T/~rmoclim/m ,lau, 27 (197:~) 367-371

~) Els~-ia" Sckntil~ Publishing Company. Am~crdam - Printed in The ~ctha4ands

I D E N T I F I C A T I O N O F N R A N D IR IN B L E N D S O F BK A N D SBR BY
THERMAL ANALYSIS

A. K. ~IRCAR

,I..tL I I ~ r

Cotpm~tian. R,.sr~rcb D~l~t~n~nt. BmTrr. T c x ~ ~I.,n.S_.4.~

tRcx~:i~-d 15 Dcccmbcr tgT/I

ARSTRACT

N R o r IR can he distinguished in blends o f BR o r SBR by their DSC e x o t h e r m

area a n d D T G peak height ratio. Exotherm areas are additive for blends o f N R a n d
less than additive for those o f IR. As a result, only those blends where N R o r I R are
the major components can be characterized.
I .~.'I"RODUCTIO.~

A m e t h o d for the identification o f natural r u b b ~ ( N R ) a n d ~ t h e t i c polyisoprene (IR) in vulcaniz~ttes has recently been published n_ T h e m e t h o d is based u p o n
the higher DSC e x o t h e r m area a n d double D T G peaks for IR. This yeas attributed to
a hi~her level o f c3-clization in the synthetic product, which probably arises as a result
o f catal)~is by residual inoreanic material present therein_ This c3-clized material
decomposes at a higher temperature, giving rise to the second D T G peak. T h e purpose
o f the present work is to extend the m e t h o d to blends o f N R o r I R with BR or SBR.
BR a n d SBR also under_--o exothermic c~.-elization, the area o f which is proportional to
the a m o u n t o f butadiene in the c o m p o u n d : . It ,~-as surmised that the exotherm area o f
these blends ~iil be higher with IR than N R . Since blends rather than the single
elastomers arc being incrcasin$1y used in indus.trial products, their identification is o f
considerable pract;.cal interest.
E~PIE~ME~'TAL

T h e experimental technique is exactly the same as described previously. A D u

P o n t 900 console fitted xlith a D S C m o d u l e x~-as used to obtain the D S C curves w. As
before, the cxotherm area in c m 2 per m E. polymer x,'as used ,,~ithout conversion to heat
o f reaction. F o r u n k n o w n samples, the total polymer was determined from the T G
eur~., the temperature for o,tset o f decomposition (320-340 "C) being determined
from the D T G c u r ~
T h e thermogra~imetric (TG) a n d derivative thermogravimetric ( D T G ) apparatus h a ~ been described previously3.

368

Xhe elastomer samples, as x,~cll as vulcanizing ingrcdient~ ~x~m o f tcchnical

evade a n d used as r c c e i ~ J . T h e f o l l o w i n [ [ r a d c s wcrc used: I R (Nat~-n ~_.'q)O). N R
(AMA-7), BR (Ameripol CB-441), a n d SBR 1 7 ! ~ T h e basic rocipe had polymer: 100,
c a r b o n black (N37~= 50, zinc oxidc= 5, stcaric acid= 3, :~ulfur: ~ 5 , and MBTS: 0.6_
A cure timc ot"30 rain at I-t5 "C x~-~sm c d for all the vulcanizatcs.

l:igut~ I s h o ~ the D ~ C cut~c~ o f the vulcanized c o m p o u n d s studicd. It m a y

be ol~;er.'cd that the peak temperatur~ for IR i~ considerably lower than the o t h e r
three ela.~tomcrs a n d that the exothcrm area per m g pol~rtcr fo!lmx~s the o r d e r o f

OE-BR (6,60 m:),~ OE-$BR (3.85 crn:L IR (3.35 cm-'), and NR (0.85 cm:). Exot!lcrm
a~
coml~r: -.'~ry u-cll ~-;th p u b i ~
v'~luc~.La'- ~
o n 40 tc~ts xvith IR (N--,t%vn
~_..~l~), t l ~ 9 5 ~ confidence limits x,-erc ~ 7~.; for individual tests and ~ 3 ~ for corn-

~3L~

C~

J"

"

<I

0
a
U

It

I~

I_ D S C ~ t ~

"

o l ' ~ R . OE-$BR. IR. and OE-BR ~ u l ~ n i ~ t c ~ (A. 6..'7 rag: IL T.21 mg; C,;s.ggsm$;

o . 7_4t m~_

I~

tW-Elll

20

40

GO

!10

|
tO0

~ari

80

GO

,SO

I~g. ! E f f c c t of N R or I R on rig cxotl~-nn arca o f O E - B R I - u k a n ~ l c ~

369

,l

s ~
I~t

Zo
80

4o
GO

~o
40

8o
20

mo

1~1~- ~- F-~lFc~'t o f N R o r I R o n t h e e x o t i ' g ' n n a n : a o ( O E - S B R

0
,.lcanh~s..

