Polymer Chemistry 16 17 I Sem
Polymer Chemistry 16 17 I Sem
Polymer Chemistry 16 17 I Sem
Polymers
(Poly) Many + (meros) Parts
This name hints at how polymers are made.
monomers
Polymers
The word, polymer, implies that polymers are
constructed from pieces (monomers) that can be
easily connected into long chains (polymer).
Polyester
Polyester is used to make bottles and fabrics.
CH2
CH2
CHCl
Polymer
CH2CH2
CH2CH2
Cl
O
H2C
CH2
CH2CH2O
HOCH2CH2OH
CH2CH2O
O
HO
CO2H
C
H
C
H
Definitions
According to the amount of repeating units
monomer : one unit
oligomer : few unit
polymer : many unit (poly many, mer part)
telechelic polymer : polymer containing reactive end
group
Definitions
DP : Degree of polymerization
The total number of repeating units contained
terminal group in a polymer
One
kind
Homopolymer
Two
Copolymer
kinds
A-B-A-B-A-B-A-B-
Types of polymer
Homopolymer : -A-A-A-A-A-A-A-ARandom copolymer : -A-B-B-A-B-A-A-BAlternating copolymer : -A-B-A-B-A-B-A-BBlock copolymer : -A-A-A-A-B-B-B-BGraft copolymer : -A-A-A-A-A-A-A-AB-B-B-B-B-
Tacticity
Classification of polymers
Natural polymer: which are found in nature in animals and plants etc. like cellul
Protein, nucleic acids, natural rubber.
r polymer in which monomeric units are joined in the form of long straight chain
xample: nylons, polyester etc. these polymer possess high density , m.p. and ten
gth due to close paking of polymer
(a) linear
nched chain polymer are mainly liner in nature, but also posses branches alon
ain. f. g. low density polyethene. These polymers possess low m.p. density and
strength as compared to the liner polymer
(b) Branched
(c)network
H2
C
H2
C
Ethene
bifunctional molecules
polythene
2R
(Initiator)
Free radicals
Azobisisobutyronitrile
M1
O
O
O
O
M1 + M
monomer
M2
M2 + M
monomer
M3
M3 + M
monomer
M4
Mn + M
monomer
Mn+1
In general
Termination steps
Termination by coupling.
Termination by disproportionation.
Termination by coupling
Termination by disproportionation
Ionic polymerization
In ionic polymerization, the active centres initiating the
chain reaction are ions. Ionic polymerization proceeds
due to the presence of catalysts and hence it is called
catalytic polymerization. Depending upon the charge of
the ion formed, the polymerization may be cationic or
anionic.
Lewis acids
Carbenium ion
salts
Propagation
Ziegler-Natta catalysts
Cl C H
2 5
Cl
TiCl4 + Al(C2H5)3
Ti
C2H5
Al
Cl
Cl
C2 H5
C2 H5
CH2
H
Cl C2
Cl
Ti
Cl
Cl
CH2
Cl
Ti
Al
C2H5
C2H5
(CH2-CH2)n C2H5
Al
Cl
Ti
Cl
Cl
H2C CH2
C2H5
H
Cl C2
Cl
Cl
C2 H5
Al
Cl C H
2 5
Cl H
C2H5
Cl
Ti
Cl
C2H5
H2C CH
Al
Cl
C2 H 5
C2H5
(CH2-CH2)n C2H5
BULK POLYMERIZATION
The simplest method of polymerization where the
reaction mixture contains only the monomer and a
monomer soluble initiator. The process generally
carried out in the by a continuous process, which
involves two stages:First Stage
Pre polymerization is carried out in nitrogen
atmosphere in in a reaction vessel , which is heated by
hot jacket and monomer and initiator is added
continuously with stirring at certain rate. The
monomer is polymerized to about 30%.
Second Stage
The polymerization mixture is highly viscous and clear,
is fed into the upper end of vertical reactor, divided
into zones, each kept at desired temperature except
the lowest one. The highest conversion of
polymerization is carried out in the lowest zone. The
resulting molten polymer is taken out with the help of
ADVANTAGE
Advantage of the high concentration
of monomer result in
High rates of polymerization
High degree of polymerization
High purity of product
High molar mass polymer are
produce
Limitations:
Difficulty in removing the last traces
of monomer
The problem of dissipating heat
produced during the polymerization
Emulsion Polymerization
The monomers are dispersed as fine droplets
(d=~1mm) in large amount of water and then
emulsified by the addition of emulsify agents
(soaps, detergent).
Then initiator is added which are usually water
soluble or monomer soluble. Very often
persulphates are used.
These ion radicals react with monomer in
emulsion form and polymerization occurs.
Finally the polymer emulsion is may be broken
by adding electrolyte followed by washing,
drying etc. of coagulated polymer.
