JOURNAL OF POLYMER SCIENCE: PAR'I' A

VOL. 2, PP. 3053-3066 (1964)

Peroxide Crosslinking of Ethylene-Propylene Rubber

L. D. LOAK, Rubber and Pla.stics Research Association of Great Britain,
Shawbury, Shrewsbury, Shropshire, England

Synopsis
The crosslinking of ethylene-propylene rubber by means of dicumyl peroxide has
been followed in detail. The overall crosslinking efficiency has been found to be about
0.4 crosslinks per peroxide molecule, and this result has been shown by stress relaxation
and permanent set experiments t o result from a mixture of both scission and crosslinking
reactions. The results obtained with two different rubbers are consistent with the view
that scission results from abstraction of a tertiary hydrogen atom while crosslinking
arises from attack at a secondary hydrogen. Such a scheme allows a relative reactivity
of tertiary:secondary of 6:l t o be calculated. The action of sulfur in peroxide cures
has been shown to be to introduce labile, presumably sulfur-containing, crosslinks. Such
labile crosslinks explain the increased tensile strength of such vulcanizates. Ally1 compounds are effective in increasing the crosslinking efficiency of the peroxide.

INTRODUCTION
The use of acyl peroxides in vulcanizing natural rubber was first suggested
nearly fifty years ago by Ostromislensky.' Since this time both acyl and
alkyl peroxides have been used t o cure natural and synthetic rubbers in
products where the use of sulfur compounds would be undesirable. The
mechanism of peroxide vulcanization in unsaturated rubbers has been the
subject of several recent investigations.2-6 Interest in peroxide curing has
greatly increased during the last few years with the introduction of the
saturated, general-purpose rubbers made by copolymerizing ethylene and
propylene since, apart from some recently discovered crosslinking agents,'
peroxides are the only known way of commercially vulcanizing these rubbers.
The use of peroxides to crosslink polyethylene is well known and has been
reported to occur with a crosslinking efficiency of ~ n i t y , ~but
, S in polypropylene it has been found to produce a mixture of crosslinking and degradation reactions.1 It is therefore to be expected that, in ethylene-propylene
rubber (EPR) also, such a combination of reactions might occur, since
tertiary hydrogen atoms are again present.
The present paper reports an investigation of the composite reaction occurring during the curing of EPR with dicumyl peroxide, and attempts to
explain the results in terms of the behavior of the different types of monomeric unit present.
3053

3054

L. D. LOAN

EXPERIMENTAL
Materials
Dicumyl peroxide was obtained from Hercules Powder Co. Ltd., and was
recrystallized from ethanol and water before use. The solvent used in the
swelling experiment was of laboratory reagent grade.
The ethylene-propylene rubbers used were obtained from Hercules
Powder Co. Ltd., and Esso Petroleum Company Ltd. The ethylene contents were 65 f 5 mole-yo and 58 f 5 mole-y0, respectively. All rubbers
were acetone-extracted for at least 36 hr. before use, except in that part of
the work in which tensile strengths were measured when the commercial
rubber was used without purification.
All compounds, with the exception of those used for tensile strength
measurement, were mixed on an unheated 6 X 2 in. two-roll laboratory
mill, and the peroxide was fully decomposed by using a press curing cycle of
70 min. at 153C. Other compounds were mixed on an 18 X 8 in. mill.

Methods
Stress-strain experiments were carried out in both compression and tension. The former type of measurement was made using the apparatus
previously described" and, in the latter, 1/4 in. strips of unswollen rubber
about 0.5 mm. thick were used.12 In both cases the results were interpreted
according to the equation
f/2Ao(A

- A-2)

CI

+ CZ A-'

where f is the applied force, A0 the cross-sectional area, A the extension ratio
(= extended length/original length), and Cl and CZare constants. In the
case of compression modulus, however, it is possible to make approximations
appropriate to the low strains used, and the modified equation

(f/Ah)(ho/GAo!

