3,406,141

United States Patent Office Patented Oct. 15, 1968

2
3,406,141 millimicrons for SAF blacks, have been recorded. See
DELAYED ACTION ACCELERATION FOR for example, Studebaker, 30 Rubber Chemistry and Tech
VULCANIZATION OF RUBBER nology 1400 (1957). The majority of HAF, ISAF and
Peter J. S. Bain, Wrexham, Denbighshire, Wales, and Alan SAF blacks currently available probably have arithmetic
Dibbo, Oswestry, Shropshire, England, assignors to mean particle diameters which lie towards the lower ends
Monsanto Chemicals Limited, London, England, a Brit of these ranges. In general a fine-particle size furnace
ish company black will have an arithmetic mean particle diameter of
No Drawing. Fied Feb. 8, 1965, Ser. No. 431,172 not more than 40 or 50 millimicrons, for instance not
Claims priority, application Great Britain, Feb. 13, 1964, more than 35 millimicrons.
6,059/64 0. Examples of furnace blacks that can be used are:
3 Claims. (CI. 260-41.5)
Philblack 1, Vulcan 6, Statex 125 and Cosmos 70 (ISAF
blacks);
ABSTRACT OF THE DISCLOSURE Philblack 0, Vulcan 3, Statex R and Cosmos 60 (HAF
Methoxycarbonylmethylenebis(N,N - dimethyldithio 5 blacks);
carbamate) is a delayed-action accelerator for vulvaniza and Philblack E. Vulcan 9, Statex 160 and Cosmos 85
tion of natural and synthetic rubber containing fine par (SAF blacks).
ticle size furnace black. Delayed action is compared to The amount of carbon black used varies in accordance
that of other members of the class and to a delayed with established technology according to the use for
action sulfenamide accelerator. 20 which the vulcanized product is required, but in the case
of vehicle tire treads, for example, is usually from 45 to
55 parts by weight per 100 parts by weight of rubber.
This invention relates to a process for the vulcaniza The preferred amount of the bis(dithiocarbamate) for
tion of rubber, more particularly to a process in which use in the process is from about 0.5 to about 0.75 part by
a delayed action accelerator is used in the vulcanization weight per 100 parts by weight of rubber.
of rubbers containing carbon black. The formula for methoxycarbonylmethylenebis(N,N-
The problem of premature vulcanization during the dimethyldithiocarbamate) is
compounding of rubber and the ensuing need for vulcani
zation accelerators having delayed action are well recog
nized in rubber technology. A satisfactory delayed action 30 * C-C-S-I-CE.COOR
accelerator is one that remains substantially inert during
compounding operations but gives a reasonably rapid
,
where R, R and R' are each methyl. Other alkoxy
rate of cure when the temperature of the mixture is raised carbonylmethylenebis(dithiocarbamates) where R is alkyl
to effect vulcanization. were tested as delayed action accelerators. Within this
Premature vulcanization is encountered mainly in the group of compounds tested, variations in the sizes of the
processing of rubber mixes containing carbon blacks as alkyl groups have, in general, little effect on the properties
reinforcing agents where the temperatures during com of the compounds, however, methoxycarbonylmethylene
pounding are unavoidably relatively high and the gap be bis(N,N-dimethyldithiocarbamate) has a significantly
tween these temperatures and the vulcanization tempera 40 longer period of delayed action than the average. Methox
ture is small. For a given accelerator system and propor ycarbonylmethylenebis(N,N-dimethyldithiocarbamate) is
tion of carbon black, the tendency of a mix to prevul the preferred member of this group because of this longer
canize is influenced by the type of carbon black, and it is delayed action when used as an accelerator.
of some significance in the case of the furnace blacks. The amount of accelerator used depends on a number
The problem is particularly serious with furnace blacks of 45 of factors, including, for example, the type of rubber and
fine particle size, of the kind for instance which are used the use for which the vulcanized product is required. The
where a high resistance to abrasion is required in the amount is, however, usually within the range of 0.25 to 5
Vulcanized product, for example, in the manufacture of parts by weight per 100 parts by weight of rubber.
