CHAPTER - I

INTRODUCTION
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INTRODUCTION

Th e emerging areas of polymer chemistry, a

sig nificant branch of orga ni c chemist ry, are plasma
. . l
po l ymer1zat1on , group t r a ns f er po l ymeriza
. t·i on 2 ,
synthesis
of funct i onal polymers 3 a nd template polymerization,
of which latter is more fruitful since it offers a
unique meth od to synthesize a polymer of desirable
structure , stereochemistry, tacticity and average molecular

weight , not only for the detailed desig n of polymeric

materials but also in view of uniform molecular weight

of some biological macromolecules like enzymes and
proteins .

Template po l ymerization , "matrix" or "replica"

polymerization, is rel ated to the gene ral field of
polymer catalysis . In template polymerizat ion we seek
to achieve polymerization of monomer units attached
to a template in a predete rmined manner and thus to

synthes i ze polymers or copolyme rs havin g precis~ structures

and microstructures complementary to those of the template .

The te mplates are linear po l ymer molecu les, carrying
groups which interact with monomer mo lecu l es , ideally

to produce a predetermined linear array of the latter .

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The outstanding characteristics of temp late

polyme i zation are as follows :

( l) The structural and co nformati o n al featu res

..,... of the temp l ate shou ld be re fle eted in the

c o rresponding dau3hter po lymer .

(2) Generally, the rate of polymerization in c r eases

as the co ncentrati o n of the templat e increases .

(3) The overall act i vatio n energy ( ~ E), for template

polymerization is less than the blank reaction :

A E (temp lat e) ( b. E (B lank)

(4) The template and the daughter polymers have

effoc t i v e 1 y identi cal average molecular weights

and molecul ar distribut i o n provided there is

no cha in transfer to template .

The mec h a ni sm of template po l yme riz ation cons i sts

of three s t eps which are as follows

(i) Complex formation

T his may take place between template

and monomer (Type I) or template and oligomers

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created in free so luti on (Type II) . Type I,

is characterized by a continuous increase

(relative rate of p olymerizati o n) with

template co n cent ration until a maximum rate
(VR max . ) is reached . At hi ghe r template con-
centration, th e rate drops . on the contrary ,

in case of type II, there is a constant maximum

value of VR at and above the critical template

con centration . Both the cases may be r ep resen te d

as foll o ws :

( Typ e I ) :
M M M M
I I I I
-T-T - T-T- + nM ~ -t-±-±-t-
(Type II)

- M· -M· - M· -M·
1 I I I
.J. I I I
- T -T-T-T - + -M• ~ -'l'-T-T - T-

( ii ) Template polymerization

M M MM -M-M-M-M-
I I I I 1 I I I
-±-±-±-±- -±-{-±-±-
( ii i ) Separation o f daughter polymers

- M-M -M-11-
1 I I I
I I I I -T-T-T-T- + -M-M-M-M-
-T-T- T-T - Template da ug ht er
polymer
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A search of litera t u re r eveal s that a number

of problems , because of limited publica t i o ns, most ly

related with biopolymers and rarely with vinyl polyme rs

as template , hav e n ot been solved in the f i e ld of template

polyme ri z ati o n . Amongst such are in ventio n of v inyl

polyme rs as new templates and eluc idati o n of kinetic s

and mechanism of such template polymerization systems ,

nature of complexation betwee n two po lym ers , mecha nism

of separ at i o n of template and daughter polymers. In

t h e prese nt wo rk, it i s thoug ht of inter es t to investigate

t he app li catio n s of various v inyl po l y me r s as template

for polymerization of va ri ous electron accepting monomers

viz . acry l o nitrile , meth yl methacrylate , v inyl acetate .

The investigations, embodied in the prese nt

mo nogra ph resu lts in invention of po l yv in yla c etate

as a new template for the radi cal pol ym e r ization of

vinyl monomers with polar groups li ke methyl methacrylate,

ac r y l o nitril e , methacrylic acid ; synd iotac ti c polymethyl

methacry l ate as a template fo r po lymeriz ati on of v iny l

acetate and poly ( 2- vinyl pyridi n e as a template fo r

poly merizati o n of methyl acrylate. Th e in flue n ce of

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template concentrati o n has been stu d ied to evaluate

various kinetic data and elucidate mechanism of template

polymerization. The template and daughter polymers

have been characterized by various spectroscopic techniques .