Ci

4-C2

is obtained, where Ah is the change in height produced by the load f and ho

is the unswollen, unstrained height.
Swelling experiments were carried out in n-decane, and were performed
by the conventional weighing technique6 in the 65 mole-% ethylene rubber
and by the enlarger method13in other cases. This method relies upon an
area measurement before and after swelling, the change in the third dimension being assumed to be similar.
Permanent set measurements were made on 0.5 mm. thick '/4 in. strips.
The strips were marked and measured, and extended by about 50%. They
were then heated in a steam pan, from which all air had been flushed, for 1
hr. at about 160C. to decompose fully the residual peroxide. The strips
were then released and allowed to relax for two or three days, after which
the final measurements to determine set were made. This technique was
employed to minimize oxidative changes in the network during the measurement.

ETHYLENEPROPYLENE RUBBER CROSSLINKING

3055

Stress relaxation measurements were made using the relaxometers described by Dunn and S~an1an.l~They were operated manually. The
strips used were cut from a peroxide-cured sheet and were swollen for some
days with a known amount of a solution of peroxide in benzene. The
solvent was then removed by evaporation. The strips were then set up in
relaxometers and the relaxation followed for 3 hr. at 140C. in nitrogen.
A nitrogen pressure slightly less than atmospheric was used to ensure that
no air could enter the apparatus and under these conditions it was found
that a large proportion of the added peroxide was lost by evaporation.
Determinations of v, were therefore made before and after relaxation to
calculate the amount of peroxide actually decomposed in the strip. To
simplify this calculation it was assumed that the peroxide loss from the
stretched part of the strip was equal to that from an unstretched end.

RESULTS AND DISCUSSION

a. Determination of Crosslink Density

Stress-strain results were used to determine C1 (or C1 Cp). The plot of

this quantity versus added peroxide is a straight line and from its slope,
assuming if necessary that Cp is constant, the change in concentration of
effective crosslinks CJRT may be obtained. The results for the rubbers

2
PEROXIDE

CONCENTRATION(^&)

Fig. 1. Determination of C1 for different peroxide concentrations for EPR containing

65 mole-% ethylene units. The upper line shows the values of Cl
C2resulting from
compression modulus experiments.

investigated are shown in Figures 1 and 2. Making the assumption,

justified previously,6that the true crosslink density differs from Cl/RT only
by an additive constant, the true crosslinking efficiency may be calculated,
and the results are shown in Table I.

3056

L. D. LOAN

PEROXIDE CONCENTRATION(%)

Fig. 2. Determination of CI for different peroxide concentrations for EPR containing 58

mole-% ethylene units.

TABLE I
Crosslinking Efficiencies in EPR
Ethylene content, mole-%

Crosslinking efficiency

58
65

0.34
0.40

Parallel determinations of uT on these rubbers using ndecane as solvent

at 25 "C. allows the calculation of the solvent-polymer interaction constant,
x, in the Flory-Rehner equation

T) -1n(l - u.) - u, - X U , ~= ( ~ C , V ~ / R (u,"~

1/2

u,)

where V1is the molar volume of the solvent. The results obtained were
0.451 for the rubber containing 58 mole-yo ethylene and 0.473 for the
rubber containing 65 mole-yo ethylene. The individual results are plotted
against the calculated curves for these x values in Figure 3. These values
are perhaps a little puzzling since n-decane might be expected to be a better
solvent for polyethylene than for polypropylene. However, the difference
8r

Ax 10

(molc/cm?)

.2

0.

- 0
015

0.20 0.25

0.30 0.35

"r

Fig. 3. Swelling data for the two EPIt's used, plotted on the theoretical curves for the
mean x values of 0.451 and 0.473.

ETHYLENE-PROPYLENE RUBBER CROSSLINKING

3057

could well be very slight and a change in the structure of the polymer chain
might account for this inversion of x values.
Earlier work on the crosslinking of E P R by peroxides has been reported
by Natta and C r e ~ p i . ~Their results appear to show a crosslinking efficiency of about 0.8 but the composition of the rubber was not given.
The low efficiencies measured in this work are most easily explained by
assuming that scission and crosslinking reactions are occurring together.
One obvious suggestion is that abstraction of the tertiary hydrogen atom
from a propylene unit results in a radical which may then rearrange to give a
polymer molecule and a smaller, but still polymeric, radical. To confirm
such an hypothesis it is necessary to make independent measurements of the
scission, if any, and crosslinking components of the reaction.

