Polymerization
Structural Features of a Polymer or Macromolecule
The word polymer literally means many (poly) units (mer). A small, simple chemical unit appears
to repeat itself a (very) large number of times in the structure of a polymer molecule or
macromolecule. The simple molecular species from which a chain polymer molecule may be
obtained or to which a polymer molecular system may be degraded is called the monomer. Some
common polymers and structural representation of the respective monomers and repeat units are
listed in Table 1.
Table 1: Some Monomers and Corresponding Polymers and Repeat Units
S.No. Monomer Polymer Repeat Unit
7. Acrylonitrile Polyacrylonitrile
8. Butadiene Polybutadiene
CH2 = CH–CH = CH2 (– CH2 –CH = CH–CH2 –) n –CH2–CH=CH–CH2 –
9. Chloroprene Polychloroprene
Polymerization of monomer styrene to polystyrene may be represented by:
Table 2: Classification of Polymers
Basis of Polymer Types Examples
Classification
1. Origin (a) Natural (as available in Natural rubber, natural silk, cellulose,
nature) proteins, starch etc.
(b) Semisynthetic Hydrogenated, halogenated and cyclo
(Man – made) (natural) rubber; cellulosics etc.
(c) Synthetic Polyethylene, polypropylene,
(Man – made) polystyrene, nylon poly-amides etc.
2. Thermal response (a) Thermoplastics (they soften Polyethylene, polypropylene,
or melt on heating and harden on polystyrene, nylon polyamides, linear
cooling over many cycles of polyester etc.
heating and cooling and retain
solubility and fusibility).
(b) Thermosetting (they usually Phenolic resin, amino resins, diene
soften or melt initially on rubbers (vulcanized), unsaturated
heating, but fast undergo polyesters.
chemical changes to finally turn
insoluble and infusible).
3. Mode of formation (a) Chain – growth or Polyethylene Polystyrene and related
addition vinyl polymers etc.
(b) Step – growth or Polyesters and polyamides,
condensation polycarbonates, etc.
4. Line Structure (a) Linear High density polyethylene (HDPE),
(having no branches) polyvinyls, polyesters etc.
(b) Branched Low density polyethylene (LDPE),
(having branches) phenolic resoles and resitols etc.
(c) Cross linked or network , C-stage amino (urea /
(having a complex network melamineformal-dehyde) resins,
structure) unsaturated polyester resin etc.
5. Application and (a) Rubbers (showing long – Natural rubber, nitrile rubber,
Physical properties range elasticity) polyurethane rubbers, silicone rubbers
etc.)
(b) Plastics (shapable under Polystyrene, PVC, nylon polyamides
pressure, aided by heat) linear aromatic polyesters and
polyamides, etc.
(c) Fibres (available in fibrillar Cotton (cellulose), natural silk,
or filamentous form) artificial silk (rayons), nylon
polyamide fibres etc.
6. Tacticity (a) Isotactic (stereoregular) Poly (α-olefins) and all vinyl and
(b) Syndiotactic (alternating) related polymers.
(c) Atactic (stereo irregular)
7. Crystallinity (a) Crystalline Polyethylene (HDPE and LDPE),
(crystallinity, > 50%) cellulose (cotton) fibre.
(b) Semi – crystalline Polybutene, cellulosics (cellulose
(crystallinity, 30 – 50%) esters (rayons) particularly if stretched)
etc.
(c) Amorphous or non- Natural rubber and most synthetic
crystalline rubbers,N-alkylated(>15% alkylation)
(crystallinity < 25%) nylon polyamides, polystyrene etc.
Table 3: Effect of Variation of Polymer Structure on Properties and Application Prospects
Step – Growth (Condensation) Polymerization
Polymerization refers to intermolecular reaction between bifunctional or polyfunctional
compounds in a manner that makes the process functionally capable of proceeding indefinitely,
avoiding formation of ring or cyclic structures. The sequence of reactions normally liberates of a
small byproduct such as H2O, HCl, etc. at each step: Eg benzene-1,4-dicarboxylic acid and ethan-
1,2-diol
These two compounds can link together to form a polymer, and water is given off:
This polymer can be represented by the following repeating unit:
The overall equation can be represented as:
Chain – Growth (Addition) Polymerization
Chain – growth or addition polymerization is a process by which unsaturated (olefinic, diolefinic,
vinylic) monomers are converted to polymers of high molecular weight exhibiting the
characteristics of typical chain reactions that takes place very fast. The chain polymerization may
be initiated or induced by heat, light or other radiations and by a host of catalysts, called initiators.
If induced by light, the process is referred to as photo polymerization.
Examples:
polychloroethene (polyvinylchloride) is used in waterproof clothing and records
H H
H H
n C C C C
Cl H
Cl H
n
polyphenylethene (polystyrene) is used in packaging
H H
H H
n C C C C
H
H
n
