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POLYMER CHEMISTRY
Lecture/Lession Plan -4
POLYMER CHEMISTRY
6.1 Rubber
Rubber is a natural elastomeric polymer whose monomer unit is cis-2-methyle-1,3-butadiene. Raw
rubber material is extracted from rubber plant which is milk like sappy and negatively charged
colloid, get polymerized bio chemically. The main source of natural rubber is rubber tree (scientific
name: Hevea Basiliensis.)
Rubber tree is found mainly in tropical countries like southern part of India, Srilanka, Malaysia,
Thailand, South America. Solid rubber is white brownish amorphous solid which is soluble in
petrol/carbon disulphide. The main compositions of latex which is extracted from rubber plant are
-
Water - 55-60 percent
Rubber (cis isoprene) - 32-35 percent
Protein - 02-03 percent
Fatty acid - 01 percent
Soluble salt - 01 percent
Ash - 0.03 percent
The approximate molecular weight of rubber polymer is 100000- 160000. Due to its cis configuration,
11
12 CHAPTER 6. POLYMER CHEMISTRY LECTURE/LESSION PLAN -4
natural rubber is well packed and they held together by Van-der Waals force of attraction. That is
why natural rubber has weak molecular force and it is called elastomer. To increase the elastic proper-
ties of rubber during rubber preparation the extracted latex is treated with sunlight/heat/chemicals
(mainly sulpher or hydrogen sulphide etc). The function of sulpher is breaking of pi electron in
rubber and make three dimensional cross linking between double bonded carbon atom by sulpher
bridge. This is called vulcanization of rubber. In this way natural rubber becomes very strong
highly elastic low abrasion resistance towards many chemicals and hard.
The Trans isomer of 2-methyle-13-butadiene is known as Gutta Percha obtained from the tree named
Dischopsis Gutta and Palagum Gutta.
Buna-S rubber is a copolymer obtained by the addition of butadiene and styrene at a ratio 3:1 in a
emulsion system in presence of free radical initiator like benzoyl peroxide or cumene hydro peroxide
with support of dextrose.
6.2. SYNTHETIC RUBBER 13
The produced rubber is called cold rubber as the polymerization carried at temperature -150 C to
50 C. At this temperature the chain length can be controlled. If the reaction temperature is 500 C
then he rubber is called hot rubber and in this case the chain can not be controlled.
Such types of synthetic rubbers are more efficient than natural rubber. These rubber have high
tensile strength, low abrasion oxidation and resistance to weather oil and acid base.
Buna -N rubber is a copolymer obtained by the addition of butadiene and acrylonitrile at a ratio
3:1 in a emulsion system in presence of free radical initiator like benzoyl peroxide or cumene hydro
peroxide. Synthetic rubbers can be vulcanized as there is weak pi bond present in the long back
bone polymeric chain.
14 CHAPTER 6. POLYMER CHEMISTRY LECTURE/LESSION PLAN -4
Such types of synthetic rubbers are more efficient than natural rubber. These rubber have high
tensile strength low abrasion oxidation and resistance to weather oil and acid base. Due to presence
of -CN group this is less resistance towards base.
Polychloroprene(Neoprene)
recycled. But during every recycling the plastic properties of the polymers are gradually decreased.
The thermosetting polymers are not recyclable. Therefore they cause major problem for our ecosys-
tem. This problem are solved by preparing plastics which get degrade spontaneously after certain
period of time (require for use). Such polymers which are biodegradable by chemical oxidation or by
micro organism are called biodegradable polymers. He the carbon-carbon bond in polymers is inert
due to non-polarity and cannot break by means of natural micro organism or by chemical treatment.
To make the polymers biodegradable it is needed to incorporate some reactive functional group in
the carbon-carbon bond of the polymer. Mainly used such type functional group is ester(-COOR)
where the carbon-carbon bond is not directly linked but linked by (-O-). Due to the incorporation
of ester functional group in between carbon-carbon bond the polymer become biodegradable.When
these polymer is buried as waste they will be degraded by microorganism through enzymatic catal-
ysis.
The beat examples of bio degradable polymers are-
Poly-hydroxy butyrate valerate(PHBV)
Poly-hydroxy butyrate (PHB)
Polyglycolic acid(PGA)
Polylactic acid(PLA)
Poly-hydroxy butyrate valerate(PHBV): It is a co-polymer.
and
(MW )
can be determined as
MW = W1 M1 + W2 M2 + W3 M3 + − − − − − − +Wn Mn
X
= Wi Mi
N1 M1 N2 M2 N3 M3 Nn Mn
= (P )M1 + ( P )M2 + ( P )M3 + − − − − +( P )Mn
Ni Mi Ni Mi Ni Mi Ni Mi
N M2 N M2 N M2 N M2
= P 1 1 + P 2 2 + P 3 3 + − − − − + Pn n
Ni Mi Ni Mi Ni Mi Ni Mi
P 2
NM
= P i i
Ni Mi
η − η Solvent
[η] = [ Solution ]
η Solvent
= η Specific
For this purpose different concentration(let 20/40/60/80 percent) of a polymer is prepared in non-
reacting solvent and the viscosity as well as specific viscosity is measured. A straight line graph
with positive slope has been plotted for specific viscosity against the concentration of the polymer.
By extrapolating the line on Y axis and where is touches the Y axis that point is the intrinsic
viscosity([η]) of the polymer.
Fig.
Then using the famous equation of Mark-Kuhn-Houwink i.e.
a
[η] = KMV
we will get the viscosity average molecular weight of the polymer. Where K and a are constant for
specific pair of polymer and solvent and obtained from the literature. It is observed that the value
of a vary in the range 0.5 to 0.9 .
18 CHAPTER 6. POLYMER CHEMISTRY LECTURE/LESSION PLAN -4
Now
a
[η] = KMV
a
log[η] = log(MV )
log[η] = logK + alogMV
Putting the respective value of two constant K and a and [η] we will get the value of MV .
MW
(PDI) =
MN