b. Separate Measurement of Crosslinking and Scission Components

One way of separating these two components of the reaction is by stress
relaxation measurements. This technique involves the measurement of the
stress necessary to maintain the sample a t a given extension, and simple
elasticity theory predicts that this stress is proportional t o the number of
strained crosslinks in the specimen. Now if a partly cured strip is extended
and the stress a t constant elongation measured as the cure proceeds, the
new crosslinks will have no effect upon the stress, since they are introduced
in the extended position, while the scissions produced in the original strained
network can be measured by the decrease in stress. Such a simplified picture is essentially that of the two-network theory first advanced by Tobolsky.lG Considering the second stage of the cure we may assume that all
new crosslinks go into the new network, a t equilibrium in the extended
position, while scissions will be equally probable in the chains of both networks. The rat.e of decrease of effective crosslinks in the original network
may be written as :

where n is the number of crosslinks per unit volume in this network and N
those in the new network, P the peroxide concentration, x the fraction of
radicals reacting to produce crosslinks and (1 - z)the fraction leading to
scission. Solution of this equation gives
1- x
~-

3x - 1

- log no/n
log P/P1

where PI is the peroxide concentration used in the initial cure to give a

crosslink concentration no and P the total amount of peroxide used. The
results are shown in Table 11. I n the calculations shown in this table, a
correction for the blank relaxation was made by assuming that the two
relaxation processes were purely additive. During such experiments much
of the peroxide is unfortunately lost by evaporation which of course leads

L. D. LOAN
TABLE I1
Stress Relaxation Results

f If0
Strip No.

P/P,

measured

R2
Q6
Q2
57
Q3
s9
Q5
R4

1.294
1.335
1.275
1.000
1.285
1.000
1.425
1.479

0.827
0.810
0.846
0.935
0.818
0.898
0.778
0.759

folf = n d n
corrected for
blank

log noh
log PlPl

1.109
1.130
0.082

0.405
0.423
0.325

0.63
0.63
0.67

1.120

0.452
0.465
0.485

0.62

1.179
1.209

Mean

0.61
0.61
0.63

to uneven distribution and hence introduces some uncertainty into the interpretation of the results.
One other convenient method of separating the scission and crosslinking
components of the reaction is the measurement of permanent set. The results may again be interpreted on the basis of the two-network theory of
Tobolsky.16 In this treatment the final length of the specimen is considered
as the length at which the two networks formed in the unextended and extended states, respectively, are a t equilibrium. From measurements of the
specimen length originally, l,, extended l,, and set, 1, the ratio of the number of crosslinksin the extended network, N , to the number in the unextended network, n,may be determined from the equation
_
N -

w1,,)3

it2)

(1/1,)3 - 1 1,

The suggested reaction scheme has already been used to obtain an expression for n in a rubber strip which has been partly cured in an extended
position. A similar derivation of N may also be made, since we have

dN/dP

z - [N/(Tz4- N ) ] [(l - 2)/2]

which leads to the solution

N
where Y

(x/Y)
[(Py- P l y ) / Y P y - 1

2x/(3x - 1). Using this equation together with that for n gives

-=

(P/P1)Y - 1

from which Y and hence x may be simply determined. The results are tabulated in Table 111.
The values of x obtained in these two ways may be used to calculate an

ETIIYLENEPROPYLENE RUBBER CROSSLlNKING

3059

TABLE I11
Results from Permanent Set Experiments

D1
2
3
5
6

2.169
2.140
1.974
1.821
1.807

3.075
3.005
3.009
2.737
2.675

1.436
1.451
1.668
1.495
1.568

2.624
2.579
2.513
2.277
2.252

1.919
2.053
1.988
2.020
1.930

1.366
1.247
1.428
1.300
1.434
Mean

0.65
0.71
0.63
0.68
0.63

.~

0.66

expected crosslinking efficiency. Since each broken chain is equivalent to

the loss of half a crosslink, the overall crosslinking efficiency will be

x -'/*(l

- X)

again assuming that all radicals from the peroxide lead to either crosslinking
or scission. This equation leads to values for E of 0.44 and 0.49 which must
be compared with the measured value of 0.40, and, when the oversimplification necessary for the theoretical treatment is considered, such agreement seems reasonable, and therefore supports the view that all of the
initiating radicals lead to either crosslinking or scission.

c. Kinetic Scheme
In the presence of peroxides, polyethylene crosslinks with an efficiency
close to unity while polypropylene shows a mixture of crosslinking and
scission reaction^.^ The present results agree with such behavior insofar
as the efficiency falls as more propylene units are introduced into the polymer. The results are, however, somewhat unexpected in that the crosslinking efficiency remains sensibly constant over the range of peroxide
concentrations investigated. Since polyethylene has been shownsp9to have
a unit crosslinking efficiency, the polymeric radicals formed from it cannot
undergo scission and a reaction scheme may be written.
D

-+

2R.

