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Bapu R Thorat
Polymers Chemistry
Dr. Bapu R Thorat
Department of Chemistry,
Government of Maharashtra,
Ismail Yusuf Arts, Science and Commerce College, Mumbai
2.1. Introduction
2.1.1. What are polymers
2.1.2. Structural Features of a Polymer
2.1.3. Classification of polymers
2.1.3.1. Origin
2.1.3.2. Thermal response
2.1.3.3. Depending on the structure of polymers
2.1.3.4. Tacticity
2.1.3.5. Plastics, Elastomers, Fibers and Liquid Resins
2.1.3.6. Addition and condensation Polymers
2.1.3.7. Organic and Inorganic Polymers
2.1.4. Copolymer and its types
2.2. Types of polymerization
2.2.1. Addition polymerization
a. Ionic polymerization
b. Free radical polymerization
2.2.2. Condensation polymerization
2.2.3. Degree of polymerization
2.3. Elastomers or Rubbers
2.3.1. Natural rubber
2.3.1.1. Gutta Percha
2.3.1.2. Vulcanization of rubber
2.3.2. Synthetic Rubbers
2.3.2.1. Styrene Rubber (Buna-S)
2.3.2.2. Nitrile Rubber (Buna-N/NBR)
2.3.2.3. Neoprene (GR-M)
2.3.2.4. Butyl Rubber (GR-I)
2.3.2.5. Polysulphide Rubber (GR-P)
2.3.3. Diene polymerization: 1,2- and 1,4- addition
2.3.3.1. Polymerization of isoprene
2.3.4. 1,3-Butadiene-styrene copolymer
2.4. Stereochemistry of polymers
2.1.
Introduction:
The macromolecular or chain molecular concept found wide acceptance and appreciation soon
after it was propounded by Staudinger in 1920. He advanced long chain structural formulas
for natural rubber, cellulosics such as cellulose nitrate, and polystyrene. Long sequences of
simple chemical units interlinked with covalent bonds came into recognition as the basic
structural feature for all polymer molecules.
Staudinger was not initially certain about the nature or identity of the terminal points or end
groups of the long chain polymer molecules. He was initially of the view that there was no need
to saturate the terminal valences and suggested that no end groups were needed or necessary.
Development and elucidation of the chain reaction theory of vinyl and related polymerization
g. Flexibility (cispolybutadiene).
h. Low thermal conductivity (polyurethrene foam).
i.
2.1.1.
A polymer is large molecule build up by the repetition of small, simple units which are joined
by covalent bonds, sometimes referred as mers. The small simple repeating unit is called as
monomer. The word polymer is derived from the Greek word poly = many and mers = parts.
The functionality of a monomer is the number of sites it has for bonding to other monomers
under the given conditions of the polymerization reaction. Thus, a bifunctional monomer, i.e.,
monomer with functionality two, can link to two other molecules under suitable conditions
Polymerisation
Ethylene
C C
H2 H2
n
Polyethylene
The addition polymers formed by the polymerization of a single monomeric species are known
as homopolymers whereas the polymers made by addition polymerization from two different
monomers are termed as copolymers. For example, Buna-S rubber which is formed from 1, 3-
Polymer
Monomer
Repeat Unit
01
CH2=CH2
Ethylene
-CH2 - CH2 -
02
H
Cl n
Polyvinyl chloride
03
CH3 n
Polypropylene
OAc n
Polyvinyl acetate
H
Ph
Cl
CH3
H
OCOCH3
Vinyl acetate
OCOCH3
H
Ph
Styrene
Ph
H
n
H
CH3
Propylene
H
05
H
Cl
Vinyl Chloride
04
Polystyrene
06
F
F n
poly (tetrafluoroethylene)
F
F
Tetrafluoroethylene
CN n
pol Acrylonitrile
H
CN
Acrylonitrile
08
CN
H
H n
Polybutadiene
2.1.3.
H
H
1,3-Butadiene
Classification of polymers:
The polymers were classified based on origin, thermal response, tacticity, etc.
Basis of classification Polymer Types
1. Origin
Natural
(as
Examples
available
in
nature)
Polyethylene,
polypropylene,
poly-
polycarbonates,
phenolics,
nylon
polypropylene,
poly-
polyamides,
linear
solubility
and
fusibility).
Thermosetting (they usually Phenolic resin, amino resins, epoxy
soften or melt initially on
resins,
diene
rubbers
(vulcanized),
Mode
of Chaingrowth or addition
formation
Stepgrowth or condensation
Polyesters
and
polycarbonates,
melamine)
polyamides,
phenol
(urea,
formaldehyde
resins,
Low
density
polyethylene
(LDPE),
resitols,
poly
(3-hydroxy
alkanoates) etc.
