Tew York, 1963,.

New York, 1964,

Arnold, London,

ce, John Wiley &

8
3lsevier, Amster.

tions, Cahnerz
Copolymerisation

8.1 INTRODUCTION
The polymerisation reactions that we dealt with in Chapter 2 used
aithera siagle monqmer or a single monomer pair, as will be seen
from the tabulated matter.

g No. Monomer/monomer pair Polymer formed

Ethylene Polyethylene
Vinyl chloride Polyvinyl chloride (Vc)
3. Methyl methacrylate Polymethyl methacrylate
Isobutylene Polyisobutylene
Butadienec Polybutadieno
Propylene oxido Polypropyleno glyco
Caprolactam Nylon 6
8. Hexamethylene dianine +
adipic acid Nylon 6,6
Bthylene glycol + toluene
diisocyanate (TDI) Polyurethane

each of the first seven cases, there is only one monomer which
In
ves the çorresponding polymer. In the last two cases, we use a
ingle monomer pair, which is (a) one diamine and one dicarboxy-
e acid for getting nylon 6,6 and (b) one diol and one diisocyanate
ir getting polyurethane,
 Ioenbo
mon
cOBLO

194 POLYMER SCIENCE

The process of polymerising

mer a single monomer
pair, is termed homopolymerisation
obtained is termed homopolymer.
a
other hand, two or more
or a single monkj
and tho polymer
monomers/monomer pairs are
th
In copolymerisation, on
)RM+M1
V
COPOLYMERISAToN.

RM,M (prôpagation reacthon (PR) type 1.

19 5. 2

simultaneously and, hence, polymeri (ii) RM,+M, RM,M, (PR type 21).
one repeat unit. the polymer is composed of more
For example, styrene-butadiene tha
first commercially rubber (SBR), Gv) RM+M, -> RM,M, (PR type 22).
copolymer obta N
made synthetic rubber, is a
by the free-radical we still1
polymerisation of two'monomers, ASSuming that all the four types of addition take place,
butadiene. It is composed of
repeat units. both styrene as well as
styrene
a
butadien
nave the growing chains ending with M, ör M, and. the possibility
r all the four types of propagation. Now, the rates of these four
In general, copolymerisation
can be represented as propagation' reactions are as follows:
xA + yB >
M+M, MM,i R kulMIM,] (8.1)
-A-A-B-A-A--A-B-B-B-B-A-B-A-B-B M,+Ma M,M RikMITM,] (8.2)
The copolymer formed is
composed of both the monomeric unid
A and B arranged at
random. The A:B ratio and the degrea M,+M M,Mi Ra1kM][M,] (8.3)
randomness depend a
on'the quantity of the individual
taken, their amenability for copolymerisation monómen M+M, M,M,; RakaMI[M,] (8.4)
mechanism used. and the polymerisation The basic assumption is that the ractivity. of any growing chain
Copolymerisation can be brought about by. depends only on the end monómer, unit carrying the frec-radical,
many
merisation reactions, with which we are already types of poly site and not on the number or type of monomer units already added
majority of the commercially important
fåmiliar. Th to the chain. The rate at which the monomers M, and M, are
copolymers, ar
however,
made by free-radical, ionic or polyconidensation polymerisation. W
consumed during the course of propagation can be expressed, as
follows:
shall therefore, confine our discussion to
these three copolymerisatioR
methods. -dMl _ k,,[M,IM,1t+k[M,IMM (8.5)
8.2 FREE-RADICAL COPOLYMERISATION'
-dMa=dt
k,M,IM,1+k,nM,JM, (8.6)
Let two monomers, M, and M,, be mixed together and Now, assuming a
using a free-radical, initiator. Once the injtiator polymerised steady state, wherein the rate of a
particular
decomposes, the chain end (say, M, disappearing is équal to the rate of formatioon
free-radical formed can attack M, or M, as follows: of the same çhain end, we can write
R+M RM, <p[M,JIM,] = k,[M,IMi
(8.7)
R+M, RM, [M k[M,]
Two polymer chains can thus be initiated, one carrying free (8.8)
radical site on monomer unit M, and the other on a
monomer unitiA combination of all
M k[M
M. After initiation, comes the process of propagation. the foregoing equations gives the copolymer
Here, thecquation';
chain carrying a free-radical site on'M1 can either add another
or M. Similarly, the chain carrying a free-radical site on M d[M M,] (lk
M,.can: a[M M [M]+M]
either add another M, or an M.. io (EnM+[M 8.9)
 cOPOLYMERISATION 197
i 96 POLYMBR
sCIENCB casily predict theinstantancous molar composition of the copoly-
The terms (denoted by mer formed. The i and r,values for some impottant monomer
as k/k,, (denoted by r) and k/ka
kiulk
terms, knówn ag t pairs are given in, Table 8.1.
"B in dhis cquation are two important
eactivity ratic monomers M, and M,..
atios for any given pair of
**Os( and r) indicate whether a growing cnan Gatyg ah8.2.1
Determination of Reactivity Ratios
freReactivity ratios of a given päir of nonomers can be experimentally
dical on a particular monomer unit would prefer to. add its ow determined by polymerising
onomèr species or the comonomer species. In other words, theratios to low conversion (usually mixtures of two monomers in varying
less than 10%, so as to minimise
COmposition of the copolymer formed, at any given instant
the cffect of thc change in the monomer ratio as polymerisation
aependent not only on the concentration of the monomer specieprogresses) and then' analysing the resultant .copolymer for its
prosent in. the system at that instant but, also
on their reactivitymonomeric compositioñ.
ratios. The point to be noted is that r1 and r, for any given pa
of monomers are dependent purely on the nature of the twofeed, Let us denote the molar concentration ratio of the monomers in the
monomers and temperâture and indepëndent of other parametors [M,/[M,J, by M and the corresponding molar concentration
ratio of the monomeric components in the polymer, [m|/{mal. by
such as the solvent, initiator and chain transfcr agent., The latte
P. The reactivity ratios r^ andr, can be omputed by plotting the
howevèr, will have a pronounced influence on the molecular weight
and the molecular weight distributión ata according to the following two methods.
of the polymer formed. The
chemical composition of the copolymer formed depends exclusivelyMayo-Lewis
on the monomer concentrations and, their reactivity ratios Method
as pef The copolymer equation [Eqn. (8.10)] can be rewritten in the IOrm
Eqn. (8.9), which can be rewritten in the following
form:
M1.[M]+[M,1
[M] r M,] + [M,]1 (8.10)
+ |-M 8.14)

