer occurs from the polymer to the
acceptor compound; the polyacetylene chain acts as a cation and the acceptor as an anion. In
the first step, polymer chain is partialy reduced by using a mild reducing agent such as Na-
napthalide in tetrahydrofuran (THF) as solvent. In this case, one electron is added to polymer
chain forming a free radical anion which is called as polaron. Similarly, in the second step
another free radical-anion is formed which is called as bipolaron. The radicals migrate towards
each other and combine to form one double bond.This bipolaron on rearrangement gives a
conducting polymer with two negative chargers as carriers of electric current. Negative charges
are compensated by Na+ ions and polymer as a whole is electrically neutral. Since negative
charges are the carriers of electric current, this type of doping is called as n doping.

Applications:
1. Polyacetylene has no commercial applications.
2. Polyacetylene as a conductive organic polymer led to many developments in materials
science.
3. Doped polyacetylene offers a good electrical conductivity, hence can be used as electrode
material in light weight rechargeable batteries.
4. I3-dopped acetylene can also be used in biosensors.

Synthesis of graphene oxide by Hummer’s method

Graphene oxide synthesis by Hummer’s method In this method, the oxidation of graphite to
graphitic oxide is accomplished by treating graphite with a water-free mixture of
concentrated sulfuric acid, sodium nitrate and potassium permanganate. The entire process
requires less than two hours for completion at < 45 ℃

Procedure:
1. The graphitic oxide was prepared by stirring 100 g. of powdered graphite flake and 50
g. of sodium nitrate into 2.3 liters sulfuric acid.
2. The ingredients were mixed in a 15-liter ice-cooled battery jar a safety measure.
During mixing 300 g. of potassium permanganate was added to the suspension
[Temperature should not exceed 20 ℃ as it may cause explosion].
3. The ice-bath was then removed and the temperature of the suspension brought to 35 ±
30 for 30 minutes.
4. As the reaction progressed, the mixture gradually thickened with a diminishing in
effervescence.
5. At the end of 20 minutes, the mixture became brownish grey colored paste with
evolution of only a small amount of gas.
6. At the end of 30 minutes, 4.6 liters of water was slowly stirred into the paste, causing
violent effervescence and an increase in temperature to 98 o C . The diluted
suspension, now brown in color, was maintained at this temperature for 15 minutes.
7. The suspension was then further diluted to approximately 14 L with warm water and
treated with 3%, hydrogen peroxide to reduce the residual permanganate and
manganese dioxide to colorless soluble manganese sulfate.
8. Upon treatment with the peroxide, the suspension turned bright yellow and it was
filtered to get yellow-brown filter cake. [The filtering was conducted while the
suspension was still warm to avoid precipitation of the slightly soluble salt of mellitic
acid formed as a side reaction].
 9. The yellow-brown filter cake was washed three times with a total of 14 liters of warm
water, the graphitic oxide residue was dispersed in 32 liters of water to approximately
0.5% solids.
10. The remaining salt impurities were removed by treating with resinous anion and
cation exchangers.
11. The remaining salt impurities were removed by treating with resinous anion and
cation exchangers.

Properties
1. Graphene is a two-dimensional, crystalline allotrope with a hexagonal lattice
structure made from pure carbon atoms.
2. They are best known for its unique properties containing high optical transparency,
the best heat conductivity at room temperature and the ability to be flexible all within
a strong, nano-sized material.
3. Graphene is recorded as having break strength of 42 N m −1, a Young's modulus of
1.0 TPa (terapascal) and an intrinsic tensile strength of 130.5 GPa (gigapascal).
4. Graphene is an electrically conductive material with high electron mobility and
electrical conductivity (consisting of 2D layers of sp2 carbon one atom thick).
5. Incorporation of rGO (reduced graphene oxide) into polymers to improve their thermal
conductivity.

Applications
1. The large, convenient production of GO has led to its emergence as a precursor for
fabricating transparent conductive films (TCFs).
2. GO is hydrophilic, stable and homogeneous colloidal suspensions in aqueous or polar
organic solvents allows for an easy dispersion process in producing TCFs on a
substrate.
3. Using monolayer GO increases the transparency of thin films due to the lower
concentration of GO in the dispersion which enables thin films to possibly obtain
higher transparency and conductivity.
4. In fact, TCFs made from GO can even have potential to replace indium tin oxide
transparent conductors.
5. Meanwhile, functionalized GO can be used as fluorescence and photo-luminescent
means in cellular imaging. The dye loaded silicon wrapped with GO is significant for
applications regarding fluorescence imaging in vitro.
6. Other applications have been applied to bio-sensing, detection and drug-carrier
materials based on its fluorescence.