Abstract:
A method for, and compositions, providing vulcanizable compounds of unsaturated polymers having an improved balance of scorch time and cure rates, ie., slow scorch times and fast cure rates, comprising adding to said vulcanizable polymers accelerating amounts of benzothiazolesulfenamides selected from the group consisting of N-oxydiethylene-2-benzothiazole sulfenamide, N-t-butyl-2-benzothiazole sulfenamide and N-cyclohexyl-2-benzothiazole sulfenamide, with N-oxydiethylenethiocarbamyl-N&#39;-t-alkyl sulfenamides wherein the alkyl radicals contain 4 to 8 carbon atoms.

Description:
This is a continuation-in-part of part copending application Ser. No. 075,803, filed on July 20, 1987, now abandoned. 
    
    
     BACKGROUND OF INVENTION 
     N-oxydiethylene-2-benzothiazole sulfenamide (OBTS), N-t-butyl-2-benzothiazole sulfenamide (BBTS), and N-cyclohexyl-2-benzothiazole sulfenamide (CTBS) are commercially available and widely used accelerators for the curing and vulcanization of unsaturated elastomers. While the scorch time of compounds containing OBTS, BBTS and CTBS are generally satisfactory, the cure rates often are slower than is desireable for many applications. An auxiliary material to be used in conjunction with the N-oxydiethylene-2-benzothiazole sulfenamide, N-t-butyl-2-benzothiazole sulfenamide, and N-cyclohexyl-2-benzothiazole sulfenamide in unsaturated polymers to enhance the cur rate without substantially altering the scorch time would be a valuable addition to the compounders art. Such a system would enhance and expand the use of the N-oxydiethylene-2-benzothiazole sulfenamide, N-t-butyl-2-benzothiazole sulfenamide and N-cyclohexyl-2-benzothiazole sulfenamide while providing the compounder with more flexibility. 
     SUMMARY OF THE INVENTION 
     The cojoint use of (1) N-oxydiethylene-2-benzothiazole sulfnamide, (2) N-t-butyl-2-benzothiazole sulfenamide or (3) N-cyclohexyl-2-benzothiazole sulfenamide and N-oxydiethylenethiocarbamyl-N&#39;-t-alkyl sulfenamides, wherein the tertiary alkyl radicals contain 4 to 8 carbon atoms, provides an improved balance of scorch times and cure rates in unsaturated polymer compounds when they are subsequently cured or vulcanized. 
     DETAILED DESCRIPTION 
     The N-oxydiethylenethiocarbamyl-N&#39;-t-alkyl sulfenamides have the structural formula ##STR1## 
     wherein R is a t-alkyl radical containing 4 to 8 carbon atoms, i.e., t-butyl, t-pentyl, 2-methyl-2-pentyl, t-octyl, 2,4,4-trimethyl-2-pentyl, and the like. 
     The N-oxydiethylenethiocarbamyl-N&#39;-t-alkyl sulfenamides are readily prepared in accordance with procedures described in U.S. Patent No. 3,985,743, Taylor, 1976. A useful procedure is to react morpholine and a t-alkylamine in a solvent with aqueous sodium hypochlorite, and then with carbon disulfide. The resulting sulfenamide is recovered from the reaction media. Preferably the reactions are conducted in an aqueous/non-aqueous medium. The medium comprises water and an organic solvent, usually a chlorinated solvent, including for example methylene chloride, ethylene dichloride, chloroform, carbon tetrachloride and the like. The temperature of reactions range from about, preferably, -10° C. to about 40° C. While an excess of amine may be used, excellent yields are obtained from about 1 mole of morpholine, 1 mole of t-alkyl amine, 1 mole of NaOCl, and 1 mole of carbon disulfide. 
     The invention is useful is preparing curable and vulcanizable compounds of unsaturated polymers, especially the unsaturated elastomers, and other polymers that may be cured or vulcanized to an elastomeric state. Typical polymers include natural rubber; cispolyisoprene; cis-polybutadiene; copolymers of butadiene-1,3 and vinylidene monomers containing the CH 2  C═ene-1,3 structure, such as styrene, acrylonitrile, alkyl acrylates and methacrylates, and others known to those skilled in the art; polychloroprene; copolymers of isobutylene and isoprene; unsaturated olefin polymers exemplified by ethylene-propylene diene copolymers, and the like known to those skilled in the art, in both solid, latex and liquid states. The vulcanizable polymers contain at least about one weight percent unsaturation and are usually cured or vulcanized with sulfur and/or sulfur containing compounds. 