where nlln,] gives the ratio of the monomers

Now, for the assumed values of ri the corresponding values of r, are
M, and M, enterd calculated for each set of valies of M and P of the' experimental
into the copolymer forned. If we express data. If we plot r, and r, for each set of M and P, we get a series
the monomer components,
m] and [m,] in terms of mole fraction instead of ofstraight lines intersecting almost at a point (Fig. 8.1). At this,
tion, the mole fraction of monomer molar'concentra
M, in the copolymer can bo
given by

d [M (8.11).
n)+m,d[MJ+d[M 7l-na
where n and are the mole fractions of manomers M^
ng
respectively, in the copolymer formed. and M
Similarly, the mole fraction actual
of monomer M, in
the monomer feed can be given by Tandomer2 of the
mon pai
M]
[M+[MI=M= I- N, (8.12)
where and N, are the mole fractions
Mg, respectively, of the monomers M, ana
in the monomer
Now, the 'copolymer, equation' feed. assumed vatues)
[Eqn. (8.9)] can be expressed as
Fig. 8.1. Plots for computing r and r, according to tho
n zCN
+N,N, Mayo-Lewis method.
NF+2N,N, (8.13)
By knowing
r +N"
and r, and also the monomer
feed ratio, we can
 cOPOLYMERISATION 3
295.
204rOLYMER SCIENCE
strictly alte
same r and r, values which We thus get a
point, all the M and P values have themonomer pair. n the copölymer chain formed. monomerfeed, ratio. Itn
tmay be
represent the actual ri and ra for the ating copolymer, irrespective of the
monomór. falling under this
individual polymerised toge-
Intoresting8 to uote that the
Fineman-Ross Methoa
cannot form homopolymers, but when
utilises the equation categOy
TheFineman-Ross method (8.15ther, Can torm an alternating
copolymer. propagation
In this case, all the four types of
M- -t
versus (MP), we get a straight lins actions or
whenr=r,=1.
are. equally possible. A chain ending
ending
with Mi cau ada
with M, can X0d
we plot M -(MJP) and. similarly, a chain
When line givin2 ther M M, or M, adding to the Mi o
intercept giving-r and the slope of the M, or M,: The probability of M,
the'ordinate
8.2). tber concentrations. The copolymer
Fig.
(+
M aepends púrely on the monomerthe mondmeric components as
formed will have thc same ratio of
Components arranged
that of the monomer feed ratio, with the two
in the chain in a purely random sequence. This case can b called
44. "ideal copolymerisation', since the copolymer composition can
e ideally controlled by adjusting the initial monomer feed ratio.
Snce the feçd compositions and the copolymer compošition
remain
constant throughout the course of the polymerisation, this type of
opolymerisation is also called the 'azeotropic copolymerisation'.
-2
(M2 P) When r,>1 and r,<1. In this case, thepropagation reaction
types 11 and 21 will be preferred to types 12 and 22 and, hence, the
(-} probability of M, entering into the copolymer chain is hgher as
Fineman
Fig. 8.2. Plot for computing ri and ra.according to the compared tó M. The copolymer formed will, therefore, be richer in
Ross imethod.
M f ra and r
differ very widely, the copolymer formed, will
comprise almost entirely M, and it will be very.difñicult to incorpo-
Reactivity Ratios. and Copolymerisation Behaviour
8.2.2. any appreciable quantity of M, in the copolymer chain. Con-
Let us recall that r = ku/ka and r, = kza/k1 When ri=11.toate Ou
propagation rate onstants are the same for the reaction
I and for the PR type 12. Hence, a chain with a radicaf end
PR tyEN O e opoIy mer composition, .to some extent, can be achieveda
adusting the mnomer foed ratios, ie, by keeping M,/M, always
1.
can add èither the M, or M2 monomer molecule with equal/ probabsess than
lity. When r, is less than 1, the, M, monomer will be added
ma hen I and ra>1. The behaviour in this cao vill
W

