Module IV

Polymer Chemistry & Stereochemistry

Part I: Polymer Chemistry

Polymers(Greek poly-, "many" + -mer, "part")

They are high molecular weight macromolecules obtained by the repetition of simple units
called ‘monomers’.The monomers may be same or different.

Homo polymer and Hetero or Copolymer

Homopolymer: one kind of repeating unit(identical monomers)

-----A—A—A—A—A------
-----B—B—B—B—B-------
Eg:-Polythene,Polypropylene,PVCetc

Hetero or Copolymer-- two or more different types of monomers.

Eg:-SBR,ABS,B.S etc

Classification
I.Based on the monomeric units

● Random---the two monomers are joined in any order

-----A—B—A—A—A—A—B—B------

● Alternating ---- the two monomers are joined in an alternating fashion

-----A—B—A—B—A—B—A—B------

● Block ---all of one type of monomers are grouped together to form a block& all of other
are grouped to form another block
----A—A—A—A—B—B—B—B------

● Graft –Main chain of homopolymer&attaching chains of hetero.

----A—A—A—A------
I
B-B-B---
II.Based on the type of Polymerisation

Two types
(1) Addition polymerization ---1,2-addition &1,4-addition
(2) Condensation polymerization --- Poly ester(-COO), Poly Amide(-CONH2),
Poly Carbonate(-O-CO), Poly ether(-O-)

(1) Addition or Chain growth or free radical polymerization: Here the polymers are formed by
by the addition of monomers (unsaturated molecules)
 (a) 1,2-addition: Here the monomer consists of a π bond.During polymerization, π bond is
converted to ϭ bond joining 1,2-positions of each monomer unit
Eg: Polythene,P.V.C etc
1 2 1 2
n CH2=CH2 ------→ (-CH2-CH2-)n
Ethylene Polythene
1 2 1 2
n CH2=CH ------→ (-CH2-CH - )n
I I
Cl Cl
Vinyl Chloride(V.C) Polyvinyl chloride(P.V.C)

(b) 1,4-addition : Here each monomer consists of two π bonds.During polymerization,one π

bond is formed at the middle (2,3-psitions) and a ϭ bond is formed by connecting 1,4-positions
of each monomer unit.
Eg: P.B.D, Chloroprene,isoprene, etc
1 2 3 4 1 2 3 4
n CH2=CH-CH=CH2 ----🡪 -( CH2-CH=CH-CH2 -)n
1,3- butadiene Poly butadiene(P.B.D)

(2) Condensation or step growth or step by step polymerization: Here the polymers are
formed due to the condensation of two different monomers with the elimination of simple
molecules like H2O,NH3,HCl etc
Eg: PET---- Polyethylene+Terephthalic acid

Copolymers
1) ABS-Acrylonitrile Butadiene Styrene

Preparation:It is prepared by polymerizing styrene with acrylonitrile in presence of butadiene

Properties

● It is an amorphous thermoplastic polymer

● Styrene gives the plastic a shiny &impervious surface
● It is hard,tough &rigid
● Good chemical resistance
● Excellent high &low T performance(can be used between-20oC&800Cc as its mechanical
properties vary with T)
● High tensile strength &stiffness
● Relatively low cost
● Excellent ductility
● Creep resistant(starts flow due to stress)
● Very High impact strength

Applications

ABS is light weight & is useful in manufacturing products like

● TV cabinets,camera bodies,computer bodiesmobile phone body etc
● Used in making parts of furniture components,coffee mill,coffee maker,
refrigerator,water purifier,microwave oven etc
● Kitchen appliance like mixer grinder
● Musical instruments
● Enclosures for electrical &electronic assemblies
● Household &consumer wares

Advanced Polymer

KEVLAR –PPTA-(Poly Paraphenylene Terephthalimide)

● KEVALR is registered trade mark name of an aromatic poly amide(aramid)

● It is an expensive high strength material(5 times stronger than steel) developed in 1965
and being developed in 1970 as a replacement of steel in racing cars

Preparation

Prepared by the condensation reaction between the monomers—Para phenylene diamine(1,4-

phenylene diamine) & Terephthaloyl Chloride(Terephthalic acid dichloride)
Structure of KEVLAR

Kevlar is very rigid polymer which tend to form planar sheet like structure.
Three types of bonds are present in the molecule
● The strongest covalent bonds in the polymer chain
● Vander waals forces between the chains
● H-bonding between –CO gp &-NH gp

Properties

● It is an extremely light mate

● High chemical resistance
● It does not corrode &absorb vibrations readily
● Kevlar fibre has high tensile strength
● High structural rigidity
● Flame resistant
● It maintains its strength &resilience to cryogenic temp.(-196oC)
● At higher T its tensile strength is reduced by about 10-20%

Applications
● Used in the field of cryogenics for its low thermal conductivity and high strength
at low T.
● Kevlar composites are used as thermal insulator for liquid hydrogen storage tanks of
cryogenic rockets
● Kevlar shows high tensile strength-to-weight ratio & used in aerospace industry
&aircraft industry
● Industrial Application:Parts of aircrafts,shiphulls,reinforced materials etc
● Military Appln:-.bullet proof vests,helmets,ballistic vests,face masks,gloves, sleeves,
jackets etc
● Sports Equipments:- race car parts,racing canoes,sport shoe,snow boards,slate
boards,motor sport helmets,archery etc
● Personal safety Equipment:-riding shoes,helmets,heat resistant gloves,body
armours,body pads etc
● Fibre optic cables used for audio data transmission