Cross linked or network (having Phenolic C-stage (resite) resin, C-stage
a complex network structure)
cured
epoxy
resin
and
Physical properties
range elasticity)
rubber,
polyurethane
Polyethylenes,
(isotactic),
polypropylene
polystyrene,
poly
filamentous form)
silk
(rayons),
poly
(ethylene
Isotactic (stereoregular)
Syndiotactic (alternative)
polymers.
Crystalline
Polyethylene
polypropylene
(HDPE
and
(isotactic),
LDPE),
stretched
(Crystallinity, 30 50%)
Amorphous or non-crystalline
2.1.3.1.
Origin:
The polymers were classified as natural and synthetic polymers. The polymers isolated from
natural resources were called as natural polymers. The examples of natural polymers were proteins and enzymes, the polysaccharides, natural rubber, natural gums, natural silk and other
natural fibers, cellulosic and lingo-cellulosic, cotton (cellulosic), and jute, ramie, flax, hemp,
sisal, coir etc.
Semi-synthetic (modified natural) polymers and synthetic polymers are also called man made
polymers. The polymers synthesized from low molecular weight compounds or monomers are
called synthetic polymers. Examples of synthetic polymers were - PVC, polystyrene,
polyethylene, synthetic rubber, PVA, polyacrylonitrile, etc.
2.1.3.2.
Some polymers soften on heating and can be converted into any shape that they can retain on
cooling. The process of heating, reshaping and retaining the same on cooling can be repeated
Thermosetting polymers
Cross-linked polymers.
Weak van der Waals intermolecular forces Chemical cross-linking make them infusible
and thus soften/melt on heating.
Examples are polystyrene, PVC, SBR, Teflon, Examples are Glyptals, epoxy polymers,
PMMA terylene.
2.1.3.3.
formaldehyde resins.
a. Linear polymer:
A molecule of a linear polymer may be schematically represented by a simple line of finite
length (straight or zigzag, but usually wavy). These linear polymers are well packed and
therefore, have high densities, high tensile (pulling) strength and high melting points. For
example, polyethylene, nylons and polyesters are examples of linear polymers.
b. Branched polymer:
A molecule of a branched polymer may, however, be represented by a line of finite length with
short or long finite length branches attached to some of the repeat units in the chain molecule.
These branched chains polymers are irregularly packed and therefore, they have lower tensile
strength and melting points than linear polymers. For example, low density polyethene,
glycogen, starch, etc.
c. Cross linked polymer:
chains are cross linked together to form a three dimensional network. These polymers
are hard, rigid and brittle because of the network structure. E.g. Bakelite, melamine and
formaldehyde resin are some examples of this type.
Tacticity:
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
b. Syndiotactic:
Ph
Ph
Ph
Ph
-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2- CH-CH2-CH-CH2-CH-CH2-CH-CH2
Ph
Ph
Ph
Ph
Ph
c. Atactic:
If the substituents are arranged randomly in a polymer chain (all substituted methylene having
random configurational arrangement) is called as atactic polymers. e.g.:- Polystyrene.
Ph
Ph
Ph
Ph
Ph
Ph
-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2-CH-CH2- CH-CH2-CH-CH2-CH-CH2-CH-CH2
Ph
Ph
Ph
Ph
The stereoregularity (e.g.:- isotaxis and syndiotaxis) usually forces the polymer chain into a
certain conformational order (e.g.:- helix or planar zig-zag), at least in solid state in some cases
also in dissolved or molten state.
Isotactic sequence is distinctive as being very regular, while atactic sequence is one that is
highly irregular. Syndiotactic sequence may be viewed as regularly irregular or vice versa.
Isotactic and syndiotactic polymers are considered as stereospecific or stereoregular while
atactic polymers are viewed as random or stereoirregular. The overall molecular symmetry
and crystallinity are in the order isotactic syndiotactic >> atactic. Isotactic polymers are
generally characterized by high melting temperature (Tm) and high mechanical properties with
relatively high resistance to solvents and chemicals.
2.1.3.5.
Depending on its ultimate form and use, a polymer can be classified as plastic, elastomers, fibre
or liquid resins.
a. Plastic:
These are linear polymers with very few cross linkages or no cross linkages at all. The
polymeric chains are held by weak van der waal forces and slide over one another. Due to lack
of cross linkages these polymers soften on heating and harden or become rigid on cooling. Thus
they can be moulded to any shape. Polythene, PVC, polystyrene are addition type polymer and
d. Resins:
Polymers used as adhesives, potting compound sealants, etc. in a liquid form are described
liquid resins. Commercially available epoxy adhesives and polysulphide sealants are typical
examples.
2.1.3.6.
There are two types of polymers according to the synthesis procedure used as (i) addition
polymer, and (ii) condensation polymer.
The addition polymer is one in which the monomers are molecules with multiple bonds which
undergo sequence of true addition reactions with each other and forming polymer, e.g.,
Polystyrene, PVC, polyethylene, polychlorostyrene etc. are the examples of addition polymers.