LnOPpoSTe o thnat for case (o). The copolymer formed wil

,readily than M, and, when r is more than 1, the reverse will oc&un
same is true of r, also. Now, depending on the values of ,
ani inerefore, be richer in M
"hevariouá copolymerisation behaviours are possible, which are no When r 2 In this case, the propagation
discussed. reaction type 12 and 21 are preferred to types 11 and 22. In other
(When tyords, while M, Ca add on to M. M can add on to M, at the
11 and 22 are rr=0.
not at all
In this case, the propagation reaction
a
pósible, and, hence, chain ending wime.time. The preterence for one of these two will depend ón the
M, will add only an M, and this M, will add only an M, whidtual values
of rand and also on the monomer fped ratios
in turn, wil adá only an M, and on. In other words, the monhen and r,
so ar caut r, copolymer formed will bo richer in
mer feed ratio notwithstanding, the copolymer formed will haveM, up to an
an equal vumber of M, and M monomeric unitsarranged aliebericher in M vaOT
and, then onwards, the copolymer will
At (-e, when monomer fed ratio
is made up of an equimolar 5quantity of the My and M,), the copolymer
 206 POLYMBR
ScIENC cOPOLYMERISATION 207
formed will have an n valuo of 0.5.(1.0., the. copolymer also.
have an components but arranpe 10r
cqual num
u equal number of M, and M, ged in
a random sequence ce). Since this composition of the monomer
monome
Es in the formation of a copolymer with the same
position, it is called *azeotropic composition. when ri is
a the azeotropic composition decreases from an N, value 05
O,5 and when r, is higher than ra there is an increase in the sa
n, all the cases, however, there is an azeotropic compositior
below which the çopolymer formed will be riçher in Mi and abovs
which it will be richer in M2- The value of N, for the azeotropia
p
composition can be arrived at from the following oquation:
mble fraction of M
(8.16)
in the monomer feed, Ni
When r = Io We get N, equal to 0.5, We can now make a com. (A) ra 1, r2
l
parison with the azeotropic copolymerisation, where both
and r
r () r r2
are unity. In such a case, any mon omer feed composition will act
as an azeotropic composition, whereas in the present case (i.e,.| (D)<1, ra>1
where r, and r, are less than one), only one particular monomer )ri and r2<1, and r1<ra
feed composition will act as an azeotropic composition. As the Plot B shows azeotropic polymerisation behaviour. Pojnts F and G
values of and r, approach unity, the copolymers formed also give the azeotropic compositions for plots C and B respectively.
tend|
to havo their compositions close, though not identical, Fig. 8.3. Plots shpwing the copolymerisation behaviour of monomer
to the|
monomer feed ratio. pairs as a function of their reactivity ratios and monomer
feed ratios.
()When r1>1 and r, > 1. uch a system does not usually
undergo random copolymerisation. It forms either a
mixture the
two homopolymers or, under certain favourable conditions, of 8.2.3 The Q-e Scheme of Alfrey and Price
block Alfrey and Price derived a semiquantitative relationship to compute
copolymers having long' sequences of M^ followed
by a long the reactivity ratios of various monomers. The method deals with
sequence of Ma.
(B Whenr, or ra ==0. Sucha system usually the resonance stàbilisation and polarisation characteristics of a
with a particular azeotropic
results in a copolymer monomer and predicts its reactivity behaviour with reference to
composition. If the mole fraction of another monomer radical. Assuming that a monomer M adds on
the monomer with a zero reactivity
ratio is below the azeotropic to a radical M, the rate constant for the propagation reaction can
composition, the azeotropic copolymer along
of the comonomer will be
with the homopolymer bewritten as
formd. If the mole fraction is higher
than the azeotropic compósition, the azeotropic ka= P,2, exp (-ee) (8.17)
will procèed until the comonomer
the monomer with zero activity
copolymerisation
is consumed and the excess of
ratio remains unpolymerised.
The copolymerisation behaviour of
the monomer pairs with various
at the growing chain end and ,
where Pi denotes a factor characterising tho state of the radical M
indicates the resonance stability
and, hence, the measure of the reactivity of the monomer
M,; e
values ofr and ra as explained above, and e refer to the polarisation characteristics of monomers M,
can be depicted as plots o
mole fractions of monomers in and M, and also to those of the radicals M, and M2, respectively.
fraction of the monomer in the the polymer (n,) against the
monomor feed (N), as mol Similarly, we have
Fig 8.3. shown in ku P01 exp (-ee) (8*
 SCIENCE conc
highly
COPOLYMERI,

