CHAPTER 13

INTRODUCTION TO
POLYMER
At the end of this lecture,
students should be able to
Determine types of polymer
Determine physical properties of polymer
Determine types of polymerization
INTRODUCTION

Pol!"er is a macro"olecule
co"#rised of re#eatin$ structural
units %oined b! co&alent bonds'

(ree) *ord +#ol!,-+"an!,, +"er,-

#arts

The re#eatin$ unit is a $rou# of

ato"s co&alentl! bonded to$ether in
a s#eci.c s#atial arran$e"ent'

Mono"er the buildin$ bloc) or

structural unit of the #ol!"er'
/0'/ POLYMERIC MATERIAL1
Polymer
Inorganic Organic
Natural Synthetic
Natural Synthetic

clays (bricks,
cement,
pottery)

sands (glass)

fibres
polysaccharides
(starch,
cellulose)

proteins
(collagen,
lignins)

polyisoprene
(rubbers)

adhesiv
es

fibres

coatings

plastics

rubbers

resins
Pol!"ers are usuall! di&ided into t*o
$rou#s accordin$ to their #h!sical or
che"ical hardenin$ #rocesses
ther"o#lastic and ther"osettin$ resins'

Ther"o#lastic solid "aterials are

#roduced b! si"#l! coolin$ a #ol!"er "elt
2#h!sical #rocess3'
e'$' #ol!st!rene, #ol!eth!lene

Ther"oset #roduced b! crosslin)in$

reaction 2che"ical #rocess3 bet*een
#ol!"er "olecules'
e'$' e#o4ies, #henol resins
Thermoplastics Thermosets
5i$h "olar "ass "olecules Lo* "olar "ass "olecules
No crosslin)in$ Crosslin)ed
1often u#on heatin$ Deco"#ose che"icall! u#on
heatin$
Can be re"elted Cannot re"elt
Rec!clable Non rec!clable
POLYMER NAME
P6C Pol!2&in!l chloride3
P1 Pol!2st!rene3
17R 1t!rene8butadiene8rubber
PET Pol!2eth!lene tere#hthalate3
P6A Pol!2&in!l acetate3
PAN Pol!2acr!lonitrile3
1AN 1t!rene8acr!lonitrile co#ol!"er
A71 Acr!lonitrile8butadiene8st!rene ter#ol!"er
/0'0 CLA11I9ICATION

Pol!"ers can be classi.ed as

Addition #ol!"ers

Condensation #ol!"ers
5o*e&er, so"e #ol!"ers are neither
condensation nor addition #ol!"ers'

Therefore, #ol!"ers are classi.ed based

on the #ol!"erisation "echanis"

Chain reaction

1te# reaction

Addition polymerisation
se:uential addition of one
bifunctional;#ol!functional "ono"er
to $ro*in$ #ol!"er chains *ithout
the eli"ination of an! #art of the
"ono"er "olecule'
P
n < M Pn</
e'$' eth!lene, e#o4ide

Condensation polymerisation
#ol!"ers for"ed fro" bifunctional
"ono"ers *ith the eli"ination of a
s"all "olecule s#ecies 2*3' The
reaction can occur bet*een an!
t*o $ro*in$ #ol!"er "olecules'
P
" < Pn P"<n < *
E'$'
Dicarbo4!lic acid < dia"ine #ol!a"ide
Dicarbo4!lic acid < dialcohol #ol!ester

Chain reaction #ol!"erisation

#rocess b! re#eated addition of
"ono"er "olecules to $ro*in$
#ol!"er chain *ithout the
eli"ination of lo* "olar "ass
"olecules'
Y= Y8C5
08C5R
Y8C508C5R8C508C5R etc'
*here Y= is an initiator
CH
2=CHR
CH
2=CHR
=
=
There are four t!#es of
inter"ediates for chain
#ol!"erisation 2based on the t!#e of
initiator3

Carbon free radical 2initiator free

radicals3

Carbocation ion 2initiator cations3

Carbanion 2initiator anions3

Carbene 2initiator coordination

co"#ounds3
Free radical process

6er! fast #rocess 2fraction of a

second3'

Re:uires initiation to start the

#rocess, then #ro#a$ation to $ro*
the #ol!"er chain'