This kind of reaction yields linear polymers without cross-links, i.e. thermoplastic polymers.
Cross linking agents for addition polymers are molecules that contain two or more double
bonds per molecule, for example divinylbenzene. Cross-linking of linear chain polymers causes
them to stiffen and retain their shape, and also makes them insoluble in solvents that dissolve
the linear chain polymer. Note that the repeat unit of addition polymers, such as polyethylene,
contains the same number of atoms as the monomer. The molecular weights of addition
polymers can be very high. The different substituents (e.g., the benzene ring in polystyrene, the
chlorine atom in PVC, etc.) added to the linear polymer backbone have a profound effect on the
physical properties of these materials, which is why polyethylene is a flexible polymer whereas
PMMA and PVC are rather stiff.
The condensation polymer is one in which a small molecule (usually water) is eliminated in the
condensation of any two monomer units. It is clear, therefore, the monomers for condensation
polymers must be (at least) bifunctional molecules in which one function on one monomer
molecule reacts with the other function on another molecule. Examples are polyamides, made
by reacting a diacid with a diamine, and polyesters, made by reacting a diacid with a diol (a
diol is a molecule containing two terminal OH groups).
2.1.3.7.
A polymer whose backbone chain is essentially made of carbon atoms is termed as organic
polymer. The atoms attached to the side valencies of the backbone carbon atoms are, however,
usually those of hydrogen, oxygen, nitrogen, etc. The majority of synthetic polymers are
organic.
In fact, the number and variety of polymers are so large thats why we refer to polymers on the
other hand, generally contains no carbon atom in their chain backbone are referred as inorganic
polymers. Glass and silicone rubber are examples of inorganic polymers.
2.1.4.
The synthesis of macromolecules composed of more than one monomeric repeating unit was
important to control the essential properties of the resulting material. In this respect, it is useful
to distinguish several ways in which different monomeric units might be incorporated in a
polymeric molecule. The following examples refer to a two component system, in which one
monomer is designated A and the other B.
Statistical copolymers: Also called random copolymers. Here the monomeric units are
distributed randomly, and sometimes unevenly, in the polymer chain:
~ABBAAABAABBBABAABA~.
Alternating copolymers: Here the monomeric units are distributed in a regular alternating
fashion, with nearly equimolar amounts of each in the chain:
~ABABABABABABABAB~.
Block copolymers: Instead of a mixed distribution of monomeric units, a long sequence or
block of one monomer is joined to a block of the second monomer:
~AAAAA-BBBBBBB~AAAAAAA~BBB~.
~AAAAAAA(BBBBBBB~)AAAAAAA(BBBB~)AAA~.
2.2.
Types of polymerization:
There are two main types of polymerization addition and condensation polymerization.
2.2.1.
Addition polymerization:
Addition polymerization, is essentially a chain reaction, and may be defined as one in which
only a small initial amount of initial energy is required to start an extensive chain reaction
converting monomers, which may be of different formulae, into polymers. This process
involves the addition of monomer units to themselves to form a growing chain by a chain
reaction mechanism. A chain reaction consists of three stages, initiation, propagation and
termination.
The mechanism of polymerization can be divided broadly into two main classes, free radical
polymerization and ionic polymerization.
a. Ionic polymerization:
Ionic polymerization was divided into cationic and anionic polymerizations. Cationic
polymerization depends on the use of catalysts which are good electron acceptors. Typical
examples are the FriedelCrafts catalysts such as aluminium chloride AlCl3 and boron
trifluoride BF3. Monomers that polymerise in the presence of these catalysts have substituents of
the electron releasing type. They include styrene C6H5CH=CH2 and the vinyl ethers
CH2=CHOCnH2n+1.
In cationic vinyl polymerization, the initiator is a cation, which is an ion with a positive
electrical charge. A pair of electrons from the carbon-carbon double bond will be attracted to
this cation, and will leave the carbon-carbon double bond to form a single bond with the
initiator. This leaves one of the former double bond carbons at a loss for electrons, and carrying
a positive charge. This new cation will react with a second monomer molecule in the same
manner as the initiator reacted with the first monomer molecule. This happens over and over
until a high molecular weight is reached, that is, a molecular weight at which the polymer is
useful for something.
Anionic initiators include reagents capable of providing negative ions, and are effective with
monomers containing electronegative substituents such as acrylonitrile CH2=CHCN and methyl
methacrylate CH2=C(CH3)COOCH3. Styrene may also be polymerised by an anionic method.
Typical catalysts include sodium in liquid ammonia, alkali metal alkyls, Grignard reagents and
triphenylmethyl sodium (C6H5)3C-Na. Ionic polymerization is not of interest in normal aqueous
polymerization since in general the carbonium ions by which cationic species are propagated
and the corresponding carbanions in anionic polymerizations are only stable in media of low
dielectric constant, and are immediately hydrolyzed by water.