     In addition to the cojoint use of N-oxydiethylene-2-benzothiazole sulfenamide, N-t-butyl-2-benzothiazole sulfenamide or N-cyclohexyl-2-benzothiazole sulfenamide and N-oxydiethylenethiocarbamyl-N&#39;-t-alkyl sulfenamide, in accordance with this invention, the usual compounding agents will be used by the man skilled in the compounding art, depending on the polymer used, the application and the physical properties desired in the cured or vulcanized products. Such materials may include activators, retarders, vulcanizing and curing agents; protective materials including antioxidants, antiozonants, anti-blocking agents, antiflex cracking agents, flame retarders, fungicides, germicides, antistatic agents and chemical and heat stabilizers; processing materials including plasticizers and softeners, processing aids, and tackifiers; extenders, fillers and reinforcing materials, and the like. Standard comcompounding ingredients include zinc oxide, carbon black, sulfur, oil, and fatty acids. 
     The amounts and ratios of the synergistic combination of N-oxydiethylene-2-benzothiazole sulfenamide, N-t-butyl-2-benzothiazole sulfenamide or N-cyclohexyl-2-benzothiazole sulfenamide with N-oxydiethylenethiocarbamyl-N&#39;-t-alkyl sulfenamide used may be varied by the man skilled in the art depending on the scorch time and cure rate or cure index desired. The amounts normally will be varied from about 0.5 to about 5 weight parts, per one hundred weight parts of polymer used, of N-oxydiethylene-2-benzothiazole sulfenamide, N-t-butyl-2-benzothiazole sulfenamide or N-cyclohexyl-2-benzothiazole sulfenamide and about 0.5 to about 10 weight parts of N-oxydiethylenethiocarbamyl-N&#39;-t-alkyl sulfenamide. The weight ratio of N-oxydiethylene-2-benzothiazole sulfenamide, N-t-butyl-2-benzothiazole sulfenamide or N-cyclohexyl2-benzothiazole sulfenamide to N-oxydiethylenethiocarbamyl-N&#39;-t-alkyl sulfenamide may be from about 0.25 to about 2. 
     In evaluating the utility of the system of this invention is the following Examples it is assumed that the physical properties of the vulcanizates are about equivalent. Then the scorch and cure rates are considered. These are determined in accordance with ASTM Test Procedure D 1646. This test provides the Mooney scorch delay, t 5 , and the cure index. In the case of the scorch, longer periods of time, larger numbers, are desirable for flexibility in operations. As to cure index, the smaller number represents a faster cure and is more desirable. In other words, the best condition is to have a compound with a long scorch time and a small cure index. 
     Another benchmark is the cure rate index, determined in the Monsanto Rheometer, ASTM D 2085. In the rubber industry it is generally accepted that as the cure rate index for a compound becomes larger, indicating a faster cure, the scorch time, t 2  or t 5  becomes less, a shorter time or smaller number, and thus the compounds are more scorchy and less desirable. 
     Contrary to this and in accordance with this invention, compounds may be provided that have increased scorch times but are faster curing, as will be shown in the Examples. The structure of the N-oxydiethylenethiocarbamyl-N&#39;-t-alkyl sulfenamide is critical and essential to the successful practice of the invention and many closely related structures do not provide the same balance of desired cured or vulcanizing properties. 
    