Ter"ination is the last #rocess to

end the #ol!"erisation #rocess'
Initiation Cl
0 0 Cl>

Pro#a$ation Cl> < C5? 5Cl < C5@>

C5@> < Cl0 C5@Cl < Cl>

Ter"ination 2@ t!#es3
2i3 di"erisation
C5@> < C5@> C5@8C5@
2ii3 dis#ro#ortionation
C5@8C50C50> < C5@2C5030C50>
C5@C5=C50 < C5@2C5030C5@
2iii3 chain transfer a chain transfer a$ent de#osits a h!dro$en *ith one
electron on the radical of a $ro*in$ #ol!"er chain and this #rocess initiate
another #ol!"erisation #rocess'
uv
Molecular *ei$ht control

In #ol!"erisation #rocess, the ai" is to

control the "olecular *ei$ht'

The follo*in$ &ariables inAuence the

"olecular *ei$ht

Te"#erature the hi$her 2o#ti"u"3 the

te"#erature, the shorter the ti"e
re:uired to #ol!"erisation'

1ol&ent *hen a #ol!"er "olecule

#reci#itates out of a solution, it *ill not
#ol!"eriBe an!"oreC therefore the
correct sol&ent is i"#ortant'

Concentration of initiator 9or

addition #ol!"erisation, hi$her
concentration of initiator *ill
result in lo*er "olecular *ei$ht
#ol!"er'

Concentration of "ono"er

T!#e of initiator the initiator

for"s radicals b! deco"#osition
reaction *hich has a half life
*hich is de#endent on
te"#erature and t!#e of
initiator'
Cationic polymerisation
ole.n deri&ati&es C5
0-C5R *ith electron8rich
substituents R

"ono"ers C50-D *ith double bonds containin$ heteroato"s or

hetero$rou#s D

rin$s *ith heteroato"s

Three $rou#s of "ono"ers can be
#ol!"erised cationicall!

Initiators 7ronsted acids

2#erchloric acid, trichloroacetic
acid, triAuoro"ethanesulfonic acid,
etc'3C Le*is acids 2AlCl
@, TiCl?, etc'3

Coinitiators *ater, carbeniu" salts 2acet!l #erchlorate3

The $ro*in$ #ol!"er chain is #ositi&el! char$ed *hich

stabilise itself b! addition of nucleo#hilic s#ecies'

6er! fe* "ono"ers are #ol!"erised cationicall! on an

industrial scale'
Monomer Application
Isobut!lene C5
0
-C2C5
@
3
0
Elasto"er, adhesi&es
6in!lethers C5
0
-C5OR Adhesi&es, te4tile aids,
#laticiBers
9or"aldeh!de C5
0
-O En$ineerin$ #lastics
Eth!lenei"ine C!clo82N5C5
0
C5
0
3 Pa#er additi&e, Aocculant
Tetrah!drofuran C!clo82O2C5
0
3
?
3 1oft se$"ent for
#ol!urethanes
Anionic polymerisation

Anionic #ol!"erisation are initiated b!

bases or Le*is bases such as al)ali
"etals, al)o4ides, a"ines, #hos#hines,
(ri$nard co"#ounds and sodiu"
na#hthalene'

The t!#e and #ro#ortion of the initiatin$

s#ecies stron$l! aEect the
#ol!"erisation rates and the tacticit! of
the #ol!"ers 2tacticit! refers to ho*
the #endant $rou#s are arran$ed in a
#ol!"eric strand F isotactic,
sindiotactic, atactic3

Narro* "olar "ass distribution

E"#lo!ed for the #roduction of

ther"o#lastics es#eciall! bloc)
co#ol!"ers 2s!rene8butadiene8
st!rene t!#e3
/0'@ P5Y1ICAL PROPERTIE1

The #h!sical #ro#erties of #ol!"er

"aterial are lar$el! deter"ined b!

Molecular *ei$ht

1tren$th of inter"olecular forces

Re$ularit! of the #ol!"er structure

9le4ibilit! of the #ol!"er "olecule

The #h!sical #ro#erties include

"eltin$ #oint, $lass transition
te"#erature, solubilit!, "elt
&iscosit!, tensile stren$th'

Meltin$ #oint a te"#erature

ran$e in *hich the &iscosit! of the
#ol!"er chan$es fro" a solid to a
li:uid 2the #ol!"er "ust be
ther"o#lastic3
(lass transition te"#erature 2T
$3 a
#oint *here there is a chan$e in #ol!"er "olecule chain
"otion *hich has drastic eEects on stren$th'

Cr!stalline "elt te"#erature 2T"3 the cr!stalline do"ains

of a #ol!"er "elt beco"e a"or#hous'

Tensile stren$th "easures ho*

diGcult it is to brea) a substance
*hen stress is a##lied to #ull it
a#art' Tensile stren$th $enerall!
increases *ith "olecular *ei$ht'
The End