Patent Publication Number: US-6992116-B2

Title: Devulcanization of cured rubber

Description:
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/437,790, filed on Jan. 3, 2003. 
    
    
     BACKGROUND OF THE INVENTION 
     After they have been worn-out during their limited service life, millions of used tires, hoses, belts and other rubber products are discarded annually. These used rubber products are typically discarded and hauled to a dump because there is very little use for them after they have served their original intended purpose. A limited number of used tires are utilized in building retaining walls as guards for protecting boats and in other similar applications. However, the number of worn-out tires that need to be disposed of annually far exceeds the demand for them in these types of applications. 
     The recycling of cured rubber products has proven to be an extremely challenging problem. This problem associated with recycling cured rubber products arises because, in the vulcanization process, the rubber becomes crosslinked with sulfur. After vulcanization, the crosslinked rubber becomes thermoset and cannot be reformed into other products. In other words, the cured rubber cannot be melted and reformed into other products like metals or thermoplastic materials. Thus, cured rubber products cannot be simply melted and recycled into new products. 
     Since the discovery of the rubber vulcanization process by Charles Goodyear in the nineteenth century, there has been interest in the recycling of cured rubber. A certain amount of cured rubber from tires and other rubber products is shredded or ground to a small particle size and incorporated into various products as a type of filler. For instance, ground rubber can be incorporated in small amounts into asphalt for surfacing roads or parking lots. Small particles of cured rubber can also be included in rubber formulations for various rubber products that do not have high performance requirements. For instance, reclaimed rubber can be ground and compounded into formulations for floor mats or tire-turf for playgrounds. However, it should be understood that the recycled rubber serves only in the capacity of a filler because it was previously cured and does not co-cure to an appreciable extent with the virgin rubber in the rubber formulation. 
     Various techniques for devulcanizing cured rubber have been developed. Devulcanization offers the advantage of rendering the rubber suitable for being reformulated and recured into new rubber articles if it can be carried out without degradation of the rubber. The recycled rubber could again be used for its original intended purpose rather than simply as a filler. In other words, the devulcanized reclaimed rubber could again be used at higher levels in applications where there are high performance requirements; such as, in manufacturing tires, hoses and belts. The large scale commercial implementation of such a devulcanization technique could potentially be used to recycle vast quantities of worn-out tires and other rubber products that are currently being discarded to landfills. However, to the present time, no devulcanization technique has proven to be commercially viable on a large scale. 
     U.S. Pat. No. 4,104,205 discloses a technique for devulcanizing sulfur-vulcanized elastomer containing polar groups which comprises applying a controlled dose of microwave energy of between 915 MHz and 2450 MHz and between 41 and 177 watt-hours per pound in an amount sufficient to sever substantially all carbon-sulfur and sulfur-sulfur bonds and insufficient to sever significant amounts of carbon-carbon bonds. 
     U.S. Pat. No. 5,284,625 discloses a continuous ultrasonic method for breaking the carbon-sulfur, sulfur-sulfur and, if desired, the carbon-carbon bonds in a vulcanized elastomer. Through the application of certain levels of ultrasonic amplitudes in the presence of pressure and optionally heat, it is reported that cured rubber can be broken down. Using this process, the rubber becomes soft, thereby enabling it to be reprocessed and reshaped in a manner similar to that employed with previously uncured elastomers. 
     U.S. Pat. No. 5,602,186 discloses a process for devulcanizing cured rubber by desulfurization, comprising the steps of: contacting rubber vulcanizate crumb with a solvent and an alkali metal to form a reaction mixture, heating the reaction mixture in the absence of oxygen and with mixing to a temperature sufficient to cause the alkali metal to react with sulfur in the rubber vulcanizate and maintaining the temperature below that at which thermal cracking of the rubber occurs, thereby devulcanizing the rubber vulcanizate. U.S. Pat. No. 5,602,186 indicates that it is preferred to control the temperature below about 300° C., or where thermal cracking of the rubber is initiated. 
     U.S. Pat. No. 5,891,926 discloses a process for devulcanizing cured rubber into devulcanized rubber that is capable of being recompounded and recured into useful rubber products, and for extracting the devulcanized rubber from the cured rubber, said process comprising (1) heating the cured rubber to a temperature which is within the range of about 150° C. to about 300° C. under a pressure of at least about 3.4×10 6  Pascals in 2-butanol to devulcanize the cured rubber into the devulcanized rubber thereby producing a mixture of solid cured rubber, solid devulcanized rubber and a solution of the devulcanized rubber in the 2-butanol, (2) removing the solution of the devulcanized rubber from the solid cured rubber and the solid devulcanized rubber, (3) cooling the solution of the devulcanized rubber in the 2-butanol to a temperature of less than about 100° C. and (4) separating the devulcanized rubber from the 2-butanol. 
     U.S. Pat. No. 6,380,269 discloses a process for devulcanizing the surface of reclaimed rubber crumb into surface devulcanized reclaimed rubber crumb that is suitable for being recompounded and recured into high performance rubber products, said process comprising the steps of (1) heating the reclaimed rubber crumb to a temperature which is within the range of about 150° C. to about 300° C. under a pressure of at least about 3.4×10 6  Pascals in the presence of 2-butanol to devulcanize the surface of the rubber crumb thereby producing a slurry of the surface devulcanized reclaimed rubber crumb in the 2-butanol, wherein the reclaimed rubber crumb has a particle size which is within the range of about 325 mesh to about 20 mesh, and (2) separating the surface devulcanized reclaimed rubber crumb from the 2-butanol. 
     SUMMARY OF THE INVENTION 
     The most effective agent for devulcanizing cured rubbers is 2-butanol. However, large quantities of 2-butanol are required to devulcanize cured rubber on the large-scale basis that is required for commercialization. This invention relates to a technique for reducing the quantity of 2-butanol that is needed in the devulcanization of cured rubber. 
     The present invention is based upon the unexpected finding that the amount of 2-butanol needed to devulcanize cured rubber can be reduced by conducting the devulcanization in the presence of carbon dioxide. In fact, the amount of 2-butanol required can be reduced by at least 50 percent in cases where the devulcanization is carried out in the presence of carbon dioxide. Since carbon dioxide is an environmentally friendly agent it does not necessarily need to be recycled for subsequent use. In any case, the utilization of carbon dioxide to reduce the quantity of 2-butanol needed leads to significant process and economic advantages. The present invention is accordingly directed to a commercially viable technique for recycling large quantities of cured rubber from reclaimed rubber articles. 
     By utilizing the process of this invention, cured rubber can be devulcanized using a simple technique without the need for microwaves, ultrasonic waves or an alkali metal. In other words, the cured rubber crumb can be devulcanized in the absence of microwaves, ultrasonic waves or an alkali metal. The employment of the process of this invention also preserves the original microstructure of the rubber and allows for it to maintain a relatively high molecular weight. Thus, the process of this invention primarily breaks sulfur-sulfur bonds and/or carbon-sulfur bonds rather than carbon-carbon bonds. The devulcanized, reclaimed rubber can accordingly be used in the same types of applications as was the original rubber. 
     The subject invention more specifically discloses a process for devulcanizing cured rubber into devulcanized rubber that is capable of being recompounded and recured into useful rubber products, said process comprising heating the cured rubber to a temperature which is within the range of about 150° C. to about 300° C. under a pressure of at least about 3.4×10 6  Pascals in the presence of a mixture of carbon dioxide and 2-butanol. 
     This invention further discloses a process for devulcanizing the surface of reclaimed rubber crumb into surface devulcanized reclaimed rubber crumb that is suitable for being recompounded and recured into high performance rubber products, said process comprising the steps of (1) heating the reclaimed rubber crumb to a temperature which is within the range of about 150° C. to about 300° C. under a pressure of at least about 3.4×10 6  Pascals in the presence of a mixture of 2-butanol and carbon dioxide to devulcanize the surface of the rubber crumb thereby producing a slurry of the surface devulcanized reclaimed rubber crumb in the mixture of 2-butanol and carbon dioxide, wherein the reclaimed rubber crumb has a particle size which is within the range of about 325 mesh to about 20 mesh, and (2) separating the surface devulcanized reclaimed rubber crumb from the mixture of 2-butanol and carbon dioxide. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Virtually any type of sulfur-cured rubber can be devulcanized by utilizing the process of this invention. For instance, it can be used to devulcanize natural rubber, synthetic polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, isoprene-butadiene rubber, styrene-isoprene rubber, styrene-isoprene-butadiene rubber, nitrile rubber, carboxylated nitrile rubber, bromobutyl rubber, chlorobutyl rubber and the like. The technique of this invention can also be used to devulcanize blends of various types of rubbers. This is important because tires and most other rubber articles are typically made using blends of various elastomers. In actual practice the reclaimed rubber devulcanized by the process of this invention will usually be a blend of various rubbers. It will in effect be a blend having the composition of the tires, hoses, belts and other rubber articles used as the source of the reclaimed rubber. 
     In one preferred embodiment of this invention only the surface of rubber crumb particles made from the cured rubber is devulcanized. This technique is described in U.S. Pat. No. 6,380,269 the teachings of which are incorporated herein by reference. This typically involves grinding the reclaimed rubber to a particle size which is within the range of about 325 mesh to about 20 mesh and then devulcanizing the surface of reclaimed rubber crumb. It has been found that by doing so the surface devulcanized reclaimed rubber can be blended into and cocured with virgin rubber. This offers a tremendous commercial advantage in that it is only necessary to devulcanize the rubber on the surface of the reclaimed rubber crumb. Thus, the cost of the devulcanization procedure is only a fraction of the cost associated with devulcanizing the total quantity of reclaimed rubber being recycled. 
     The surface devulcanized reclaimed rubber can be used in manufacturing rubber articles that demand high performance characteristics (such as, tires, hoses and belts) when blended with virgin rubbers in quantities of up to about 40 phr. In fact, such blends of the surface devulcanized reclaimed rubber with virgin elastomers have cure properties and tensile properties that are comparable to blends made with totally virgin materials. 
     In devulcanizing only the surface of the rubber crumb is important for the rubber crumb treated by the process of this invention to first be reduced to a particle size which is within the range of about 325 mesh (44 microns) to about 20 mesh (840 microns). This can be accomplished by any mechanical means that will result in the particle size of the crumb rubber being reduced to be within the desired size range. For instance, the reclaimed rubber can be ground, cut or chopped to the desired particle size. It is normally preferred for the reclaimed rubber crumb to have a particle size which is within the range of about 100 mesh (149 microns) to about 40 mesh (420 microns). It is typically most preferred for the reclaimed rubber crumb particles to have a particle size of about 60 mesh (250 microns) to about 40 mesh (about 420 microns). 
     If the particle size of the surface devulcanized reclaimed rubber crumb made by the technique of this invention is larger than about 20 mesh (840 microns), it will compromise the physical properties of products manufactured therewith. Thus, it would not be suitable for use in manufacturing high performance rubber products; such as, tires, hoses or power transmission belts. On the other hand, the large scale commercial benefit of the present invention is reduced as the particle size of the reclaimed rubber crumb is reduced. This is because the benefit of devulcanizing only the surface of the reclaimed rubber crumb is lost as particle size is reduced. This is, of course, because the ratio of the volume of the core of the crumb rubber particles (which are not devulcanized) to the volume of the shell of the crumb rubber particles (which are devulcanized) is reduced. Thus, a higher percentage of the reclaimed rubber is devulcanized at smaller particle sizes which is detrimental from an economic standpoint. At particle sizes of less than about 325 mesh (44 microns), the economic benefits of devulcanizing only the surface of the rubber particles is believed to be lost because virtually the total quantity of the crumb rubber is devulcanized rather than just its surface. However, in some applications it may be desirable to fully devulcanize the entire quantity of the rubber being recycled. In such cases the use of carbon dioxide in accordance with this invention to reduce the quantity of 2-butanol required is of even greater significance. 
     The devulcanization process of this invention can be carried out by simply heating the cured reclaimed rubber crumb in the presence of a mixture of 2-butanol and carbon dioxide to a temperature of at least about 150° C. under a pressure of at least about 3.4×10 6  Pascals (Pa). It is normally preferred for the temperature to be no more than about 300° C. to minimize the level of polymer degradation. In other words, if the devulcanization process is conducted at a temperature of no more than about 300° C., the sulfur-sulfur and/or carbon-sulfur bonds in the cured rubber can be broken preferentially to the carbon-carbon bonds in the rubber. Thus, by carrying out the devulcanization process at a temperature of 300° C. or less, the molecular weight of the rubber can be maintained at a high level. For this reason, the devulcanization process will typically be conducted at a temperature which is within the range of about 150° C. to about 300° C. 
     It is normally preferred for the devulcanization process to be carried out at a temperature that is within the range of about 200° C. to about 280° C. The most preferred devulcanization temperatures are within the range of about 240° C. to about 270° C. The pressure employed will typically be within the range of about 3.4×10 6  Pascals (500 lbs/in 2 ) to about 3.4×10 7  Pascals (5000 lbs/in 2 ). It is normally preferred to utilize a pressure which is within the range of about 6.9×10 6  Pascals (1000 lbs/in 2) to about 2.8×10 7  Pascals (4000 lbs/in 2 ). It is generally most preferred to utilize a pressure which is within the range of about 1.7×10 7  Pascals (2500 lbs/in 2 ) to about 2.4×10 7  Pascals (3500 lbs/in 2 ). It is normally preferred for the cured rubber being devulcanized to be emersed in a bath that is comprised of a mixture of 2-butanol and carbon dioxide. In any case, it is important to protect the devulcanized rubber from oxygen during the time that it is at an elevated temperature. 
     The weight ratio of carbon dioxide to 2-butanol will typically be within the range of 5:95 to 70:30. The weight ratio of carbon dioxide to 2-butanol will preferably be within the range of 20:80 to 60:40, and will more preferable be within the range of 30:70 to 55:45. 
     The rubber crumb will be subjected to the devulcanization for a period of time that is sufficient to substantially devulcanize at least the shell of the crumb particles. As has been explained in some cases it is not necessary to devulcanize the rubber in the core of the crumb particles. The optimal amount of time required to devulcanize the rubber crumb particles is dependent upon the temperature, the pressure and the particle size of the rubber crumb. However, the devulcanization time will typically be within the range of about 1 minute to about 60 minutes. The devulcanization will typically be carried out over a period of about 5 minutes to about 40 minutes. The devulcanization will more commonly be carried out over a period of about 10 minutes to about 30 minutes. 
     After the devulcanization has been completed, the devulcanized reclaimed rubber crumb is separated from the mixture of 2-butanol and carbon dioxide. Since the devulcanized rubber is somewhat soluble in the mixture of 2-butanol and carbon dioxide at elevated temperatures, the separation will typically be carried out at a temperature of less than about 100° C. The devulcanized reclaimed rubber crumb can be recovered from the mixture of 2-butanol and carbon dioxide utilizing conventional techniques for separating solids from liquids and gases. For instance, decantation, filtration, centrification or a similar technique can be used to recover the devulcanized reclaimed rubber crumb and other solid residue (such as, carbon black, silica, clay and metals) from the mixture of 2-butanol and carbon dioxide. 
     The devulcanized reclaimed rubber made by the process of this invention can then be recompounded and recured into high performance rubber products; such as, tires, hoses and belts. The weight average molecular weight of the rubber can be maintained at a high level of over 100,000 and typically over 150,000. In some cases, a weight average molecular weight of over 200,000 can be maintained. The devulcanization technique of this invention does not significantly change the microstructure of the rubber and it can accordingly be used in the same types of applications as was the original rubber. In other words, the devulcanized rubber can be recompounded and recured into the same types of rubber articles as was the original rubber. 
     In cases where only the surface of the rubber crumb particles are devulcanized the reclaimed rubber crumb is comprised of a core and an outer shell. The rubber in the outer shell of the crumb rubber particles is devulcanized to a high degree. Thus, the rubber in the shell of the surface devulcanized rubber crumb will again be capable of being cured with sulfur. The surface devulcanized reclaimed rubber crumb is accordingly capable of being cocured with virgin elastomers. However, the rubber in the core of the surface devulcanized reclaimed rubber crumb is a cured rubber. The surface devulcanized reclaimed rubber crumb is useful in blends with other elastomers at any ratio of volume of the devulcanized shell to volume of the cured core. However, for economic reasons, it is desirable to minimize the volume of the devulcanized outer shell and maximize the volume of the cured core. 
     Rubber compounds that contain up to about 40 phr (parts per hundred parts by weight of rubber) of the surface devulcanized reclaimed rubber crumb can be made and utilized in manufacturing high performance rubber products. In most cases, about 10 phr to about 40 phr of the surface devulcanized reclaimed rubber will be blended with about 60 phr to about 90 phr of one or more virgin elastomers. The virgin elastomer can be virtually any type of rubbery polymer other than reclaimed rubber. For instance, the virgin rubber can be natural rubber, synthetic polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, isoprene-butadiene rubber, styrene-isoprene rubber, styrene-isoprene-butadiene rubber, nitrile rubber, carboxylated nitrile rubber, bromobutyl rubber or chlorobutyl rubber. 
     The surface devulcanized reclaimed rubber will typically be employed in such blends at a level of about 15 phr to about 35 phr. It is normally preferred for the surface devulcanized reclaimed rubber to be present in such blends at a level of about 20 phr to about 30 phr. It is generally more preferred for the surface devulcanized reclaimed rubber to be present in such blends at a level of about 25 phr to about 30 phr. 
     A preferred use for surface devulcanized reclaimed rubber is in making tire tread rubber compounds. Such tire tread compounds will typically be comprised of (a) about 10 phr to about 30 phr of a surface devulcanized reclaimed rubber crumb, wherein said surface devulcanized reclaimed rubber crumb is comprised of a core and an outer shell, wherein the core is comprised of a cured rubber and wherein the outer shell is comprised of a devulcanized rubber, and (b) about 70 phr to about 90 phr of a sulfur-curable virgin rubber. The sulfur-curable virgin rubber will typically be natural rubber, synthetic polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, isoprene-butadiene rubber, styrene-isoprene rubber, styrene-isoprene-butadiene rubber or a blend thereof. It is normally preferred for the surface devulcanized reclaimed rubber to be present at a level of 10 phr to 40 phr and it is most preferred for the surface devulcanized reclaimed rubber to be present at a level of 25 phr to about 30 phr. 
     This invention is illustrated by the following examples which are merely for the purpose of illustration and are not to be regarded as limiting the scope of the invention or the manner in which it can be practiced. Unless specifically indicated otherwise, parts and percentages are given by weight. 
     COMPARATIVE EXAMPLES 1–10 
     U.S. Pat. No. 5,891,926 shows that 2-butanol is superior to other alcohols in the devulcanization of cured rubbers. U.S. Pat. No. 5,891,926 shows a series of experiments wherein cured styrene-butadiene rubber (SBR) containing 23.5 percent bound styrene was devulcanized in various alcohols, including methanol, ethanol, 1-butanol, 1-propanol, 2-propanol, 2-butanol, isobutyl alcohol, 4-methyl-2-pentanol and 1-pentanol. The alcohol was injected into a Hewlett-Packard 5890A gas chromatograph at a pressure of 2.1×10 7  Pascals (3000 lbs/in 2 ) with an ISCO LC-5000 syringe pump. The Hewlett-Packard 5890A gas chromatograph was not used in the capacity of a chromatographic instrument. The chromatograph was used solely to provide a temperature controllable environment. In other words, the chromatograph was used in the capacity of a heating oven. The sample vessel in the gas chromatograph contained about 0.55 grams of cured SBR samples which were devulcanized and extracted by the alcohol that passed through the sample vessel which was inline with an all-metal flow path. 
     In the procedure used, the SBR samples were initially heated to a temperature of 150° C. and maintained at that temperature under static conditions for 10 minutes in the alcohol which was, of course, under the pressure of 2.1×10 7  Pascals (3000 lbs/in 2 ) Then, the alcohol was allowed to flow through the system at a flow rate of 1–2 ml per minute at a temperature of 150° C. for 20 minutes with the alcohol exiting the chromatograph being collected and the amount of devulcanized SBR that was extracted being measured. 
     Then, the temperature of the sample chamber was increased to 200° C. and was maintained at that temperature under static conditions for 10 additional minutes with the alcohol still being maintained at a pressure of 2.1×10 7  Pascals (3000 lbs/in 2 ). Then, the alcohol was again allowed to flow through the system at a flow rate of 1–2 ml per minute at a temperature of 200° C. for 20 minutes with the alcohol exiting the chromatograph being collected and with the amount of devulcanized SBR that was extracted being measured. 
     Then, the temperature of the sample chamber was increased to 250° C. and was maintained at that temperature under static conditions for 10 additional minutes with the alcohol being maintained at a pressure of 2.1×10 7  Pascals (3000 lbs/in 2 ). Then, the alcohol was again allowed to flow through the system at a flow rate of 1–2 ml per minute at a temperature of 250° C. for 20 minutes with the alcohol exiting the chromatograph being collected and with the amount of devulcanized SBR extracted by the alcohol being measured. 
     Finally, the temperature of the sample chamber was increased to 300° C. and was maintained at that temperature under static conditions for 10 additional minutes with the alcohol being maintained at a pressure of 2.1×10 7  Pascals (3000 lbs/in 2 ). Then, the alcohol was again allowed to flow through the system at a flow rate of 1–2 ml per minute at a temperature of 300° C. for 20 minutes with the alcohol exiting the chromatograph being collected and with the amount of devulcanized SBR extracted by the alcohol being measured. 
     The cumulative percentage of devulcanized SBR that was extracted from the cured SBR sample with each of the alcohols evaluated at 150° C., 200° C., 250° C. and 300° is reported in Table I. Example 2 is a repeat of Example 1. Examples 3–10 are examples where alcohols other than 2-butanol were used for the devulcanization. 
     
       
         
           
               
               
               
               
               
               
             
               
                   
                 TABLE I 
               
               
                   
                   
               
               
                   
                 Alcohol 
                 150° C. 
                 200° C. 
                 250° C. 
                 300° C. 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 1 
                 2-butanol 
                 38%  
                 82% 
                 90% 
                 93% 
               
               
                 2 
                 2-butanol 
                 40%  
                 70% 
                 85% 
                 92% 
               
               
                 3 
                 methanol 
                 2% 
                  3% 
                  4% 
                  7% 
               
               
                 4 
                 ethanol 
                 2% 
                  4% 
                  9% 
                 20% 
               
               
                 5 
                 1-propanol 
                 3% 
                 16% 
                 43% 
                 69% 
               
               
                 6 
                 2-propanol 
                 2% 
                  7% 
                 13% 
                 25% 
               
               
                 7 
                 1-butanol 
                 4% 
                 19% 
                 57% 
                 86% 
               
               
                 8 
                 isobutyl alcohol 
                 2% 
                 10% 
                 44% 
                 74% 
               
               
                 9 
                 1-pentanol 
                 3% 
                 11% 
                 42% 
                 89% 
               
               
                 10 
                 4-methyl-2-pentanol 
                 2% 
                 11% 
                 33% 
                 68% 
               
               
                   
               
            
           
         
       
     
     As can be seen from Table I, 2-butanol was far better than any of the other alcohols evaluated. It was particularly superior at lower temperatures. In fact, at 200° C., it extracted at least 70 percent of the SBR and, at 250° C., it extracted at least 85 percent of the SBR. The utilization of lower temperatures is, of course, desirable because less polymer degradation occurs at lower temperatures. The devulcanized SBR samples that were extracted were determined to have the same microstructure as the original SBR samples. 
     COMPARATIVE EXAMPLES 11–18 
     In this series of experiments from U.S. Pat. No. 5,891,926, the general procedure utilized in Examples 1–10 was repeated except that temperature was held constant at 250° C. and the alcohol was allowed to flow continuously at a rate of 1–2 ml per minute for 20 minutes at pressure. In this series of experiments, 2-butanol was used exclusively as the alcohol for the devulcanizations. Cured SBR samples that contained no filler, carbon black, silica or a combination of carbon black and silica were devulcanized and extracted with the 2-butanol. The SBR had an original weight average molecular weight of about 400,000. The weight average molecular weights of the devulcanized SBR samples recovered are reported in Table II. 
     
       
         
           
               
               
               
             
               
                 TABLE II 
               
               
                   
               
               
                 Example 
                 Filler 
                 Molecular Weight* 
               
               
                   
               
             
            
               
                 11 
                 no filler 
                 181,000 
               
               
                 12 
                 no filler 
                 186,000 
               
               
                 13 
                 silica 
                 244,000 
               
               
                 14 
                 silica 
                 293,000 
               
               
                 15 
                 carbon black 
                 197,000 
               
               
                 16 
                 carbon black 
                 216,000 
               
               
                 17 
                 carbon black/silica 
                 177,000 
               
               
                 18 
                 carbon black/silica 
                 177,000 
               
               
                   
               
               
                 *The molecular weights reported are weight average molecular weights. 
               
            
           
         
       
     
     As can be seen from Table II, the devulcanization technique can be used for rubber samples that contained silica, carbon black or a combination of silica and carbon black. Table II also shows that the devulcanization technique did not greatly reduce the molecular weight of the rubber. Thus, the devulcanization procedure destroyed sulfur-sulfur bonds and/or carbon-sulfur bonds without destroying a significant number of carbon-carbon bonds in the rubber. 
     EXAMPLES 19–22 
     In this series of experiments a one liter reactor capable of holding 150 grams of cured rubber for devulcanization was utilized in all of the experiments. These devulcanization experiments were conducted in static or dynamic modes (both modes with or without agitation) using 2-butanol alone or a mixture of 2-butanol and carbon dioxide under supercritical conditions as the devulcanization agent. 
     Compounding evaluations confirmed that the addition of 20 phr (parts by weight per 100 parts by weight of rubber) of rubber devulcanized by utilizing the technique of this invention can be added to a standard tire tread compound with minimal effect on cure, modulus or elongation. Tensile strength is slightly decreased in most cases, but can be compensated for by increasing the level of curative in the tire tread compound formulation. Experiments conducted in the static mode show a temperature dependence, with greater changes occurring at higher temperatures. Dynamic mode experiments were only conducted at 260° C. and had the same relative effect as the static mode at that temperature. The experiments that employed a mixture of 2-butanol and carbon dioxide (CO 2 ) at levels up to 50% produced changes in the devulcanized rubber similar to those obtained when using only 2-butanol under supercritical conditions. However, the use of carbon dioxide can reduce the process cost and may be used to remove any residual 2-butanol in the devulcanized rubber. A summary of the typical properties obtained at the 20 phr level is shown in Table III. The compound made in Example 19 was a control that was made without including devulcanized rubber. 
     Samples were treated under the same conditions and were combined and mixed in a Research Kobe mixer to evaluate processing, use of more devulcanized rubber in the tire tread formulation, and to perform additional tests. Generally, the addition of the devulcanized rubber to the tread formulations improved mixing and milling compared to similar amounts of untreated rubber. The compounds made with devulcanized rubber had better tack and banded better on a mill than untreated rubber and in some cases processed better on the mill than the control with no recycle material. 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE III 
               
               
                   
               
               
                 Example 
                 19 
                 20 
                 21 
                 22 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Temperature 
                 — 
                 270° 
                 C. 
                 270° 
                 C. 
                 270° 
                 C. 
               
               
                 Pressure 
                 — 
                 900 
                 psig 
                 900 
                 psig 
                 900 
                 psig 
               
               
                 Time 
                 — 
                 20 
                 min 
                 20 
                 min 
                 20 
                 min 
               
            
           
           
               
               
               
               
               
            
               
                 Mode 
                 — 
                 Dynamic 
                 Static 
                 Dynamic 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Cosolvent 
                 — 
                 30% 
                 CO 2   
                 50% 
                 CO 2   
                 50% 
                 CO 2   
               
               
                 Recycle 
                 20 phr 
                 20 
                 phr 
                 20 
                 phr 
                 20 
                 phr 
               
               
                 Level 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                   
               
               
                 Rheometer Properties at 150° C. (minutes) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Torque Max 
                 37 
                 35.9 
                 38.3 
                 36.6 
               
               
                   
                 Torque Min 
                 13 
                 11.3 
                 11.7 
                 11.1 
               
               
                   
                 Delta 
                 24 
                 24.6 
                 26.6 
                 25.5 
               
               
                   
                 Torque 
               
               
                   
                 Ts1 
                 5.5 
                 6 
                 6.4 
                 6.7 
               
               
                   
                 T25 
                 7.8 
                 8.4 
                 9.1 
                 9.9 
               
               
                   
                 T90 
                 17.1 
                 16.4 
                 16.6 
                 17.3 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                   
               
               
                 Physical Properties 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Tensile 
                   15 MPa 
                 17.5 MPa 
                 17.7 MPa 
                 16.5 MPa 
               
               
                 Elongation 
                 575% 
                 673% 
                 689% 
                 660% 
               
               
                 100% Mod. 
                 1.36 MPa 
                 1.43 MPa 
                 1.35 MPa 
                 1.25 MPa 
               
               
                 300% Mod. 
                 6.08 MPa 
                  6.59 Mpa      
                  6.4 MPa 
                 6.22 MPa 
               
               
                   
               
            
           
         
       
     
     Variations in the present invention are possible in light of the description of it provided herein. While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention. It is, therefore, to be understood that changes can be made in the particular embodiments described which will be within the full intended scope of the invention as defined by the following appended claims.