monomers
MER
d of
POLY etaiis
In Details
208 ScENCR values of
OLYMER
Tabdo B.2 Q helixes. chapters.
Now, we know that r which can be rewritten as int
.3).
coniguri

e exp (e) Monomer 1.15 0.Tm m

-
PO, exp (-ee) 1.20 priate
arious
Acrylio ncid 0..60 Line

or -exp ) (8.19) Acrylonitril

Putadiene
.39
0.30
1 1.05
1.06
s.3.1

and xp l-e ) (8.20) n-buty acrylato

n-butyl vinyl ether
0.087
1.03
-J.21
0.33
and e values have been assigned to many monomers taking p-chloro styreno 48
standard 0.02
styrene as the standard. Styrene has been chosen as themonomers Chloro triftuoro othy leno 0.22
because it undergóos copolymerisation with most of the o.52
Several monomers have been copolymerised with styrcne and tho.
Ethyl acrylato 0.015 0.20

and r, values for the respective monomer (M,) and styrene (M,) Ethylene
1.37
- 0.74
that of
have been computed. Then, a standard value of Q= and
1
5-ethy1 2-vinyl pyridino 0.96
other 0.033
e 8 have becn assigned to styrene and the Q-e values for Isobutyleno 2.25
monomers have been calculated (from r, and r, values obtainod Maleic anhydrido
o.23
experimentally) using Eqns. (8.19) and (8,20). Q-e values for somo 1.12 0.81
Mothacrylo nitrile
monomers are given in Table 8.2. 0.42 0. 60
r, and ra
Once Qe values for different monomers are known, the Mathyl acrylato
0.74 40
can be com-
values for any chosen pair among those monomers actual
Methyl methacry lato
1.63 o.39
puted from Eqns. (8.19) and (8.20) without the need for P-nitro styrene
experimontation. The Q-e scheme suggests that: (a) monomers with Propylon
0.002 0.78
monomers with
widely difering Q values do not copolymerise; (b) 1.0 0.1 80
Styrene (assumed standard)
widely differing e values have a tendency to. form alternating o.049 I.22
copolymers; and () monomers having roughly equal Q values and Tetrafhuoro ethyleno
o.019 1.86
almost identical e values will undergo azeotropic copolymerisation. Trichiloro ethylene
0.22
Vinyl acetato o.026 -

8.24 Copolymer Composition at Higher Conversions composition of Vinyl chloride 0.044 0.20
The copolymer equation, from which-we predict the com- Vinylidene chloride 0.22 o.36
the copolymer formed, speaks only of the instantaneous molar 16 0.70
position of the copolymer formed from a given monomer feed with Vinyl isocyanato
particular values of r and r We cannot predict the overall com- 2-vinyl pyridine .30 o.50
position of the copolymer formed at higher conversions, say, 50-60%
conversion, as encountered in most of the ind ustrial processes. This
is Data fro Polymer Hándbook, Eds. Brandrup, J. and Immergut, B: H
so because the moment copolymerisation begins (except in the case John Wiley & Sons, Naw York, 1975,
of azeotropic composition), the ratio of the unconsumed monomers
continuously drifts away from the initial monomer feed ratio. The chain in the same ratio as that of the initial feed. Usually, th
continuous change in the monomer ratio is the result of the relative monomer with a higher reactivity ratio is consumed sooner and
hence, the monomer mixturo bocomes progresively poorer ia tha
rate of consumption of the two monomers not being the same
and, hence, the two monomers do not enter into the copolymer
200

POLY MER SCIENCE CEPACAL AND 0METRICAL

SIRDCURE 153
concen trated solutions or swollen gels, they Lincar Brached
helixes. In highly rconnected cell structure Cro-Lke
form interconnccted ctwork or appro
these conformations will be given in
(Fig. S5.3). Details of we deal mainly with
forthcoming sections,
priate chapters. In the
various configurations.
Cross-linked Polymers ogooooog
5.3.1 Linear, Brsnched and can exist in three different types of oo000000o0oo0o00
Homopolymers and copolymers ogooooodoongooo oooogoobboogoeo
chain configurations, viz., lnear, branched or cross-linked. Consi
a homopolymer and a PyCPVAC copolymer. Their struc ogpotoooo
der PVC or a hnear chain type: Here, each coodooooõocciooo
tures, shown in Fig 52, are on eithe
monomeric unit is linked wth two other monomeric units
side, forming a continuous straight chain. Monomeric units are?
added on to each other, ike railway bogies, forming a long train. i
A lineár polymer can be schematically represënted by a single
linne.