The modern methods of polymerization are the ZieglerNatta catalysts and group transfer
polymerization catalysts.
b. Free radical polymerization:
A free radical may be defined as an intermediate compound containing an odd number of
electrons, but which do not carry an electric charge and are not free ions. The decomposition of
oxidizing agents of the peroxide type, as well as compounds such as azodiisobutyronitrile
(AIBN) which decomposes into two radicals of (CH3)2C-CN and nitrogen (N2). These free
radicals were used as initiator for the addition reaction.
Initiation: The first stage of the chain reaction, the initiation process, consists of the attack of the
free radical on one of the doubly bonded carbon atoms of the monomer. One electron of the
double bond pairs with the odd electron of the free radical to form a bond between the latter
Propagation: During a chain reaction, most of the time is spent in the propagation phase as the
polymer chain grows. In the propagation phase, the newly-formed activated monomer attacks
and attaches to the double bond of another monomer molecule. This addition occurs again and
again to make the long polymer chain.
Termination: The final stage is termination, which may take place by one of several processes.
One of these is combination of two growing chains reacting together; an alternative is
disproportionation through transfer of a hydrogen atom and chain transfer. Chain transfer may
take place via a monomer, and may be regarded as a transfer of a proton or of a hydrogen atom.
Most common solvents are sufficiently active to take part in chain transfer termination, the
aliphatic straight-chain hydrocarbons and benzene being amongst the least active.
Example: Polymerization of ethane to polythene consists of heating or exposing to light a
mixture of ethene with small amount of benzoyl peroxide as the initiator.
2.2.2.
Condensation polymerization:
In this, the monomers condensed with each others with the elimination of a small molecule like
H2O, ROH or NH3, etc. The reaction is called (step growth) condensation polymerization and
the product formed is called condensation polymer. The process involves the elimination of by
product molecules; therefore, the molecular mass of the polymer is not the integral multiple of
the monomer units.
Polyester (e.g., terene or terelene or dacron) is prepared by the condensation polymerization of
dicarboxylic acid with dihydroxy alcohols.
The aliphatic polyamides are generally known as NYLONS. There are different types of nylons
and are usually indicated by a numbering system. This number gives the number of carbon
atoms present in the monomer molecules. Aliphatic Nylon have M.P. of 250-300C.
e.g. Nylon-6,6: It is obtained by the polymerization of adipic acid with hexamethylene diamine.
Addition polymerization
Involves
unsaturated
monomer
Condensation polymerization
like Involves
substances
with
at
least
ethylene, vinyl groups like chloride, styrene functional ethylene glycol (2-OH groups),
At any instant, only monomer and polymers No monomer. Mixtures of dimers, trimers
are present.
Initiator
is
to
catalyze
polymerization.
No small molecules are eliminated.
Polymers
made
are,
for
2.2.3.
Degree of polymerization:
The length and molecular weight of the polymer depends on the number of repeating units
(monomers) present in the chain. The total number of monomers present in the polymer chain
is called as degree of polymerization. It is denoted by later Dp.
The molecular weight of the polymer will be then, the product of degree of polymerization and
molecular weight of repeating (monomer) unit.
Molecular weight
of polymer
Molecular weight
of monomer
Dp
Elastomers or Rubbers:
Natural rubber:
Natural rubber is obtained in the form of latex from rubber trees (Hevea brasiliensis). The latex
normally contains 30-60% rubber. It can be used, as such, in the latex form or the solid rubber
can be coagulated from the latex using 1% acetic acid solution. Natural rubber is a highly soft
and elastic material. Natural rubber is a polymerized form of isoprene (2-Methyl-1,3-butadiene):
Polymerization of isoprene yields polymers containing varying degrees of cis-1,4- and trans-1, 4
as well as 1, 2 or 3, 4-vinyl units in the molecule, depending upon the initiator and the solvent
systems employed. Under controlled conditions, polyisoprene containing up to 96% cisconfiguration can be obtained by using a lithium alkyl initiator and anhydrous oxygen free
aliphatic hydrocarbon solvents.
2.3.1.1.
Gutta Percha:
It is obtained from the mature leaves of dichopsis gutta and palagum gutta trees. Gutta percha
may be recovered by solvent extraction, when insoluble resins and gums are separated.
Alternatively the mature leaves are ground carefully; treated with water at about 70C for half
an hour and then poured into cold water. When gutta percha floats on water surface and is
removed. The structure of gutta is as follows:
Both the cis- as well as trans-varieties occur in nature as natural rubber and gutta-percha,
respectively. Natural rubber is a highly soft and elastic material. It is soluble in carbon
disulphide and petrol. Whereas, Gutta-percha is a hard thermoplastic solid and dissolves in
petrol only on heating and get separated from solution when cooled. Structurally, gutta-percha
is trans-polyisoprene; whereas natural rubber is cis-polyisoprene.
2.3.1.2.
