Polymer
Polymer
POLYMERS
Introduction :
Polymers form the backbone of the modern civilization and arc the chief products of
the modern chemical industries. Polymers. (Greek poly means many and mer means
unit or part), are very high molecular mass compounds, each molecule of which
consists a very large number of simple structural units joined together through
covalent bonds in regular fashion. The simple molecules from which the repeating
structural units are derived are called monomer, and the process by which these simple
molecules, i.e., monomers are converted into polymers is called polymerisation.
Classification of Polymers :
They are available in nature (animals or plants). Examples of such polymers arc:
natural rubber (1, 4-cis-polyisoprene), natural silk, cellulose, starch, proteins. etc.
Polymers such as polysaccharides (starch, cellulose), proteins and nucleic acids
etc.. which control various life processes in plants and animals are called
biopolymers.
Polymers which can be easily softened when heated and hardened with little change
in their properties. They can be softened or plasticized repeatedly on application of
thermal energy, without much change in properties if treated with certain precautions.
e.g. polyolefins, polystyrene, nylons, linear polyesters and polyethers, polyvinyl
chloride, Teflon etc. They normally remain soluble and fusible after many cycles of
heating and cooling.
Certain plastics do not soften very much on heating. These can be easily softened by
the addition of some organic compound which are called plasticizers. For example.
Polyvinyl chloride (PVC) is very stiff and hard but it is made soft by adding plasticizer
e.g. Dioctyl phthalate (DOP).
(C) Fibres :
Polymers which have strong intermolecular forces between chains. These forces are
either H–bonds or dipole-dipole interaction. These are closely packed with a high
tensile strength and less elasticity. Therefore, they have sharp melting points. These
polymers are long, thin and thread like and can be woven in fabrics. Some of the
example of these polymers are Nylon-66. Dacron. etc.
(D) Elastomers :
Polymer with elastic character like rubber. In elastomers the polymer chains are bound
together by weakest intermolecular forces. These are easily stretched by applying small
stress and regains its original shape when stress is removed. For example, natural
rubber.
The natural rubber is a gummy material which has poor elasticity. However, when
natural rubber is heated with 3-5% sulphur, it becomes non-sticky and more elastic.
This process is called vulcanization and product formed is vulcanized rubber which
has better tensile strength and resistance to abrasion than natural rubber.
They are formed from olefins, diolefinic, vinylic and related monomers. They all have
–C–C– linkages along the main chains of the polymer molecules and usually no other
atom appears in the main chain. These polymers are formed by simple additions of
monomer molecules to each other in quick succession by a chain mechanism. This is
known as addition polymerization or chain–growth polymerization. The examples
of such polymers are: polyethylene, polypropylene, polystyrene, polybutadiene,
polyvinyl chloride. etc.
A polymer formed by the condensation of two or more than two different monomers
with the elimination of the species like water, ammonia, hydrogen chloride or alcohol
etc., is called condensation polymer. In this type of polymerization generally each
monomer contains two functional groups.
Besides –C–C– linkages, they contain atoms such as O, N, S, etc., at regular intervals in
the main chain. The process of their formation is called condensation polymerization
or step–growth polymerization. Polyamides. polyesters, polyethers. polyurethanes,
terylene, bakelite, epoxy resins and alkyd resins, etc., are examples of condensation
polymers.
These can schematically be represented by lines of finite lengths with well packed
structure, having high densities, high tensile (puffing) strength and high melting
points. They are formed from olefinic, vinylic or related polymerization under suitable
conditions or by condensation polymerization of bifunctional monomers. Linear
polymers such as high density polyethylene, polyvinyl chloride, polystyrene. Nylon-6,
etc. are soluble and fusible.
They can be schematically represented by lines of finite lengths with the short or long
branch structures of repeated units. The branches appear as a consequence of
uncontrolled side reactions during polymerization or by design of polymerization.
Branched polymers are usually more readily soluble and fusible than linear polymers
of comparable chain length or molecular weight. For example, low density polythene,
glycogen, starch etc.
(C) Cross-linked or Network Polymers :
If N1, N2, N3 ... are the number of molecules with molecular masses
̅ N = N1M1+N2M2+N3M3+ …
M N +N +N
1 2 3
̅ N = ∑(Ni Mi )
This may be expressed as M ∑N i
where Ni is the number of molecules of the type ith with molecular mass Mi.