In some cases, hoWever, while the polymer chain is growing in

a linear manner, some side growth also takes place from the main
chain. In such cases, while most of thee monomeric units are linke
with two others on either side, some monomeric units
may also be
Fis as.
linked with a third monomeric unit. Such polymer molecules will Schecsic repres
eross-inked polyme
have an overwhelmingly linear chain, with a few short side chains
or branches attached at random points. These are called branched
polymer molecu les', the shape of wiich càn be réprescnted by aO0&&00000C00e0000e0e00 e0oo
line with a few. branches.
During polymerisation, a large number of branchèd polymer
molecules may be formed and, on further polymerisation, the side 0e0e0eoe0e0e0e0e0e0e0e0e0
chains from one molecule could possibly interact with those from
the ncighbouring ones. Since there are many inolecules present with
side chains attached at random positions, the process
of the in
a f0000OO0O8O000000000S90&O
ogeyme
teruniting of side chains of neighbouring molecules results in
single molecule with a crisš-crossed network of chain segments in
all the three dimensions. Such a polymer is called a cross-linked or .

network polymer.
representations liiear, bräinched and network poy-00000000600000000po0odo0o aat poe
of
mer molecules are shown in Fig. 5.4-

5.3.2 Random, Alternating, Block and Graft Copolymers

When two different repeat units in a copolymer are distributed at Ris 5.5 Schemste represenatian of dižerent ypeš ot copolymer
random throughout the chain, tho polymer is called a trandom structures
copolymer. In certain copolymers, a more orderod sequenco o
 poly
POLYMER
Stwo
144 POLYMER sCIENCB
CHEMICAL AND GEOMETRICAL
STRUCTURE and
repeat units is seen and then theso copolymer are termed alternat paper. The structure 14
ing, block or graft copolymers. tion is thcn as shown of polyethylene in a planar zigzag configura- Y
When two repeat units are distributed alternatoly tntg in Fig. 5.6. In doing
this, of course, we have
chain, the polymer is termed an 'alternating copolymer. nered about the free rotation around each
Single bond and the carbon-carbon
various resultant
When a sequence.or block of one repeat unit 1s TOow Cgment. It is seen from Fig.
spatial positions of the paly:
5,6 that all carbon atoms are
block of another repeat unit, which, in turn, is followed by a block
of the ffrst repeat unit and so on, the polymer is called a 'block
.copolymer. Block copolymers are, therefgre, linear molecuts in
which both repeat units are consecutively distributed in fairly long
sequences.
Graft copolymers, on the other hand, are branched molecules
where the main chain is made entiroly of one repeat unit, while the
H H H H

branch-chains are made of yet another repeat unit.

Figure 5.5 shows schematicrepresentations of various copolymers Plane formed by the-C-C-back bono
Bond projecting above the plane of paper
5.3.3 Stereo-regular Polymers Bond projecting below the plane of papér
o: Catom
In stereo-r gular polymers, each monomer segment is in a regulat Fig. 5.6. Planar zigzag structure
of polyethylene molecule.
configuration, giving a definite structural regularity to the polym
molecule as a whole. This structural-regularity, in,a poyuner, attached to each other through' single bonds which are arranged in
arise due. to what are trmed as "optical. and "geomnetri o z1gzag mannér considering their bond angles. All carbon' atoms
merisms of the main chain atoms or substituents in the polynee in the plane of the paper but hydrogen atoms attached to the
molecnle. The meaning of these two isomerisms is nów explained.carbon atoms protrude away, up or down, from the plane of the
paper. The hydrogen atoms
above or below the plane of.the paper
Optical Isomerism are interchangeable. without altering
the overall polyethyene struc-
Optical isomerism has its origin in the way diterent substituentare. This is possi ble because in polyethylene allhydrogen atoms
sit on an asymmetric carbon atom in a polymer wattached to
molecule.we car carbon atoms are indistinguishable.
give an example. A polyethylene molecule has fully saturated But imagine that.one of the hydrogen atoms in all ethylene
units
bon atoms with the following chemical formula: of this polymer is substituted by a substituent R (such as CH,
Cl or CN). The polymer
-CH-CH,-CH-CH,-CH,-CH will then have the chemical formula
way,
-CH-CHR-OH-CHR--CH-CHR- and its structural for-
We can write this, formula in à linear structural showing nomuia would be as follows:
various atoms are attached (but without bothering about the bond
angles and molecular plane) as follows: HH H HH H H E H H H H

nsuch a polymer chain, every, alternate carbon atom can be con

Let us now assume that the carbon-carbon bonds are
plane of this paper and that the bonds between the carbon
all on the|Hdered
atom atom, WnICu we designate as ,
to De asymmetric. This means that the alternate carbon
carries four different substituents
and its substituent'atoms are either below or above the plane of tno
se,confgura.
we
CHEMICAL AND