vehicle tire treads. Although the process is particularly suitable for the
We have now found that a certain bis(dithiocarbamate) 50 vulcanization of natural rubber, it can also be applied to
is a very effective delayed action accelerator for the vul the vulcanization of other polydiene hydrocarbon rubbers,
canization of natural rubber and related synthetic rub including for instance synthetic cis-polyisoprene, polybu
bers in which fine-particle size furnace blacks are used as tadienes, and styrene-butadiene copolymers. Synthetic
reinforcing agents. This bis(dithiocarbamate) is methoxy rubbers produced from one or more dienes and minor
carbonylmethylenebis (N.N - dimethyldithiocarbamate) amounts of other comonomers are regarded as “polydiene
which is a new compound and is claimed as such. hydrocarbon rubbers," but the term does not include rub
The invention includes a process for the production of bers that contain a major proportion of a component
a reinforced vulcanized rubber, in which a furnace black other than a hydrocarbon diene.
having a fine particle size, sulfur, and an accelerating Sulfur is normally employed in the process in con
amount of the delayed action accelerator methoxycar 60 ventional amounts according to the type of rubber con
bonylmethylenebis(N,N-dimethyldithiocarbamate) are in cerned and end use required. These amounts are gener
corporated into a polydiene hydrocarbon rubber and the ally from about 1 part to about 5 parts by weight per
mixture is vulcanized. 100 parts by weight of rubber, and in the case of tire
The class of fine-particle size furnace blacks includes tread stocks from about 2 to 3 parts by weight per 100
those generally termed "high abrasion furnace” (HAF), 65 parts by weight of rubber.
"intermediate super abrasion furnace' (ISAF) and “super If desired, the sulfur can be supplied in the form of
abrasion furnace' (SAF) blacks, in order of decreasing a sulfur-containing vulcanizing agent such as for in
particle size. The actual particle sizes vary somewhat, and stance an amine disulfide or thiuram disulfide.
arithmetic mean particle diameters (determined by elec Compounding of the rubber prior to vulcanization can
tron microscopy) within the range 24 to 35 millimicrons 70 be carried out by conventional means and under conven
for HAF blacks, within the range 17.5 to 27.5 milli tional temperature conditions, using for example a roll
microns for ISAF blacks, and within the range 14 to 27 mill or internal mixer. Normally, other commonly used
 3,406,141 4
3
ingredients, for example zinc oxide, stearic acid and an tained on two established delayed action accelerators of
antidegradant will also be incorporated into the rubber the Sulfenamide class, are given in the following table.
prior to vulcanization. Each figure is the mean of two determinations.
The vulcanization proper is carried out at a temperature TABLE 1.
appropriate to the particular rubber concerned, for ex Mooney Time to
ample, in the case of natural rubber, at a temperature in Scorch optimum
the range 135-155 C. Compound TOL-10)
121 C.
at cure at
140°. C.
The new dithiocarbamate can be made by the reac (minutes) (minutes),
tion of the salt, preferably an alkali metal salt, of the
dimethyl substituted dithiocarbamic acid with the methyl O Methoxycarbonylmethylenebis.
(N,N-dimethyldithiocarbanate).-----...-
- .
29
.. . . ....
22
ester of a dihaloacetic acid, for example dichloroacetic Neopentyloxycarbonylmethylene
bis(N,N-dimethyldithiocarbamate).------ 24 24
acid. n-Heptyloxycarbonylmethylene
The process is conveniently conducted in an inert sol bis(N,N-dimethyidithiocarbamate).----...-
Methyl bis(morpholino-(thiocarbonyl)
22 22
vent as reaction medium. The solvent can be aqueous thiolacetate------------------------------ . . . . 24. 22.....
but is preferably organic. Acetone, which may option 5 Methyl bis(2,6-dimethylmorpholino
(thiocarbonyl)thioacetate.--------------- 24 22
ally contain a small amount of water, has been found N-cyclohexylbenzthiazyl-2-sulfenamide----- 28 24
particularly suitable for this purpose. Dimethylform 2(morpholinothio)benzothiazole------------ 32 28
amide or alcohols also can be used, the alkyl radical of
the alcohol preferably being the same as the alkyl group
esterifying the dihaloacetic acid. 20 All the dithiocarbamates show a useful degree of de
An elevated temperature, for example one in the range layed action, and a satisfactory cure rate. Methoxycar
50-120' C. is usually required for a practical reaction bonyl - methylenebis(N,N-dimethyldithiocarbamate) is
rate, and where an inert solvent is employed the required seen to be outstanding in having a delayed action in the
temperature can often conveniently be maintained by same range as the sulfenamides while giving a signifi
boiling the reaction mixture under reflux. 25 cantly faster rate of cure. -
The invention is illustrated by the following examples. EXAMPLE 3
EXAMPLE 1.
This example describes the compound and production This example gives the results of experiments carried
of methoxycarbonylmethylenebis(N,N-dimethyldithiocar 30 out to compare the effect of different types of furnace
bamate) from methyl dichloroacetate and sodium N,N- black on delayed action and cure rate in stocks contain
dimethyldithiocarbamate. ing methoxycarbonylmethylenebis(N,N-dimethyldithio
400 grams (2.8 mol.) of methyl dichloroacetate were carbamate) (designated A in Table 2) and 20morpholin
added during 1% hours to a stirred suspension of 800 othio)benzothiazole (designated B in Table 2) as ac
grams of sodium N,N-dimethyldithiocarbamate in 3 liters celerators, again using the Mooney viscometer and Agfa
of acetone in a 5-liter flask fitted with a reflux condenser. Vulcameter respectively. The stocks had the composition:
The reaction was exothermic, and refluxing occurred Parts by weight
after 4 hour. After the addition was complete, the re Smoked sheets ------------------------------- 100
action mixture was heated under reflux for a further two Carbon black -------------------------------- 50
hours. A white precipitate formed during the reaction, Zinc oxide ----------------------------------- 5
and after cooling, this was collected by filtration. The Stearic acid ----------------------- ---------- 3
solid was washed with water until free from chloride and Process oil ---------------------------------- 3
dried, giving 800 grams (91.5% yield) of methoxycar Sulfur -------------------------------------- 2.5
bonylmethylenebis(N,N-dimethyldithiocarbamate). Crys 45
Accelerator ---------------------------------- 0.5
tallization from 8 liters of a mixture of 9 parts by volume
of dioxane and 1 part by volume of dimethylformamide The results are shown in Table 2 below.
gave 700 grams of a purified product having a melting TABLE 2
point of 213 C. (with decomposition). (Found: C,
35.04; H, 5.22; N, 9.01; S, 40.57. C9H16N2O2S requires Accelerator Carbon Black
Mooney Scorch
at 121 C.
Time to
Optimum Cure
C,34.60; H, 5.16; N, 8.97; S, 41.02%). T(L-10) at 140 C.
EXAMPLE 2 (minutes) (minutes)
26 17
This example describes experiments designed to assess 30
20
23
5
the delayed action and cure rates of a number of methyl 9 22
enebis-(dithiocarbamates) in a natural rubber stock con 12
3
6
25
taining an HAF black (Vulcan 3).
The stock was a typical tire tread stock having the
following composition: Methoxycarbonylmethylenebis(N,N - dimethyldithio
Material: . Parts by weight 60 carbamate) is seen to give in all cases a significantly faster
Smoked sheets -------------------------- 100 rate of cure than the sulfenamide accelerator, while having
High abrasion furnace black -------------- 50 a comparable delayed action, particularly with ISAF and
Zinc oxide ------------------------------ 5 SAF blacks. -
Stearic acid ----------------------------- 3 It is intended to cover all changes and modifications of
Tackol 2 (process oil) ------------------- 3 65 the examples of the invention herein, chosen for purposes
Sulfur --------------------------------- 2.5 of disclosure which do not constitute departures from the
Accelerator ----------------------------- 0.5 spirit and scope of the invention.
The test for delayed action was the standard Mooney What is claimed is:
viscosity procedure carried out at 121 C. The period 1. A process for the production of a reinforced vul
of delayed action was recorded as the time taken for the 70 canized polydiene hydrocarbon rubber in which a furnace
viscosity reading to reach 10 units above the minimum. black having fine particle size, sulfur, and an accelerating
Cure rate was determined by recording the time taken amount of methoxycarbonylmethylenebis(N,N-dimethyl
for the stock to obtain 90% of its optimum cure at 140 dithiocarbamate) are incorporated into a polydiene hydro
C. as measured by the Agfa Vulcameter. carbon rubber and the mixture is vulcanized.
The results, which include for comparison figures ob 75 2. A process for the production of a reinforced vul
 5
3,406,141
6
canized natural rubber in which a furnace black having References Cited
fine particle size, sulfur, and an accelerating amount of UNITED STATES PATENTS
methoxycarbonylmethylenebis(N,N - dimethyldithiocar
bamate) are incorporated into natural rubber and the 2,188,280 1/1940 Lichty ------------- 260-793
mixture is vulcanized.
3. A vulcanizable rubber composition comprising poly 5 FOREIGN PATENTS
diene hydrocarbon rubber, a furnace black having a fine 406,379 3/1934 Great Britain.
particle size, sulfur, and an accelerating amount of me
thoxycarbonylmethylenebis(N,N - dimethyldithiocarba JULIUS FROME, Primary Examiner.
mate). 10 J. E. CALLAGHAN, Assistant Examiner.