    
     In the following Examples, in testing the various sulfenamides, the levels used are based upon an equal molar basis. Examples 1-5 demonstrate the advantages of the invention. Example 6 shows that other sulfenamides, even with similar structures, do not provide the scorch times and cure indexes provided by the N-oxydiethylenethiocarbamyl-N&#39;-t-alkyl sulfenamides. An advantage of use of the N-oxydiethylenethiocarbamyl-N&#39;-t-alkyl sulfenamide is that less can be used to obtain the desired effect than that required for other materials. These N-oxydiethylenethiocarbamyl-N&#39;-t-alkyl sulfenamides are more easily dispersed in elastomers and are very soluble in elastomers such as natural rubber, increasing the ease of incorporation, as well as preventing blooming of stocks. Further, the lower temperature of melting of these materials allows for desirable higher speed processing of compounds. 
     EXAMPLE 1 
     N-oxydiethylenethiocarbamyl-N&#39;-t-butyl 
     sulfenamide 
     To a reactor, equipped with a stirrer and cooling bath, containing 87.12 grams (1.0 mole) of morpholine and 73.14 grams (1.0 mole) of t-butylamine in 1000 ml of methylene chloride, there was added 591.3 grams of a 12.59% aqueous solution (1.0 mole) of sodium hypochlorite, with stirring, at a temperature of 0°-10° C. After ten minutes at this temperature, the mixture was allowed to warm up to 20° C. by removing the cooling bath. At this point 76.14 grams (1.0 mole) of carbon disulfide was added at a rate to maintain the solution at a temperature of 32°-35° C. After the addition was completed, the reaction mixture was stirred for an additional 15 minutes. Agitation was stopped and the reaction mixture allowed to separate into aqueous and organic phases. The phases were separated. Th eorganic phase was washed with water, and dried with sodium sulfate. The dried solution was heated to evaporate the solvent. A light yellow solid was obtained. This solid was slurried in 200-300 ml of hexane, filtered, rinsed with cold hexane and dried. 165 grams of N-oxydiethylenethiocarbamyl-N&#39;-t-butyl sulfenamide was obtained. The melting point was 66-69° C. The field desorption/mass spectrum indicated a molecular mass of 234. 
     EXAMPLE 2 
     To demonstrate the utility of the sulfenamide of Example 1 in combination with N-oxydiethylene-2-benzothiazole sulfenamide (OBTS), and in comparison to N-oxydiethylenethiocarbamyl-N&#39;-oxydiethylene sulfenamide (CR-18), in natural rubber, a series of compounds were prepared following this general recipe: 
     
         ______________________________________Component            Weight parts______________________________________Natural rubber       100.0Zinc oxide           4.5Stearic acid         2.0Carbon black (HAF)   50.0Paraffin wax.sup.1   1.0Aromatic petroleum oil.sup.2                10.0Sulfur               2.0N--1,3-dimethylbutyl-N&#39;--phenyl-                1.5p-phenylenediamine.sup.3______________________________________ .sup.1 Sunolite 240 .sup.2 Sundex 790 .sup.3 Antozite 67F 
    
     Seven compounds were prepared using varying amounts of the sulfenamide of Example 1, N-oxydiethylenethiocarbamyl-N&#39;-t-butyl sulfenamide (BTOS), N-oxydiethylene-2-benzothiazole sulfenamide (OTBS) and N-oxydiethylenethiocarbamyl-N&#39;-oxydiethylene sulfenamide and tested as shown in Table I. The Monsanto Rheometer data were obtained in accordance with ASTM Test Procedure D 2084,  the Mooney scorch data were obtained in accordance with ASTM test procedure D 1646, and the Stress Strain data were obtained in accordance with ASTM test procedure D 412. These data clearly demonstrate the unexpected improvement in the balance of scorch and cure rates obtained in natural rubber when the novel combination of sulfenamides is employed. 
     