,
GEOMETRICAL STRUuCTURE 147
OLYMER SCIENCR

R and two polymer chain scgments of chain lengtn m and n

As showna

X-CH2tCH-CHm CH CH
R
R R

Here, X denotes end groups. -ddd-d-d (IsOTACTIC)

or
Each of these C atoms provides a site for optical isomerism.
Each such site can exhibit cither d- or -type isomerism, depending
on whether the R group is located below the plane of carbon-car
bon chain or above. The regularity or the order in which the
successive asymmetric carbon sites, C*, exhibit thoir d- or 1-form
gives rise to three different types of isomeric structuro in tho poly-
mer molecule. The structures shown in Fig. 5.7 wlf clarify the con-
cept In structure L, we have all thcR groups located on one side of
the plane of the carbon-carbon chain. In structure II, we have the
R groups located alternatively above' and below' the plane of the
carbon-carbon chain and in structure III, we have them locatod
randomly. Polymers having structure I are called isotactic; those -d d-Ha (SYNDIOTACTIC)
having structure II are called syndiotactic; while the third type' are or
known as atactic or heterotactic. These three types of polymers --d -d1
have the same chemical structuro, but exhibit ontirely diferent
propertics because of their differing configurations and the result-
ing geometrical structure. Atactic polymers. are, for instanco, gene
rally low melting and casily soluble, while isotactic and syndiotactio
polymers are high molting and less soluble:

Geometric Isomerism
In optical isomerism, while single bond CC atoms are involved,
in geometric isomerism double bond C=C atoms are inyolved.
Geometric isomerism arises from different configurations of the -d-d-HdH (ATACTIC OR HETEROTACTIo
substituents on a carbon-carbon double bond and depends on how or
the substituent groups are positionea. For example, let us consider --d-Hd
1, 3-butadiene polymerisation. The butadiene monomer has two
double bonds in its structure:
Fig. 5.7. Planar zigzag structure of polymer molccules showing:
HH H H (D isotactic, (1) syndiotactic, and (1I) heterotactic co
figurations. (Hydrogen atoms are not shown for the
purpose of clarity.)
148 POLYMER SCENCE

It can polymerise as shown CHEMICAL

AND GROMETRICAL
STRUCiURB 149
- the successive carbon-carbon
n CH2 CH- CH= CH2 4CH-CH CH-CHn straight and stiffened chain segments, the molecule assumnes
ower elongation. rod-like structure (Fig. 5.9) and
exhibits
éach repeat
The resultant polymer structure has a double bond in
unit of H
-CH CH=CH-CH,- CH CH2 CH CH2
Each of these double bonds provides a site for a steric isomerism, CH CH2 CH
depending on whether. the CH, groups attached to the carbon *

atoms on either side of the double bond are close to or away from .
each other. The two possible conflgurations (Fig. 5.8) are: (a) where cis-POLYBUTADIENE)
both the -CH, groups arë on the same side of the double bond
close t each other (called cis-configuration), and (b) where they H H
are on the opposite sides and quit apart, (calíed trans-configuT
ation).
(trans-POLYBUTADIENE)
CH -CH2-CH-
CH CH
CHCH CH CH2
cH
cis-configuration trans-conffguration
L

1,2 vinyl comîiguration H2 CH2

HcH
EH
H2 CH
CH
H2 CHz
Fig S.8. Cis, trans- and 1, 2 vinyl configurationg of butadjeno idi (1,2-PoiYBUTADIENE)
units in polybutadieno molecula .
Fig, 5.9. Configurations of 100% cis-. 100% trans-
A third coniguration; cálled 1, 2 vinyl confguration, is also 1, 2-polybutadiene molécules:"
and r00
possible: sce Fig 5.3 n
the case of 1, 2 vinyl configuration,
however, the thre,types of optical isomerisi, i,e., atactic, isotactio In practice, however, polymerisation' of
or 100% trans is extremely difficult, and wo butadiene to 100% cis
.
and syndiotactic configurations, arë póssible. It maj also be, seen usually obtäin mizxtures
a
from this figure that in cis-conßguratión; there is tanding back .
of cis- and trans-configurations, randomly. dístribüted,throughiout
the chain length (presence of 1, 2-vinyl structiure
ofathe carbon- carbon chain, whereas, in trans-conflguration, there is als- possible)
(Fig.5.9). Depending. on the ratio of cis- to trans-chain
is straghtening önt of thecarbon-carbön cháini During the poly- present, the polymer can exhibit èjther high
segments
merisatión of 1, 3-butadiene; if áll repea units take the cis-confi- orlówelongation.
guration, wo get a 100% cis-polybutadiene and due ,to bendingg
back.of all the successive çarbon-carbon chain segments, the mole-
cule as a whole asumes a shape of a $pring (Fig. 5.9) and exhibits Books for urther Reading
good elongation. On the othet hand during polymerisation,
the repeat units take, trans-conflguration,
if all Natta, G. and Damurso, F. Stereoregular Polymers arid Stereospecific Poly
the resultant polymer is
a 100% trans-polybutadiene and duo to.the straightening
merisations, Pergamón, Oxförd, 1967.
out of al Bevey, F.A., Polymer Conformation and Coriguration, Academic; New
1969.
York,
Koening, J.L., Chemical Microstructure of Polymer Chain, John Wiley
Sons, New York, 1980. &
 ReleatT
Polymerizationjtechniques UNIT-1

are exothermic and the main

Polymerization techniques: Polymerization reactions
dissipate the heat from the reaction
concern during polymerization is to effectively
heat sensitive polymer products.
mixture to avoid explosion and also for running
The main polymer processes are-