(1)
CH3

R.

+ Pr

P"'.(-CH2-C-CH2-)

(24

CH3

P'"-

P'.

I
+ P(-CHZ- + CH2=C-CH2-or
R - + Pe

-*

-CH=CH2
P".

P
2P". -* P
2P"'- + P or 2P
P'. + P". -+p
2P'.

x"

H-CH,-)

(2b)

L. D. LOAN

3060

+ p. + p

P.

(9)

Termination steps involving R . + inactive molecules

(10-13)

where D represents the undecomposed peroxide and R. the resulting primary radical which, when dicumyl peroxide is used, will be a cumyloxy
radical or a methyl radical; Pe and Pr denote the methylene and ethylidene
groups of the polymeric chain and PI., P., and I l l r . are primary, secondaiy, and tertiary polymeric radicals. All terminatiou steps shown separately have been assumed to occur by combination. The CH&HP radical
possibly formed in reaction (2b) may be considered as a primary radical,
since combination with PI- will essentially lead to a trifunctional crosslink.
I n crosslinking experiments the dicumyl peroxide is known to decompose
by the steps
CHI
CH3
I
c6&--t%o~-c-c&
AH3

CHI
1
C8H6-C-O.

AH3

+RH

CeH5-

AH3

Ce,Hs--C&CH3

rt
I

OH

+ R.

CHI

+ CHI.

and the cumyl alcohol and acetophenone formed may be measured by

means of infrared spectroscopy.6 In the present work with EPR it was
found that all the peroxide was converted into these two products, showing
that cumyloxy radicals did not take part to any significant extent in the
termination reactions. Also since the reactivity of methyl radicals is
much higher than that of a peroxy radical they also will probably react
only with the large excess of polymeric material present and it is therefore
reasonable to assume that the primary radicals do not take part in the
termination steps. Reactions (lo)-( 13) may therefore be neglected.
Reactions (2b), (6), (8), and (9) show competing reactions for the loss
of PI. radicals. The first of these reactions is of first order and the others
of second order in radical concentration and thus the proportion of the tertiary radicals decaying by the first-order reaction should depend upon the
total radical concentration at any time. Such a dependence would, of
course, lead to a change in crosslinking efficiency with initiator concentration, a dependence which is not found in practice. Scission has, however,
been shown to occur by means of stress-relaxation experiments and therefore reaction (2b) must be included and reactions (6), @), and (9), which
provide an alternative path for the loss of P., must be excluded. Thus
we may replace reactions (2a) and (2b) by the single step:
R.

+ Pr

-f

P.

+ I.

(2)

The crosslinking efficiency resulting from such a scheme must be calculated next, and some allowance must therefore be made for the production of
trifunctional links by reaction (7). Since these each join three polymer
chains compared with the four associated with a normal tetrafunctional

ETHYLENE-PROPYLENE RUBBER CROSSLINKING

3061

link, they will each be counted as three-quarters of a tetrafunctional crosslink. Thus for each pair of primary radicals decaying finally (after
propagation reactions) by step (4) we may count one scission, by step ( 5 )
one crosslink and by step (7) three-quarters of a crosslink and one scission
or a net increase of one-quarter of a crosslink. The rate of crosslinking
is therefore given by

On making the usual stationary state assumption and putting kT2 =

krks this equation leads to an efficiency of crosslinking (moles of crosslinks

per mole of peroxide) of

E = (2 - K)/[2(1

+K)]

where K = kz [Pr]/k, [Pel and this ratio has been assumed to be the same for
attack by both methyl and cumyloxy radicals. The two crosslinking
efficiencies measured may therefore be used to determine kz/k3 and the calculated values of 3.0 and 3.1 are in excellent agreement. In the calculation,
all methylene groups of the polymeric chain were assumed to be equally reactive.
As stated above, k2/k3 has been assumed to be equal for both methyl and
cumyloxy radicals; the ratio for cumyloxy radicals may, however, be determined independently from an analysis of ketone and alcohol formed in
the reaction. The way in which these two products are formed has been
shown above, and, since the unimolecular rearrangement of cumyloxy radicals will occur at a constant rate irrespective of medium, we may write:

+ ~[CHPEPR]

(ketone/a~coho~)dodecane
- kz [CHEPR]
-

(ketone/ alcohol)EPR

k3

[CH2dodecanel

The results of product analyses on EPR lead to a figure for the ketone/
alcohol ratio of 0.4. The ketone/alcohol ratio for dodecane has been measured by gas chromatographic analysis as 0.72 at 153 "C.l7 Several divergent
measurements of this ratio for ndecane hate been quoted in the literature,
but our value agrees reasonably well with Amberg's interpolated value of
A ratio of 0.72 leads to a value for kz/k3 of 3.8. It is doubtful if this
can be considered to be significantly different from the previously calculated
value of 3.1.
Although the ratio of the reactivities of secondary and primary hydrogen
atoms toward cumyloxy radicals has not been previously measured, several
such measurements have been made by using tert-butoxy radicals. The
results vary from 5.5 at 4OoC.l8through 4.0 a t 1350C.19to 2.5 at 160C.,20
and the present results of between 6.2 and 7.6 at 153C. (now expressed per
C-H bond) show that cumyloxy radicals are somewhat more selective than
tert-butoxy radicals with respect to hydrogen abstraction.

3062

L. D. LOAN

d. Effect of Sulfur in Vulcanization

The tensile properties of peroxide-cured EPR are known to be improved
by the addition of small quantities of sulfur prior to c ~ r i n g . ~ ~ - 2The
3
action of this sulfur has been the subject of much speculation, the most
common suggestion being that i t in some way stabilizes the tertiary radical
formed by hydrogen abstraction from a propylene unit, thus preventing or
a t least reducing the scission reaction.

1.0

20

30

GRAM ATOMS OF SULPHUR/ MOLES PEROXIDE

Fig. 4. The effect of sulfur on crosslink density in two peroxide cures.

I n an attempt to verify this explanation, EPR/peroxide gum vulcanizates

containing various amounts of sulfur were prepared, and swelling measurements carried out. The results are shown in Figure 4 for two peroxide
levels. These results show that the increase in crosslinking achieved is
quite small, equivalent only to about 0.5% peroxide in a 3% compound. Such a small gain is obviously insufficient to explain the large improvement in tensile properties and the present investigation was therefore
extended to carbon black-containing stocks in which the technological advantages mentioned above are observed. The measurements made included tensile strength and stress a t 300% elongation. The results are
shown in Table IV.
TABLE IT
Effect of Sulfur in EPR Vulcanization
Compound
EPR, parts
HAF black, parts
Dicumyl peroxide, parts
Sulfur, parts
Tensile strength, psi
Stress at 300%, psi
vT in n-decane

100
50
3
0.3

100
50
3
-

2870
1730
0.338

1780
730
0.273

100

3
0.3
200

0.147

100

250
0.141

These results show that while the effect of sulfur upon the tensile strength
and v, of the black-loaded compounds is large, only minor change-s are produced in the gums (on the equipment used the tensile strength values of
200 and 250 must be considered as not significantly different). The fact

ETHY LENEPROPYLENE RUBBER CROSSLINKING

3063

that sulfur can only improve the vulcanixate properties in the presence of
carbon black is unexpected, so measurements, similar to those tabulated
above, were made in natural rubber cures. The results are shown in Table
V. The results of this table show a rather different effect: the presence of
sulfur is found to reduce the crosslinking efficiency slightly and to leave
the tensile strength unchanged. The reduction of crosslinking efficiency is
quite simply explained as due to a small amount of inhibition of the radical
crosslinking by the sulfur.
TABLE V
Effect of Sulfur in NR Vulcanizates
Compound
Smoked sheets, parts
HAF black, parts
Dicumyl peroxide, parts
Sulfur, parts
Tensile strength, psi
Stress at 300%, psi
v, in n-decane