                                           TABLE I__________________________________________________________________________Compound           1  2  3  4  5  6  7__________________________________________________________________________OBTS - weight parts              0.8      0.2                          0.2                             0.2                                0.24CR-18 - weight parts  0.6   0.4BTOS - weight parts      0.6   0.4                             0.38                                0.36Monsanto Rheometer, 1° ARC, 302° F.Maximum torque, in lbs.              30.4                 28.4                    28.4                       31.2                          31.5                             31.1                                34.0Minimum torque, in lbs.              5.6                 5.7                    5.7                       6.2                          6.3                             6.4                                6.4M.sub.H -M.sub.L   24.8                 22.7                    22.7                       25.0                          25.2                             24.7                                27.6Scorch time (t.sub.2), min.              5.7                 4.8                    4.6                       5.4                          4.8                             5.0                                4.9Cure time (t.sub.90), min.              12.8                 12.1                    10.5                       10.7                          9.2                             9.4                                8.8Cure time (t.sub.95),min.              14.5                 13.3                    11.7                       11.5                          10.0                             10.2                                9.6Cure rate index    14.1                 13.7                    16.9                       18.9                          22.7                             22.7                                25.6Mooney Scorch, ML at 250° F.t.sub.5  (min.)    37.4                 28.3                    25.3                       32.9                          33.7                             30.6                                33.0t.sub.35  (min.)   42.2                 33.0                    28.9                       37.2                          36.5                             33.4                                35.4Cure Index         4.8                 4.7                    3.6                       4.3                          2.8                             2.8                                2.4Stress Strain, Opt.Cure (t.sub.95) at 302° F.Tensile strength, psi              4093                 4010                    3793                       4202                          4296                             4145                                4231Elongation, %      591                 607                    613                       598                          601                             570                                615300% Modulus, psi  1568                 1500                    1349                       1591                          1650                             1724                                1556Shore A2 hardness  58.3                 55.5                    56.7                       60.4                          61.0                             57.8                                60.7__________________________________________________________________________ 
    
     EXAMPLE 3 
     To demonstrate the utility of the sulfenamide of Example 1 in combination with N-oxydiethylene-2-benzothiazole sulfenamide (OBTS), and in comparison to N-oxydiethylenethiocarbamyl-N&#39;-oxydiethylene sulfenamide (CR-18), in styrene-butadiene rubber, a series of compounds were prepared following this general recipe: 
     
         ______________________________________Component        Weight parts______________________________________Ameripol 1712.sup.1            55.0Ameripol 1500.sup.1            25.0Taktene 1203.sup.2            35.0Zinc oxide       3.0Stearic acid     2.0Carbon black (HAF)            70.0Sundex 8125      20.0Antozite 67F     2.0Agerite Resin D.sup.3            2.0Sulfur           2.0______________________________________ .sup.1 Styrenebutadiene rubbers, 22-24% bound styrene .sup.2 Polybutadiene .sup.3 Polymerized dihydroquinoline 
    
     Nine compounds were prepared using varying amounts of the sulfenamide of Example 1, N-oxydiethylenethiocarbamyl-N&#39;-t-butyl sulfenamide (BTOS), N-oxydiethylene-2-benzothiazole sulfenamide (OBTS) and N-oxyethylenethiocarbamyl-N&#39;-oxydiethylene sulfenamide (CR-18) and tested as shown in Table II. The Monsanto Rheometer data were obtained in accordance with ASTM Test Procedure D 2084, the Mooney scorch data were obtained in accordance with ASTM test procedure D 1646, and the Stress Strain data were obtained in accordance with ASTM test procedure D 412. These data show the excellent results obtained using smaller total amounts of the novel combination of sulfenamides, as compared to larger amounts of either sulfenamide used alone. 
     
