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JOURNAL OF POLYMER SCIENCE: Polymer Chemistry Edition

VOL. 11, 1505-1515 (1973)

Studies on the Nature of Multiple Glass


Transitions in Low Acrylonitrile,
Butadiene-Acrylonitrile Rubbers
M. R. AMBLER, Chemical Materials Development, The
Goodyear Tire & Rubber Company, Akron, Ohio 44308

synopsis
A study of the occurrence of multiple glass transitions in acrylonitrile-butadiene rubbers (NBR) has been made. Copolymerization theory was used to predict the change
in comonomer composition with conversion for comonomer ratios both above and below the calculated azeotropic composition of 64% butadiene/36% acrylonitrile by
weight. The results of these calculations suggested that multiple glass transitions,
which occur only in NBR of less than 36% acrylonitrile, were due to an inccjmpatibility
of copolymer species of divergent comonomer compositions. This was shown by differential thermal analysis to be the case for various experimental polymers of known
comonomer composition. A series of NBRs was prepared by incremental addition of
acrylonitrile monomer during polymerization, and the resultant glass transition temperatures were evaluated. Results obtained showed that experimental samples which
had single glass transitions also had a much narrower spread of comonomer species than
the corresponding rubber polymerized with the use of full initial charge of both monomers. The data indicate that NBRs having a single glass transition, regardless of
acrylonitrile content, may be prepared by incremental addition of acrylonitrile monomer
during polymerization. Existing copolymerization theory appears to be adequate for
predicting incremental monomer addition schedules suitable for the polymerization of
NBRs having a single glass transition.

Introduction
A limited amount of information has been published about the occurrence
of multiple glass transitions in acrylonitrile-butadiene rubbers (NBR).
Chandler and Collins reported the presence of multiple glass transitions
as detected by differential thermal analysis (DTA) in NBRs having acrylonitrile contents less than 360/,. Cheng,2in a later publication, reported the
occurrence of multiple glass transitions as arising from the melting of cisl14-polybutadiene crystallites. An extensive study has been reported by
Landi, in which he discusses the relationship between multiple glass transitions and copolymerization parameters in low-acrylonitrile NBRs.
Studies of a similar nature have been performed in this laboratory.
Calculations based upon copolymerization theory have been made for several acrylonitrile-butadiene copolymers of differing comonomer contents,
and various experimental samples were prepared and analyzed for their
1505

@ 1973 by John Wiley & Sons, Inc.

M. R. AMBLER

1506

glass transition temperatures t o verify the results of these calculations.


Incremental addition of monomer during polymerization was also studied
as a means of producing NBR types with a single glass transition.

Experimental
The DuPont 900 differential thermal analyzer equipped with a differential scanning calorimeter cell was used for all analyses. Sample weights
of 20-30 mg, a heating rate of lO"C/min. and sensitivity of 0.2"C/in.
were used throughout the study. Some of the samples were mill-massed
before analysis, while others were analyzed in the original form. All samples were cooled from ambient t o - 150C with liquid nitrogen and then
heated t o 100C.
Samples were analyzed for bound acrylonitrile content by using the
Kjeldahl technique. The reported acrylonitrile contents reflect the bound
acrylonitrile content of the rubber after extraction t o remove organic
nonrubber constituents.

Discussion
I n copolymerization theory, the dependence of the composition of the
polymer formed on the composition of the monomer feed can be expressed
by

F1

(rh2

+ f1f2)/(rlfl2 + 2f1.f~+ rzfz2)

(1)

where F1 represents the mole fraction of monomer M1 in the increment of


copolymer formed at a given stage in the polymerization, and fl and f 2
represent the mole fractions of unreacted monomers &I,and &I2(with reactivity ratios r1 and rz)in the feed.4a
For the NBR copolymerization system, the composition of the increment
of polymer formed a t a monomer composition specified by fl is readily calculated from eq. (1) if the monomer reactivity ratios r1 and r2 are known.
The reactivity ratios for acrylonitrile (Ml) and butadiene (Mz)
have been
reported in the literature5as r1 = 0.02; r2 = 0.39. F1 as a function of f1
was calculated by using these values of rl and r2 and plotted as shown in
Figure 1. The dotted diagonal line would represent the point a t which
fl = F1. It is apparent that the mole fraction Fl (composition of polymer)
in general does not equal f1 (composition of monomer feed), but a t f1 =
0.38 the composition of polymer being formed coincides with that of the
monomer mixture (axeotropic mixture). At f1 > 0.38, the polymer being
formed will contain a smaller fraction of monomer M1 than that of the
monomer feed (i.e., f1 > F1). At f1 < 0.38, the opposite is true (i.e., f1 <
F1). Thus, one would expect from this that when a copolymerization is
carried out a t fl < 0.38, the acrylonitrile content of the monomer feed will
continually decrease with conversion, which should result in a continual
decrease in acrylonitrile content of the polymer formed as conversion progresses. The opposite effect should be evident atf1> 0.38.