If m1, m2, m3…… are the masses of species with molecular masses M1, M2, M3…..
respectively, then the weight average molecular mass is
̅ w = m1M1+m2M2+m3M3
M or ̅ w = ∑(mi Mi )
M
m +m +m
1 2 3 ∑N i
∑(Ni M2i )
But mi = Ni Mi , so that Mw = ∑(Ni Mi )
Poly dispersity index : The ratio of weight average molecular mass to the number
average molecular mass is called poly diversity index, PDI.
̅w
M
PDI = ̅n
M
7. Terylene 8. Cellulose
1. Polyolefins : These are generally obtained from ethylene or its derivatives. The
polymerization normally takes place at a temperature between 473–673 K under
high pressure and in the presence of traces of oxygen.
465− 485 K
nCH2 = CH2 ⎯⎯⎯⎯⎯
High pressure
→ ( −CH2 − CH2 − )n
Ethylene Polyethylene
Uses : Its major uses are as packing films, pipes, containers, laboratory apparatus,
bottles, buckets, toys, mould articles and electrical insulators.
It may be noted that these days two types of polythene are used which have widely
different properties. These are, low density polythene (LDPE) and high density
polythene (HDPE).
On the other hand, high density polythene is prepared by heating ethylene at about
333-343 K under a pressure of 6–7 atm in the presence of a catalyst such as
triethylaluminium and titatnium tetrachloride (known as Zeigler Natta catalyst).
333−343 K. 6 −7 atm
nCH2 = CH2 ⎯⎯⎯⎯⎯⎯⎯
Zeigler Natta catalyst
→ ( −CH2 − CH2 − )n
Polyethylene
This polymer consists of linear chains and therefore, the molecules can get closely
packed in space. It has, therefore, high density (0.97 g/cm3), and higher melting point
(403 K). It is quite harder, tougher and has greater tensile strength than low density
polythene.
It is used in the manufacture of containers, buckets, tubes, pipes, house wears etc.
− CH − CH2 −
nCH3 − CH = CH2 ⎯⎯⎯⎯⎯→ | Zeigler
Natta catalyst
Pr opylene
CH3
n
Uses :
• For manufacturing liners of bags, lining material for TV cabinets and refrigerators,
• For making ropes, fibres, heat shrinkable wraps for records and other articles.
Vinyl cyanide can be prepared by treating acetylene with HCN in the presence of
Ba(CN)2
Ba(CN)2
HC CH + HCN → H2 C = CH − CN
Vinyl cyanide
Uses :
CH3 CH3
| ⎯⎯⎯⎯⎯
Polymerisation |
→
CH2 = C − CH = CH2 CH2 = C − CH = CH2
n
n
Isoprene Polyisoprene
Rubber has an average chain length of 5000 monomer units of isoprene. Since each
repeating units in polyisoprene contains a double bond, it may have either cis-or a
trans-orientation. Natural rubber has cis-stereochemistry while gutta percha,
obtained by free radical polymerisation of isoprene, has trans-configuration.
Properties :
2. It undergoes long range reversible extension even under relatively small applied
force.
3. It has weak intermolecular forces and occasional cross-linking. With no highly
polar substituents, intermolecular attraction is largely limited to van der Waal's
forces. But these are weak because of all cis-configuration about the double bond.
4. The trans-configuration permits highly regular zig-zags that fit together well while
the cis-configuration does not.
• Vulcanized Rubber :
Natural rubber is soft and tacky (sticky) and becomes even more so at high
temperature and brittle at low temperatures. It has a large water absorption
capacity, low tensile strength and resistance to abrasion. It is also not resistant to
the action of organic solvents and is also easily attacked by oxidising agents. These
disadvantages are removed by ‘VULCANISATION’ which involves addition of
sulphur to rubber and heating the mixture at 373-415 K. The vulcanized rubber
thus obtained has excellent elasticity, low water absorption tendency and resistant
to the action of organic solvents and oxidising agents. During vulcanization,
sulphur bridges or cross-links between polymeric chains are introduced through
their relative allylic positions.
These crosslinks make rubber hard and stronger and remove the tackiness of natural
rubber since the individual chains cannot slip past each other due to sulphur bridges.
Thus rubber can be stretched only to a certain extent and hydrocarbon chains have
the tendency to regain their shape when tension is removed.
• Synthetic Rubber :
To improve the qualities of natural rubber and to meet the ever increasing
demands of mankind, a number of forms of synthetic rubber have been prepared.
(i) Cis-Polybutadiene : This polymer has properties similar to those of natural rubber
and can also be vulcanised in the same way. It is prepared by the polymerisation
of 1,3–butadiene in the presence of Zeigler-Natta catalyst [i.e., a mixture of
(C2H5)3Al and TiCl4].