Polymerization process
ennancactrua
Dejaketsunw

Heterogenous
Homogenous

Emulsion Suspension
Bulk Solution

polymerization occurs in
polymerization process: this process, the In monomer. So
Homogenous vessel containing only
solvents or in a reaction
one phase, may be in a respectively.
solution and bulk polymerization
methods,
there two main
 Polymerization techniquees

i
.Bulk Polymerization : This method involves only the monomer molecule, an initiator
and a chain transter agent ( if necessary). The monomer is taken in the liquid state and
the initiators is dissolved in the monomer. The chain transfer agents whenever used to
control the molecular weight, is also dissolved in the monomer. Therefore the whole
system is theretore in a homogenous phase. The reaction mass is heated or exposed to
mass
light source for initiating the polymerization and kept under agitation for proper
of the medium
and heat transfer. As the polymerization proceeds, the viscosity
a broad molecular
increases and mixing become progressively difficult, leading to
weight distribution.
is the purest form of
The product of polymerization obtained from this type of process
disadvantage of
polymer, and the greatest yield of polymer per unit volume. The main
diffusion of the growing polymer
this method is that as the medium gets viscous, the
chain become restricted, collisions becomes less and
thereby termination becomes
of polymerization increases
difficult. Due to active radical sites accumulation, the rate
reactions can leads to an
enormously and sometimes, the uncontrolled exothermic
acceleratlon".
explosion. The whole phenomenon is called "auto
styrene or methyl methaclates toget
Examples: The free radical polymerization of
ang also of vinyl chloride to get PVC
transparent moulding powder and cast sheets
resins.
 Polymerization techniques

ii.Solution Polymerization: In this process, the monomer is dissolved in a suitable

inert solvent along with the chain transfer agents wherever used. The free radical
initiator is also dissolved in the solvent medium whereas for ionic and
coordination catalyst, can be dissolved or suspended. The solvent enhances the
heat capacity, thereby reducing the viscosity and promotes proper heat transfer.

Solution polymerization techniques can advantageously be used where the

polymer is used in solution form ( as adhesive and coating compositions).
Chain transfer to the solvent used can not be ruled out, hence it is difficult to
obtain very high molecular weight products.
The polymer formed will also have to be isolated from the solution either by
evaporation or precipitation in a non-solvent and removal of their final traces is
always extremely difficult.
Examples: production of Polyacrylonitrile by free radical polymerization,
polyisobutylene by cationic polymerization, poly(vinyl acetate) ta be converted to
poly(vinyl alcohol).
 Polymerization techniques
-

Solution and bulk polymerization

HOmogenous Adyantace Disacdvantages

heat control important; broad

Bulk Minimum
(Batch type) contamination, Simple molecular weight distribution
equipment
Bulk Better heat control; Requires reactant agitation, material
(Continuous) narrower molecular transfer, separation and recycling
weight distribution
complete
Solution Easy
Easy agitation; may Requires some agitation;
is very difficult for
allow longer chains to solvent removal
recovery; solvent chain
be formed; easy heat polymer
control transfer may be possible but
undesired,
 Polymerization techniques

Homogenous polymerization process

i. Suspension Polymerization : In order to control the enormous amount of heat release
in bulk polymerization, suspension Polymerization method was developed. Only water
insoluble monomer can be polymerized by this technique. The monomer is suspended
in water in the form of fine droplets, which are stabilized and prevented from coalescing
by using suitable water soluble protective colloids, surface active agents and by stirring.
Agitators are used along with suspending agents in the aqueous phase in order to
maintain a specific droplet size and dispersion. The size of the droplets formed depends
on the monomer-water ratio, the type and concentration of stabilizing agents and also
on the type and speed of the agitation employed. Since each monomer droplets are
isolated and independent of other droplets, each of these droplets act as tiny bulk
reactors. Heat transfer occurs from the droplets to the water having large heat capacity
and low viscosity.
As the entire bulk of the monomer is divided into innumerable
tiny droplets, control of
so the product has a narrow
the kinetic chain length of the polymer is also quite good,
proceeds to 100% conversion and thea
molecular weight distribution. The polymerization
product is obtained as a spherical beads or pearls.
So, the technique is also know as
Bead or Pearl polymerization.
 Polymerization techniques

Homogenous polymerization process

i.Suspension Polymerization (continued) Isolation of the polymer becomes easy as
this this involves only the filtration of the bead and removal of the surface active
agents and protective colloids by just washing with water.
The water washed and dried product can be used as such for molding purposes or
can be dissolved in a suitable solvent medium for use as an adhesive and coating
agents.
Examples: Expandable polystyrene beads from which polystyrene foams are made),
(

styrene-divinyl benzene copolymer beads( ion exchange) by free radical initiators.