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MULTIPLE GLASS TRANSITIONS


1.0

0.8

0.6
F1
0.4

0.2

0.2

0.4

0.6

0.8

1.0

fl

Fig. 1. Monomer feed vs. copolymer formed.

It is possible to express the change in f1 as a function of eonversion


according to the method of Skeist.6 This procedure has been summarized
by Fl01-y.~~Skeist expressed the change from the initial monomer feed
composition (fl)o to some valuefl as an integral as shown in eq. (2) :
f1

In ( M / M o ) =

(fdo

dfll(F1 - f1)

(2)

Equations (1) and (2) are combined to form eq. (3).

(3)
When the appropriate values of r1 and r2 for acrylonitrile and butadiene are
used, eq. (3) can be integrated to yield an equation expressing the degree
of conversion 1 - ( A l / M o )required for a change in monomer feed composition from (f&toji.
By repeating the integration for various suitable values of f1, it is possible
to construct the relationship between f1 and degree of conversion. Then,
with the aid of eq. (l),the incremental composition of the copolymer formed
(Fl) can be expressed as a function of the conversion. This was done for
several monomer charge ratios and the results plotted, as shown in Figurv
2. For F1 = 0.35, the acrylonitrile content of the copolymer formed will
not change with conversion, as is evident from Figure 1. At F1 values
greater than 0.38 (acrylonitrile > 36Oj,), the acrylonitrile content gradually
increases, but only at conversion levels greater than 90% is the magnitude
of the change in F1 very large. Also, the farther one gets from (F1)o =
0.38, the sooner does the incremental copolymer formed begin to show

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M. R. AMBLER

0.6

0.5

0.2

0.1

20

40

60

80

100

PERCENT CONVERSION

Fig. 2. Instantaneous copolymer formed vs. conversion.

deviations from earlier copolymer contents. At F1 values less than 0.3s


(acrylonitrile < 36%, the region of multiple glass transitions), the curves
take on a different shape altogether. As conversion increases, F1 decreases
at a much faster rate and at surprisingly low conversion levels deviates
drastically from the initial copolymer composition. The fact that most
commercial polymers are prepared to high conversions (850/, or higher)
would explain why multiple glass transitions are formed a t acrylonitrile
contents less than 36y0while for NBRs above this value, there is no problem with regard to producing multiple glass transitions at high conversions.
The data in Figure 2 also suggest that at lower conversion levels the integral
composition of acrylonitrile content should be rather uniform, the deviating copolymer composition being formed only a t somewhat higher conversions. From the calculated F1 data shown for specific
values,
other data for intermediate values of (F& can be adequately estimated.
(It should be pointed out that the ordinate in Fig. 2 is the instantaheous
copolymer composition being formed a t the specified conversion level, as
shown by Skeist. The polymer formed over the entire range of conversion will consist of the sum of the increments of polymer differing progressively in their mole fractions, Fl.)
Similar calculations can be made even when a portion of the acrylonitrile
monomer charge is held back at the start of the polymerization and added
incrementally as polymerization proceeds. The integrated solution of
eq. ( 2 ) was applied in the same manner as discussed previously for a series
of incremental monomer addition schedules for several monomer charge

MULTIPLE GLASS TRANSITIONS

1509

TABLE I
Incremental Monomer Addition Schedules
~~

Sample
no.