TABLE I
l X O T I i l [ t ~ l AISEA~ IrqZl~ ~'~,"l~,~ot~-.~ A~'%'D I K - q ~ _

IIU~E.",,:D5

A r c : l . cslrl 2

Pol~amcrs

NR
NR~OE-SSR
NR:OE-$BR

NR~OE-SBR
~R:OE-SI3R
OE-SBR
!R
IR~OE-SBR

IR~OE-SBR
IR~OE-SBR

IR~OE-SBR
I R~OE-SBR

puted a ~ r a ~

R;ztio

aOt~l

additive

20:$0
4O=60

O.$5
3.$2
~61

3-~-.~
~65

60:40
S0:20

20:SO

40=60
.'~0:~0
~:40
S0:20

LI~

!.30
~.~$
3.35
3.65

~05
!.45

.~.35

3.T5
3.65

3.22
~91
~74

3.~
3_55
3.4:$

o f I i ~ tests. T h e effects of'different c o m p o u n d i n g ingJ~-dicnts has b ~ n

reported before ~. Within the range o f technical recipes (sulfur, 1 . 7 5 - ~ 7 S ; carbon
black, 30-7>-'), variation o f the different ingredients has m i n i m a l effect.
Figure 2 shows the effect o f dilution o f O E - B R with either N R or IR. Corres p o n d i n g curves for O E - $ B R are p r ~ e n t c d in i:i~.. 3. It m a y be o b ~ r v c d that whereas
the c x o t h c r m area o f blcnd~ o f N R x~th either BR or S B R f o l l o w s a m o r e or less
linear c u r l ~ w i t h c o m p o s i t i o n , those for IR d o not. IR d o e s not act c o m p l e t e l y as a
diluent as the c x o t h c r m areas are slightly higher than for B R or S B R alone, but m u c h
looser than the a d d i t i ~ value. This m a y be d u e to the fact that IR has a relatively big
e n d o t h e r m a r o u n d 4 1 0 - 4 2 0 "C (Fig. 1) which negates the gain to the BR or $ B R

370

...... llR:Ol[-Iit~
. . . . UI: m [ - m l

110 ~ 0
11020

3~

// !
am
Frf.. 4 - D T 6

ix,..

~:en'~ of N R~OE-BR and I IL~OE-BR bk'n~

9 . ~ $ m~:; . . . .

9.95 m;!-

exotherm. T h e I o ~ e r peak temperature for I R m y also I ~ e a n ad~er~e effect on the

xotherm ~ r e ~ O n the other hand. N R c n d o t h c r m L~x~ry s m a l l a n d its peak tempera
lure is about the same as B R o r SBR, ~ Ihe exotherm arcas arc a1~out equal to Ihe
:~dditi~e ~ l u e _ T h i s is illuslrated in Table I for NR~OE-SBR a n d IR~OE-SBR,
where b o l h calculated additive a n d aclual experimental ~ l u e ~ are presented. T h e
approximate additive x~Ime for N R [ O E - B R o r NR~OE-SBR systems indicates nonintervenlion ofc3~lization o r cr_J~linkin~ reactions, probably by" formation o f c r o s s bonds o f two polymers_
A s a result o f the different behavior o f I R a n d N R , the l a r ~ difference in xoOw_rm a r e ~ o f these polymers is minimized in the blends studied, a l t h o u g h N R blends
still hat~e m u c h lower exotherm a r e a ~ It is apparent from Figs. 2 a n d 3 a n d Table I
l h a t N R a n d I R can be positively distinguished in these blends by their exotherm areas
when I g o r N R composition is 40:.~ o r abo,~e_ Also, the peak temperature for I R
blends in this ran~ee is normally beJow 360 "C as compared to 370 "C o r hi eher for N R
blends. However, peak temperature c a n serve only as a n indication, as it varies with
composition.
D T G curves also provide some help in distinguishing N R a n d I R where t h e ~
polymers are the m a j o r c o m p o n e n l s in the blend. T h i s is exemplified in Fig. 4 for the
80 parts N R o r I R , 20 p a r e O E - B R blends. T h e peak height ratio Hdltz is ~ 1 8 for
N R - B R a s compared t o 1~40 for I R - B R c o m p o u n d . F o r compositiom; Io~*r than
o~
60t,,
I R o r H R , the peak height ratios are very similar. A t these c o m p o ~ l i o n s , the
characleristic second peak for I R (42t)-430 ~C) ~
mith the B R o r S B R peaks a n d
s o is indistinguishable.
7 ( 3 curves d o n o t show a n y c h a r a d e r ~ i difference, b u t are necessary for unk n o w n samples in o r d e r to calculate the a m o u n t o f polymer so t h a t the arca~Ymg
poisoner ca n b e evaluatex[.
C h a r a c t e r i ~ l i o n o f B R o r S B R in these blends poses n o problem, d u e to large

371

d i f f e r e n ~ in exotherm area, g]__-t~transition tempcraturc, and D T G peak temperat u f t s ~. ~Vhcn this is known, the thermoo_raphs will not only identify N R or IR but
also will provide an approximate idea of the ratio of the poi~'mers from the exothcrm
area, with the limitations mentioned above.

IR and N R can be d i s t i n ~ i s h e d in a blend of either BR or SBR if the polyisoprenes constitute more than 4 0 ~ of the total polymer.
A C K ~'~OW!:v3rZG- E M E ~

The author wishes to thank D. A. 5weigart for the T G and D T G experiments.

Thanks are also due to J. M. Huber Corporation for pcrmission to publish this paper.
REF~RF~CI~

! A . K . Sircar. Rib/mot Chrm. Tcrhm~l...~3 (19T/) 7 !.

"~ A . K . Sirc~r and T. G. l.~mond.J. AppI. Pol.r~. .~-i_17 ~

A- I~. ~ r c n r and 1". G. l ~ m o n d . R ~ e r

4

(19 7~) ~ .

Ckrm. TcrhmJl.. ~ (1975) 30!.

A-K.Sifc~r:andT. G.~oRulJlxrrC~no.

Tcrh~l.,4~(1972)~29.