Typical stabilizer used: Gelatin, methyl cellulose, poly(vinyl alcohol), sodium
polyacrylate.
ii. Emulsion Polymerization : This is the most widely used method of
polymerization. In emulsion polymerization, the monomer is dispersed ln an
aqueous phase as fine droplets which are then stabilized (emulsified) by surface
colloids and also by
active agents (surfactantS- Soaps or detergents), protective
of fatty aclds and of aryl
certain buffers. The surfactants can be cationic alkali salts
(

glycosides). An water soluble Initlators

and alkyl sulfonic acids), or non-ionic (alkyl
are used (persulfates).
 Polymerization techniques

ii .Emulsion Polymerization (continued): Surfactants serves the purpose of lowering

the surface tension at the monomer water interface and facilitate emulsification of
the monomer in water. The surfactant will form micelles when their concentration
exceeds critical micelle concentration (CMC), that are dispersed throughout the
a
solution. In micelle formation, the emulsifier molecule aggregates in such way that
the polar end of the molecule align themselves outward and the hydrocarbon end
thee
come close to each other at the interior. Due to the close proximity of
hydrocarbon ends of all emulsifier molecule, the interior of the micelle acts
a
hydrocarbon phase where the monomer can be stabilized.
yophobic Partt
Critical Micelle Concentration
Lyomilic Pirg
(CMC): The highest
concentration wherein all the
molecules are in the dispersed
state or the Concentration
beyond which only the micelle
formation is possible is known as Surfactant Molecules Micelle
CMC.
 Polymerization techniques

ii.Emulsion Polymerization (continued): Now when the monomer is added and

agitated, emulsitication take place. The resultant emulsion is a complex system: A
molecular solution of the emulsifier in water is the continuous phase wherein the
monomer droplets and micelle (having solubilized monomer at their interior) are
uniformly dispersed.
Emulsion systems generally utilize a .
Monorner
Iuitiator

water soluble initiators as persulfate

Surfaciant

or hydrogen peroxide. With the more

and more polymer formation, the Conumious Phase

polymer aggregate into fine particles Micelle Fornation

and get surrounded and then S Polyinerizatun

stabilized by the emulsifier layer of

the micelle.
stabilized by the
the polymerization, the fine particles of the polymer
At the end of This milky white
in the aqueous layer.
emulsifier and dispersed uniformly adhesives, water
Latex. The latex either can be used for making
dispersion is called can be isolated from the
latex by
etc. or the polymer
soluble emulsion paints electrolyte) by spray drying or freezing.
destabilizing the emulsion (using
 Polymerization techniques

is the most
ii.Emulsion Polymerization (continued): Emulsion polymerization
such as vinyl chloride,
widely used industrial technique( polymerization of monomer
etc.)
butadiene, chloroprene, vinyl acetate, acrylates, methacrylate
Styrene-butadiene copolymer: Monomer:
Polystyrene: Monomer (styrene), Initiator Initiator( Potassium
(Potassium Persulfate), Buffer (Disodium styrene and butadiene (1:3),
Sodiumn Lauryl
phosphate), water, and Persulfate), and emulsifier(
Hydrogen agent)
Lauryl sulfate) sulfate), Lorol mercaptan (chain transfer
emulsifier( Sodium
kndncalMAka.iana.laae.

isadvantages
Heterogenous GVantages

Easy heat Polymer may require additional

control; Easy
Emulsion purification; difficult
agitation; latex may be directly cleanup and
usable; high molecular weight to
eliminate entrenched coagulants,
emulsifiers, surfactants
and narrow distribution
Easy agitation; higher purity Sensitive to agitation; contamination
Suspension
by stabilizer possible, washing,
product when compared to
drying and compacting may be be
emulsion, granular polymer
requiredd
directly usable.
 Polymers

CLASSIFICATION ACCORDING
TO PHYSICAL PROPERTIEs
Polymers can also be classified according
to physical properties as i. ThermoplastiC
ii.Thermosetting; ii. Elastomers ;iv. Fibers
I. Thermoplastic: The polymers in this category are composed of monomers which are linear or
have moderate branching. They can be melted repeatedly and casted into various shapes and
structures. They are soluble in solvents, but do not have appreciable thermal resistance
properties. Vinyls, cellulose derivatives, polyethene and polypropylene are the examples of
thermoplastic polymers.
ii. Thermosetting: There are some polymers which, when heated, decompose, and hence, cannot
be reshaped. Such polymers have a complex 3-D network (cross-linked or branched) and are
called Thermosetting Polymers. They are generally insoluble in solvents and have good heat
resistance quality. Thermosetting polymers include phenol-formaldehyde, urea-aldehyde,
Silicones.

ii. Elastomers: These are resistant solids which have considerable flexibility. They are composed
of polymers with glass transition temperature below room temperature.
One major difference between elastomers and plastics is that the elastomer is in a liquld state,
while plastics are in the glassy state. Examples of elastomers are Butadiene, Butadlene co
polymers and their derivatives, silicones
iv. Fibers: These are solids which can form thread like structures and have high tenslle strength
-

Examples of fibers are Polyamides, Polyesters, Polyurethanes, Protein derivatives.