                       TABLE II______________________________________Compound             1        2      3______________________________________OBTS-weight parts    1.43            0.43CR-18-weight parts                   0.64BTOS-weight parts             1.01Monsanto Rheometer, 1° ARC, 320° F.Maximum torque, in lbs.                32.5     32.0   32.7Minimum torque, in lbs.                7.0      7.0    6.7M.sub.H -M.sub.L     25.5     25.0   26.0Scorch time (t.sub.2), min.                5.5      4.3    5.5Cure time (t.sub.90), min.                10.04    8.8    11.3Cure time (t.sub.95), min.                12.1     10.0   12.7Cure rate index      20.4     22.5   17.2Mooney Scorch, ML at 280° F.t.sub.5 (min.)       19.0     12.8   17.2t.sub.35 (min.)      21.4     14.9   20.4Cure Index           2.4      2.1    3.2Stress Strain, Opt. Cure (t.sub.95) at 320° F.Tensile strength, psi                3067     3064   3048Elongation, %        590      535    530300% Modulus, psi    1218     1476   1452Shore A2 hardness    63       64.8   62.9______________________________________Compound             4        5      6______________________________________OBTS-weight parts    0.43     0.40   0.43CR-18-weight partsBTOS-weight parts    0.64     0.60   0.60Monsanto Rheometer, 1° ARC, 320° F.Maximum torque, in lbs.                32.5     32.0   32.4Minimum torque, in lbs.                7.1      7.0    7.0M.sub.H -M.sub.L     25.4     25.0   25.4Scorch time (t.sub.2), min.                5.3      5.5    5.4Cure time (t.sub.90), min.                9.5      9.7    8.9Cure time (t.sub.95), min.                10.6     10.7   10.9Cure rate index      23.8     23.8   28.6Mooney Scorch, ML at 280° F.t.sub.5 (min.)       18.0     19.0   18.7t.sub.35 (min.)      20.4     21.5   21.5Cure Index           2.4      2.5    2.8Stress Strain, Opt. Cure (t.sub.95) at 320° F.Tensile strength, psi                2966     3120   3015Elongation, %        508      548    518300% Modulus, psi    1484     1440   1486Shore A2 hardness    63.5     63.9   64.1______________________________________Compound             7        8      9______________________________________OBTS-weight parts    0.33     0.25   0.50CR-18-weight partsBTOS-weight parts    0.67     0.75   0.50Monsanto Rheometer, 1° ARC, 320° F.Maximum torque, in lbs.                32.5     32.5   31.5Minimum torque, in lbs.                7.4      7.5    7.2M.sub.H -M.sub.L     25.1     25.0   24.3Scorch time (t.sub.2), min.                5.3      5.0    5.7Cure time (t.sub.90), min.                9.6      9.2    10.6Cure time (t.sub.95), min.                10.6     10.2   11.7Cure rate index      23.3     23.8   20.4Mooney Scorch, ML at 280° F.t.sub.5 (min.)       16.0     15.9   17.2t.sub.35 (min.)      18.4     18.4   20.1Cure Index           2.0      2.5    2.9Stress Strain, Opt. Cure (t.sub.95) at 320° F.Tensile strength, psi                3053     2793   2909Elongation, %        550      485    561300% Modulus, psi    1406     1499   1278Shore A2 hardness    66.9     67.8   68______________________________________ 
    