Butadiene/
acrylonitrile

Conversion

76

Parts
acrylonitrile

Parts
butadiene

71

67/33

70/30

19
3.5
3.5
3.5
3.5
8.5
4.3
4.3
4.3
4.3
4.3
10.5
3.0
3.0
3.0
3.0

67
-

76

0
11.5
28.8
43.7
57.5
0
11.5
23.0
34.5
46.0
57.5
0
27.6
36.8
46.0
57.5

100

77.5/22.5

70
-

77.5

ratios below 360/, acrylonitrile. These schedules were each evaluated for
their theoretical change in copolymer composition with conversion in an
effort to find the ones which appeared t o hold the copolymer composition
constant to a sufficiently high conversion. Three examples will be discussed here. Calculations were made for three monomer charge ratios:
67/33, 70/30, and 77.5/22.5 wt-% butadiene/acrylonitrile. The addition
schedules for each charge ratio (based upon 100 parts total monomer) are
listed in Table I, with the calculated change of F1 with conversion for
these three shown in Figures 3-5. The graphs take the form of a step
function, each step corresponding t o an acrylonitrile monomer addition.
I n Figure 3, the charge ratio 67/33 now shows the extreme drop in
calculated F1 to be a t the 90-95yo conversion level, whereas from Figure 2
i t was found t o be a t the 85y0 level. Figure 4 shows that for a 70/30
charge ratio the drop in calculated Fl is also shifted t o the 90-'95y0 conversion level, while it was estimated from Figure 2 t o be in the region of
70-75a/, conversion. The charge ratio 77.5/22.5 (Fig. 5) now shows the
drop in calculated F1 t o be shifted from Soy0 conversion (Fig. 2 ) t o 85y0
conversion. Polymerization studies with the use of these incremental
addition schedules and DTA evaluations of the polymers were now made t o
deduce whether the apparent control of comonomer composition for these
three samples would result in a single glass transition.

Results
The T, values for 18 commercially available NBR polymers were determined, with the results shown in Figure 6. All the samples studied
yielded data in agreement with that predicted by Collins,' who reported

M. R. AMBLER

1510

0.5
F1

0.4

0.3

0.2

0.1

20

40

60

80

100

PERCENT CONVERSION

Fig. 3. Instantaneous copolymer vs. conversion;


schedule.

sample 71, incremental addition

that at acrylonitrile contents lower than 36% acrylonitrile, multiple glass


transitions T , were obtained. There is remarkably little scatter to the
data points, the three line segments each being linear. The data indicate
that the temperature span between the two glass transitions of any polymer in the multiple T , region becomes greater as per cent acrylonitrile
decreases, indicating that the glass transition region for these samples is
becoming much broader, encompassing a wider range of temperatures.

0.5
0.4

F1

0.3

0.2

0.1

20

40

80

60

100

PERCENT CONVERSION

Fig. 4. Instantaneous copolymer vs. conversion;


schedule.

sample 76, incremental addition

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MULLTPLE GLASS TRANSITIONS

0.5
F1

0.4

40

20

80

60

100

PERCENT CONVERSION

Fig. 5. Instantaneous copolymer vs. conversion; sample 100, incremental addition


schedule.

A second experiment was prompted by the speculation by Collins that the


occurrence of multiple glass transitions might be due to mixtures of incompatible copolymer species. It was reasoned that if incompatibility
was indeed the basis for multiple glass transitions in NBR, a physical
mixture of two NBRs with differing glass transitions should show reten-

-20

-30

1-

t-DOUBLE Ts

-70

t S I N G L E Tg-

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M. R. AMBLER

-100

-80

-60

-40
-20
TEMPERATURE, "C

20

Fig. 7. Incompatibility of NBR blend.

tion of both transitions and show little or no smearing of the individual


glass transitions. Therefore, two NBR samples of differing acrylonitrile
contents were selected and their Tovalues obtained by DTA. A 50/50
mix of the two rubbers was made by mixing on a laboratory mill. The
final sample showed virtually full retention of both glass transitions, as
can be seen in Figure 7. Neither T , appeared t o be smeared or influenced
by the glass transition characteristics of the other component. Thus, i t
can be seen t h a t (a) the multiple glass transition is related t o the incompatibility of differing copolymer compositions (in agreement with the
conclusion of Collins), and (b) with decreasing acrylonitrile content, both
the breadth of the copolymer species and the temperature range of the
multiple T, increase (Figs. 2 and 6).
A third experiment was initiated t o determine whether the multiple
glass transition (as determined by DTA) in the rubber occurred early in
the polymerization or only at high conversions or at specific conversion
levels as perhaps implied in Figure 2. Two samples were polymerized by
using a n 80/20 butadiene/acrylonitrile full initial charge polymerization
(samples 65 and 66). Both batches were sampled at various conversions.
The results are shown in Figures 8 and 9. For both batches, a single glass
transition was noted up to about 5oy0conversion. At higher conversions,
two glass transitions were found. The second T, formed was found t o be a
lower-temperature To,meaning that the polymer formed later in the reaction was a species of lower acrylonitrile content, again in agreement with
the results of Figure 2.
Polymerizations were next carried out by using the incremental addition
schedules discussed earlier. Each of the three polymerizations was taken
t o 850/, conversion. The DTA curves of the three samples are shown in
Figure 10. The Tofor sample 71 can be seen t o be a single glass transition,
appearing very' sharp and exhibiting no broadening of the transition a t
either the beginning or end of the transition region. Sample 76 also had a