Vulcanization of rubber:
Natural rubber becomes soft at high temperature (>335 K) and brittle at low temperatures (<283
K) and shows high water absorption capacity. It is soluble in non-polar solvents and is nonresistant to attack by oxidizing agents. To improve upon these physical properties, a process,
called vulcanization is carried out. This process consists of heating a mixture of raw rubber with
sulphur and an appropriate additive at a temperature range between 373 K to 415 K. On
vulcanization, sulphur forms cross links at the reactive sites of double bonds and thus the
rubber gets stiffened. In the manufacture of tyre rubber, 5% of sulphur is used as a crosslinking
agent. The probable structures of vulcanized rubber molecules are depicted below:
2.3.2.
Synthetic Rubbers:
Styrene butadiene rubber (SBR) is prepared by the copolymerization of butadiene (75%) and
styrene (25%) in an emulsion system at 50C in the presences of catalyst such as cumene
hydroperoxide. SBR is also known as Buna-S or GR-S. Styrene rubber have high abrasion
resistance, high load bearing capacity, low oxidation resistance, swells in oil and solvents, like
natural rubber SBR also vulcanized and produce cold rubber, which has greater tensile strength
and greater abrasion resistance.
SBR is used in motor tyres, shoes soles, footwear components, insulation of wire and cables,
carpet backing, gaskets, adhesives, etc.
2.3.2.2.
Nitrile rubber (GR-A) has low swelling, low solubility, goods tensile strength and abrasion
resistance even after imersion in gasoline or oils. It has good heat resistance. It is used in fuel
tanks, gasoline hoses, as an adhesive and in the form of latex for impregnating paper, teather
and textiles.
2.3.2.3.
Neoprene (GR-M):
Butyl rubber is amorphous under normal conditions but gets crystallized on stretching. It has
excellent resistance to heat, abrasion, ageing, chemicals (such as H2SO4, HNO3, HCl or HF),
polar solvents (like alcohol and acetone) but is soluble in hydrocarbon solvents like benzene.
Butyl rubber is used as inner tubes because its superior impermeability to gases. It is used for
wire and insulation. It is used in the production of tyres.
2.3.2.5.
Polysulphide rubber, also known as Thiokol, is prepared by the reaction between sodium
polysulphide (Na2S) and ethylene dichloride (CH2ClCH2Cl).
Thiokols are those elastomers in which sulphur forms a part of the polymer chain. It has
extremely good resistance to mineral oils, fuel oxygen, ozone and sunlight. It is also
impermeable to gases. It cannot be vulcanized and hence does not form hard rubber. It has poor
strength and abrasion resistance.
2.3.3.
When there are unsaturated sites along a polymer chain, several different isomeric forms are
possible. 1,3-butadiene can be polymerized to give 1,2-poly(1,3-butadiene) or either of two
geometric isomers of 1,4-poly(1,3-butadiene). The numbers preceding the poly prefix designate
the first and last carbon atoms of the backbone repeating unit. 1,2-poly(1,3-butadiene) has a
vinyl-type structure, where the substituent group (ethene) contains an unsaturated site; therefore,
this geometric isomer can be atactic, syndiotactic, or isotactic. In the case of the commercially
more important 1,4-poly(1,3-butadiene), all four carbons in the repeating unit lie along the chain.
Carbons 1 and 4 can lie either on the same side of the central double bond (i.e., cisconfiguration) or on the opposite side (i.e., trans-configuration). The structure of polybutadiene
used in SBR rubber (i.e., a copolymer of styrene and butadiene) is principally the trans-1,4
isomer
2.3.3.1.
Polymerization of isoprene:
Polyisoprene, polymer of isoprene (C5H8) that is the primary chemical constituent of natural
rubber, resins balata and gutta-percha, and of the synthetic equivalents of these materials.
Depending on its molecular structure, polyisoprene can be a resilient, elastic polymer
(elastomer), as in the case of natural rubber and isoprene rubber, or a tough, leathery resin, as in
the case of natural and synthetic balata or gutta-percha.
The chemical structure of isoprene can be represented as CH2=C(CH3)CH=CH2. As the
repeating units of polyisoprene, the four isomers have the following structures:
Of these four isomers, the most important are the cis-1,4 polymer and the trans-1,4 polymer.
Isoprene rubber (IR) is manufactured by the polymerization of synthetic isoprene, which is
obtained from the thermal cracking of the naphtha fraction of petroleum. Polymerization is
conducted in solution, using both anionic and Ziegler-Natta catalysts. The product is at most 98
percent cis-1,4 polyisoprene, and its structure is not as regular as natural rubber in other
respects.
Unlike the cis-1,4 polymer, however, the trans-1,4 polymer is highly crystalline, so balata and
gutta-percha are tough, hard, and leathery materials properties that led in the 19th century to
their use as sheathings for underwater cables and golf balls. The trans-1,4 polymer can also be
synthesized with Ziegler-Natta catalysts, yielding a synthetic balata of similar properties that
also is employed in golf-ball covers as well as in orthopedic devices such as splints and braces.