(ii) Buna Rubbers : Butadiene polymerises in the presence of sodium to give a rubber
substitute viz. BuNa. It is of two types :
It is more rigid responds less to heat and very resistant to swelling action of petrol,
oils and other organic solvents.
(b) Buna-S or GRS : It is a copolymer of three moles of butadiene and one mole of
styrene and is an elastomer.
O
n(CF2 = CF2 ) ⎯⎯⎯⎯ 2
870 −102K
→ −(CF2 − CF2−)n
Tetrafluoroethylene Polytetrafluoroethylene
or Teflon
It is thermoplastic polymer with a high softening point (600 K). It is very tough and
difficult to work. It is inert to most chemicals except fluorine and molten alkali
metals. It withstands high temperatures. Its electrical properties make it an ideal
insulating material for high frequency installation.
Due to its chemical inertness and high thermal stability, it is used in making non
stick utensils. For this purpose, a thin layer of Teflon is coated on the inner side of
the vessel. It is also used for making gaskets, pump packings, valves, seals, non-
lubricated bearings, filter cloth, etc.
4. Poly Vinyl Chloride : It is commonly named as PVC. It's starting material is vinyl
chloride (CH2 = CH – Cl). It is prepared by the polymerisation of vinyl chloride in
presence of peroxides.
PVC is by and large a linear polymer, colourless and thermoplastic in nature and having
a chloride content of about 56.8%. The polymer is thermally unstable and extensive
heating transforms it into a dark coloured residue resembling polyacetyline and
liberating HCl as the volatile. It is insoluble in all hydrocarbons as events. It possesses
flame retardation and self extinguishing characteristics.
PVC is a pliable (easily moulded) polymer and thus has a wide range of applications.
(i) When plasticised with high boiling esters such as di-n-butylphthalte, it is used for
making raincoats, hand bags. plastic dolls, etc.
(ii) It is a good electrical insulator and hence is used for coating wires, cables and
other electrical goods.
5. Nylon : These are polymers having amide linkage and are known as polyamides.
These are prepared by the condensation polymerization of dibasic acid with
diamines or their equivalents.
It is tough, elastic and has high tensible strength. It is used in the manufacture of
carpets. textile fibres and bristles for brushes.
The ortho and para substituted phenols can undergo polymerization to produce a
cross-linked polymer known as bakelite.
Uses :
Soft bakelites with low degree of polymerization are used for making glue for binding
laminated wooden planks and in varnishes. High degree polymerization gives hard
bakelites which are used for making combs, fountain pens, barrels, electrical goods,
formica table tops and many other products.
It is a very strong fibre and is used for making cloth by mixing with cotton,
magnetic recording tapes, etc.
Uses :
These films are suitable in electrical applications and packaging and as magnetic
recording tapes. The fibre is made by a melt spinning process. Poly ethylene
terephthalate is the most important synthetic fiber to have found widespread textile
applications either alone or more commonly as different blends with cotton or wool.
The fibre is widely known as Terylene or Dacron. The polyester fibres possess good
crease resistance and wash and wear properties. A sizable fraction of the polyester
fibre is used as the reinforcing cord in the tyre and related industry.
(i) Cellulose Nitrate : Cellulose nitrate is the oldest cellulosic or cellulose derivative
known and it is the only inorganic ester of cellulose of commercial importance.
Nitration of cellulose is carried out by using a mixture of HNO3 and H2SO4 over a
specific time period under controlled conditions of temperature and mixed acid
composition. The transformation of cellulose (R – Cell – OH) into the nitrate may
be written as :
(ii) Cellulose Acetate : The most important organic ester of cellulose is cellulose
acetate. Cellulose acetate is prepared by acylation of cellulose using a mixture of
acetic anhydride and glacial acetic acid as the acetylating agent under a controlled
condition. Small proportion of H2SO4 is used as catalyst.
A major outlet of cellulose acetate is in the area of sheets, films and membranes.
its exceptional clarity makes it suited for photographic films. Injection moulded
items include tooth brush handles, combs, etc. Films are useful in packaging and
wrapping. The toughness, low flammability (compared to cellulose nitrate), good
clarity are advantageous. On the other hand its high water absorption, poor
solvent and chemical resistance and limited heat resistance and dimensional
stability are its limitations.
