Polymers and polymerization

The joining together of many small molecules to form a very large/huge molecule.
nM (M)n
This equation states that ‘n’ number of single simple (or mixture of) molecules combine
together to form a single huge molecule having ‘n’ number of simple single molecules.

The simple compounds from which polymers are made are called monomers (M).
Eg propene poly(propene)

H H H H
H H H H

n C C C C n C C C C

Cl H CH3 H
Cl H CH3 H
n n

Eg but-2-ene poly(but-2-ene)

Ethene  poly(ethene) / polythene H CH3

H CH3

n C C C C
Many useful polymers are addition polymers made by this process:
CH3 H
 polyethene is used in plastic bags and in crates CH3 H
n
 polypropene is used in plastic tubing
 polychloroethene (polyvinylchloride) is used in waterproof clothing and records
Polymerization is the process of linking monomers together to form a polymer. 
The conditions under which this happens is as follows.
Ethene is heated up to about 200 deg.C. under a pressure of about
1000/1500 atmospheres in the presence of Oxygen which acts as a
catalyst.
Another method was devised in which the high temperatures and
pressures were not used. The catalyst used were known as Ziegler
initiators or Ziegler catalyst called after the German chemist who
discovered them in the 1950's. These catalyst were organic
peroxides or organo-metallic compounds.
Polymer properties
Polymers often have these properties in
common. They are:
•chemically unreactive Polymer name Typical use Properties
•solids at room temperature
•plastic – they can be molded into shape Poly(ethene) or Strong and hard-
Plastic bags
•electrical insulators polythene wearing
•strong and hard-wearing
The table shows some polymers, their typical uses, and Strong, hard-
the properties that make them suitable for these uses: PVC Water pipes wearing, chemically
unreactive

Outer layer of Electrical insulator,

PVC
electric wires hard-wearing

Can be made into

Nylon Clothing fibres, strong and
flexible

Can be made into

Lycra Sports clothing fibres, very elastic
and tough
Common applications of polymers
Field Uses
Agriculture and Are used in and on soil to improve aeration, provide mulch, and
agribusiness promote plant growth and health.

Medicine Many biomaterials, especially heart valve replacements and blood

 
vessels, are made of polymers like Dacron, Teflon and polyurethane.

Consumer Science Plastic containers of all shapes and sizes are light weight and
 
economically less expensive than the more traditional containers.
Clothing, floor coverings, garbage disposal bags, and packaging are
other polymer applications.

Industry Automobile parts, windshields for fighter planes, pipes, tanks,

packing materials, insulation, wood substitutes, adhesives, matrix
for composites, and elastomers are all polymer applications used in
the industrial market.

Sports Playground equipment, various balls, golf clubs,

  swimming pools, and protective helmets are often
produced from polymers.
It is useful to distinguish four polymerization procedures fitting this general description.
•  Radical Polymerization The initiator is a radical, and the propagating site of reactivity (*) is a carbon
radical.
•  Cationic Polymerization The initiator is an acid, and the propagating site of reactivity (*) is a
carbocation.
•  Anionic Polymerization The initiator is a nucleophile, and the propagating site of reactivity (*) is a
carbanion.
•  Coordination Catalytic Polymerization The initiator is a transition metal complex, and the propagating
site of reactivity (*) is a terminal catalytic complex.
There are 3 principal classes of polymers – thermoplastics, thermosets, and elastomers. Differentiation
between these classes is best defined by their behaviors under applied heat.

•Thermoplastic polymers can be either amorphous or crystalline. They behave in a relatively ductile manner
but often have low strength.
•Thermosetting polymers are always amorphous and are generally strong and rigid but often brittle.
•Elastomers are always amorphous and are used in service above their glass transition temperature (Tg).
They have the unique ability to elastically deform by extremely large amounts without permanent damage
to their shape.

Polymers may be naturally found in plants and animals (natural polymers) or may be man-made (synthetic
polymers). Different polymers have a number of unique physical and chemical properties due to which they
find usage in everyday life.
Classification of Polymers based on the Source of Availability
There are three types of classification under this category, namely, Natural, Synthetic, and Semi-synthetic
Polymers.

Natural Polymers:
They occur naturally and are found in plants and animals. For example proteins, starch, cellulose, and rubber.
To add up, we also have biodegradable polymers which are called biopolymers.
Natural Polymers
which include proteins starch, cellulose, and rubber.
Synthetic Polymers,
include bakelite, perspex, terylene (a polyester) and nylon (a polyamide). These are man-made polymers, which are
also called plastics.
Natura rubber
latex tapped from a rubber tree (Hevea brasiliensis) in Malaysia.
Semi-synthetic Polymers:
They are derived from naturally occurring polymers and undergo further chemical modification. For example,
cellulose nitrate, cellulose acetate.

Synthetic Polymers:
These are man-made polymers. Plastic is the most common and widely used synthetic polymer. It is used in
industries and various dairy products. For example, nylon-6, 6, polyether’s etc.
Examples of naturally occurring polymers are silk, wool, DNA, cellulose, and proteins.
Classification Based on Polymerization
•Addition Polymerization: Example, poly ethane, Teflon, Polyvinyl chloride (PVC)
•Condensation Polymerization: Example, Nylon -6, 6, perylene, polyesters.