1,3-Butadiene-styrene copolymer:
It is a type of polymerization reaction in which a mixture of more than one monomeric species
is allowed to polymerize and form a polymer called copolymer. Copolymer contains multiple
units of each monomer. For example: 1, 3-Butadiene and styrene can undergo copolymerization
to form butadiene styrene copolymer.
2.4.
Stereochemistry of polymers:
To discussing the shape of polymeric molecules, one must distinguish carefully between the
configuration and confirmations. Configurations of molecules are sterric arrangement which are
symmetrically related to one another and can not change from one to another without breaking
the chemical bond. e.g.:- Cis- and trans- isomers of unsaturated compounds, cyclopropanes
derivatives, and D- and L- configurations of a molecules containing asymmetrical carbon atoms
or other centers of chirality.
The confirmations are sterric arrangements that can occurs through rotations about the single
bonds, and are due the fact that certain orientations have lower energies than the others. e.g.:Gauche and trans configurations of -substituted paraffines and two forms of cyclohexane.
If substituent is present at any CH2- carbon atom, it becomes asymmetric in nature. Therefore,
it is classified into a three different classes according to the nature of substituent Isotactic,
Syndiotactic and Atactic (discussed above).
2.4.1.
Ziegler-Natta catalyst:
These are a special type of coordination catalysts, comprising two components, which are
generally referred to as the catalyst and the co-catalyst. The catalyst component consists of
halides of IV-VIII group elements having transition valence and the co-catalysts are organo-
The active centres, from where the polymer chain growth propagates are formed at the surface
of the solid phase of the catalyst complex, and the monomer is complexed with the metal ion of
the active centre before its insertion into the growing chain.
The complex formed, now acts as the active centre. The monomers then attached towards the
TiC bond (C from the alkyl group R) in the active centre, when it forms a -complex with the
Ti ion.
The bonds between R and Ti opens up producing an electron deficient Ti and a carbanion at R.
The Ti ion attracts the -electrons pair or the monomer and forms -bond. This transition state
now gives rise to the chain growth at the metal carbon bond, regenerating the active centre:
Repeating the whole sequence, with the addition of second monomer molecule, we will get the
structure of the resultant chain growth as:
The five coordinated titanium ions on the surface of the catalyst is assumed to have a vacant
orbitals as shown at 6 in the following structure:
After the chemisorption of aluminium alkyl on the TiCl3 crystal, Ti3+ is alkylated by an exchange
mechanism, as follows:
Once the active catalyst is formed, the monomer is attached towards the vacant orbital which
then forms a transition complex with the Ti.
The transition state quickly gives rise to the growth of the polymer chain by the monomeric
insertion at the Ti-Et bond.
2.5.
2.5.1.
Addition polymers:
2.5.1.1.
Polyethylene:
2.5.1.2.
Polypropylene:
Polypropylene can be made with different tacticities. Most polypropylene we use is isotactic.
This means that all the methyl groups are on the same side of the chain. But sometimes we use
atactic polypropylene. Atactic means that the methyl groups are placed randomly on both sides
of the chain.
It is a strong, stain and impact-resistant, lightweight polymer with high heat resistance (melting
point=160 degrees C). Because of these properties, there are many uses for polypropylene; it is
used in containers (barrels, tanks, etc.), fabrics, sinks, ducts, and as a chemical resistant lining.
Polypropylene can sometimes use cross-linkage to bond to other polymers of polypropylene,
but it depends on its environment. Polypropylene is used for packing of textile material and
food, lining of bags, gramophone records, ropes, carpet fibres, etc. Polypropylene fibers are
resistant to solvents and other chemicals, to bacteriological growth and to abrasion.
2.5.1.3.
PVC:
The monomer units are vinyl chloride molecules. PVC is prepared by heating vinyl chloride in
an inert solvent in the presence of dibenzoyl peroxide.
PVC is a hard horny material. However, it can be made to acquire any degree of pliability by
the addition of a plasticizer. It is resistant to chemicals as well as heat. It is used for making rain
coats, hand bags, toys, hosepipes, gramophone records, electrical insulation and floor covering.
PVC fibers have medium tenacity, high elongation, and high degree of shrinkage (up to 40%) at
relatively low temperature (100C). They have virtually zero moisture regain and excellent
2.5.1.4.
Polystyrene:
2.5.1.5.
Polyacrylonitrile:
Polyacrylonitrile (PAN), also known as polyvinyl cyanide, has the following structure:
Acrylonitrile can be made either by the direct catalytic addition of HCN to acetylene, or by the
addition of HCN to ethylene oxide to give ethylene cyanohydrin, followed by dehydration.