100
50
3
0.3

100
50
3
-

2400
1800
0.363

2400
2300
0.388

3
0.3

100
3
-

1840
125
0.260

1810
190
0.281

100
-

The action of the sulfur in the EPR-peroxide cures therefore is not certain. The increase in tensile strength without any large increase in crosslink density as measured in gum vulcanizates could result from the formation of labile, sulfur-containing crosslinks capable of rearranging when the
rubber is under strain. To investigate this possibility further, stress
relaxation experiments in vacuum were carried out with sulfur-containing
vulcanizates. The results are shown in Figure 5 . The curves in the figure
show that the early relaxation is much greater in the case of sulfur-containing vulcanizates while the final rate of relaxation, the result of a small
amount of thermal instability in the network, is similar in all three curves.
This early relaxation could arise from either a certain number of labile
bonds or from a number of thermally unstable bonds. To distinguish between these possibilities samples of the cure with highest sulfur content

Fig. 5. Stress relaxation curves for cures produced with different sulfur: peroxide
ratios (the curves are labeled with the ratio gram atoms of sulfur: gram-molecules of
dicumyl peroxide).

3064

L. D. LOAN

were swollen in decane before and after being heated to 160C. for 1 hr.
No change in v, was observed, showing that labile crosslinks are present in
this cure. These crosslinks are probably of a polysulfidic nature2' and may
be similar to those conferring superior tensile properties to sulfur cures of
natural rubber.
Sulfur-containing peroxide vulcanizates have been previously reported
as showing high permanent set compared with pure peroxide cures.21
Such behavior could also be explained by the presence of labile crosslinks
which might not rearrange quickly at the low stress present during recovery.
It thus seems possible that the action of sulfur in EPR peroxide vulcanisates may in part be due to the introduction of labile crosslinks which allow
a certain amount of rearrangement to occur in the strained network.
Measurement of crosslink density in gum vulcanizates shows little change
when sulfur is introduced. This explanation is, however, unlikely to account fully for the large improvement in tensile properties produced by
small amounts of sulfur. Other changes, for instance the large change in
v, produced by sulfur in a black-loaded vulcanizate, remain to be explained.

e. Effect of Ally1 Compounds in Vulcanization

Although sulfur has been shown to have only a minor effect upon crosslinking efficiency it is evident from the suggested reaction scheme that
suitable transfer agents could increase it markedly. Ally1 compounds
have been found to increase the radiation crosslinking of polyvinyl chloride,26and the effect of triallyl cyanurate in peroxide curing was therefore
investigated. Vulcanizates were prepared with various concentrations of
triallyl cyanurate and the resultant values of v, in n-decane show that a
maximum increase in v,, corresponding to a 100% increase in crosslinking
efficiency, occurs at a molar ratio of peroxide :triallyl cyanurate of about
1 :1. The use of other allyl compounds has recently been reported.26~*
The vulcanizates obtained with such curing systems show no disproportionate increase in tensile strength, and the stress relaxation behavior is
identical with that of simple peroxide cures. The increase in crosslinking
efficiency is therefore probably explained by addition reactions between
polymeric and allyl radicals, and such reactions appear to lead to stable
chemical crosslinks.
The author wishes t o thank the Hercules Powder Company for their support of this
work which forms part of the RAPRA general research program.

References
1. Ostromislensky, I. I., J. Russ. P h p . Chem. SOC.,
47,1885(1915).
2. Moore, C.G., and W. F. Watson, J . Polymer Sci.,19.237 (1956).
3. Amberg, L. O., and W. D. Willis, Proc. Intern. Rubber Conf., Washington D. C.,
1959,p. 565.
4. Parks, C. R., and 0. Lorenz, J . Polymer Sci., 50,287 (1961).
5. Thomaa, D.K., J . Appl. Polymer SCi., 6, 613 (1962).