Mixed organic esters of cellulose also have been developed commercially. The
most important mixed esters are cellulose acetate butyrate and cellulose acetate
propionate. Cellulose acetate butyrate is more suitable than cellulose acetate for
movie films. Its excellent appearance and clarity, toughness and ease of
mouldability are of special advantage. The mixed ester is used in the making of
automobile parts, tool handles, toys, telephone housing and pipes.
Biodegradable Polymers :
Aliphatic polyesters are one of the important classes of biodegradable poylmers. Some
examples are given below :
(A) Poly -hydroxybutyrate-co--hydroxy valerate (PHBV) :
Question: The partial structure of neoprene, a polymer is given below. Identify the
monomer unit. L2
Solution:
Solution:
Solution:
Buna-N → Copolymer of 1, 3-butadine and acrylnitride
Question: Arrange the following in the increasing order of their intermolecular forces
L3
Solution:
Column-I Column-II
(a) cellulose (p) Natural polymer
(b) Nylon-6,6 (q) Synthetic polymer
(c) protein (r) Amide linkage
(d) sucrose (s) Glycoside linkage
Solution:
Question: L2
Solution: (a)
LECTURE-10
Vitamins
It has been observed that certain organic compounds are required in small amounts
in our diet but their deficiency causes specific diseases. These compounds are called
vitamins. Most of the vitamins cannot be synthesized in our body but plants can
synthesis almost all of them, so they are considered as essential food factors. However,
the bacteria of the gut can produce some of the vitamins required buy us. All the
vitamins are generally available in our diet. Different vitamins belong to various
chemical classes and it is difficult to define them on the basis of structure. They are
generally regarded as organic compounds required in the diet in small amounts to
perform specific biological functions for normal maintenance of optimum growth and
health of the organism. Vitamins are designated by alphabets A, B, C, D, etc. Some of
them are further named as sub-groups e.g. B1, B2, B6, B12, etc. Excess of vitamins is also
harmful and vitamin pills should not be taken without the advice of doctor.
The term “Vitamin” was coined from the word vital + amine since the earlier
identified compounds had amino groups. Later work showed that most of them did
not contain amino group, so the letter ‘e’ was dropped and the term vitamin is used
these days.
Classification of Vitamins
Vitamins are classified into two groups depending upon their solubility in water or fat.
(i) Fat soluble vitamins: Vitamins which are soluble in fat and oils but insoluble in
water are kept in this group. These are vitamins A, D, E and K. They are stored in
liver and adipose (fat storing) tissues.
(ii) Water soluble vitamins : B group vitamins and vitamin C are soluble in water so
they are grouped together. Water soluble vitamins must be supplied regularly in
diet because they are readily excreted in urine and cannot be stored (except
vitamin B12) in our body.
Some important vitamins, their sources and diseases caused by their deficiency
are listed in Table.
Table : Some important Vitamins, their Sources and their Deficiency Diseases
Nucleic Fluids
Every generation of each and every species resembles its ancestors in many ways. How
are these characteristics transmitted from one generation to the next? It has been
observed that nucleus of a living cell is responsible for this transmission of inherent
characters, also called heredity. The particles in nucleus of the cell, responsible for
heredity, are called chromosomes which are made up proteins and another type of
biomolecules called nuclei acids. These are mainly of two types, the deoxyribonucleic
acid (DNA) and ribonucleic acid (RNA). Since nucleic acids are long chain polymers of
nucleotides, so they are also called polynucleotides.
Complete hydrolysis of DNA (or RNA) yields a pentose sugar, phosphoric acid and
nitrogen containing heterocyclic compounds (called bases). In DNA molecules, the
sugar moiety is -D-2-deoxyribose whereas in RNA molecule, tis is -D-ribose.
DNA contains four bases viz. adenine (A), guanine (G), cytosine (C) and thymine (T).
RNA also contains four bases, the first three bases are same as in DNA but the fourth
one is uracil (U).
Structure of Nucleic Acids
DNA is the chemical basis of heredity and may be regarded as the reserve of genetic
information . DNA is exclusively responsible for maintaining the identity of different
species of organisms over millions of years. A DNA molecule is capable of self
duplication during cell division and identical DNA strands are transferred to daughter
cells. Another important function of nucleic acids is the protein synthesis in the cell.
Actually, the proteins are synthesised by various RNA molecules in the cell but he
message for the synthesis of a particular protein is present in DNA.
Solution: (d)
Solution: (a)
Solution: (b)
(a) B1 (b) B2
Solution: (c)
Solution: (d)
Solution: (b)
Solution: (b)