PAN has a remarkable resistance to heat up to around 220C and exhibits very good mechanical
properties. PAN is used to produce fibres known as PAN fibres. The copolymers of PAN with
butadiene (nitrile rubber) are a material of great industrial importance.
2.5.1.6.
Polyvinylalcohol:
Polyvinyl Alcohol is generally known as PVA. It is most commonly used in adhesive products
and for making other polymers. Unlike other vinyl polymers, polyvinyl alcohol is not
synthesised via polymerisation of the vinyl alcohol. They are produced by the polymerization of
the stable vinyl actetate monomer, where subsequent hydrolysis of polyvinyl acetate yields the
polyvinyl alcohol polymer.
PVA is pretty inert; does not react very much/easily. It has excellent film forming, emulsifying
and adhesive properties. It is resistant to oil, grease and solvent. PVA is fully degradable and is a
quick dissolver. The degradation of PVA is influenced by its crystalline structure and molecular
weight. It is used in water transfer printing process. It is used in eye drops and hard contact lens
solution as a lubricant. When eyes become dry due to a reduced production of mucin by the
conjunctiva, PVA reduces the surface tension of the tears and also has similar properties to the
mucin. The PVA fibres were used as reinforcement fibres in concrete. PVA is also used in PET
bottles as carbon layer because it helps to degrade when the bottle thrown away.
PVA fibers are normally water soluble. However, subsequent acetylation of the OH groups or
an after-treatment with formaldehyde renders PVA fibers resistant to boiling water. PVA fibers
have generally poor elastic recovery and wrinkle easily. They do not burn easily and have a
good chemical and biological stability. PVA fibers exist in a wide range of tenacity.
2.5.1.7.
Teflon:
Teflon is a very tough material and is resistant towards heat, action of acids or bases. It is bad
conductor of electricity. Teflon is used for coating utensils to make them non-sticking, making
seals and gaskets which can with stand high pressures, insulation for high frequency electrical
installations.
2.5.2.
2.5.2.1.
Condensation polymers:
Polyesters:
Polyamides:
Polyamides are prepared by the melt polycondensation between dicarboxylic acids and
diamines. They have the general structure as follows:
4. Kelvar: It is a aromatic polyamide similar to nylons, but in benzene rings rather than
aliphatic chains linked to the amide groups CONH. It is prepared by the
condensation polymerization of terephthalic acid dichloride and 1,4-diaminobenzene.
Kelvar is exceptionally strong. This is due to the stronger intermolecular forces between
neighboring chains. It also has high heat stability. Kelvar is used in tyres, brakes, clutches
linging and other car parts, bullet proof vests, motor cycle helmets, aerospace and aircraft
industries.
2.5.2.3.
Polyurethanes:
The physical properties, as well as the chemical structure, of polyurethane depend on the
structure of the original reactants, in particular the alkyl groups in both isocyanide and diol.
The important properties of polyurethanes are Water repellent, autoahderente, light weight,
chemical resistance, fire resistance, etc. Most of the polyurethanes are thermosetting polymers
that do not melt when heated, thermoplastic polyurethanes are also available. Polyurethanes
can be found in liquid coatings and paints, tough elastomers such as roller blade wheels, rigid
insulation, soft flexible foam, elastic fibre or as an integral skin, rigid foams, chemical resistance
coatings, etc.
2.5.2.4.
Phenol-formaldehyde resin:
Phenol - formaldehyde polymers are the oldest synthetic polymers. These are obtained by the
condensation reaction of phenol with formaldehyde in the presence of either an acid or a base
catalyst.
The reaction starts with the initial formation of o-and/or p-hydroxymethylphenol derivatives,
which further react with phenol to form compounds having rings joined to each other through
CH2 groups. The initial product could be a linear product Novolac used in paints.
Novolac on heating with formaldehyde undergoes cross linking to form an infusible solid mass
called bakelite. It is used for making combs, phonograph records, electrical switches and
handles of various utensils.
These resins are hard, rigid, water resistant, heat resistant and can be mixed with wide range of
materials for the industrial and residential uses. The phenolic resins are chemical such as acids,
salts, organic solvents resistant, stable in harsh marine environment, low weight and high
strength, flammable resistance, less toxic, etc. They are easily attacked by alkalies due to
presence of free hydroxy groups. It possesses electrical insulating properties due to low thermal
conductivity.
The phenolic resins are used in adhesives, coatings, and molding compounds. They were used
to fabricate insulators, plugs, switches and also used as cation exchanger resin in water
softening.
2.5.2.5.
Epoxy resin:
Epoxy resins are defined as polymer molecules containing more than one epoxy groups. The
epoxy group also termed as oxirane or ethoxyline group. There are two main categories of
epoxy resins, namely the glycidyl epoxy and non-glycidyl epoxy resins. The glycidyl epoxies
are further classified as glycidyl ether, glycidyl ester and glycidyl amine. Glycidyl ether epoxies
These resins are thermosetting polymers and are used as adhesives, high performance coatings,
potting and encapsulating materials. These resins have excellent electrical properties, low
shrinkage, good adhesion to many metals and resistance to moisture, thermal and mechanical
shock. The applications of epoxy resins were extended as electronic material and in the
aerospace industry by improving its flame and thermal resistance.