     EXAMPLE 4 
     N-oxydiethylenethiocarbamyl-N&#39;-(2,4,4-trimethyl-2-pentyl) sulfenamide 
     To a reactor, equipped with a stirrer and cooling bath, containing 8.71 grams (0.1 mole) of morpholine and 12.92 grams (0.1 mole) of t-octylamine in 100 ml of hexane, there was added 55.22 grams of an 13.48% aqueous solution (0.1 mole) of sodium hypochlorite, with stirring, at a temperature of 0°-10° C. After ten minutes at this temperature, the mixture was allowed to warm up to 20° C. by removing the cooling bath. At this point 7.61 grams (0.1 mole) of carbon disulfide was added at a rate to maintain the solution at a temperature of 32°-35° C. After the addition was completed, the reaction mixture was stirred for an additional 15 minutes. Agitation was stopped and a solid precipitate was removed by filtration to give 13 grams of product. This solid was slurried in 200 ml of hexane and filtered to remove the solid impurity. The filtrate was heated to remove the hexane. Ten grams of white, flaky and crystalline N-oxydiethylenethiocarbamyl-N&#39;-(2,4,4-trimethyl-2-pentyl) sulfenamide was obtained. The melting point was 73°-75° C. The field desorption/mass spectrum indicated a molecular mass of 290. 
     The N-oxydiethylenethiocarbamyl-N&#39;-(2,4,4-trimethyl-2-pentyl)sulfenamide was tested in the same recipe set forth in Example 3 in amount of 1.25 weight parts. The resulting vulcanizate compounds had a Scorch Time, t 2 , of 5.4 min.; a Cure Time, t 90 , of 10.5 min.; and a Cure Rate Index of 19.6. The Mooney Scorch values obtained were, t 5 , 15.3 min,; with a Cure Index of 2.4. The tensile strength of the vulcanized compounds was 2901 psi; the percent elongation was 555; and the 300% modulus was 1278 psi. 
     EXAMPLE 5 
     N-oxydiethylenethiocarbamyl-N&#39;-t-pentyl sulfenamide 
     To a reactor, equipped with a stirrer and cooling bath, containing 8.75 grams (0.1 mole) of morpholine and 8.72 grams (0.1 mole) of t-amylamine in 100 ml of hexane, there was added 55.22 grams of an 13.48% aqueous solution (0.1 mole) of sodium hypochlorite, with stirring, at a temperature of 0°-10° C. After ten minutes at this temperature, the mixture was allowed to warm up to 20° C. by removing the cooling bath. At this point 7.61 grams (0.1 mole) of carbon disulfide was added at a rate to maintain the solution at a temperature of 32°-35° C. After the addition was completed, the reaction mixture was stirred for an additional 15 minutes. Agitation was stopped and the reaction mixture allowed to separate into aqueous and organic phases. The phases were separated. The organic phase was washed with water, and dried with sodium sulfate. The dried solution was heated to evaporate the solvent. A yellow oil was obtained which crystallized on standing. This solid was recrystallized from methanol. 8.0 grams of N-oxydiethylenethiocarbamyl-N&#39;-t-pentyl sulfenamide was obtained. The field desorption/mass spectrum indicated a molecular mass of 248. 
     The N-oxydiethylenethiocarbamyl-N&#39;-t-pentyl sulfenamide was tested in the same recipe set forth in Example 3, in an amount of 1.07 weight parts. The resulting compound had a Scorch Time, t 2 , of 5.0 min.; a Cure Time, t 90 , of 9.3 min.; and a Cure Rate Index of 23.3. The Mooney Scorch values were, a t 5 , of 13.0 min, and a Cure Index of 2.2. The tensile strength of vulcanizates of the compound was 2817 psi; elongation of 539% and a 300% modulus of 1301 psi. 
     EXAMPLE 6 
     Following the procedure and recipes of Example 3, N-oxybis(2-methylethylene)-thiocarbamyl-N&#39;-t-butyl sulfenamide (2), structurally related to N-oxydiethylenethiocarbamyl-N&#39;-t-alkyl sulfenamides, but not a part of this invention, was compared to N-oxydiethylenethiocarbamyl-N&#39;-t-butyl sulfenamide (1). The amounts used and the results obtained are set forth in Table IV. The sulfenamides of the compounds are identified by the numbers above. 
     
                       TABLE III______________________________________Compound                1      2______________________________________Compound (1)-weight parts                   1.01Compound (2)-weight parts      1.13Monsanto Rheometer, 1° ARC, 320° F.Maximum torque, in lbs. 32.0   27.8Minimum torque, in lbs. 6.9    7.2M.sub.H -M.sub.L        25.1   20.6Scorch time (t.sub.2), min.                   5.3    5.7Cure time (t.sub.90), min.                   9.9    14.6Cure time (t.sub.95), min.                   11.0   16.6Cure rate index         21.7   11.2Mooney Scorch, ML at 280° F.t.sub.5 (min.)          15.9   16.3t.sub.35 (min.)         18.5   20.5Cure Index              2.6    4.2Stress Strain, Opt. Cure (t.sub.95) at 320° F.Tensile strength, psi   2939   3142Elongation, %           470    619300% Modulus, psi       1653   1186Shore A2 hardness       70     67______________________________________ 
    
     Referring to Data Table III, Mooney Scorch Data, the Scorch time (t 5 ) of the two compounds is substantially equivalent, the Scorch time (t 5 ) of (2) being only about 2.5% longer than (1). However, the real and critical difference is in the Cure Index. The Cure Index of (1) is 2.6, about 61.5% lesser, or faster, than (2) having a Cure Index of 4.2. 
     EXAMPLE 7 
     To demonstrate the utility of the sulfenamide of Example 1 in combination with N-t-butyl-2-benzothiazole sulfenamide (BBTS) and N-cyclohexyl-2-benzothiazole sulfenamide (CTBS) in styrene-butadiene rubber, a series of compounds were prepared following this general recipe: 
     