MULTIPLE GLASS TRANSITIONS

1513

18.1% CONVERSION

34.3% CONVERSION

\
Tg = -36C

36.3% CONVERSION
Tg

-38C

48.0% CONVERSION

64.9%CONVERSION
Tg = -37'C

l-

a
75.9% CONVERSION

Tg = -38C

85.0% CONVERSION
Tg = -54, -39C
Tg

-60, -39C

Tg = -63, -36C
TEMPERATURE, "C

Fig. 8. DTA scans of NBR obtained with full initial charge polymerization; sample 65.

single To but was not as sharp a transition as that of sample 71. The T,
for sample 100 was also found t o be single, but was again somewhat broader
than that of sample 71 and showed a rounding of the T , a t the high-temperature end. The T , (as i t was extrapolated from the DTA curve) of
sample 76 was found t o be lower than that of sample 100, even though
the monomer charge ratios suggested that sample 76 should have had a
27.6% CONVERSION

48.3% CONVERSION

Tg * -38C

85.0% CONVERSION

Tg' -409:

lg -68. -40C
TEMPERATURE, "C

Fig. 9. DTA scans of NBR obtained with full initial charge polymerization; sample 66.

M. R. AMBLER

1514

higher T,. This should not be considered unreasonable, however, because


the same monomer charge ratio, when added in different addition schedules
during polymerization, would not be expected to have the same T,. It
follows, therefore, that different charge ratios made with different addition
schedules also might not correlate in T,. The different addition schedules
probably yield different T , values by producing slightly different distributions of comonomer composition, and the summation of this entire range
of composition determines the measured transition region.

SAMPLE 76
(70130)

Ts -55OC
SAMPLE 1W
(77.51 22.5)

TEMPERATURE. 'C

Fig. 10. DTA scans of NBR obtained with incremental addition polymerization.

It was found that not only the T , values for the three samples but also
the specific characteristics of the transition curve shapes were reproducible.
The significance of these characteristic transition curve shapes appears t o
be related t o the breadth of copolymer composition resulting from the
incremental addition schedules used. I n Figure 3, the incremental schedule
employed for sample 71 showed a relatively small change in calculated I'$
from zero t o 85% conversion, (i.e., the final polymer species would have
theoretical PI contents ranging from approximately 0.29 t o 0.36). Sample
76 indicated a much broader range of F1, from 0.12 t o 0.38 (Fig. 4). Sample
100 showed an even broader range of Fl, from approximately zero (for a
brief time in the polymerisation) t o 0.34 (Fig. 5).
It would appear that these three polymer samples, having single glass
transitions, correlated well with the theoretical copolymerization calculations that predicted a relatively narrow breadth of copolymer composition
species in these polymers. Copolymerization theory appears t o be adequate for predicting NBR's that will have single glass transitions.

MULTIPLE GLASS TRANSITIONS

1515

Conclusions
Results presented here show that the broadness of the glass transition of
NBR (in particular, the occurrence of multiple glass transitions) is a consequence of the incompatibility of copolymer species of widely differing
comonomer contents. Copolymerization theory was found t o be adequate
for predicting changes in copolymer composition during polymerization,
as indicated by the occurrence of multiple glass transitions. Evidence is
presented which shows that multiple glass transitions occur only when
the copolymerization is taken t o high conversion; a t low conversions,
polymers having single glass transitions exist. Copolymerization theory
was successfully coupled with incremental addition of monomer t o predict
the means of making NBR with a single glass transition. Evidence is
presented which suggests that DTA is not only adequate t o determine the
experimental T , of a copolymer, but, also the broadness of the experimental T , curve, and the characteristic transition curve shape appears to
be an indicator of the distribution of copolymer species in the polymer.
The author wishes to thank The Goodyear Tire & Rubber Company for permisson
to publish this work and D. C. Grimm for the polymerization of experimental samples.

References
1. L. A. Chandler and E. A. Collins, paper presented at American Chemical Society
Meeting, 1968; Polym. Prqrints, 9, No. 2, 1416 (1968).
2. F. S. Cheng and J. L. Kardos, paper presented at American Chemical Society Meeting, 1969; Polvm. Preprints, 12,No. 2, 615 (1969).
3. V R Landi, Rubber Chem. Technol., 4 5 , 2 2 2 (1972).
4. P. J. Flory, Principles of Polymer Chemistry, Cornell Univ. Press, N.Y., Ithaca,
1953 (a) p. 180; (b) p. 185.
5. F. It. Mayo and C. Walling, Chem. Rev., 46, 191 (1950).
6. J. Skeist, J . Amer. Chem. SOC.,68, 1781 (1946).

Received February 21,1973