ETHYLENEPROPYLENE RUBBER CROSSLINKING

3065

6. Loan, L. D., J . Appl. Polymer Sci., 7, 2259 (1963).

7. Wei, P. E., and J. Rehner, Rubber Chem. Technol.,35,133 (1962).
8. Endries, G. F., quoted by A. A. Miller, J . Polymer Sci., 42,441 (1960).
9. Rado, R., Vysokomol. Soedin., 4,1746 (1962).
10. Rado, R., D. Simunkova, and L. Malyak, Vysokomol. Soedin., 4,304 (1962).
11. Loan, L. D., Techniquesof Polymer Science, SOC.Chem. Ind., London, 1963, p. 24.
12. Gumbrell, S. M., L. Mullins, and R. S. Rivlin, Trans. Faraday SOC.,49, 1495
(1953).
13. Gardner, J. C., and D. I. James, Trans.Inst. Rubber Ind., in press.
14. Dunn, J. R., and J. Scanlan, J . Appl. Polymer Sci., 4,34 (1960).
15. Natta, G., and G. Crespi, Rubber Age, 87,459 (1960).
16. Andrews, R. D., A. V. Tobolsky, and E. E. Hanson, J. Appl. Phys., 17, 352
(1946).
17. Loan, L. D., and L. J. Maieey, unpublished resulta.
18. Walling, C., and B. B. Jacknow, J . Am. Chem. SOC.,82,6108 (1960).
19. Williams, A. L., E. A. Oberright, and J. W. Brooks, J . Am. Chem. SOC.,78, 1190
(1956).
20. Brook, J. H. T., Zrans. Faraday Soc., 53,327 (1957).
21. Amberg, L. O., paper presented at 4th Rubber Technology Conference, London,
1962.
22. Enjay Chemical Co., Enjay Technical Bulletin D-23.
23. di Giulio, E., and G. Ballini, paper presented a t Deutache Kautachuk-Geselleschaft Conference, West Berlin, 1960.
24. Wanless, G. G., P. E. Wei, and J. Rehner, Rubber Chem. Technol., 35,118 (1962).
25. Pinner, S. H., Nature, 182,1108 (1959).
26. Robinson, A. E., J. V. Marra, and L. 0. Amberg, Ind. Eng. Chem. Prod. Dev., 1,
78 (1962).
27. FUSCO,
J. V., Rubber World, 147,48 (1963).

R6um6
Le pontage du caoutachouc dethylhne-propylbne par le peroxyde de dicumyle a 6t6
Btudie in detail. Lefficacite de pontage est de 0,4 ponts par mol6cule de peroxyde.
Ceci rbulte de la concurrence entre des reactions de rupture et de pontage; cest ce
quont montr6 des 6tudes de tension-r6laxation e t de d6formation permanente de Ikchantillon. Les rbultats obtenus avec deux caoutchoucs differenta sont en accord avec
lhypothhse dune rupture due A lextraction dun hydroghne tertiaire e t dun pontage
rbultant dune attaque de lhydrogbne secondaire. Ce schema permet le calcul de la
reactivit6 relative de lhydrogbne tertiaire par rapport A lhydroghne secondaire: 6: 1.
Laction du soufre dans le traitement thermique avec peroxyde introduit des pontages
labiles, probablement des ponts contenant du soufre. La prbence de ces ponts labiles
expliquerait Iaugmentation de la force de rupture dam de produita vulcanisds de cette
manibre. Les produits allyliques augmentent Iefficacitb du peroxyde dans la r6action
de pontage.

Zusammenfassung
Die Vernetzung von Xthylen-Propylenkautschuk mittels Dicumylperoxyd wurde
genauer verfolgt. Die Bruttovernetzungsausbeutewurde zu etwa 0,4 Vernetzungsstellen pro Peroxydniolekul bestinimt und durch Spannungsrelaxations- und Dauerverforrnungsversuche wurde geaeigt, daas dieser Wert durch gleichzeitige Spaltungs- und
Vernetzungsreaktionen zustande konimt. Die a n zwei verschiedenen Kautschukproben erhaltenen Ergebnisse lassen sich mit der Annahme erklaren, daas die Spaltung
durch Angriff a n einem tertiaren Waaserstoffatom, die Vernetzung jedoch durch einen
solchen an einem sekundaren Wasaerstoff ausgelost wird. Dieses Schema fiihrt zu

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L. D. LOAS

einem Reaktivitatsverhaltnis tertiar :sekundar von 6 :1. Die Wirkung des Schwefels
bei der Peroxyvulkanisation besteht in einer Einfuhrung von labilen, wahrscheinlich
schwefelhaltigen Vernetzungen. Diese labilen Vernetsungen konnen die erhohte
Zugfestigkeit solcher Vulkanisate erklaren. Allylverbinbungen bewirken eine Erhohung
der Vernetzungsausbeute des Peroxyds.

Received July 1, 1963