For example PVC etc.
Emulsion Polymerization
Emulsion Polymerization
Disadvantages of emulsion polymerization
include:
For dry (isolated) polymers, water removal
is an energy-intensive process
Emulsion polymerizations are usually
designed to operate at high conversion of
monomer to polymer. This can result in
significant chain transfer to polymer.
Suspension
Polymerization
In this methods monomer is dispersed as relatively
large droplets (10-100 mm) in water.
It is kept in suspension by mechanical agitation.
The catalyst is then added and imitation take places.
As the polymerization will proceeds, the viscosity will
of dispersed drops increases and become sticky.
At this stage suspension is stabilize by small amount
of suspension stabilizer.
When the reaction is complete, the reaction products
(in form of pearl) is washed dried and used.
Disadvantages
The method can be adopted for only water insoluble
polymers
It is difficult to control the particle size
Yield per reaction value is low.
temperatureTgis
always
lower
than
Factors affecting Tg
Upon heating through the glass transition temperature,
the amorphous solid polymer transform from a rigid to a
rubbery state and the molecules which are virtually
frozen in position below Tg begin to experience rotational
and translational motions above Tg
1) The presence of bulky side groups increase Tg.
2) Polar side atoms or groups of atoms increase Tg.
3) Double chain bonds and aromatic chain groups which
tend to stiffen the molecular backbone increases T g.
4) Increase in the molecular weight also tends to raise
the glass transition temperature.
5) A small amount of branching will tend to lower Tg; on
the other hand , a high density of branches reduces
chain mobility, and elevates glass transition
Mw
Ni
M2i Ni Mi
Ni M i
Ni
Ni
M2i Ni Mi
Mw
2
2
2
50(10000)
+
35(12000)
+
15(14000)
=
(50x10000)+(35x12000)+(15x14000)
Mn
DP=
Molecular weight of monomer
Ans. = 269 (DP)
benzoyl peroxide
C
Tetrafluoro ethene
Polytetrafluoroethene (PTFE)
roperties of TEFLON:
Uses
Nylon:
A man-made polymer
Nylon is used in
clothes, shoes, jackets,
belts, Tires, ropes and
various accessories.
lons are used for fibers, use in making cloths, carpets etc.
ey are used for moulding purposes for gears, bearing, electrical equipme
ey are also used for making filaments for ropes, for tooth brushes and fil
roperties of Nylons
hey
hey
hey
hey
OH
HCHO
CH2OH
CH2OH
OH
OH
roperties of Bakelite:
Uses
Epoxy resins
Rubbers (Elastomers)
Highly amorphous
Highly random
orientation
Elastic properties
Stressed
In tension
No Stress
Natural Rubber
Natural rubber is cis-1,4-polyisoprene, a polymer
of isoprene (2-methyl-1-3- butadiene). It is a
stereo regular polymer with all the pendent
methyl groups in the linear polymer chain lying in
one side.
H
H
H
C
H
C
C
H
C
H
Cis-polyisoprene
Vulcanization
Vulcanization is a process, through which elasticity of the rubbers
increases and reduces plasticity by the formation of a crosslinked
molecular network.
Vulcanizationisdonebyheatingtherubberwithsulfurorother
vulcanizingagentsunderpressure
Tetramethylthiuram disulfide
Compounding of Rubber
Compoundingismixingoftherawrubber(syntheticornatural)with
othersubstancessoastoimparttheproductspecificpropertiessuitable
forparticularjob.
(1)Softener and plasticizers are added to give the rubber greater tenacity
and adhesion. For e.g. vegetable oil, waxes, stearic acid.
(2) Vulcanizing agents: sulfur, sulfur monochloride, benzoyl chloride etc.
(3) Accelerators: These materials drastically shorten the time required for
vulcanization. 2-mercaptol, Benzothiazole etc.
(4) Antioxidants: Natural rubbers has a tendency to perish due to the
oxidation. For this reason antioxidants are required, such as complex
amine, phosphites etc.
(5) Reinforcing fillers: theses materials gives strength and rigidity to the
rubber products. For e.g. CaCO3, ZnO etc.
(6) Colouring agents
Condensation/StepReaction
Growth occurs throughout matrix by
reaction between monomers, oligomers,
and polymers
DPa low to moderate
Addition/ChainReaction
Growth occurs by successive addition of
monomer units to limited number of
growing chains
DP can be very high
Some examples:
A polymer made
form just one
monomer is
polyethylene. It
is the most
common plastic
you see.
It is used for
bottles, buckets,
jugs, containers,
toys, even
synthetic
lumber, and
many other
things.
Polyethylene
city:
head-to-tail configuration, in which the functional groups are all on the same sid
hain is called isotactic polymer
e arrangement of functional groups are at random around the main chain, is calle
ctic polymer e.g. polypropylene