2.5.2.6.
Polycarbonates:
The polycarbonates are the polyester of phenol and carbonic acid. It was synthesized by the
condensation of diphenols in which the two OH groups are on separate aromatic rings such as
bisphenol A and aliphatic derivative of carbonic acid such as phosgene (COCl 2) or a carbonate
diester [CO(OR)2].
This is a polymer that combines transparency, lightness and strength with just enough
flexibility not to be brittle. It is resistant to water and many organic compounds. It is transparent
Recyclable polymers:
Plastics are usually disposed of in one of three ways: discarded, combusted, or recycled. Of the
three options, recycling is least implemented. Because the disposal or combustion of plastics
leads to detrimental health and environmental effects, short and long term solutions need to be
established. A potential short-term solution would be the development of new technology to
boost recycling rates. The current recycling system requires a labor-intensive sorting step which
contributes to the low amounts of plastic being recycled. Technology that eliminates the sorting
process could potentially increase recycling rates. However, because all plastics cannot be
recycled indefinitely, a long-term solution is also needed. The advancement of biopolymers that
will degrade faster than regular plastic polymers that end up in landfills would decrease
environmental pollution while providing compost for plant nutrition.
2.6.1.
A large number of polymers are quite resistant to the environmental degradation processes and
are thus responsible for the accumulation of polymeric solid waste materials. These solid wastes
cause acute environmental problems and remain undegraded for quite a long time. In view of
the general awareness and concern for the problems created by the polymeric solid wastes,
certain new biodegradable synthetic polymers have been designed and developed.
Plastics derived from natural materials, such as cellulose, starch and hydroxycarboxylic acids
are more easily decomposed when exposed to oxygen, water, soil organisms and sunlight than
are most petroleum based polymers. The glycoside linkages in polysaccharides and the ester
groups in polyesters represent points of attack by the enzymes of microorganisms that facilitate
their decomposition. Such biodegradable materials can be composted, broken down and
returned to the earth as useful nutrients. The two natural polyesters that are finding increasing
use
as
replacements
polyhydroxyalkanoates
for
petroleum
(PHA),
the
based
latter
plastics
most
are
commonly
polylactide
as
(PLA)
copolymers
and
with
polyhydroxybutyrate (PHB). Structures for these polymers and their monomer precursors are
shown below.
b. Nylon 2nylon 6:
It is an alternating polyamide copolymer of glycine (H2NCH2COOH) and amino caproic acid
[H2N-(CH2)5-COOH] and is biodegradable.
2.6.2.
enhancers
or
as
oxygen
transport
macromolecules.
e.g.
silicon
rubber,
Additives to polymers:
2.7.1.
Plasticizers:
Plasticizers are usually high boiling organic liquids or low melting solids. Polymers are often
inherently rigid and brittle. Plasticizers are added to improve flexibility, softness and suitability
for different processing applications. Plasticizers are chemically and thermally stable; their
addition also enhances the stability and reduces the degradation of the host polymers. They are
of various chemical types, some being used in specified products only. Plasticized polymers can
be moulded, sprayed, and used in a coating in an uncured liquid form. Calendaring, extrusion
and moulding of the polymer melt are other methods used in processing. Polyvinyl chloride
accounts for about 80% of plasticizer production and use since it is especially suitable for
Stabilizers:
Stabilizers are needed to protect the structure of polymers and pigments against degradation
induced by physical conditions, such as heat and light, or chemical attacks, such as that of
atmospheric oxygen. Heat stabilizers can be organotin compounds, metal salts, epoxies,
pentavalent phosphorous compounds, and their mixtures. Chemicals that absorb ultraviolet
light include benzophenones, benzotriazoles, salicylates, acrylates, and organonickel
compounds.
Heat stabilizers: PVC polymers and co-polymers have poor resistance to heat, which is a major
disadvantage. The stabilizers used in PVC formulations are organic compounds of metals.
Commonly used heat stabilizers are tin compounds, such as dibutyltin bis(alkyl maleate) and
dibutyltin (isooctyl mercaptoacetate), used for plastics which come into contact with food
products, and lead compounds, such as dibasic lead stearate and dibasic lead phosphite. In
some countries the use of stabilizers containing cadmium are banned because of their toxicity.
UV stabilizers: Hindered amine light stabilizers (HALS) can be used in pigmented polymers
and are specifically suitable for the protection of white or blue PP fibres. They also act as
antioxidants. A high concentration of titanium dioxide can also serve as a stabilizer against the
degrading effects of UV light.
2.7.3.
Fillers: