Abstract:
Tire flexing components having improved ozone and flex and weather resistance are prepared by blending a general purpose rubber with a chlorinated EPDM containing about 0.1 to about 0.9 wt. % chlorine. The products so formed are useful for tire components that are subject to severe flexing such as coverstrips and sidewalls.

Description:
CROSS-REFERENCE 
     This application is a continuation-in-part of Ser. No. 444,313, filed Feb. 21, 1974 now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     General purpose rubbers are employed in the manufacture of a wide variety of rubber articles including automotive tires. The term &#34;general purpose rubber&#34; as used in the specification and claims means the highly unsaturated rubbers of commerce illustrative of which are styrene butadiene rubber (SBR), polyisoprene, polybutadiene, natural rubber, etc. While these rubbers exhibit excellent physical properties in their vulcanized state, they are subject to attack by elemental oxygen, especially ozone. The resistance to oxidation and oxidative degeneration may be improved by the addition of an antioxidant or antiozonant at a concomitant increased cost in the rubber product. 
     It is well known in the art to improve the ozone resistance of such general purpose rubbers by blending the general purpose rubber (GPR) with an EPDM terpolymer. See, for example, U.S. Pat. No. 3,492,371, incorporated herein by reference. 
     It has been found that the EPDM rubber may be made more compatible with the GPR by brominating the EPDM. See, for example, U.S. Pat. No. 3,524,826, incorporated herein by reference. The disclosures of that patent teach that a requirement for operability of the invention is that the EPDM contain at least one wt. % bromine. The blends so formed have improved ozone resistance in addition to outstanding physical properties. 
     Heretofore, although compositions of GPR and EPDM demonstrated improved ozone resistance, they were lacking in flex properties and therefore had limited application in tire flexing components. 
     SUMMARY OF THE INVENTION 
     It has surprisingly been discovered that tire  sidewalls and coverstrips having superior ozone, flex and weather resistance can be prepared from vulcanizates based on binary blends of 70-75 wt. % of a general purpose rubber and 25-30% of a halogenated EPDM. 
     The compositions so formed have excellent tensile strengths. These compositions are non-staining and do not require costly antidegradants for stability. 
     DETAILED DESCRIPTION 
     This invention relates to a method for improving the flex, ozone and weather resistance of general purpose rubbers. In particular, this invention relates to a blend of general purpose rubbers comprising about 70-75% of a general purpose rubber and 25-30 wt. % of a halogenated EPDM. The term &#34;EPDM&#34; as used in the specification and claims is used in the sense of its definition as found in ASTM D-1418-64, and is intended to mean a terpolymer containing ethylene and propylene in the backbone and diene enchainment with residual unsaturation in the sidechains. Illustrative methods for producing these terpolymers are found in U.S. Pat. No. 3,280,082, British Pat. No. 1,030,989 and French Pat. No. 1,386,600. 
     The term &#34;tire flexing component&#34; as used in the specification and claims means automotive or truck tire sidewalls, coverstrips or treads. 
     The preferred polymers contain about 45 to abut 80 wt. % ethylene and about 2 to about 10 wt. % diene monomer. The balance of the polymer is propylene. Preferably, the polymer contains 50 to 60 wt. % ethylene, e.g., 56 wt. %, and about 2.6 to 4 wt. % diene monomer, e.g., 3.3 wt. %. The diene monomer is a non-conjugated diene. Illustrative of these non-conjugated diene monomers which may be used in the terpolymer (EPDM) are hexadiene, dicyclopentadiene, ethylidene norbornene, methylene norbornene, propylidene norbornene and methyltetrahydroindene. A typical EPDM is Vistalon 3509 (Exxon Chemical Company, U.S.A.), a polymer having a Mooney Viscosity at 212° F. of about 90 prepared from a monomer blend having an ethylene content of about 56 wt. % and a non-conjugated diene content (methylene norbornene) of about 2.6 wt. %. Typical of an EPDM containing ethylidene norbornene as a diene monomer is Vistalon 4608 (Exxon Chemical Company, U.S.A.), a polymer having a Mooney Viscosity at 260° F. of about 62, and an ethylene content of about 56 wt. %. 
     Methods for preparing halogenated EPDM are well known in the art. The halogenated polymers may be prepared by reacting an EPDM consisting of ethylene, an alpha-olefin other than ethylene, and a small amount of non-conjugated diolefin with a halogen or halogens, such as chlorine or bromine in a chlorinated hydrocarbon such as carbon tetrachloride, chloroform, trichloroethylene, tetrachloroethylene, or monochlorobenzene in the presence or absence of a free radical initiator, e.g., UV light or chemical initiators, etc. When a mixture of chlorine and bromine is used, usually bromination is effected first and chlorination follows. 
     Illustrative of chlorinated EPDM is chlorinated Vistalon 6505 (Exxon Chemical Company, U.S.A.) having the following properties: ethylene content, 48 wt. %; ethylene norbornene content, 9 wt. %; and a chlorine content of 0.65 wt. %. The polymer has an iodine number of 18.6 and a Mooney Viscosity ML 260 of 67. 
     The chlorinated EPDM usefuul in the practice of this invention contains about 0.1 to bout 0.9 wt. % chlorine, more preferably about 0.3 to about 0.7 wt. % chlorine, with optimum results being observed in the 0.55 to 0.65 wt. % chlorine range. 
     The chlorinated EPDM blends of this invention comprise at least 25 parts per hundred by weight of chlorinated EPDM based on the general purpose rubber. Preferably, the composition comprises about 25 to about 40 phr chlorinated EPDM; more preferably about 25 to about 35 phr; most preferably about 25 to about 30 phr. 
     Preferred highly unsaturated rubbers for use in the blends of this invention are styrene-butadiene rubber, polybutadiene rubber and natural rubber and blends of same, particularly blends comprising 25 to 75% by weight of natural rubber with the balance being styrene-butadiene rubber or polybutadiene rubber. 
     The advantages of the instant invention may be more readily appreciated by reference to the following examples. 
    
    
     EXAMPLE 1 -- Halogenation of EPDM 
     A. Typical Solution Halogenation Procedure 
     A 5-l round bottom flask was fitted with stirrer, condenser, thermometer, and a temperature controller. Normal heptane (3 l) was placed into the flask and heated to 80° C. EPDM (150 g) was cut into small pieces, placed into the flask, and stirred for 6-24 hours until completely dissolved. N-halosuccinimide and 0.20 g of benzoyl peroxide were added and the mixture was stirred for 4-33 hours to effect the halogenation. The mixture was cooled to ambient temperature and the insoluble by-products allowed to settle. The solution was decanted into a separating funnel and the polymer was precipitated by slowly adding the heptane solution to 2 volumes of vigorously stirring acetone. After drying to constant weight under vaccum at 40° C., Ca. 146 g of polymer was recovered. 
     B. Typical Neat Halogenation Procedure 
     EPDM (100 g), 1,3-dihalo-5,5-dimethylhydantoin (DMH) and (optionally) 0.5 g of benzoyl peroxide were thoroughly blended on a cool rubber mill. The amount of DMH was chosen such that the theoretical amount of reactive halogen was 0.5-1.0 g. The mixture was then heated between mylar sheets in a hydraulic press at 320° F. for 20 minutes to effect the halogenation. 
     EXAMPLE 2 -- Polymers Prepared Via Solution Chlorination 
     Various ethylene-propylene-diene monomer polymers were chlorinated by the solution methods set forth in Example 1 using N-chlorosuccinimide as the chlorinating agent. The results are shown in Table I. 
     
                                           TABLE I__________________________________________________________________________Chlorinating       Reaction             Wt. %     IodineEPDM Agent  Time, hrs.             Halogen                  ML-260                       Number                            I.V.__________________________________________________________________________V-460825 g NCS       24    0.26 94   7.2  2.4V-460840 g NCS       17    0.93 146  3.2  3.6V-650540 g NCS       5     0.33 66   18.4 2.4V-650525 g NCS       24    0.63 67   18.6 2.5__________________________________________________________________________ NCS = N-Chlorosuccinimide 
    
     EXAMPLE 3 
     Various blends of general purpose rubber were prepared using EPDM, chloro-EPDM and halogenated butyl rubber in an effort to improve the physical properties of the general purpose rubber. All the vulcanizates described in this example were press cured for 30 minutes at 307° F. Formulations used in this example are as follows: 
     
         ______________________________________Component           Parts per hundred______________________________________Elastomer as shownCarbon Black (FEF)  50Plasticizer (Flexon 580 oil)               12Sunolite 127 wax    1.5Stearic acid        1Zinc oxide          3Sulfur              0.4Mercaptobenzothiazyl-disulfide (MBTS)    0.6Alkylphenol polysulfide(Vultac #5)         2.0______________________________________ 
    
     
                                           TABLE II__________________________________________________________________________CHLORINATED VISTALON-6505 IN A BLACK COVERSTRIP FORMULATION                    1    2      3    4    5__________________________________________________________________________CHLORO-EPDM.sup.(1)     25    30V-6505                               25   12.5 22.5HT-1068.sup.(2)                           12.5 22.5RSS #1.sup.(3)          45    42     45   45   33SBR-1500.sup.(4)        30    28     30   30   22Shore A                 51    55     51   54   60300% Modulus, psi       780   940    750  1050 1350Tensile Strength, psi   2010  1930   1690 1980 1860Elongation, %           610   590    580  510  41050 pphm O.sub.3, 100° F.σ.sub.c (Ter/typ), psi                   152/159                         ˜173/&gt;181                                60/63                                     48/58                                          ˜196/&gt;213ε.sub.c (Ter/typ), %                   200/226                         ˜260/&gt;299                                52/56                                     33/43                                          ˜192/&gt;241ω.sup.c (Ter/typ), psi                   176/207                         ˜260/&gt;309                                17/20                                     8.5/14                                          ˜221/&gt;295E, psi                  233   239    177  195  30250 pphm O.sub.3, 100° F. o-30%extensionHours to fail           &gt;300  &gt;300   &lt;4   4    &gt;300Fatigue-to-Failure, 0-100% extensionKilocycles to fail (JapaneseIndustrial Standard), avg.                   81    71     46   69   77Goodrich Flex; 100° C., 15# load, 1/4&#34; strokeMinutes to rupture      11    --     6.5  6    --Outdoor Dynamic WeatheringHours to fail           280   --     &lt;24  &lt;24  280__________________________________________________________________________ Notes: .sup.(1) Chlorinated Vistalon 6505 prepared by the method of Example 2 containing 0.63% chlorine. .sup.(2) Chlorinated butyl rubber having a Mooney Viscosity (ML, 1+3) at 260° F. of 50-60, a viscosity average molcular weight of about 450,000 and 1.3 wt. % chlorine. .sup.(3) Ribbed smoked sheet - natural rubber. .sup.4 Emulsion polymerized styrene-butadiene copolymer comprising about 24% styrene having a Mooney Viscosity of about 52 (ML, 1+4) at 212.degree F. 
    
     EXAMPLE 4 
     Various compositions were prepared in a sidewall formulation. The samples were press cured for 30 minutes at 307° F. The formulation used in the example was as follows: 
     
         ______________________________________Component           Parts per hundred______________________________________Elastomers as shownCarbon Black (GPF)  60Flexon 580 Plasticizer Oil               30Stearic acid        2Zinc oxide          3Sulfur              0.8MBTS                0.8Vultac #5           1.5______________________________________ 
    
     
                                           TABLE III__________________________________________________________________________CHLORINATED VISTALON-6505 IN A WHOLE SIDEWALL FORMULATION               6     7     8    9    10__________________________________________________________________________CHLORO-EPDM (same as Table II)               25    30V-6505                          25   17.5 22.5HT-1068                              17.5 22.5Rss #1              37.5  35    37.5 32.5 27.5SBR-1500            37.5  35    37.5 32.5 27.5Shore A             49    49    48   49   49300% Modulus, psi   550   590   620  710  790Tensile Strength, psi               1470  1590  1380 1480 1500Elongation, %       680   680   600  590  55050 phm O.sub.3, 100° F.σ.sub.c (Ter/typ), psi               109/&gt;134                     105/˜139                           38/47                                58/70                                     169/˜181ε.sub.c (Ter/typ), %               165/&gt;348                     167/˜323                           38/51                                53/72                                     251/˜320ω.sub.c (Ter/typ), psi               104/&gt;266                     113/˜256                           7.7/14                                17/28                                     244/˜331E, psi              174   182   139  167  235Fatigue-to-Failure, 0-100% extensionKilocycles to fail (JapaneseIndustrial Standard), avg.               102   107   70   84   98Outdoor Dynamic WeatheringHours to fail       132   &gt;280  &lt;24  36   250__________________________________________________________________________ 
    
     Run 5 of Table II and Run 10 of Table III show the current state of the art in that in order to achieve the outstanding properties shown, 45 phr of specialty elastomer is required. The composition of this invention of the other hand (Runs 1, 2, 6 and 7) requires only 25-30 phr to achieve the same results, resulting in obvious economics. 
     In the tabulated data set forth above, the most significant property for evaluation of ozone resistance is ω c  (Ter/typ), psi, the critical stored energy density. When a comparison is made, for example, of the values given in Runs 1 and 2, which are examples of the invention, with Runs 3 and 4 which are comparative examples using approximately the same amounts of specialty elastomers, the improvement is readily apparent. The values for Runs 3 and 4 would be unacceptable and these compositions would be unsuitable for commercial tire components. The effectiveness of the compositions of the present invention is brought out by comparison with Run No. 5 where twice as much specialty elastomer is required to achieve acceptable ozone and weather resistance values. The same comparisons and conclusions are evident from a review of Table III.