:,,©

l~f,~",yc;cn

00©! . . . . .
 I

A pofyiijer can suffer demdatioo mainly at two stages of its life~

Fint, during the fabrication process
. and secondly. during its daily
-

usa1e. Many of the fabrication

. . processes such as extrusion or
moulding iov9lve beating, which the P,olymer may not be able to
endure and, as a consequence, niaY just degrade. Similarly, in the
.,. bustle~ustle of modern life, plastic articles have to face mechanical
stresses, solar radiations, atmospheric o:xyge~ moisture etc., and this
r,an degtatle the polymer.
 While polymer degradation is generally undesirable, it can some-
times be put to- advantage also. Porpexample, when a spa~t
re-enters tbe earth's atmosphere, intense beat is generated, which
is sufficient to .melt the metal and even make the craft explode. 1'0
avoid such a situation. the spacecraft.is covered by a 'heat shield',
w.hich is a polymcr•based material. As tJie heat shield encounters
a high tem~rature on re-eotry, the material chars atad degrades
and, in the process, takes away tbc·severie heat and thus protects
the spacecraft.
 Types of Degradation
Polymer depa.dation is brioadly or two typos: (i) chain-end degra•
datioo and (ii) random degradation. In the first type, the de~da-
tion starts from the chain ends, rcsuldog in successive releaseoftbe
monomeric units (Pig. JO.l). • This phenomenon is actually the
rie~erse of the pro~gation step in chain poly~erisation. For this
reason. this type of degiadation is also called •depolymerisation•.
Pis. 10.1 Schematic repli n ion lymcr molecule undcr-
soiog - • • - - . (Each block in the dia-
gram _ , • unlt).
 A good examp - aia-eod degradation lis p~o-
vided by tbe . ·on of non-terminated (i.e.,
living) P9ly «· . rough tbc anionic mecha•
nism. This pol.y nbydrous tettahydriofuran,
upon heating fr dcrgoes deu,adation from
the chai.n end · · n in sueb a manner that,
at 50cc, th - oto the monomer
 - - - -
important precaution to be taken js that the system should be kept
free f:rom moisture and other impurities such as oxygen.. and carbon
d;oxide. The process is, interestingly enougb1, reversible. Hence, by
simply cooling the system back to - 700Ct the 'polymer can be
obtained qualitati,,ely. Polymcis formed by chain reaction polymeri-
sation are more susceptible lo ing (or chain-\!nd d1:gra-
 The second t _odom point along
the polyme · . _ s (Fis. J0.2J and,
hence, the JS of degradation
could be _ _lycondeasa1ion process
as illustr · ing
M.,
 --- . . 1111 11111

ir I I I-
I

pig. 10.2, Schem polymer molc<nlle under-

- ck io tha dia-B[am
Here, the polymer de1radea to lower molecular weight fragmeatJ
but (unlike In chain-end dearadatioo) practically no monomer is
H,berated.
Almost all polymers canunder3orandomdegradation. Polyesters,
for example, undeigo hydrolytic degradation, resulting in ehaill
., .
sc,,ss1on:
 '

Further, in, rando . tbylene for: instance, a

hy<lrogen atom • another and yield two
fraginents, as sh
 The break-
hi ..... ....a...
pl degrades . C, givi -l. ougb
th \1.C dcgrad . highly com n nature.
_seem1 to pJa ajor roJC;. W apparently
. me f ree•radical tR), produced ~ither from impuri.
ties tbe reaction te- turic being reached. attacks
th . . an • • a simultaneous transfer
of . . sit
PVC, w _ 1 . ·yelow, orange,
brown , n ·onoftlle conjuptecl
~double hicb. i . on tlae de . or degrada-
tion. • le of HCl i~ this ~eaction is -talyttc since the dep•
-datio es Caster as •soon as HC\ is evolv,ed. Any material
which _ away HC1 from the. reaction sphere can, tberefo~
arrest t · - radation and stabilise ~he polymer. lt, is for this reason
that P . ailable in market contains certain additives called
·stabilisers• which react with HCl and remove, it from the system.
Zinc octoate, sodium carbonate, certain salts of calcium or barium
or lead, many amines, certain organo-tin comp.ound~and also some
epoxidised vegetable •oils are usetl as stabilisers for PVC.
 Thermal degradation

Heat is one of the most common types of energy in nature. Thermal energy could
promote the movement of the polymer chain, leading to the degradation and
decompose of the polymer, as well as the decrease in a series of properties, such as
mechanical property.