         ______________________________________Component        Weight parts______________________________________Ameripol 1712.sup.1            55.0Ameripol 1500    25.0Taktene 1203.sup.2            35.0Zinc oxide       3.0Stearic acid     2.0Carbon black (HAF)            70.0Sundex 8125      20.0Antozite 67F     2.0Agerite Resin D.sup.3            2.0Sulfur           2.0______________________________________ .sup.1 Styrenebutadiene rubbers, 22-24% bound styrene .sup.2 Polybutadiene .sup.3 Polymerized dihydroquinoline 
    
     Five compounds were prepared using the sulfenamide of Example 1, N-oxydiethylenethiocarbamyl-N&#39;-t-butyl sulfenamide (BTOS), with (1) N-t-butyl-2-benzothiazole sulfenamide (BBTS) and (2) N-cyclohexyl-2-benzothiazole sulfenamide (CTBS), and tested as shown in Table IV. The Monsanto Rheometer data were obtained in accordance with ASTM Test Procedure D 2084, the Mooney scorch data were obtained in accordance with ASTM test procedure D 1646, and the Stress Strain data were obtained in accordance with ASTM test procedure D 412. These data show the excellent results obtained using the novel combination of sulfenamide (BTOS) and these two benzothiazole sulfenamides. The Mooney Scorch times (t 5 ) are longer for the combination of N-oxydiethylenethiocarbamyl-N&#39;-t-butyl sulfenamide with N-t-butyl-2-benzothiazole sulfenamide (BBTS) or N-cyclohexyl-2-benzothiazole sulfenamide (CTBS) than that obtained with the equivalent amount of BBTS or CTBS alone. Also the cure rates of the combinations are obviously faster than BBTS or CTBS alone. Thus, by means of the novel combinations of this invention, a desired increase in scorch delay is obtained with no loss, and often, a gain in cure rate. This is not true of the combination of N-oxydiethylenethiocarbamyl-N&#39;-t-butyl sulfenamide with other commercially available benzothiazole accelerators. These commercially available accelerators include: N-dicyclohexyl-2-benzothiazole-sulfenamide (DCBS), N-diisopropyl-2-benzothizazolesulfenamide (DIBS), 2-mercaptobenzothiazole (MBT), 2-benzothiazyl disulfide (MBTS) or 4-morpholino-2-benzothiazyl disulfide (Morfax). This is demonstrated in the following Example 8. 
     
                                           TABLE IV__________________________________________________________________________Compound           1   2  3    4  5__________________________________________________________________________BBTS - weight parts    1.35    0.40                             0.45CTBS - weight parts       1.50BTOS - weight parts              1.01        0.61                             0.61Monsanto Rheometer, 1° ARC, 320° F.Maximum torque, in lbs.              31.2                  32.3                     31.5 32.0                             32.1Minimun torque, in lbs.              7.8 7.6                     7.1  8.1                             8.3M.sub.H -M.sub.L   23.4                  24.7                     24.4 23.9                             23.8Scorch time (t.sub.2), min.              5.3 5.6                     5.7  6.6                             6.4Cure time (t.sub.90), min.              10.1                  12.1                     10.8 11.4                             10.6Cure time (t.sub.95), min.              11.2                  13.7                     12.3 12.6                             11.7Cure rate index    18.6                  13.9                     16.9 18.7                             20.6Mooney Scorch, ML at 280° F.t.sub.5  (min.)    16.9                  19.0                     17.8 22.5                             21.0t.sub.35  (min.)   19.2                  22.1                     19.2 24.8                             23.0Cure Index         2.3 3.1                     2.0  2.3                             2.0Stress Strain, Opt. Cure (t.sub.95) at 320° F.Tensile strength, psi              2954                  2749                     2999 2821                             2766Elongation, %      581 548                     583  559                             555300% Modulus, psi  1218                  1217                     1243 1209                             1205__________________________________________________________________________ 
    
     EXAMPLE 8 
     The procedure from Example 7 was followed, including using the same base recipe and five commercial sulfenamide accelerators. The test results are found in Table V. 
     After an evaluation of the data it is reaily apparent that the improved balance of scorch times and cure rates obtained with the N-oxydiethylenethiocarbamyl-N&#39;-alkyl sulfenamides of this invention in combination with N-oxydiethylene-2-benzothiazole sulfenamide, N-t-butyl-2-benzothiazole sulfenamide and N-cyclohexyl-2-benzothiazole sulfenamide are not obtained with other closely related benzothiazole accelerators as demonstrated in these tests in this Example. The combination of BTOS with MBTS results in a scorch delay that is about an average of that of the two additives of the combination. BTOS with MBT exhibits a scorch delay shorter than either additive alone. Although some increase in cure index may be noted, there is still not obtained the desired balance of both increased cure rates and scorch delay. This is also the results noted with Morfax, DIBS and DCBS with BTOS. The scorch times are less for the combination than for Morfax, DIBS and DCBS alone, thus no advantage, and although the cure rates have been increased some this still does not provide the desirable balance obtained in accordance with the invention. 
     
                       TABLE V______________________________________Compound             1      2      3    4______________________________________MBT                         0.95MBTS                               0.95Morfax                                  1.62DIBSDCBSBTOS-weight parts    1.01Monsanto Rheometer, 1° ARC, 320° F.Maximum torque, in lbs.                31.2   24.8   25.8 34.0Minimum torque, in lbs.                7.8    8.2    7.9  8.3M.sub.H -M.sub.L     23.4   16.6   17.9 25.7Scorch time (t.sub.2), min.                5.3    5.9    5.1  4.3Cure time (t.sub.90), min.                10.1   22.0   20.8 10.5Cure time (t.sub.95), min.                11.2   25.3   24.4 12.3Cure rate index      18.6   3.8    6.0  14.8Mooney Scorch, ML at 280° F.t.sub.5 (min.)       16.9   17.2   14.0 12.5t.sub.35 (min.)      19.2   23.9   21.2 15.6Cure Index           2.3    6.7    7.2  3.1Stress Strain, Opt. Cure (t.sub.95)at 320° F.Tensile strength, psi                2954   2781   2715 3017Elongation, %        581    802    759  557300% Modulus, psi    1218   716    729  1331______________________________________Compound             5      6      7    8______________________________________MBT                                0.28MBTS                                    0.30MorfaxDIBS                 1.52DCBS                        1.97BTOS-weight parts                  0.61 0.61Monsanto Rheometer, 1° ARC, 320° F.Maximum torque, in lbs.                31.1   30.9   30.7 30.4Minimum torque, in lbs.                7.6    8.3    8.2  7.4M.sub.H -M.sub.L     23.5   22.6   22.5 23.0Scorch time (t.sub.2), min.                8.4    8.9    4.0  4.7Cure time (t.sub.90), min.                18.9   19.1   8.2  9.0Cure time (t.sub.95), min.                20.6   20.9   9.5  10.4Cure rate index      8.1    8.2    22.3 21.0Mooney Scorch, ML at 280° F.t.sub.5 (min.)       28.5   30.5   12.5 15.4t.sub.35 (min.)      35.2   37.0   14.5 17.4Cure Index           6.7    6.5    2.0  2.0Stress Strain, Opt. Cure (t.sub.95) at 320° F.Tensile strength, psi                3019   3072   2769 2803Elongation, %        612    650    609  604300% Modulus, psi    1151   1081   1030 1056______________________________________Compound             9        10     11______________________________________MBTMBTSMorfax               0.48DIBS                          0.45DCBS                                 0.59BTOS-weight parts    0.61     0.61   0.61Monsanto Rheometer, 1° ARC, 320° F.Maximum torque, in lbs.                33.4     30.5   31.2Minimum torque, in lbs.                8.2      7.4    8.1M.sub.H -M.sub.L     25.2     23.1   23.1Scorch time (t.sub.2), min.                4.2      6.2    6.1Cure time (t.sub.90), min.                8.2      12.4   12.1Cure time (t.sub.95), min.                9.5      13.9   13.6Cure rate index      22.0     14.3   14.6Mooney Scorch, ML at 280° F.t.sub.5 (min.)       13.0     19.4   19.2t.sub.35 (min.)      15.0     22.3   22.0Cure Index           2.0      2.9    2.8Stress Strain, Opt. Cure (t.sub.95) at 320° F.Tensile strength, psi                2937     2946   3108Elongation, %        552      622    634300% Modulus, psi    1315     1103   1161______________________________________