Classification Based on Monomers

•Homomer: In this type, a single type of monomer unit is present. For example, Polyethene
•Heteropolymer or co-polymer: It consists of different types of monomer units. For example, nylon -6, 6

Classification Based on Molecular Forces

•Elastomers: These are rubber-like solids weak interaction forces are present. For example, Rubber.
•Fibres: Strong, tough, high tensile strength and strong forces of interaction are present. For example, nylon -6, 6.
•Thermoplastics: These have intermediate forces of attraction. For example, polyvinyl chloride.
•Thermosetting polymers: These polymers greatly improve the material’s mechanical properties. It provides
enhanced chemical and heat resistance. For example, phenolics, epoxies, and silicones.
 Some Common Addition Polymers
Name(s) Formula Monomer Properties Uses
Polyethylene –(CH2-CH2)n– ethylene
CH2=CH2 soft, waxy solid film wrap, plastic bags
low density (LDPE)
Polyethylene ethylene electrical insulation
–(CH2-CH2)n– CH2=CH2 rigid, translucent solid
high density (HDPE) bottles, toys
Polypropylene propylene atactic: soft, elastic solid similar to LDPE
–[CH2-CH(CH3)]n– CH2=CHCH3
(PP) different grades isotactic: hard, strong solid carpet, upholstery
Poly(vinyl chloride) vinyl chloride
–(CH2-CHCl)n– strong rigid solid pipes, siding, flooring
(PVC) CH2=CHCl
Poly(vinylidene chloride) vinylidene chloride
–(CH2-CCl2)n– CH2=CCl2 dense, high-melting solid seat covers, films
(Saran A)
Polystyrene styrene hard, rigid, clear solid toys, cabinets
–[CH2-CH(C6H5)]n– CH2=CHC6H5
(PS) soluble in organic solvents packaging (foamed)
Polyacrylonitrile acrylonitrile high-melting solid rugs, blankets
–(CH2-CHCN)n– CH2=CHCN
(PAN, Orlon, Acrilan) soluble in organic solvents clothing
Polytetrafluoroethylene tetrafluoroethylene non-stick surfaces
–(CF2-CF2)n– resistant, smooth solid
(PTFE, Teflon) CF2=CF2 electrical insulation
Poly(methyl methacrylate) methyl methacrylate lighting covers, signs
–[CH2-C(CH3)CO2CH3]n– hard, transparent solid
(PMMA, Lucite, Plexiglas) CH2=C(CH3)CO2CH3 skylights
Poly(vinyl acetate) vinyl acetate
–(CH2-CHOCOCH3)n– soft, sticky solid latex paints, adhesives
(PVAc) CH2=CHOCOCH3
cis-Polyisoprene isoprene requires vulcanization
–[CH2-CH=C(CH3)-CH2]n– soft, sticky solid
natural rubber CH2=CH-C(CH3)=CH2 for practical use

Polychloroprene (cis + trans) –[CH -CH=CCl-CH ] – chloroprene synthetic rubber

CH2=CH-CCl=CH2 tough, rubbery solid
(Neoprene) 2 2 n
oil resistant
 Some Condensation Polymers
Formula Type Components Tg ºC Tm ºC
~[CO(CH2)4CO-OCH2CH2O]n~ polyester HO2C-(CH2)4-CO2H <0 50
HO-CH2CH2-OH 
polyester para HO2C-C6H4-CO2H 70 265
Dacron HO-CH2CH2-OH 
Mylar
polyester meta HO2C-C6H4-CO2H 50 240
HO-CH2CH2-OH 

polycarbonate (HO-C6H4-)2C(CH3)2 150 267

Lexan   (Bisphenol A)
X2C=O
  (X = OCH3 or Cl)
polyamide HO2C-(CH2)4-CO2H 45 265
~[CO(CH2)4CO-NH(CH2)6NH]n~ Nylon 66 H2N-(CH2)6-NH2 
polyamide 53 223
~[CO(CH2)5NH]n~ Nylon 6
Perlon
polyamide para HO2C-C6H4-CO2H --- 500
Kevlar para H2N-C6H4-NH2 

polyamide meta HO2C-C6H4-CO2H 273 390

Nomex meta H2N-C6H4-NH2 

polyurethane HOCH2CH2OH 52 ---

Spandex
 Some Condensation Polymers
Formula Type Components Tg ºC Tm ºC
~[CO(CH2)4CO-OCH2CH2O]n~ polyester HO2C-(CH2)4-CO2H < 0 50
HO-CH2CH2-OH
polyester para HO2C-C6H4-CO2H 70 265
Dacron HO-CH2CH2-OH
Mylar
polyester meta HO2C-C6H4-CO2H 50 240
HO-CH2CH2-OH

polycarbonate (HO-C6H4-)2C(CH3)2 150 267

Lexan (Bisphenol A)
X2C=O
(X = OCH3 or Cl)

polyamide HO2C-(CH2)4-CO2H 45 265

~[CO(CH2)4CO-NH(CH2)6NH]n~ Nylon 66 H2N-(CH2)6-NH2
polyamide 53 223
~[CO(CH2)5NH]n~ Nylon 6
Perlon
polyamide para HO2C-C6H4-CO2H --- 500
Kevlar para H2N-C6H4-NH2

polyamide meta HO2C-C6H4-CO2H 273 390

Nomex meta H2N-C6H4-NH2

polyurethane HOCH2CH2OH 52 ---

Spandex