At certain elevated temperatures, polymers' the physical and chemical properties of

polymers will be changed spontaneously
 The chemieal bon0s aosorro en0ugh energy from neat in polymers,
resulting in the breaking 0f these chemical b@rads and then pr0ducing
some free radicals. The formed free radicals are extremely active, and
they would react with the molecules around. Hence, more chains can be
further broken, and more free radicals are generated.

Subsequently, many parameters of polymers would be changed, including

molecular weight, molar weight distribution, degree of
crystallinity, degree of branc:hing, and so on. As the reaction process, the
variation in mass, state, shape even color can be observed.

As a result, the workin~ performance, such as mechanical or thermal

performance of the polymers, would alter dramatically, being prone to
cause the failure of the material.
Photo
Ph0tocl of chain
fi·acuu-e caused by ptiot0sensitive gi·o11ps
in tl1e p0i¥Jµe1· chains boxyl. cru.·bonyl~ and
lmsa • bo11ds d11e to e actio11 of light and the
p1·ese xyge11 [7]. It is an i1npo11a11:t ki.I1d of 1netl1od
f 01· IJO y1ne1· degi·adatio11 iI1 otu. daily life. Ligl1t is lISt1all1;
l1sed as tl1e s011.11. ce to pr·o • • I'gy· fo1· elect1·011s ll1 tl1e
polyi11e • tl1e poly"l excited b)7 ligl1t to
p1·O1110t Jle -b1·eakii1g 1·eactio11.
Photodegra

Photode a : tion of
photode a ymers
coul g direct
degr ir ion. For direct
degra rb phot directly.
and pol y transfonned fio1n
the grol [16]. During this
process!' pol~eF molecu ar chains coulcl be broken~ and
n1olecula1· weight · lly decreases. ~ l e for an
indiJ:ect degradatio roces ene1. gY, of photons is
abso1~bed bv a s11bstance i.J:0111nent~ fn. stly _"''hich
col1ld p1,01note the subst n excited state. A11d then_
tl1e polyine1· n10 • uced to a11 excited state.
wl1ich will 1·est • f pol)TJ.11e1·s by
b1·eaki11g do,
Biodegradatiorn
Biodegi-·adable polyin,e ol e1·~ which
ca11 be complete! wi aid of
11ric1·001·ganis1ns like n be dissolved into
wate1· ai1d degi·aded by C CO2~ and metal-salt.
U11til 11ow . tl1e 111ost corm s l1sed are polylactic
acid (PLA): pol • ) and olymethyl
 - - - - - -
sl1ccinate (PBS) [25]. With the developme nt of
biodegi·ada tion technology!' envi1·0111nental p1·oble1ns can
be gi..adl1ally solved la1·gely. At the same time. these
wastes ca11 be converted into diffe1·ent l1seft1l mate1ials or
cl1emicals. wlrich col1ld ftuthe1· p1·01note the de,,elopme nt
of eco1101nics and life.
 In 1·ecent years~ the biode~·adable polyme1· has been
vvidely used as envit'onmental-fiien dly p1·otection
lllate1ials (1vlulch fo1· agiiculnu·e, constiuction), packaging
lllate1ials (Packaging film~ gai·bage bags_ food packaging
bags),_ biologically ftmctional Inate1ials: tnedical lllate1ials
(ba11dages_ sl1i·gical s11n1i·es)~ and 1lla11y othe1. fields. It also
sl1ov\rs t11liqt1e adva11tages ~ompa1·ed \;\1itl1 sir1gle-l1se
plastic p1·odt1cts.
Mechanical Degradation

A simple compound mch as·water or ...... not be broten up

by subjecting it to mechanical .
stirring or milling. But a poly
a solvent, when subjettcd to
goes considerable molecular' 4.- ·
in the rubber industry, rub
• nsang rom say, hi&b _eed
- p:5Jystyrene. diuolved ia
tirring or beating, under-
r fragmen a o. In fact,
• • by. p ss10 ttlirougll
 - -
two rotating rollers to reduce. it.a molecular weight and makc it
-

more processable. This masticatiop converts hard and tough rubber

into a soft, supple and even semisolid mass. Now, what happeos·to
the nabber at a molceu,lar level wbeo it is so masticated?
I
 .
Let us tlrst remember that mbber is polyisoprene with the folio-
•
wtng structure: •

(lsopreae uni· (lsopiene unit)

~olyisopre
ID polyisopNlle. the bonds which art most wlilerablo for ICiasion
are the CH1-CH1 links between lho iaopmae units, These bonds
ia •the susceptible regions cleave wh,n the polymer is subjected to
mechanical strCsses tn the form or milling or masticatiOn. The net
effect is that• the big molecule is· brolc:en or soissioned into small
•

parts. This scission attbo molecular leve'J r,eflects oo the gross pro-
perties of the polymer.